mission duration but great to be with you again. We'd just like to welcome everyone to the mid-deck of the space shuttle Discovery. We're on a 124th orbit around the Earth since our launch last Thursday. The mission has been going great. We've completed eight days of intense pilot operations. The folks at KSC has given us a great vehicle in Discovery. She has operated flawlessly for the last eight days. And just to let you know where we are, we're currently 160 nautical miles above the surface of the Earth and we're in the South Pacific and during the press conference we'll be passing across South America and Northern Europe. And JSCPO, we're ready for questions. This is Marsha Dunn of the Associated Press for one or more of the rookies. I'm wondering what your biggest surprise about space flight has been so far and I'm thinking more of the day-to-day stuff, not necessarily the scientific experiments. So now I'm a rookie and this has certainly been the how much fun and how initially awkward it can be floating around in the freefall situation that we have here and also how efficient it can be for storing things. It's been really going to miss that when we get back on Earth. How the day-to-day activities change. Getting up in the morning and washing and getting ready for the day is a lot different here and take for granted when we're in gravity. Like spit out your toothpaste and it always goes... You do that a little bit differently and the whole morning routine changes tremendously. That was the biggest surprise for me. I guess what I would add to that is after about five or six days up here, you get kind of used to the funny attitudes up here where up can be anywhere, down can be anywhere. It could do to working upside down and whatever. It feels kind of natural after five or six days. Japanese investigators say this is the last space test of the MFD. And I'm wondering, do you think it's ready for her when it flies next time on the International Space Station? Could you sort of give a report card please? It's an A-plus. It's really been fun for Steve and I to fly the arms through all the different scenarios that we have. And it's performed very well and there are some things we really could not even test on the ground. Some of the compliance functions. And we sort of feel like test pilots up here trying out the arm and we have taken it to the edge of its envelope and tested every possible mode. And I think we have a lot of good data and we still are learning a lot about it and we'll be ready for International Space Station. This is Seth Bornstein from the Orlando Sentinel. Actually, Jan, if you can keep this, just to follow up on that question, you've had little problems with the computer commands and you've had sort of stop and go with the arm. Has that at all been frustrating or annoying? Or is it something you just really don't even notice that much? I don't notice it when something happens like that, but as I said, this is sort of a test flight of this hardware and it's performed very well. And in the compliance mode, the flexible compliance mode is something we can't test in 1G, in the gravity of Earth. And so that has really been where we've had the surprises. So we really didn't know what to expect there and the fact that we had to play with arm a little bit more to get it to do what we wanted to do really was not a worry to us. It's something that was kind of interesting to see how the different compliance modes worked. As far as the ground commanding, that went very well. Most of the day we only missed one run at the end when we lost the computer lock. So we proved that the ground commanding works and I think that was really a real triumph to command the arm from the ground and that really proves that we'll be ready for that for International Space Station. So the few little glitches we've had, I think, really proved that the system works well and the surprises that we have had are understood and we certainly can work on those and be ready, as I said. And one for Kurt Brown there. There's a long streak now going this year and into much of last year for first day landings, first day attempt landings at KSC with very few diversions to California. Do you feel under pressure that you're going to have to land here at KSC on the first day? And why do you think it is that shuttles aren't being waved off for weather much in landing on the first try now? Probably the pressure's not on me. It may be on mission control. They do all the real weather investigation prior to giving us a go for the orbit burn, but we obviously trust their judgment quite well and we'll be ready to go wherever they send us. I don't want to say we're just lucky, but obviously every shuttle landing that we do, we always look at the weather very, very strongly so that we understand what it will do within the next hour or so after the burn. So we have to give a lot of credit to our space meteorology group. They do a great job at looking at the weather and forecasting it and I think they're just that good. If they give us a go for the orbit, we can come on in there. Pete Caltteri with the West Kentucky News for Brearney. As a principal investigator on the MIMS, I was wondering if you could comment on the status and the effectiveness of both the units that are now on orbit and in particular how the MIR unit, its results, have impacted on what you did on shuttle. We've been up there for about a year and we've learned a fair bit from that and on basis of those results, we actually adjusted the design of this one a little bit to improve on that. In the data that I've sent to the ground from this unit, the folks on the ground report back up that we've got about a four to five improvement in the performance of this system and that's largely because of the small changes we've made in the design of this system. This has been from me reasonably well. We've been surprised by a couple of things that we're dealing with and we had one maintenance issue that we've solved I think now and we're in operation here again. But the units have performed quite well. I think they certainly improved the vibration environment for experiments of the type that we're going to do in the next few years on the space station. With all these icy comets coming into the atmosphere, I know they're not ice by the time they reach your orbit but they're water vapor. Is it going to be possible to see if you guys are flying through water vapor or can you any test or whatever to determine this? That's a good question and this is a brand new theory about icy snowballs pelting the Earth from deep space and possibly a source of water on the Earth's surface or at least hydroxyl in the Earth's atmosphere. Where we are now, 160 miles out, we're well above the Earth's atmosphere and so we don't expect to find water or any components of water up where we are. But we have deployed the Crystal Spa satellite and the Marci instrument on that satellite and both the Crystal and the Marci are taking detailed explorations at the middle atmosphere and making new discoveries since we put it out about eight days ago. And one of the very interesting bits of data that's come in and this is very fresh data so it hasn't really been analyzed to its fullest extent is that there is a large amount of hydroxyl, which is a component that's both involved in the water being in the atmosphere and also is one of the major players in the destruction of ozone in the atmosphere. So it's important to know about hydroxyl and there's a lot of it in the middle atmosphere between about 40 and 60 miles. We need to learn more about that and I think the Crystal Spa and the Marci instruments out there right now are going to tell us a lot more about how much water is there and give us a lot to think about and Commander can you tell me what's the proudest accomplishment of this flight as you see it for you and your crew? We have to say the spectrum of the activities we have on board and the number of activities we have on board. As I mentioned in the opening we've completed eight days of very intense payload operations and all those have gone very smoothly. We've had a few things to slow us down. We've gotten behind in the timeline a little bit but due to the shortening efforts of the folks on the ground we're able to blend those back in where right where we should be. I'd have to be very proud of my crew doing all that. With three rookies on board they have to adapt the space flight first and then work the payload operations and they've done an excellent job of that and with all the activities we have it's going to be one of the shuttle missions that we can look back and be very, very proud of. And I guess one for Kent Rominger since he's kind of lonely there. Aren't you going to be doing much of the rendezvous activity tomorrow and can you take us through a few steps of what's going to happen? The rendezvous is actually a team effort with all of us on board. In particular obviously Commander Kurt Brand myself and then Robert Kirby have done the primary amount of training for the rendezvous. But the rendezvous will start actually before we get into the rendezvous checklist which is four hours, about five hours before the actual grapple of the satellite. Some of our burns will begin phasiness to close back in on Krista's paws. Krista's paws is approximately 35 miles behind us right now. We're out in front of it. And we do some phasing burns to raise our orbit to slow us down relative to Krista and let us close on it. We actually hop over the top of Krista and do a full circle loop all the way back around it and we stop and come up from below for a while and then continue that first full circle loop back around to being out in front of it again where we started. Except this time we're only 300 feet out in front of it instead of 30 miles and then we close on into that final grapple.


There is like one term that I'm gonna mention to you just based on like This is the reason why I had to submit the URL to like be re-indexed and that's microformats. Oh All right, so can we talk about like they still think like I haven't really had to do a lot of SEO optimization for a while And like I knew microformats was such a huge thing because let's say you've got a product page And it has reviews on it and you want to show the little stars and like all of that kind of rich content And and every time I made a tweak and we deploy it I would have to then submit to get re-crawled and see like if you know the results got more rich and That was definitely like a very slow feedback cycle So like what is the state like is microformats still a thing and like Are there better resources out there right now for us to be able to pull that rich content out? I'm gonna be very happy on we have much better things So they're still a thing that they are now called structured data and we are using Jason LD so late Jason for linked data Yeah, this is this is all new terms to me, right? You're probably used like literally the Mac micro data Attributes an HTML. Yeah, exactly. I will use them and they were very hit-and-miss. Yes It was very easy to just like mess up one tiny thing and the validated and catch it And then it the stars would disappear. Yeah, and we have moved on from there Okay, that's how schema.org is a is an open source organization where people can submit or discuss or change or like do stuff with Semantic data that I want to want to put on the web and is participating There's much more semantic data out there that we are so then we are supporting in search results But a bunch of it is supported in search results So for instance if you have like an event that we want to have showing up with like the location And if you can like get tickets and who's the performer and all that kind of stuff If you have a recipe where you might have an image or the instructions on how to make it all the time It takes to make it and reviews how nice this this recipe might be Articles books and TV series all sorts of things we have documentation on that specifically as well If you go to developers to google.com search You find all the supported types and they show up nicely in the search results So you get like a little preview picture and then you get the stars and all that kind of stuff would have been amazing It's fantastic. It's Jason Which is so much easier Jason in it. It's so much easier. It's just like not little like meta Yes, so you have like your Jason blob and we have what's called the structure data testing tool That is a little dated by now, but it supports generally basically everything that we know of Shows up as either valid or invalid and then we have the rich results test because the structure data test while being very generic It's also not very specific to what you want to achieve You want to probably achieve the nice little stars showing up in the search results This is what we call rich results Mm-hmm, and there's the rich results test for it and that even gives you a preview of how that might look like in the search results There's no guarantee that it does look like that in the search results because people have been using it to like spam stuff Like yeah, I have a bazoolian reviews and they're like, yeah, you just like have some JavaScript generating fake reviews That's not really Well, how do how do you actually like use the tool because I remember you used to have to dump your entire HTML file in there You don't know if you did it too many times you got like timed out, right? Yeah, that doesn't happen anymore And you can so you have two options. You can dump a URL in it Which is nice and you can even use like n gawk or something if you have a local Or or you can even also still do like you dump your HTML in there We execute the JavaScript if you're using JavaScript within that code dump.  Sorry. Sorry, and you write it in and then Reruns it and you're like, okay, cool. This is what I wanted and it can take it back to you and Yeah, we have that tool. We have search console that gives you like a life View of what happens on your page also for micro data. Sorry for structured data. Yeah, micro data is not that much of a thing but The structure data is still going strong. It sounds like it's coming a long way. That's very exciting It does if I if I'm ever working for large retailer ever again If you have a blog at the article markup, you might get Oh, so okay, I'm gonna look at the schema for that that would be like author and stuff and other sources might pull the data as well Right, it's it's an open source format. So theoretically voice assistants could use it as well So just imagine if you have it like a recipe blog And then you stand in the kitchen go like hey assistant Thing whatever it is whatever company you're you're you're choosing there's like a variety of options these days, right? And then the thing goes like yeah, Martin's apple pie first step take some apples and peel them And you're like, oh, okay fair enough You know that can come from the structure data as well. So that's pretty cool. That is really cool I didn't I didn't even think of those use cases. I just always thought about specials else


Welcome to Module 1. In today's session we will be introducing the effects of prenatal alcohol exposure on the developing brain. Our objectives are to explain that due to the teratogenic or toxic properties of alcohol, prenatal exposure to alcohol leads to brain entry that is scattered across areas of functioning related to the progression or hierarchical way that the brain develops. The impact of alcohol on the developing brain affects individuals differently and this means that making predictions about specific strengths and challenges can be difficult both within and between affected individuals. However we do know based on the pattern of brain growth that the greatest areas of difficulty will typically be in regions of the brain that are further from the brainstem. We would like you to note three core messages when considering prenatal alcohol exposure and the process of brain development. First that alcohol is a teratogen. Second that the brain grows from bottom to top. And third because of the way the brain grows some regions are more impacted by alcohol than others. We will explain each of these three core messages further. Alcohol is a teratogen which means two things. One that alcohol can cross the placental barrier and two alcohol is capable of interfering with the development of the growing embryo and fetus. Although exact amounts of alcohol exposure needed to impact the developing brain are unknown, exposure to alcohol during pregnancy can impact development and can lead to a fetal alcohol spectrum disorder. It is the pattern of injury to the developing brain and the resultant impact on function that will be considered in the course of this and the following modules. The brain grows from bottom to top. It begins as a tube and it is from this tube that brain cells move upward and outward to gradually build the brain. Another way to think about brain growth is that it is like a cauliflower. Beginning with the stem the brain grows upward and outward. To support the way the brain grows first glial cells the support cells of the brain begin to move upward and outward branching off from the tube essentially forming scaffolding that supports the movement of the brain cells. The brain cells called neurons climb up the scaffolding moving to a specified location and in some cases replicating to form more neurons. Some neurons have a short journey, others have a long journey. When alcohol is introduced to the process of brain growth it may disrupt the cells in many ways damaging the basic scaffolding, confusing the neurons so they are unsure of where they need to go and or killing the neurons themselves. Which specific neurons are impacted depends on the timing and the amount of alcohol exposure. Consequently the impact to the developing brain is diverse and scattered. Because damage is so variable it is difficult to predict what challenges a specific individual with an FASD may face and it is important to remember that understanding one individual may not provide insight into another individual with an FASD. Similarly what may be a useful support to one person may not work with another. As a result of the variable pattern of impact caused by prenatal alcohol exposure it becomes crucial that we are able to respond to the needs of each individual in a flexible, adaptive way. A recipe card approach will not be effective. Rather we need to be prepared to be versatile in our interactions with individuals with an FASD. Although the impact of prenatal alcohol exposure on the brain is highly variable there are some areas of brain function that are more vulnerable to the impact of the alcohol. Consider the upward and outward progression of the neurons and glial cells that was just described. Which neurons may be more vulnerable to the exposure of alcohol, those traveling a short distance or those traveling a long distance? The correct answer is those with further to travel as there is a greater likelihood of misdirection and greater dependence on lower level systems to function effectively. The regions farther from the center are often referred to as higher cortical functions and include functions such as problem solving. Our basic functions, heartbeat and breathing are in the lowest region. In the middle are many of our species survival components including our fight and flight responses as well as our sexual drive. Thus in FASD we find the basic systems intact and the middle systems also known as the limbic systems generally functional but the higher systems required to manage those limbic systems for example management of a desire to fight to defend are most affected. So an individual with FASD may be very good at protecting themselves from a perceived threat either by fighting or running away but may not be as good at determining whether something really is a threat or deciding how best to respond to that threat given a specific context. Responding to an unintentional bump in a shopping mall or school hallway with a punch may reflect this misinterpretation of threat and a poor threat response and this behavior is a reflection of injury to the brain not an indication of mean or oppositional behavior. Thinking of the brain this way requires us to change our perceptions so that we can support alternatives rather than punish an individual for behavior that resulted from brain injury from prenatal alcohol exposure. In module one we have provided a brief introduction to the effects of prenatal alcohol exposure on the developing brain. Three core messages covered in this module were first alcohol is a tarratogen. Second the brain grows from bottom to top and third because of the way the brain grows some regions are more impacted by alcohol than others although exact amounts of alcohol exposure needed to impact the developing brain are unknown exposure to alcohol during pregnancy can impact development and can lead to a fetal alcohol spectrum disorder. How the developing brain is impacted depends on the timing and amount of alcohol exposure and is therefore highly variable. As a result it becomes crucial that we are able to respond to the needs of an individual in a flexible adaptive way. For example individuals with an FASD may have adequate limbic system functioning related to the fight or flight response and sexual drives but they struggle with higher cortical functions related to things like emotional problem solving and behavior management. In the next module we will explore brain functioning and FASD a bit further and explain how a process-based approach to understanding behavior is helpful when responding to individuals with an FASD.


Good morning, ladies and gentlemen, I'm very pleased to be here. From yesterday to today, the conference is talking about the mainly development and economic institutional reforms. So let me introduce you a little bit different on the institutional framework on environment protection in Vietnam and some recent reforms and development. So the outline of my presentation is firstly to review some Vietnam environment and context now and then provide you a review on the policy and institutional arrangement on environment protection in Vietnam, some recent developments and lessons learned. In other Vietnam context, you know that we have achieved quite a remarkable economic role, but it has slowed down from 2008 until now. And with the economic role, our poverty reduction have achieved also a remarkable success, which is Vietnam is one of the examples of the event in this field. The reason for that is we have pushed up the industrialization process of the country. You see here in terms of the industrial production value and the number of the labor in the industrial sector. And also the share of the industry sector of the GDP is increasing while the agriculture is decreasing. But we have to emphasize that the economic role of Vietnam is brown with the environment degradation. The picture here shows you the air pollution, the total solid particulate concentration in mixed cities in Vietnam continuously exceeded the standard. You see the red line and the blue line. Most monitoring data in the Hanoi, Hue, Danang, Ho Chi Minh City and many others exceeded the standard. And also the surface water is polluted, the data here shows for the BOD-5 in the Saigon River in the period of 2007 to 2011 exceeded the standard. And also the biodiversity decline is another issue while we have degradation in terms of ecosystem, especially here is the mangrove area, the decline in the number of the wild animals. It is increasing in the Red Book and also alliance plants and animals in the country. Another very, very pressing issue for Vietnam also is climate change impact. Vietnam has been forecasted to be one of the most seriously affected countries by climate change in the world. And the Maekong River Delta is one of the three most seriously affected in the world together with Danang and the Ngong River Delta. In the past 50 years the temperature of Vietnam has raised 0.5 to 0.7 and the C11 rise, another issue of Vietnam, has risen about 20 centimeters. And it is forecasted that by the end of this century the temperature would increase by 2 to 3 centigrade and C11 rise would raise one meter. If that happened you would see that the Maekong River would be submerged under the sea water. So about the institutional framework on environmental protection in Vietnam. Firstly about the legislation, policy in legislation. In Vietnam we have, in terms of environmental protection law, we have the law on environmental protection adopted in 1993 firstly and then revised in 2005 and now this has been amended in the last week adopted by the National Assembly. We have biotic law in 2008, we have law on environmental protection tax in 2010. And beside that we have related sector laws including like landage law, water resource law, law on forest development and protection, law on fisheries, law on saving and efficient use of energy and etc. About the environmental protection policy we can divide it into four groups. The third one is a pollution prevention and control. The second one is a rehabilitation of degraded area and improvement of environmental quality. The third one is the sustainable use of natural resources and biodiversity conservation. And the fourth one is responding to the policy on responding to climate change. I'll give you in a little bit a detail of these four groups so you can imagine on how is our policies. First on pollution prevention and control. We do the strategic environmental assessment or we call it SEA and the environmental impact assessment to prevent the future environmental pollution impact. We also require production, trade and services to control environmental protection in their activities and also to promote cleaner production, waste studies and applying the ISO 14000. And we do promote the integrated waste management with the 3R concept, reduce, reuse and recycle to control the illegal waste imports and also importing of outdated technology and equipment and to handle completely with zero polluting establishment we go with craft villages and environmental health spots. In Vietnam we have around 1400 craft villages which are so seriously polluting sources. A second group is rehabilitation of the degraded area and improvement of environmental quality. We are now conducting treatment of contaminated sites by Asian deoxyne in Da Nang, Binh Hoa. These sites are polluted by the war, the American war. We are also conducting treatment of canine lakes and other field sites contaminated by wastewater in urban area. And we are also improving the air, trying to improve the air quality in urban areas by promoting public transportation, application of tighter vacant standards and usage of cleaner fuel. We are also improving the water supply in the urban and rural area and we also rehabilitating and degraded natural ecosystem especially in the coastal mangrove forests. About the promote of sustainability use of natural resources and conservation of biodiversity, we are trying to protect the land environment from pollution infertility and desertification and to improve the water resources use, the efficiency of water resources use and reducing the water scarcity within reason and between seasons. We try to increase our forest cover by planting the forest and also to protect the natural forest. Now the biodiversity conservation, we develop a system of natural and protected areas and to maintain these protected areas. And we develop and implement programs on water species conservation, control of invasive alliance and conservation of gene and control the risk posed by the genetically modified organism. Here you can see the changing of the forest cover in Vietnam from 1943 until 2012. Talking about the policy on strength and capacity in respect to climate change, our priorities is adaptation because the emission of Vietnam is not high as compared with other countries. We try to strengthen our capacity on monitoring for casting and warning on climate change and disaster. We are developing the infrastructure like sea dyes and dams for prevention and restraint of impact by sea level rise of a disaster. And also we have a strategy on the mitigation of the damage from natural disaster. About mitigation, we promote energy efficiencies, promote the development of renewable energy and also, as I said before, is increasing the GHZ sink through the forest plantation. We are also carrying out the GHZ inventories to report to the UN FCC and also implementing national appropriate mitigation actions. Those are the four groups of policies on environmental protection in Vietnam. Let me share with you some institutional arrangements on environmental protection. Vertically, our administration divided in four levels, national, provincial and district and commode level. And at the national level, the MONDRAE, the Ministry of Natural Resources and Environment is the Responsible Ministry for Environmental Protection, besides it covers also other natural resources, sub-sector like land use, water resource, geology, marine, sea and island and et cetera. Under MONDRAE, we have the Vietnam Environment Administration, or VA, responsible for the environment management. At the provincial level, we have the Department of Natural Resources Environment, we call LONGRAE, under which we have also the Environmental Protection Agency, or EPA, responsible for environmental protection within the province in Vietnam. We have 63 provinces. And at District 7, we have a division on the Natural Resources Environment, and at the commode level, we have usually have the environment officer. Horizontally in Vietnam, the environment protection is decentralized to other ministries also. So here you can see that MONDRAE is a focus for environmental protection, but in other ministries like Ministry of Industry and Trade, Ministry of Construction, Ministry of Rural and Rural Development, they have a department on the Responsible for Environmental Protection. And maybe different from other countries, we have Environment and Police, it's under Ministry of Police in Vietnam. So those are the institutional framework on environmental protection in Vietnam. Now I would like to share with you some recent reforms in the field of environmental protection in Vietnam. Firstly, it is the national strategy on green growth. You see in the first part of the presentation that the economic growth in Vietnam is brown. So the government adopts this national strategy for green growth in 2012 is trying to change to shift the brown model of growth into the green. And the objective is the green growth as the means to achieve the low carbon and enrich national capital to become a principal direction of sustainable economic development in Vietnam. And the key area of this strategy is three areas that firstly is reducing the greenhouse emission intensities. And secondly is greening production and thirdly is greening lifestyle and consumption. Second reform I would like to share with you is this adopted last week in the law on environmental protection is the environmental planning. Environmental planning is this law refers to the ecological and front-front toning and also the plan on the environmental infrastructure for environmental protection. Ecological and front-front toning here is to divide the country into different ecologic zones for different development or conservation purpose. And this division is based on the ecological characteristics, resource potential and adaptation capacity to climate change of the region. The third one is the realization of extended producer responsibilities. Extended producer responsibility is the tool in the pollution control that requires producer and importer of certain products have the responsibility to like to take back and treat in an environmentally friendly manner these discarded products. And these tools have been applied in many other countries, especially in developed countries but Vietnam. It has been introduced in 2005 but now is realized by the Prime Minister decision. And the last reform I would like to share here is the payment for forest environment services. Maybe Vietnam is the first country in Asia to apply this tool. This has been piloted two years in 2008, 2009 and then applied nationwide from 2010 by a decree of the government. The mechanism of this tool is that the company and the hydropower companies, water supply company and tourism company in downstream of river pay to the forest household that keep the forest, protect the forest in upstream of river to protect the forest so that keep the water and keep the dam not to avoid the sediment. So the payer here is a hydropower plant, water supply company, tourism companies and the pay is the forest protection house of upstream communities, upstream area. The rate here is 20 Vietnam Dong per kilowatt hour of hydroelectricities, 40 Vietnam Dong per cubic meter of water supplies and 1 to 2 percent of gross revenue of eco tourism companies. The revenues from 2009 until last year, 2013 is around 140 millions of US dollars and mainly come from the hydro power plants. However, there are still some difficulties in this birthment of this collected revenue, meaning that only 45 percent of this collected revenue have been paid to the household. It is due to difficulties in inventory of the forest and the type of forest, etc. So some lessons learned from this environment protection in Vietnam in some recent reform is that we are witnessing that green economy can become a new world paradigm and recommended by the UN for the developing country like Vietnam with the concept of tracing us to enrichment of natural capital, low carbon development and low zero waste developments. We see that institutional reform play an important role to create enabling conditions for promoting the green world. Participation of communities and business sector are very important in implementation of this institutional reform and governments just play a trick-or-ring role. In some cases, like in case of the payment for forest environment services, to ensure success, this policy should be better be piloted in a small area before applied nationwide. Then it's key to bring into the success. Also lesson learned from other countries are very important in international support play quality role for successful implementation such as a case of payment for environmental services. So thank you very much for your attention.


Coming up on DTNS with the NBC YouTube fight and temporary peace means the reality behind the let's encrypt failure and what the US wants to do to stop swapping. This is the Daily Tech News for Friday, October 1st. Welcome to Rocktober 2021 in Los Angeles. I'm Tom Merritt. And from Studio Redwood. I'm Sarah Lane. And from somewhere in St. Louis. I'm Patrick Norton. Draw on the top tech stories from Cleveland. I'm Len Peralta. And on the show's producer, Roger Chang. We were just talking sports teams. Choosing who to cheer for and who to cheer against and why some people think baseball is boring. Get that wider conversation on our expanded show, Good Day Internet. Become a member at patreon.com slash DTNS. That is where you can join our top patrons like Dustin Campbell, Tim Deputy, and Brandon Brooks. Let us begin with a few tech things you should know. Nigerian President Muhammadu Buhari ordered the country's ban on Twitter be lifted on the condition it's used for business and positive engagements. Nigeria banned Twitter back on June 5th after the platform deleted one of the president's tweets. Nothing but ads and cat pics. Taiwan Economy Minister Wang Mehua said in an interview Thursday that Taiwan needs Malaysia's help to resolve the global shortage of auto semiconductors, particularly in auto chip packaging. Manufacturing happens a lot in Taiwan. Packaging of the chips happens in Malaysia. Wang said that Taiwan is a major chip producer, but companies in Malaysia provide services not offered by Taiwanese firms. Malaysia is home to suppliers and factories serving seven conductor makers such as STM, Microelectronics, Infineon, and automakers like Toyota and Ford. The California Department of Motor Vehicles granted Waymo and Cruise permission to operate general public autonomous vehicle rides under certain conditions within the state. Cruise's permit allows five autonomous, no human vehicle deployments for commercial services in part of San Francisco between the hours of 10am and 6pm at a maximum speed of 30 miles per hour with good weather conditions only. So if it's super foggy, can't be driving. Waymo can operate in parts of San Francisco and also San Mateo counties with a speed limit of 65 miles per hour with good weather visibility, but must put human drivers behind the wheel as well. The California Public Utilities Commission needs to sign off on deployment permits for both companies before paid passenger rides can begin. The human drivers in San Mateo are so they can turn around and explain. I can't go faster than the 65. I'm sorry. It's against the rule. Google has ended its plans to offer bank accounts from Citigroup and Stanford Federal Credit Union to users of Google Pay not going to happen. Google says that instead it will focus on, quote, delivering digital enablement for banks and other financial service providers rather than us serving as the provider of these services. Foxconn bought an Ohio EV factory from the EV startup Lordstown Motors in a $230 million deal. Lordstown Motors will remain a tenant at the plant and will work with Foxconn to build its upcoming electric pickup truck at the facility. All right, let's talk a little more about the spat fight brawl between NBC and YouTube TV. It's what I consider a sign that over the top multi-channel streaming services have come into maturity. It's a good old-fashioned carriage dispute. It goes back into the 80s even and find examples of cable companies and television networks blasting each other on air about who's at fault for losing channels. Well, NBC started running messages in the versions of its broadcasting cable channels that aired on YouTube TV. Warning viewers that greedy Google is going to drop its channels on Thursday and gave them a website where they could go complain to Google and everything. Google made a blog post saying it just wants to pay the same as all the other services that carry NBC channels. It's not asking for anything special. It also promised to lower the monthly fee of YouTube TV by $10 per month if NBC channels became unavailable. Thursday night came and went and the NBC channel stayed up. A spokesperson for NBC Universal said in a statement that NBC Universal and YouTube TV have agreed to a short extension while parties continue talks. They did not say how long that extension was for. Basically, NBC wants to keep its rates to YouTube TV high and wants Google to bundle in Peacock as an offering for YouTube TV. The way it bundles services like HBO Max, for instance. Although ours technical sources say that Peacock idea is now off the table that they're just talking rates. One question for you guys. Are these two companies fighting over scraps? I mean, multi-channel services on cable are declining. And while YouTube TV is doing better than some of these, these multi-channel over the Internet services are not booming. Patrick, what do you think? I don't know. It's been so exhausting over the last couple of years watching, you know, this company won't, you know, Amazon doesn't do this or this doesn't do that or that doesn't these. And yes, this is an old fashioned carriage spat. And I just feel like YouTube's promising itself or pushing itself that it's the replacement for cable because there's still a staggering number of cable users out there. And they need NBC to do that.  I mean, it's, it's, I just feel like multi, I'm so not into any bundle of channels where 90% of the channels I don't watch, I'm paying for. Yeah, I heard Sarah giggling there. Where it's just like, oh, 437 channels in the average person skims nine and watches more than four hours a week on like two or three. I think that was the numbers they told us years ago. It's just, you know, as long as there's, as long as there's carriage and platforms and fire TV and Apple TV and Roku TV and Google TV and YouTube TV and cable networks and. Pissy little, you know, ISPs that want to extort more money out of, you know, Netflix or any other channel. This is this is just never going away. It's never going away, Tom. Well, from somebody who pays for YouTube TV, I, I don't know. I don't know if I'm in the minority here, but I was like, I'd like to pay $55 a month instead of 65 who cares make NBC go away. It's fine. But during the Olympics, this would be much more of a headache, right? So it's interesting timing that this is all happening when it's happening. We also don't know how long the talks are being extended. You know, I sort of imagine someone being like, when do I pull the plug and NBC is like not yet or YouTube TV or who, you know, whoever we're still talking, give it a week. But, but I, I like YouTube TV is the only multi-channel cable alternative I have subscribed to for any length of time. It's just a lot cheaper than anything I could have gotten in the past. Even when you get like Comcast specials and stuff, it's like it's only $65 for the first year and then they jack it way up. I don't pay for any add-ons.  I like it a lot, but I also completely agree that really I'm mostly paying for ESPN and maybe, you know, an award show here and there. Most of the channels go unwatched. I am certainly paying for stuff that I don't use, but it's kind of my best option right now for variety. I think you drive yourself crazy if you think about the stuff you're not watching. What I try to do personally is say, what do I need out of the service? And is it worth what they would make me pay for it? And pretend I'm only paying for that. Because a lot of people were complaining, speaking of ESPN, a lot of people were complaining, why can't I just get ESPN? I'm like, look, ESPN is probably going to charge you $20 a month if you just got ESPN, which you can do right now. You can go to Sling TV. Of course, I think it's now $30 or $35 a month, but back when I was making this argument in the early days, it was only 20. You could go to Sling TV, get ESPN, and only pay $20 a month or now $35 a month. If that's worth it to you, just do that. And people are like, yeah, but then I get all those other channels. I'm like, pretend you don't. If all you want is ESPN, just pay that amount and get it. People get caught up in like, yeah, but I want to pay for just ESPN, which that's a different way of looking at it. But I do think we're headed towards a world where you will, ESPN Plus will eventually get more and more things and become paying for ESPN. And I'm curious if these multi-channel systems will stay up then, because I pay for Direct TV Stream because we get sportsnet LA, which my wife uses to watch the Dodgers, and it's the only way to get it outside of Spectrum Cable, that there is. And then I also use it to watch NHL Network and MLB Network and stuff. But if we could get all of those out of cart, we might not get Direct TV Stream. It would depend on the cost, I guess. I mean, it's crazy. I'm looking at the list of NBC shows, and I'm laughing because I'm so detached from Cable. I'm so detached from the networks, but it's like America's Got Talent, 6 million viewers, American and Jewary, or 3.3 million viewers. This is us, 5.57 million viewers, Chicago Fire, Chicago Med, Chicago PD, 6 to 7 million viewers, law and order, law and order. It's interesting watching this whole, I had a conversation with somebody trying to explain to my, actually with my boys, talking about the miracle, the movie about the 1980 hockey team, and how everybody knew where they were when that happened. Because it was such this huge event, and it was something that everybody watched and was available anywhere anybody had a television, and just how fragmented things are today. Yeah. I mean, all those NBC shows you can get on Peacock, a lot of the Fox stuff is going to end up showing up on 2B, it looks like. So the shows at least will still be available even if the multi-channel services go away. It's all going to change. Yeah.  He's like, hold on, like, so ESPN Plus is not going to show me this? Like what am I paying for? And I was like, I don't know. It's like, there's still so many questions about what exactly do I get with what I'm paying for, and if I'm saving money, what am I missing? So yeah, there's work to be done. There's a long time for the transition to happen, for sure. Yeah. Well, the standalone version of Microsoft Office 2021 launches on October 5th, and Microsoft just announced some details. If you don't subscribe to Office or you don't want to subscribe to Office, here's what you need to know. The major consumer version, Office Home and Student for Windows and Mac will be $150 and includes Word, Excel, PowerPoint, OneNote, and Teams. Microsoft 365 costs $70 per year or $7 per month with the family plan for up to six people running $100 per year and $10 per month. It adds OneDrive, Microsoft Editor, and Microsoft Family Safety, plus Access and Publisher for PCs. Office Home and Business 2021 costs $250 and adds Outlook and the right to use it in a business setting. In both versions, you get the new refreshed ribbon interface to match Windows 11. And coming over from the Microsoft 365 subscription versions are Excel and PowerPoint improvements with things like better inking and Outlook translation. You can now also collaborate on documents in real time, and there is OneDrive support and Teams integration as well. I'm glad you brought up the Microsoft 365 stuff, because I see a lot of people in our chat room and Discord saying, I don't want to subscribe, I just want to buy the thing, and they get very excited when the standalone version finally comes out. But you don't get as much, and I know there's still good reasons to just get the standalone, but you don't get the collaboration. You don't get OneDrive. Well, now you're getting the collaboration. Okay, but you still don't get OneDrive. You still don't get the continuing updates. Patrick, what do you think is the sensible reason to get the standalone version of Office versus the ongoing subscription? I was laughing because I was reading this story in pre-show, because I just canceled my office subscription simply because I only needed it for a client I was working with and not working with them, and I don't feel like paying $100 for an app I never use. I don't really understand why anybody still buys most of this stuff. And I also realized that this office is still the standard in so many organizations, in so many organizations most people work with. But yeah, it doesn't, I don't get the alternative. Microsoft Family is like $99 a year, and it covers everybody in the house, so I don't really know why you would go for some of these versions. It makes no sense to me. There must be something we're missing that it offers, but I got nothing. Yeah, well, I'm sure the legitimate uses are there. Feedback at datatechnewshow.com.  Do you use Libra Office or just Google Docs? I still do so much writing and text editors, and I play around with different ones. But yeah, for most stuff I do collaborative, I do with Docs because it seems to work so much better than every other tool I've used for collaborative projects. Well, another good thing to use is a free security certificate on your website. Let's Encrypt offers free security certificates. They're most famous for enabling secure connections for websites, but they're often used in devices and used by enterprises, especially for Internet of Things devices to keep their connections secure, which is important. But if you know anything about security certificates, you know they expire every so often. In fact, I just got a notice that Let's Encrypt was updating my new security certificate for the website. It's a safety measure. Make sure the service you're using is still active and all that. One of Let's Encrypt's earliest certificates called IDENTRUS to DST root CAX3. You don't need to memorize that, but that's what it's called. Expired at 10 a.m. Eastern Thursday, September 30th. Now, this was not a surprise. Let's Encrypt gave lots of advanced warning. Of course, every certificate also says when it's going to expire. But Let's Encrypt foreign people like, hey, if you're using this one back in May, they said you need to be aware that it's going away September 30th. And we know a lot of you have this, but even with that advanced warning, a lot of folks didn't get the new certificate updated in time. Some of the bigger ones that had issues were Shopify, QuickBooks, Heroku, Fortinet, Rocket League, Shopify, for instance, acknowledged the problem and had its logins restored by 3.30 p.m. Eastern. So this hasn't caused widespread, ongoing outages. But you may think, well, it's obvious and easy to update a certificate. Why didn't you do it? Well, it's usually not just in one place. Sometimes developers within companies will implement a certificate without documenting it properly when they're developing somebody and nobody knows it's there until it fails. Modern root chaining allows for redundancies to back these things up, but you may have an older system that doesn't benefit from root chaining and you may not realize that. It can also affect consumer devices if the user hasn't kept their operating system or firmware up to date. So if you've got a system that's older than Mac OS 2016 or Windows XP Service Pack 3, Android 7.1.1, those all have reported issues as have older PlayStations, including PlayStation 4s that aren't up to date on the firmware. Companies that want to prevent future problems with other certificates expiring can do a test, set your system clock on the server forward after the certificate expires, and then see if your root chaining works properly or not. There's other ways to do this in other workarounds, but if you were seeing reports about this or if you're trying to play Rocket League or use QuickBooks and you were running into this problem, this explains what was going on out there. Did you know anything, either of you? Actually, yes. I did get an email from a service provider of sorts who said, yeah, there's some security stuff. Please stand by it. I just was like, it's not affecting me. So I didn't really understand what was going on until I read this story today. I mean, the solution is it's like quadrupled. To be on top of your... Yeah, the developer needs to be a better communicator. The folks who use encryption certificates need to not pretend that it's not going to be a problem six months after they're told it's going to be a problem. And then, you know, kind of everybody needs to understand that certificates are in multiple places and it's not just a matter of pressing a button and everything is fine. I guess that's threefold. Yeah, and I don't think most pretend it's not a problem. I really do think most just can't find all the instances. Maybe they need to prioritize it higher. I don't know. But yeah, I think it's a problem not knowing where all the certificates are. It's one thing when you have one website like us. It's a lot more complicated when you have an intricate system like an enterprise. Or if some junior level or middle level or even upper level staffer leaves and for some reason there... I mean, literally, there's an organization I worked at, big media company, somebody left, and nobody knew that that was the only person that knew how to actually, in this case, pay for the domain... They were the only person to have the domain name registrar access. It's amazing how much... There's so many things... There's so many failure points if you don't do a good job communicating or making sure we know what the tools are and what the dates are. But it's also kind of Shopify, QuickBooks, Rocket League. These are all complex systems, right? These are big organizations. Oops. Yeah, the bigger the organization, the more likely this is to happen, it feels like. Yeah. Hey, folks, this weekend we're released gaming news monthly. So if you're into gaming news, check that out. Jen Cutter is going to round up the month's biggest video gaming news in about 15 minutes for you to make it easy for you to be up-to-date, whether you're a hardcore gamer or just thinking about getting into video gaming. The monthly summary is going to bring you up to speed. You don't have to do anything. It's just going to show up in your DTNS feed this weekend. I just wanted to make sure you knew. SimSwapping is a practice where an attacker uses personal information about somebody, usually something they've found on the Internet, social security numbers, stuff like that, to contact a cell phone carrier and get the phone number of that person transferred to a new SIM card under the attacker's control. Once the attacker has that phone number, they can use it to access accounts that use that phone number for things like password recovery or SMS second factor. So the U.S. Federal Communications Commission has proposed new rules to prevent SimSwapping and what's called Port Out Fraud. That's basically the same as SimSwapping but going to a new carrier, not just to a new phone within the same carrier. The rules would require more secure methods for verifying identity. So before a transfer happens, the FCC proposes that a customer should have to do something like one of the following. Use a pre-established password. Some already do that right now. T-Mobile does that. Get a one-time code sent by text or voice to the existing SIM card to say like, hey, somebody's trying to change this. Is that you? Maybe a pre-registered backup number of another phone or have a code emailed to a pre-registered email address. Either one of those would help if you lost your phone and somebody was trying to swim SimSwap. The FCC seeks comments on which of these is secure enough and which should be required. So the FCC, in this case, is doing an actual notice for proposed rulemaking saying we want to change the rule. What should we change it to? Community? Security community? Talk to us. What should we do with the good options? The FCC also asks if there are more secure methods or whether carriers should comply with existing NIST digital identity guidelines. But instead of just saying we should do that, they're saying, hey, would that be a problem? Is that a good idea? They also propose requiring carriers to notify a customer when a SIM switch or port-out request is made before it is completed. Again, some carriers already do this, but they are thinking maybe we should just make that the standard for everybody. Another thing about this notice for proposed rulemaking is it really was a proposal. It wasn't, we're going to do this. Tell us if it's a bad idea. It was, hey, here are the options. Help us figure out what the best way to make a standard is. This is just so long overdue. It's been interesting to watch domain name registrars, which seems to be a theme for me today. Cell phone company. If somebody gets your number or access to your number, there's just amount of control over access to pretty much everything in their life. And it's kind of shocking how easy this is in some cases and all too often even a marginally talented social engineer with some patients can scam their way into your number if they want it. And this is, hey, I love it when they actually ask for the best way to do it. I think it's really interesting to see what the responses from this are and what the responses are like from different companies. That's always tremendously revealing about how different companies are thinking about security, but I welcome anything that, you know, well, I'll knock on both when I say this. I generally welcome anything that makes us more secure and makes it harder to steal these crucial points in our ability to be ourselves online. One thing I was impressed with in reading through the notice, I was reading and it said, maybe yes, should be sent to the phone before the SIM has changed and I was like, yeah, but there's that other way of without SIM swapping of getting a hold of a text message that you could use. The next paragraph was, but we know there's another way for text messages to be so should there be other ways like email and I was like, oh man, they really did the research on this one. Good job. It's nice when they do that.  Between May of 2018 and September of this year, Netflix's data traffic on South Korean ISP SK broadband rose 24 times to 1.2 trillion bits per second. A testament to the popularity of Squid Game and DP on Netflix, particularly in South Korea. SK has sued Netflix to pay for the costs of managing extra network traffic caused by all those Netflix users. In a previous lawsuit last June, the Seoul Central District Court ruled that SK delivers a service provided at a cost, and it is reasonable for Netflix to be obligated to provide something in return for the service. Netflix argues that SK subscribers already pay the ISP for usage and appealed the ruling, which should be heard in December. SK says Amazon, Apple and Facebook all pay network usage fees. Google and YouTube don't. Netflix reached a deal with Comcast seven years ago on similar issues to this month. Yeah. The significance of this, I think, is that it's South Korean ISP. South Korea has some of the best, highest, fastest bandwidth in the world. It's like too much, too much even for us. I don't know how they got their deals with Apple, Facebook and Amazon, but I guarantee you none of them are doing 1.2 trillion bits per second the way Netflix is. And it's a testament to how successful Netflix has been in providing shows to the South Korean market as well. Yeah.  You must help. And I know there's probably a temptation to want to bring in net neutrality and start talking about that here, but the deal that Netflix reached with Comcast was more about transit and more about peering than it was about net neutrality. And that's because Netflix said, look, we are not going to pay you to reach our customers, but we understand that there is a bandwidth trading going around and maybe we're acting more like a CDN than we are just a website. And I imagine that's probably what's going on with SK Broadband as well, and Netflix is going to hold that line in court as long as it can until it's exhausted, all its appeals. My guess is they come to a similar arrangement like they did with Comcast where there's some sort of peering involved, some sort of payment exchanges, and I'm guessing that's what Amazon, Apple and Facebook did too. But man, squid game, real popular all around the world. That's all I've heard about only over the last week, but it's, yeah, it's all the rage, I guess. I mean, and DP, you mentioned DP. That's a show about military police that have to hunt down draft or not draft evaders, but military deserters, people who go AWOL because there's mandatory military service in South Korea. Great show too. Not as well known outside of South Korea, but if you get nothing else from this bandwidth and transit story, get two recommendations for good Netflix shows. All right. Tell us about what's going on with the Wayback machine. It seems to be looking forward. Yeah, the Wayback machine, which was created 25 years ago by the nonprofit, the Internet Archive, shows anybody that's interested in historical data about how a web page looked in the past, even when the page or the entire website has been removed or totally changed. Now the Internet Archive has created what it calls the Wayforward machine. The preview is what we might expect in another 25 years. That would be 2046. When Ars Technica took it for a spin with Ars' own URL, it was served the following message. Quote, content on the site you're trying to access is protected by the content truth gateway. We cannot guarantee the accuracy of free content. It was followed up with a dummy credit card system payment form. Another message said, the content owner has made this content unavailable in your political block. The copyright on this material has been extended for an additional 200 years. So you're probably getting the idea the Wayforward machine's goal is to raise awareness about ongoing threats. For example, there are some from the book publishers toward the Wayback machine against the way that the Wayback machine stores copies of copyrighted works and makes them available to the public. The EFF, Mozilla, Fight for the Future, Week and Media Foundation are among a few of those who support the Internet Archives initiative. Yeah, it's a stunt and it's kind of exaggerated. But definitely hitting all the issues, overreach on copyright protection, paywalls, all that together. And I'm a big supporter of Archive, the Internet Archive. We've used them to host our things in the past and we support them. So go check it out. It's good stuff. Alright, let's check out the mail bag. This one comes from Bob. Bob says he's from the future and he also works at the Broward County Library in Florida. Bob says, you asked about possible solutions for the new Astro robot for Amazon outside of the house. I have the library on the waiting list to get one. We're going to test it for customers in a couple of ways. One, to help guide customers to a particular section in the library where the 3D printers are, for example. Two, for assisting staff with customer service. We could have Astro go check the shelf to see if an item is there so we can confirm for a customer an item is there. Bob says, will this work? Who knows? But this is why we explore new technologies. See what I love about this is Bob is being an example of what I like, which is skeptical. I'm not sure it's going to work, but not afraid. But let's try it. Let's see what the pitfalls are. Maybe there's a new thing that Astro can make possible. Good stuff. Thank you, Bob. Let us know how it works out, too. Absolutely. And if you have any on the ground stories like Bob does, please do share them with us. We love to hear the stuff. Questions, comments, all of it goes to feedback at DailyTechNewShow.com. We also have a brand new boss to thank, and that boss's name is Lee Chisholm. Lee just started back in us on Patreon, so thank you, Lee. You've made our weekend already. Lee Chisholm. Ah, that's great. Look at Lee. He's smart. Lee is like, I will get all the applause to myself by becoming a patron on October 1st at the very beginning of the month. Well done, Lee. Good work, Lee. Thank you, Len Peralta for illustrating today's show. What have you been drawing, Len? Well, everybody loves a good old fashion carrier fight, right? And that's what this is all about. Yeah. It's fight night. It's good. It's got fight night. It's a peacock versus a TV. Come on. And it's all, like Patrick said, it's all a big money grab anyway, so that's what this image that's what this image is depicting. It's the peacock versus the tube and who will win? Well, probably the almighty dollar eventually will win, but you can get this image if you're one of my Patreon subscribers at Patreon.com forward slash Len or at my online store at LenPeraltaStore.com which also, by the way, I've started just to put out my custom drawn holiday card. So if you want to get an early jump on the holiday, so you can go ahead and go over to LenPeraltaStore.com and get those. So thank you so much for looking. Good work as always, Len. Also, great to have Patrick Norton here today. Patrick, where can people keep up with all that you do? Oh my goodness, abxl.com is the podcast I host with Robert Herron, talking about home theater and audio. We did a bunch of stuff talking about Kan Jam this week and you can tweet at Patrick Norton if you want to talk to me that way. Excellent. Well, we are live on this show Monday through Friday at 4.30 p.m. Eastern. That's 2030 UTC and you can find out more at DailyTechNewShow.com slash live. Tom will be working on Monday and Rich and I will talk to you Monday. Until then, have a great weekend. This week's episodes of DailyTechNewShow were created by the following people, host producer and writer Tom Merritt, host producer and writer Sarah Lane, executive producer and Booker Roger Chang, producer, writer and host Rich Strafilino, video producer and Twitch producer Joe Coontz, associate producer Anthony Lemos, Spanish language host, writer and producer Dan Campos, news host, writer and producer Jen Cutter, science correspondent Dr. Nikki Ackermans, social media producer and moderator Zoe Detterding, our mods! Beatmaster W. Scottis 1, BioCow, Captain Kipper Jack Shit, Steve Guadirama, Paul Rees, Matthew J. Stevens and J.D. Galloway, modern video hosting by Dan Christensen, video feed by Sean Wei, music and art provided by Martin Bell, Dan Looters, Mustafa A, ACAST, Creative Arts and Len Peralta, live art performed by Len Peralta, ACAST ad support from Trace Gaynor, Patreon ad support from Stefan Brown, contributors for this week's show included Scott Johnson, Justin Robert Young and Patrick Norton and our guest this week was Aaron Carlton thanks to all the patrons who make this show possible. This show is part of the Frog Pants Network. Get more at frogpants.com Bob hopes you have enjoyed this program.


Hello and welcome you all for today's lecture. I hope you got the chance to go through what we discussed last time. After we had looked at the recap of the sharpness epoxidation, we looked at the how normal olefins which do not have an allylic alcohol or any hydrox group in the vicinity of the double bond, simple olefins, how can they be epoxidized using selen complex based metal oxo complexes. And we initially looked at how the C2 symmetry based 1, 2 diamines can be prepared and also how we can get the aldehydes especially the salicyldehyde which we discussed. And they are not easy to prepare and therefore we looked at the some method for making and we need substituent here and substituent here. That means a substituent ortho to the hydroxy group and para to the hydroxy group is what is required. And of course we used 2 different types of amines and one of them was of this kind where of course we had the C2 symmetry based amine and the other one with cyclic system and this is how these 2 amines were taken up and of course we try to look at how we can resolve them or how we can get them optically pure and in a C2 symmetric fashion. So what we looked at it is just one example is shown here is with this 1, 2 di phenyl 1, 2 diaminoethane type of C2 symmetry based amine leads to this complex and the cyclohexane based 1, 2 diamine leads to this particular manganese oxo complex. And we looked at how the epoxidation prevents the particular phenyl group allows blocking up of the olefin approaching from this side. It also blocks the approach from this side here and it also blocks from this side where the tertiary brittle group blocks and eventually what is allowed is that you have an RL group on this side and RSS group this side the large group on the other side and the small group towards the lower side and that allows epoxidation to take place where this phenyl group does not come into the way and therefore the epoxidation occurs. Whereas with the cyclohexyl amine case we very clearly saw that how this actually oriented hydrogen blocks the orientation of the large group onto this side. That means if we have to epoxidize the olefin has to be oriented in this fashion of course we discuss that this side, this side and this side is blocked because of the tertiary brittle groups from all the 3 sides and this is the only side where the olefin can approach and this is the hydrogen which stops according to the Jacobson's hypothesis. On the other hand the same molecule can approach the or oxo complex according to Katsuki but then he invokes the pi-pi interaction but the result is the same as we discussed. So we saw how these epoxidations take place which are not dependent on the requirement that there should be a hydroxy group in the vicinity of the olefin and therefore it is a very very very important reaction. Now we look at the condensation of aromatic aldehyde that is salicyldehyde derivatives with C2 symmetry base means like these two to form the corresponding saline complexes in presence of manganese triacetate. In the preparation of these saline complexes we have a choice where we can either have PF6Cl or acetate ions as the counter ion which also act as ligands. Now what happens in these reactions that it has been found that the salicyldehyde derivatives are not generally very easy to prepare as we have seen the preparation of one of them where it was relatively difficult to get that particular salicyldehyde derivative which is this one. Now iodosobenzene is also not found to be a practical source of oxygen because it leads to the formation of iodobenzene as a side product which needs to be removed by chromatographic means because it cannot be removed by simple washing with water. Instead of iodosobenzene people prefer to use sodium hypochloride or DMDO because the byproducts that are formed are easily washable by water. In addition to that it has also been found that additives such as amine enoxides like n-methylmorphid enoxide like this NMO or porfinyl pyridine enoxide BPMO are used and they are found to be enhancing the rate, increase the yield and also the inertial selectivity. They act as axial colegants and also stabilize the manganese-5 oxo complex which is obtained by the oxidation of these manganese-3 saline complexes. It is also found that electron donating groups at the paraposition of the aromatic system stabilize the manganese-5 oxo complexes and thus the rate of oxygen transfer from that manganese-5 oxo complex decreases which implies late transition state that increases the alkene interaction with saline ligand being more important. Now we look at how the aldehyde can also be introduced onto the aromatic system by using another reaction where a paraformaldehyde is taken. This is paraformaldehyde basically it is a polymer of formaldehyde that is how it looks like. You have a paraformaldehyde which in the presence of acid would decompose. So you can start with a simple phenol and you can introduce the tertiary brittle group here like this but of course we can here have any other group also. So in any case that is not so important. The important point is that you have a hydroxy group which is what allows the introduction of the aldehyde group onto the ortho position. So once we have introduced the tertiary brittle group then form paraformaldehyde is reacted with it in the presence of mg plus that is mg plus 2 either as magnesium chloride or this type of magnesium salt in the presence of a base like triethylamine. So what is happening is that this polymeric formaldehyde decomposes in the presence of acid to form monomeric formaldehyde and then the protonation or say you have a Lewis acid in the form of magnesium chloride for example here something like this that allows delta positive to form here and delta negative to form here and then of course we can expect something like this to happen to form this intermediate. And then this intermediate then is allowed to interact with the triethylamine and then of course we can expect that something of this kind will happen and of course we can get the aromatic system becoming like this. Now what we have done in the process is we have introduced here this group adjacent to the alpha position of the hydroxy that means ortho position. And now what can happen is that this particular bond can break and we can anticipate that there is a hydride transfer to this and we can get the CH3O minus coming out and MgCl plus coming out of course will eventually come out and then we get this hydroxy group attached that means this CH2O MgCl has now become the formaldehyde group and which upon acidification gives the corresponding aldehyde. So this is how a phenol can be converted to the corresponding ortho formyl phenol or salicyldehyde. So if we take any derivative of phenol of having a substituents at ortho and para position and one vacant position here then of course we can carry out such a reaction to form the corresponding formyl group onto the vacant ortho position here. So we can not only have simple salicyldehyde but many substituted salicyldehydes as we have seen it here. So this is how the mechanism of the introduction of the formal group at the ortho position of the phenol occurs. Now what are the examples that we can look at the Jacobson-Katzuki based reaction that is if we take an olefin of this kind that gives the epoxide that is formed on this choosing this oxo complex and as one can anticipate that this is sterically hindered position because of the two geminal dimethyl groups and therefore the opening occurs from this side and the nucleophile of from here with carbon-nitrogen bond is formed here from the alpha side because the epoxide is beta and therefore such a product is formed. So we can have a regio and stereoselective opening of the epoxide and lead to now as you can see there are two asymmetric centers with two different functional groups the hatch to it. Now if we take an alpha beta unsaturated ester of this kind which has a phenyl group on one hand and ester group on the other hand other side of it and then we have a cis double bond and if we react the same with the same catalyst and same oxo complex as is here and considering that the ester group is smaller compared to a large phenyl group then of course epoxidation would occur the same way as we discussed earlier in the case of two methyl styrene and of course when this epoxide is formed the ammonia attacks on to this particular carbon atom this goes off because we have we can anticipate that the carbon oxygen bond can break and developing a positive charge at the benzylic position. So you can have expect a slightly delta positive here under these conditions where amine attacks and we get this particular amino alcohol and then of course we can expect that essentially we can convert that into this particular kind of orientation of the amino alcohol or alpha hydroxy ester and what is found that if we take isopropyl ester that seems to have get a different epoxide like for example if you have a CO2IPR that is isopropyl group then it appears that this particular group seems to be acting as a larger than a real group here and then we get this epoxide when we take this particular olefin which is cis double bond alpha beta unsaturated ester and that gives this epoxide which has been converted into an hypertensive agent and antihypertensive agent actually it should not be an hypertensive agent it is an antihypertensive agent. So, dill t as m so this is the structure of that where this hydroxy group is of course coming up there and this particular aryl group is also coming up from this epoxide. So, it is a long synthesis that we will not go through it but then the idea is that the simple epoxide which can be easily made in optically pure form as you can see is like 96% enantiomically pure and then of course you can convert it into the important antihypertensive agent. Apart from cis disubstituted olefins even tri-substituted olefins have been found to give high enantiose selectivity in the epoxidation cases. We can also carry out kinetic resolution using these catalysts that have been found. For example, if we start here as an asymmetric center and we begin with a racemic molecule that means we do not have an optically pure molecule and then we take a catalyst which is Rr oriented one of the manganese III complex and react with oxidizing agents such as metachloropropylbenzoic acid and what is found which is mentioned here in the general of practical chemistry in 1999 that one of the two enantiomers gets epoxidized and the other one which is what they wanted to use for something else which gets un-epoxidized and therefore resolved. So this is a kinetic resolution in terms of which olefin gets epoxidized faster and which one does not and therefore we can resolve it. But this kind of saline complex also has been used as a more or less like a Lewis acid catalyst which is chiral like for example if we start with this kind of racemic epoxide a simple small molecular weight epoxide like this and if we use this catalytic amount of the manganese III complex and intention is not to do epoxidation because there is no olefin epoxidation does not occur and therefore what happens is that the catalyst behaves more like a Lewis acid and from the racemic epoxide when the Lewis acid attaches to it the water which is present in the medium and that is the reason why we take low molecular weight so that molecule is somewhat soluble in water and one of them gets opened at this particular position and the other one remains unopened. So the rate of reaction of the rate of opening of the epoxide is different for two different enantiomers of the same epoxide. So that also allows as a result you can get this epoxide here or you can get the diol having a hydroxy group here which is determined from the epoxide that has been utilized for this purpose and this has been published in 1997 in science. Now what exactly is the mechanism of this reaction? A lot of work has been done in this regard and we can summarize the observations and also the suggestions. It has been observed that cis 1, 2 disubstituted alkenes lead to the formation of cis epoxides that means there is a cis selectivity in these cases. This suggests that the reaction may proceed via a 2 plus 1 concerted pathway like this for example if this olefin comes in contact with this manganese 5 oxo complex then there is a possibility of a 2 plus 1 cycloaddition leading to this particular transition state which then releases the cis epoxide and of course manganese 3 complex for further oxidation. Alternatively what they have suggested that the reaction might proceed via metalloxytane intermediate through 2 plus 2 pathway. For example this manganese 5 oxo complex when it comes in contact with this cis olefin then we can expect that 2 plus 2 cycloaddition occurs to form this manganese oxytane intermediate which if it collapses without any intermediate to be formed then of course we can get the cis epoxide. On the other hand what has also been found that in conjugated alkenes a form mixture of cis and trans epoxide is formed and that suggests the possibility of a radical pathway and that has been proposed in this particular manganese oxytane type of pathway that if this particular carbon manganese bond cleaves homolytically then of course we can get a radical at this particular carbon atom and then that will allow a cc bond rotation here and eventually lead to the formation of the trans epoxide. Of course it can also lead to the formation of cis epoxide so a mixture of cis and trans epoxide can form. Now the cis and trans ratio has also been found to be dependent on the oxidant additive and the catalyst in some cases. So these are the observations and these are the suggestions so there is a possibility of this kind of mechanism that may be operating and therefore it is relatively acceptable to invoke such a mechanism. Now this is an example in which what is seen that as I mentioned that the reaction depends upon oxidant additive and the catalyst that is used. So if we use SS catalyst and you use sodium hypochlorite what is found is that if we start with this olefin we get 100% is olefin the epoxidation does not make any change in terms of stereochemistry. In a similar fashion this gives you 100% cis and in this case it also gives 100% cis but when you use Iroso benzene in both the cases then of course what is found is that we get 57% cis product and 43% is ring open product. The ring open product means this cyclopropane gets opened and in a similar fashion here 83% and 17% is cyclopropane ring open product. So how is it expected that the cyclopropane ring will open? It is only possible if there is a possibility of cyclopropane opening through a radical intermediator. So we can expect supposing if this is what is the case then we if we put it here phenyl group here then this intermediate has to come somehow of this kind epoxidation would allow the radical to form in this fashion. So we can expect the oxygen to come here and manganese to come in here and the rest of the things but then radical has to be here which allows the opening of the cyclopropane to take place. So this is what is found in the case of phenyl Iodosobenzene but that does not happen in the case of sodium hypochloride. So actually the change of oxygen leads to ring open products but the epoxide is still cis as you can see that the epoxide is still cis. So it means that there is a possibility of the reaction proceeding via metalloxytane intermediate and then opens up to form the ring open product via radical means or it closes immediately without isomerization to form the cis epoxide. So this is what is mentioned in this particular paper that you can read. Now we start another topic which is asymmetric dihydroxylation originally the dihydroxylation of an olefin for example if we start with an olefin and we can get the corresponding diol which is a cis diol which is 1 to cis diol and this kind of once a cis diol has been found by reacting olefins with osmium tetroxide and what is found that reaction proceeds very likely through such kind of osmium intermediate which can be reduced and we can get the corresponding diol. The reduction can be done with hydrogen sulphide or sodium sulphide and of course we can get the corresponding diol. Originally osmium tetroxide was used in a stoichiometric fashion and but then it was a very reliable dihydroxylation that even tetra substituted olefins react readily that means the reactivity of the osmium tetroxide is very high. Then it was also found which is a very important observation that the addition of amines or pyridines increase the rate probably forming such an electron rich complex as it is here. As you can see that the osmium tetroxide here is an electron deficient in terms of oxygen being there as oxygen double bond O4 of them and therefore this particular osmium atom is very electrophilic and therefore any nitrogen would prefer to bind it very easily and therefore such a intermediate can allow. When such a reaction happens then of course now we have a leaving group here at the same time we have a nucleophilic oxygen here and of course we have three of the osmium oxygen double bond which are electrophilically oriented and therefore you know epox this dihydroxylation occurs very fast. And the original dihydroxylation reaction using stoichiometric amount of osmium tetroxide as I mentioned above is that it is very reliable and useful but it is expensive. And since the osmium tetroxide is volatile and it is also extremely toxic so even to do a reaction on a small scale people were not particularly very comfortable with it and it was not a convenient proposition to do the reaction at small scale involving the use of osmium tetroxide in a stoichiometric fashion. However since there was this very important observation that any kind of double bonds can react and therefore there was a need to improvise this particular procedure as this proves to be a very advantageous situation that any kind of double bonds can react and therefore over the years the dihydroxylation procedure has been modified to operate catalytically and more rapidly and giving better yield that means in terms of osmium if the osmium tetroxide could be made catalytic in terms of its usage then the reaction is definitely going to be very useful and therefore because of the expensive nature toxic nature the co-oxidants were used and one of the co-oxidants was this sodium chloride, osmium tetroxide and the other one was osmium tetroxide and hydrogen peroxide which is known as mules reagent but in these cases over oxidation occurs and the aldehyde or the ketone are formed and therefore it was not a very convenient method for making use of these kinds of oxidants but then there have been many other modifications which are reported in the literature and eventually the osmium tetroxide was made to be used in a catalytic fashion and we will discuss the remaining part of the osmium tetroxide based dihydroxylation in the next class till then you can go through what I have mentioned today and then see you next time till then bye and thank you.


So you're from Barcode Eye. So who are you? Yeah, kind of, yeah, owner of this company. So what is Barcode Eye? Barcode, like a barcode reader for smart glasses. So you do an application for head mounted display computers, right? Yes. Or smart glasses. So what happens with the application? So picture or data came from a barcode. So you just look at it and then what happens? Yeah, yeah. So picture come up. So can we see something? Can you show a demo? Okay. Yeah. So the picture come up inside the glass? Yes, exactly. All right, so what do you see in there? See or like picture or kind of information or user or... Can you try to take it off? No. Can you try to film inside like this? Yeah, I think because you can see, yeah, this. Yeah, demo right here. So it's new. Yeah, new. What did your company do before? What did your company do before? Before, now, like, law enforcement business. Yeah, we actually have a law. All right, so what is it doing right now? Yes, scanning. Scanning. Scanning all the barcodes over here. Scanning barcodes and showing information. Showing information like picture or data. Is it possible to do it with something else than barcodes or it has to be a barcode? Is it for a store? Where would you put this? Yeah, like a library or a museum or a store or a warehouse or a hospital. Yeah, the office.