text:
Electron-transporting foldable alternating copolymers of perylenediimide and flexible macromolecular chains
Tsuneaki Sakurai, Naomi Orito, Shusaku Nagano, Kenichi Kato, Masaki Takata, Shu Seki
Tuning the electrical conductivity of conjugated macromolecules by nanostructure ordering plays a key role in developing carrier transporting materials applicable to flexible organic electronic devices. Alternating copolymers of perylene-3,4,9,10-tetracarboxylic acid diimide (PDI) and flexible macromonomers, poly(dimethylsiloxane) (PDMS), poly(ethylene glycol) (PEG), or poly(propylene glycol) (PPG), were synthesized via simple polycondensation reactions between 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and bis-amine-terminated corresponding macromonomers. Dynamic traces of absorption and fluorescence spectra of the series of alternating copolymers, with the indication of PDI chromophores, suggested the more foldable nature in tetrahydrofuran of the PDMS-based polymer than of the PEG- and PPG-based polymers. The folding capability of these polymers in solution was confirmed by fluorescence spectra and the absolute fluorescence quantum efficiency values. In the solid films, the condensed state of the polymers showed X-ray diffraction patterns of periodic structures, which depend on the type of macromolecular chains: PEG showed a highly crystallized state in contrast to the slightly crystalline PDI molecules in the PDMS and PPG-based polymers. Photoconductivity upon ultraviolet excitation has been screened by noncontact microwave measurements, and the mobility of electrons has also been characterized based on the kinetic traces of radical anions on the PDI chromophores. The negligible optical absorption observed from the PDMS-based polymers revealed the lowest photocarrier generation yield among the prepared polymers. The observed low conductivity for the PDMS-based, most foldable polymers possibly results from a lower photo-charge generation yield and thermal fluctuations of the flexible PDMS chains. The PEG-based polymer marked the largest electron mobility of 0.2 cm 2 V 1 s 1 , reflecting the highly crystalline nature of the PEG chains.
Materials Chemistry Frontiers
https://doi.org/10.1039/c7qm00616k
10.1039/c7qm00616k
Dive into the research topics of 'Electron-transporting foldable alternating copolymers of perylenediimide and flexible macromolecular chains'. Together they form a unique fingerprint.
Polymer Chemistry 100%
Poly(ethylene Glycol) Chemistry 66%
Fluorescence Spectroscopy Chemistry 66%
Glycol Chemistry 55%
Polydimethylsiloxane Chemical Engineering 55%
Ethylene Biochemistry, Genetics and Molecular Biology 55%
Plasma Desorption Mass Spectroscopy Chemistry 44%
Propene Chemistry 33%
Sakurai, T., Orito, N., Nagano, S., Kato, K., Takata, M., & Seki, S. (2018). Electron-transporting foldable alternating copolymers of perylenediimide and flexible macromolecular chains. Materials Chemistry Frontiers, 2(4), 718-729. https://doi.org/10.1039/c7qm00616k
Electron-transporting foldable alternating copolymers of perylenediimide and flexible macromolecular chains. / Sakurai, Tsuneaki; Orito, Naomi; Nagano, Shusaku et al.
In: Materials Chemistry Frontiers, Vol. 2, No. 4, 2018, p. 718-729.
Sakurai, T, Orito, N, Nagano, S, Kato, K, Takata, M & Seki, S 2018, 'Electron-transporting foldable alternating copolymers of perylenediimide and flexible macromolecular chains', Materials Chemistry Frontiers, vol. 2, no. 4, pp. 718-729. https://doi.org/10.1039/c7qm00616k
Sakurai T, Orito N, Nagano S, Kato K, Takata M, Seki S. Electron-transporting foldable alternating copolymers of perylenediimide and flexible macromolecular chains. Materials Chemistry Frontiers. 2018;2(4):718-729. doi: 10.1039/c7qm00616k
Sakurai, Tsuneaki ; Orito, Naomi ; Nagano, Shusaku et al. / Electron-transporting foldable alternating copolymers of perylenediimide and flexible macromolecular chains. In: Materials Chemistry Frontiers. 2018 ; Vol. 2, No. 4. pp. 718-729.
@article{90eb0dfc36e64936a6571bfab939da5d,
title = "Electron-transporting foldable alternating copolymers of perylenediimide and flexible macromolecular chains",
abstract = " Tuning the electrical conductivity of conjugated macromolecules by nanostructure ordering plays a key role in developing carrier transporting materials applicable to flexible organic electronic devices. Alternating copolymers of perylene-3,4,9,10-tetracarboxylic acid diimide (PDI) and flexible macromonomers, poly(dimethylsiloxane) (PDMS), poly(ethylene glycol) (PEG), or poly(propylene glycol) (PPG), were synthesized via simple polycondensation reactions between 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and bis-amine-terminated corresponding macromonomers. Dynamic traces of absorption and fluorescence spectra of the series of alternating copolymers, with the indication of PDI chromophores, suggested the more foldable nature in tetrahydrofuran of the PDMS-based polymer than of the PEG- and PPG-based polymers. The folding capability of these polymers in solution was confirmed by fluorescence spectra and the absolute fluorescence quantum efficiency values. In the solid films, the condensed state of the polymers showed X-ray diffraction patterns of periodic structures, which depend on the type of macromolecular chains: PEG showed a highly crystallized state in contrast to the slightly crystalline PDI molecules in the PDMS and PPG-based polymers. Photoconductivity upon ultraviolet excitation has been screened by noncontact microwave measurements, and the mobility of electrons has also been characterized based on the kinetic traces of radical anions on the PDI chromophores. The negligible optical absorption observed from the PDMS-based polymers revealed the lowest photocarrier generation yield among the prepared polymers. The observed low conductivity for the PDMS-based, most foldable polymers possibly results from a lower photo-charge generation yield and thermal fluctuations of the flexible PDMS chains. The PEG-based polymer marked the largest electron mobility of 0.2 cm 2 V 1 s 1 , reflecting the highly crystalline nature of the PEG chains.",
author = "Tsuneaki Sakurai and Naomi Orito and Shusaku Nagano and Kenichi Kato and Masaki Takata and Shu Seki",
note = "Funding Information: This work was partially supported by the Grant-in-Aid for Scientific Research (No. 26102011, 15K21721, 26249145, and Funding Information: 17H04880) from Japan Society for the Promotion of Science (JSPS) and research grants from the Ogasawara Foundation for the Promotion of Science & Engineering, Tateisi Science and Technology Foundation, the Eno Science Foundation, and Iketani Science and Technology Foundation. The synchrotron radiation experiments were performed at BL44B2 in SPring-8 with the approval of RIKEN (Proposal No. 20160014). GI-XS experiments were conducted in Nagoya University, supported by Nanotechnology Platform Program of MEXT, Japan (Proposal No. S-16-NU-0017). We also acknowledge Prof. Akihiro Ito for the evaluation of absolute photoluminescence quantum yield and DLS measurements for Prof. Kenji Matsuda and Prof. Takashi Hirose in Kyoto University. Publisher Copyright: This journal is {\textcopyright} The Royal Society of Chemistry and the Chinese Chemical Society 2018",
doi = "10.1039/c7qm00616k",
journal = "Materials Chemistry Frontiers",
T1 - Electron-transporting foldable alternating copolymers of perylenediimide and flexible macromolecular chains
AU - Sakurai, Tsuneaki
AU - Orito, Naomi
AU - Nagano, Shusaku
AU - Kato, Kenichi
AU - Takata, Masaki
AU - Seki, Shu
N1 - Funding Information: This work was partially supported by the Grant-in-Aid for Scientific Research (No. 26102011, 15K21721, 26249145, and Funding Information: 17H04880) from Japan Society for the Promotion of Science (JSPS) and research grants from the Ogasawara Foundation for the Promotion of Science & Engineering, Tateisi Science and Technology Foundation, the Eno Science Foundation, and Iketani Science and Technology Foundation. The synchrotron radiation experiments were performed at BL44B2 in SPring-8 with the approval of RIKEN (Proposal No. 20160014). GI-XS experiments were conducted in Nagoya University, supported by Nanotechnology Platform Program of MEXT, Japan (Proposal No. S-16-NU-0017). We also acknowledge Prof. Akihiro Ito for the evaluation of absolute photoluminescence quantum yield and DLS measurements for Prof. Kenji Matsuda and Prof. Takashi Hirose in Kyoto University. Publisher Copyright: This journal is © The Royal Society of Chemistry and the Chinese Chemical Society 2018
N2 - Tuning the electrical conductivity of conjugated macromolecules by nanostructure ordering plays a key role in developing carrier transporting materials applicable to flexible organic electronic devices. Alternating copolymers of perylene-3,4,9,10-tetracarboxylic acid diimide (PDI) and flexible macromonomers, poly(dimethylsiloxane) (PDMS), poly(ethylene glycol) (PEG), or poly(propylene glycol) (PPG), were synthesized via simple polycondensation reactions between 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and bis-amine-terminated corresponding macromonomers. Dynamic traces of absorption and fluorescence spectra of the series of alternating copolymers, with the indication of PDI chromophores, suggested the more foldable nature in tetrahydrofuran of the PDMS-based polymer than of the PEG- and PPG-based polymers. The folding capability of these polymers in solution was confirmed by fluorescence spectra and the absolute fluorescence quantum efficiency values. In the solid films, the condensed state of the polymers showed X-ray diffraction patterns of periodic structures, which depend on the type of macromolecular chains: PEG showed a highly crystallized state in contrast to the slightly crystalline PDI molecules in the PDMS and PPG-based polymers. Photoconductivity upon ultraviolet excitation has been screened by noncontact microwave measurements, and the mobility of electrons has also been characterized based on the kinetic traces of radical anions on the PDI chromophores. The negligible optical absorption observed from the PDMS-based polymers revealed the lowest photocarrier generation yield among the prepared polymers. The observed low conductivity for the PDMS-based, most foldable polymers possibly results from a lower photo-charge generation yield and thermal fluctuations of the flexible PDMS chains. The PEG-based polymer marked the largest electron mobility of 0.2 cm 2 V 1 s 1 , reflecting the highly crystalline nature of the PEG chains.
AB - Tuning the electrical conductivity of conjugated macromolecules by nanostructure ordering plays a key role in developing carrier transporting materials applicable to flexible organic electronic devices. Alternating copolymers of perylene-3,4,9,10-tetracarboxylic acid diimide (PDI) and flexible macromonomers, poly(dimethylsiloxane) (PDMS), poly(ethylene glycol) (PEG), or poly(propylene glycol) (PPG), were synthesized via simple polycondensation reactions between 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and bis-amine-terminated corresponding macromonomers. Dynamic traces of absorption and fluorescence spectra of the series of alternating copolymers, with the indication of PDI chromophores, suggested the more foldable nature in tetrahydrofuran of the PDMS-based polymer than of the PEG- and PPG-based polymers. The folding capability of these polymers in solution was confirmed by fluorescence spectra and the absolute fluorescence quantum efficiency values. In the solid films, the condensed state of the polymers showed X-ray diffraction patterns of periodic structures, which depend on the type of macromolecular chains: PEG showed a highly crystallized state in contrast to the slightly crystalline PDI molecules in the PDMS and PPG-based polymers. Photoconductivity upon ultraviolet excitation has been screened by noncontact microwave measurements, and the mobility of electrons has also been characterized based on the kinetic traces of radical anions on the PDI chromophores. The negligible optical absorption observed from the PDMS-based polymers revealed the lowest photocarrier generation yield among the prepared polymers. The observed low conductivity for the PDMS-based, most foldable polymers possibly results from a lower photo-charge generation yield and thermal fluctuations of the flexible PDMS chains. The PEG-based polymer marked the largest electron mobility of 0.2 cm 2 V 1 s 1 , reflecting the highly crystalline nature of the PEG chains.
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text:
One foe is too many
Bikash Mohapatra
– March 11, 2019Posted in: Features
Both singles finals of the 2019 All England Open were about two players facing their nemesis. While one fought hard and emerged triumphant the other succumbed to his inner demons yet again.
By Bikash Mohapatra. Photos: Badmintonphoto
Coming into the 2019 All England Open final, Chen Yufei had never beaten Tai Tzu-Ying. It was 11 straight defeats in under two years for the Hangzhou native, against the world #1 from Chinese Taipei. Chen had indeed taken Tai to the distance the last three times they squared up. She however, found it tough to cross the line.
It wasn't as if Tai was only Chen's nemesis. More than half a dozen other major players consider the Kaohsiung native their bête noire, and with good reason. For a good part of the last three years, Tai has been the most dominant and consistent woman on the circuit, reaching 19 finals and winning 14 of them. More importantly, and more often than not, many players have trouble reading her deceptive game, and therefore fail to execute their respective game-plans.
She had dominated Arena Birmingham in both 2017 and 2018, losing just one game each year en route to the title. This year the narrative seemed no different either. In the last eight, Tai took on perennial Indian hope Saina Nehwal – another player who seems clueless when playing her – and dealt her a 13th straight defeat, before besting Japan's Akane Yamaguchi in the semi-finals, in what was a repeat of last year's final.
The stage was set for the 24-year-old to complete a hat-trick of All England titles. Chen was meant to have a peripheral part in the narrative, a supporting role so to speak. She rewrote the script. And how!
Taking a leaf from last year's tournament, where she was the only player to take a game off the champion, and showing remarkable mental fortitude, Chen never lost her grip and finally sealed the match 21-17, 21-17 to become the first women's singles champion from China in Birmingham since Wang Shixian in 2014.
It is without doubt the biggest title of Chen's fledgling career. Whether she will be able to build on this success and become the next female superstar from China – and secure a place in the pantheon of greats, alongside venerable names like Han Aiping, Li Lingwei, Ye Zhaoying, Gong Zhichao, Xie Xingfang, Li Xuerui and Wang Yihan – is something best reserved for future discussions. For the moment, suffice it to say this is one result the former World Junior Champion will cherish forever.
If Chen reaped the rewards for being mentally strong and not losing her grip in the match despite facing her nemesis, Viktor Axelsen paid a heavy price for doing exactly the opposite in the men's singles final.
Kento Momota is to the Dane what Tai is to the Chinese. However, unlike Chen, Axelsen is no upstart. The 25-year-old has been on the circuit for quite a few years, has won big tournaments and reached the world #1 ranking. Therefore, his struggle against the Japanese star isn't about a lack of experience or an inadequate skill-set. It has to do with the mind.
Unlike Chen, who despite not having beaten Tai before had put up a fight on more than one occasion, Axelsen has with each passing match seemed more and more clueless against Momota. The last occasion the Dane beat the Japanese was in 2014, when both the players weren't a patch of what they are today.
Coming into the final in Birmingham, Axelsen was at the receiving end in his nine previous matches against his successor as world #1, failing to even win a game in the last six.
However, on this occasion he was in his best form in a year – a year marred by health issues, injuries, and withdrawals.
A week prior to Momota's German Open victory, Axelsen had also won a title in the lead-up to the All England, the triumph at the Spain Masters Super 300 being his first tournament win in more than a year.
Besides, he had helped Denmark retain the title on home soil at the European Mixed Team Championships. Not to forget he began the year with successive semi-final showings at the Malaysia and Indonesia Masters, losing to Momota in the latter.
At the All England, both the current and former World Champions were going for their maiden title in the tournament. In fact, neither had previously advanced beyond the quarter-finals at Arena Birmingham.
Neither featured at the tournament last year, Axelsen being forced to pull out of the tournament with an injury and Momota – on a comeback trail after serving a year-long ban for gambling – failing to make the cut owing to his low ranking.
Both made emphatic returns to one of the sport's biggest of stages. Momota didn't drop a game en route to the final. Axelsen took out the defending champion, China's Shi Yuqi.
Both had ample motivation. While no Japanese man had hitherto won the singles title at the world's oldest tournament, the last instance of a Dane doing so was a good 20 years back.
However, Momota without doubt was the more confident of the two when it came to their chances. In fact when Axelsen was asked about the possibility of repeating Peter Gade's feat and ending the two-decade Danish drought, his response was far from convincing.
It won't be an exaggeration to say mentally he wasn't entirely confident as regards his chances. And it's probably this self doubt that far outweighed the realization that he was playing in his maiden All England final.
By the time he understood the importance of the occasion Momota had raced through the opening game 21-11. To his credit, Axelsen recovered well, winning the second game 21-15 and carrying forward the momentum into the early stages of the third.
Then the self doubt resurfaced.
Instead of consolidating his grip on the match, Axelsen allowed Momota not just to come back but also to establish a substantial advantage. The Japanese didn't need any further favour, sealing the third game 21-15 and with it, his maiden All England title.
In the final analysis, as much as Momota deserves credit for his win, his consistency and mental fortitude, it also owes to the fact that Axelsen has a mental block when facing his Japanese rival.
The Dane has extremely poor records against both Chen Long and Lee Chong Wei, the only other top players (besides Momota) against whom he has a negative head to head record. Time and again though he has managed to beat these two, going on to build on that success.
However, take a quick look at Momota's titles list and Axelsen's name figures as a beaten finalist quite a few times. It is not just an indication of the Dane's perennial struggles against his Japanese opponent but also a cruel pointer to his mental toughness, rather the lack of it while playing his nemesis.
Tags: All England, Kento Momota, Opinion, Viktor Axelsen
About Bikash Mohapatra
Bikash Mohapatra is a Hamburg-based consultant and writer whose work has featured in various international publications such as the Guardian Network, The Diplomat, Asia Times, Eurasian Review, Stuff.co.nz, The Ascent and The Times of India.

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Rumoured new Amazon site in Havant bidding for change in traffic rules
Two teenagers found dead at south coast beauty spot as police launch appeal to establish circumstances surrounding the deaths
Hampshire police offer free bike security marking for Portsmouth students and residents
Portsmouth City Council and Hampshire Constabulary have joined forces to offer residents and students free security marking for their bikes.
By Neil.fatkin1
Tuesday, 9th July 2019, 9:58 am
Updated Tuesday, 9th July 2019, 7:01 pm
Hampshire Police and Portsmouth City Council are offering a free bike security marking service.
Each bike will be permanently marked with a unique code and added to the national Bike Register database.
If a bike is stolen the security markings enable police to reunite it with its owner. Markings can also act as a deterrent to would-be thieves as the bike is less easy to sell.
Starting this month, security marking will be offered on a first-come, first-served basis at the Bike Doctor marquee, next to the fountain on Commercial Road. Markings will take place between 10am and midday on Wednesday, July 10 and 24, August 7 and 21, September 4 and 18.
The service will also be available at the University of Portsmouth Library in Cambridge Road on October 3 and 31, November 28 and January 23.
Leigh Park football coach Alfie Morel found guilty of sexual abusing boys 'who looked up to him'
Hampshire man jailed for numerous attempts to communicate sexually and meet with a child
Tiny Royal Navy boat fends off Spanish warship approaching British waters near Gibraltar
Section of Southsea promenade to close for two years to allow for sea defence work


text:
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http://www.maani.us/xml_charts/images/scroll.gif
My question is simple. Given a hypothetical height of 100px, can I somehow block users from reaching the last 20% when scrolling downwards? ie, "block" it at 80px without changing the height of the element? I'm hoping for a CSS solution :)

A: Given a div with hypothetical height of 100px, you could use absolute or relative positioning:
div {
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}

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According to a statement from the Massachusetts State Police, this morning, at approximately 7:51 a.m., troopers from the State Police Barracks in Cheshire responded to reports of a crash on Lanesborough Road in Cheshire, in front of house #80.
Upon arrival, Trooper Kyle Jolin discovered that a 2014 Nissan Altima, driven by William M. Morrissette, 26, of Adams, was traveling east on Lanesborough Road, when for reasons still under investigation, the vehicle crossed the westbound lane, exited the roadway and struck a tree. An off-duty North Adams firefighter arrived on scene first, extricated Morrissette and began CPR on him. Morrissette was subsequently transported by Adams EMS to Berkshire Medical Center where he was pronounced deceased by medical personnel.
The remaining facts and circumstances of the crash are currently under investigation by troopers from the Cheshire Barracks. Troop B Headquarters, State Police Crime Scene Services Section, State Police Collision Analysis Reconstruction Section, troopers assigned to the State Police Detective Unit of Berkshire County. The Cheshire Fire Department and Adams EMS, all assisted on scene.


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text:
EdX Release on 10 November 2015
November 10, 2015 | By Carol Tong (edX)
EdX has just released the newest version of the edX Platform on edx.org and edX Edge.
This release includes the following changes.
In edX Insights, you can now see course start and end dates and follow LMS links to the courseware or Instructor Dashboard.
Also in edX Insights, you can now, while reviewing a graph of learners' viewing patterns for a video, select Expand Preview to immediately play that video. For more information, see Engagement with Course Video in Using edX Insights.
Documentation changes include the addition of an index of edX feature flags in the Installing, Configuring, and Running the Open edX Platform guide, and a section about best practices for designing courses for the mobile experience in the Building and Running an edX Course guide.
For more information about the changes in this release and in our previous releases, see the edX Release Notes. You can access the weekly release notes, as well as all other edX documentation, at docs.edx.org.


Above: Republican Chris Tague, shown above in a campaign image from his website, raised almost $20,000 in his successful bid to beat Schoharie County Town Supervisor Gene Milone on Nov. 3.
The political dynamics of Schoharie County were significantly altered when voters ousted a pair of Democratic town supervisors on Tuesday, Nov. 3, leaving the county GOP firmly in control of the county board by an almost five-to-one weighted vote margin.
In the upset of the evening, incumbent Middleburgh Supervisor Jim Buzon was defeated by political newcomer, Gerald "Pete" Coppolo, 359 to 326 despite Coppolo leading an under-the-radar campaign that began when he nominated himself for the Republican nomination in August.
Elected as supervisor in the aftermath of Tropical Storms Irene and Lee in 2011, Buzon has served as an influential player on the county board, from his advocacy for the controversial and costly stream bank project to his support for the recently-created position of county administrator.
Buzon, however, had faced substantial criticism for overseeing a fractious and ineffective Middleburgh town council, which led Middleburgh Village Mayor Matthew Avitabile to publicly endorse his opponent in a Facebook post claiming that many of the village's accomplishments have been "in spite of infighting within town government."
Impacting more than just the town, Coppolo's upset victory flips the Middleburgh's 352 weighted votes on the county board of supervisors from the Democratic party to the Republicans. The newcomer's approach to governing remains a mystery, as the former county supervisor of maintenance is an unknown quantity politically.
Two years after running as the face of the anti-Conservative party during a period of pro-government reform fervor that took hold of county politics, two-term incumbent Schoharie Town Supervisor Gene Milone was ousted by Schoharie County GOP Vice-Chairman Chris Tague in an expensive three-way race yesterday.
Topping the polls with 50.1 percent of the vote, Tague is responsible for the most expensive campaign of the election season. According to the most recent data available from the state board of elections, the Republican bigwig raised just shy of $20,000 and spent more than $16,000 of that on his successful bid to defeat Milone.
Tague's upset was made easier by Milone's support for building a new Public Safety Facility at the one-time Seebold Farm on Route 30 in the town of Schoharie. Vehemently opposed by nearby landowners, Milone's support for the approved location spurred resident Wanda Colyer to launch her own bid for supervisor, which received 7.3 percent of the vote.
Another major pick-up for the GOP, Schoharie's 326 weighted votes will be shifted away from the Democratic Party to the command of the county Republican's vice chairman, who is the heir-apparent to succeed longtime Chairman Lewis Wilson as head of the local party in the near future.
In one of the only bright spots for county Democrats, incumbent Blenheim Supervisor Shawn Smith lived to serve another day after surviving one of the strongest challenges of the election cycle by defeating former Secretary of State Gail Shaffer 77 to 60 in a surprisingly negative campaign.
A lifelong Democrat and one-time Albany power broker, Shaffer was supported by the town's Republicans and had doggedly attacked Smith, a country lawyer who serves as the municipal attorney for several towns and villages within the county, for allegedly having a conflict of interest in the issue of New York Power Authority re-licensing. The NYPA is one of Blenheim's largest landowners.
"Negative campaigning doesn't work," Smith told the Watershed Post after his victory Tuesday night. "Gail spread tons of lies about me, but people are smarter than that," he said.
Looking toward the future, Smith said, "I'm excited for another term to finish the work we started the last two years."
Although Smith has authored several successful resolutions opposing natural gas pipeline expansion and is viewed as a rising star in his party, he holds only 33 weighted votes on the county board, or 1.1 percent of the overall total.
Overall, after all was said and done, the Republican Party walked away with control of 12 of 16 supervisor seats on the county board. With those seats comes control of approximately 82.9 percent weighted votes. The Democrats, by contrast, have only four seats under their control for a paltry 17.1 percent of the weighted votes.
Furthermore, the combination of Republican upsets, opposed victories and unopposed wins will usher in five new GOP supervisors at the start of the new legislative term in January.
However, it remains to be seen how this new influx of Republican supervisors will fit into the county's evolving political dynamic, which is making room for new roots with the gradual step away from power by County Treasurer Bill Cherry, who was re-elected last night without opposition.
Newly-hired County Administrator Steve Wilson, whose post is a result of the efforts of reformers who were ousted last night, began his first day of work on Monday.
Republican candidate David Simkins defeated his Democratic opponent Walter Berdan 124 to 98 to become the new town supervisor of Broome. Simkins is the fourth individual to be elected supervisor in the past four elections in the small town.
Incumbent Village of Cobleskill Mayor Linda Holmes was re-elected without any opposition, while incumbent Town Supervisor Leo McAllister was re-elected by almost 500 votes over Democratic challenger Christina Knee, 665 to186.
Although it initially appeared that Schoharie County Chief Deputy Duane Tillapaugh had one of the worst nights in politics, receiving only 19 votes for Seward town council out of 408 cast, he actually received 190 votes out of 579 cast. The Schoharie County Board of Elections accidentally ommitted the zero in its inital unofficial election results, which were posted on its website for almost an entire day. Tillapaugh had served on the town board in the past and had failed to receive the Republican nomination for County Sheriff in the 2013 election.
Board of Supervisors Chairman and incumbent Esperance Town Supervisor Earl VanWormer was re-elected without challenge.
Correction: Due to an error in the unofficial election results posted on the Schoharie County Board of Elections website on election night, Duane Tillapaugh appeared to receive only 19 votes in the race for Seward Town Council. In fact, he received 190 votes out of 579 cast, second to the front-runner, Nancy Kniskern, and ahead of his two other opponents.


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The cell is the basic functional unit of all known living organisms. The cell is the smallest unit of life that can replicate independently.
Cells group to form tissues. Tissues have a specialized functions. Examples of tissues include blood, muscle and bone.
Different tissues group to form organs. Examples of organs include stomach, liver, heart and brain.
Organs form organ systems which perform a particular function which maintains homeostasis and maintains normal health.
The digestive system is an example of an organ system. It is responsible for digesting and absorbing food. It consists of a number of organs including the stomach and intestines.


text:
Review: 'Bloodlands' shows why Brits make the best dramas
The gritty series, debuting March 15 on Acorn TV, is set in Northern Ireland.
Neil Justin March 14, 2021Updated: March 16, 2021, 5:34 pm
James Nesbitt stars in Acorn TV's four-part thriller, "Bloodlands," premiering Monday. (Steffan Hill/BBC/HTM Televison/TNS)
Photo: Steffan Hill, HTM Televison / TNS
When it comes to detective shows, no one commits to murder quite like the British.
While American whodunits bend over backward to justify gunplay and visits to strip clubs, our friends across the pond focus on mood and anguish, a deadly combination when done right.
"Bloodlands" does it right.
The four-part thriller, premiering March 15 on Acorn TV, tells the story of Tom Brannick, a veteran detective in Northern Ireland investigating the kidnapping of an ex-IRA leader. The culprit appears to be the same assassin who killed Brannick's wife and others trying to put an end to "The Troubles" more than 20 years ago.
Brannick is about as far from Sonny Crockett as you could get. He favors drab sweaters. The bags under his eyes could pocket bullets. Late at night, he cries.
His persona matches the scenery. Though the countryside looks like a proper setting for a picnic, it's far from glamorous. Director Pete Travis opts for dimly lit rooms and conditions so windy that you wonder how the actors manage to stay standing. The fact that the country was torn apart so recently is never far from the viewer's mind.
"For those not familiar with Northern Ireland, I want them to hopefully come away with a sense of a place that finds itself thriving and really booming to move forward but also carrying the profoundly tragic memories of a violent past," said creator Chris Brandon, whom Deadline named one of the Top 10 British rising writers last year. "Trying to deal with those two things at the same time is a conflict I wanted to centralize in the lead character. I like that idea of neglected frontiers. I suppose that fed into telling a story that really used the landscape of Northern Ireland to underline the drama that the lead character was going through."
The approach has the potential of packing as much punch as lukewarm tea. But Brandon and executive producer Jed Mercurio, best known for shepherding "Line of Duty" and "Bodyguard," know how to keep the viewers stimulated.
It starts with casting James Nesbitt as Brannick. You may recognize the actor from his dual roles in the 2007 BBC production of "Jekyll," in which he played the title doctor and his alter ego, Mr. Hyde.
"In some ways, this role didn't seem like as much fun," Nesbitt said during a virtual news conference with the "Bloodlands" production team. "I don't mean that as disrespect. Jekyll was such a show-offy role. You could do whatever the hell you wanted with that. But with this, you just had to have the confidence. The writing is so, so good. You could never have acted before in your life, and you could make some of Chris' writing sing."
All modesty aside, Nesbitt's performance is essential to selling a twist at the end of the second episode that will have you reeling. But the revelation doesn't work unless you're fully invested in the characters.
'Bloodlands'
When: Begins streaming March 15
Where: Acorn TV
"Without believability, we have nothing," Nesbitt said. "I think the audience nowadays are saying, 'Why have they made that decision? Do I go along with it? Can I understand it?' That's what I love about the notion of a thriller. You can be shocked, but then you try and understand why."
The twist is almost sure to shock you. The fact that the Brits have created another addictive detective series? That's no surprise at all.
Neil Justin
Jujutsu Kaisen 0: The Movie
Take Me to the River New Orleans
Ryoma! The Prince Of Tennis Shinsei Gekijouban Tennis No Ouji-sama


What can you tell me about Pratunam?
This neighbourhood stretches from Victory Monument to Ratchathewi BTS stations, which we shall class as Phaya Thai, which can be walked in around 20 minutes. Phaya Thai is an excellent hub for getting in and out of the city and is a great place to start if you have never been to Bangkok before, or if you are on a budget.
Many newbies head towards Khao San Road, but the place it a little too watered down regarding Bangkok's urban culture, and you'll miss out on what the city really has to offer.
The Pratunam area is full of hostels, and Phaya Thai BTS Station offers excellent transport links to the rest of the city and the airport. You are also within walking distance to Bangkok's biggest and best shopping malls at Siam Square (See Siam Shopping Adventure).
There are several bars within staggering distance of Phaya Thai (see Victory Monument Dance), which is useful if you want to avoid taxis once the Skytrain finishes after midnight. The Rock Pub, and others, is only a 10 minute walk from Phaya Thai.
The Airport Rail Link terminates at Phaya Thai BTS station so you can travel to and from Suvarnabhumi Airport in around 30 mins (45 Baht). You are also pretty close to Don Muang Airport via taxi (200 baht).
As usual, the area is full of small malls that offer many amenities for weary travellers including the Century Movie Plaza with a cinema on the top floor, though many films are dubbed in Thai, so be sure to check beforehand. The mall also has some affordable Japanese (Ramen) and Western fast food joints. And, of course, there are tonnes of great places to sample some of Bangkok's world famous Thai cuisines.
There are some hostels in the vicinity of the BTS station. Check out Sleep Lab, Vimarn and The Quarter hostels for dorm rooms. For hotels, the Florida Hotel can be booked online for around 900 baht (avoid the walk in prices) or The Sukosol hotel for around 2600 a night with an excellent swimming pool and hotel bar. The Sukosol is also home to Lin Fa Resturant offering some of the best Dim Sum in Bangkok.
Best reached by Phaya Thai BTS station.


If a friend decides to come or bails at the last minute, no worries: you can add or remove stops during your trip as necessary.
To try it out, tap "where to?" then the "+" icon. Then, just add the addresses of your stops, and request the ride. If a friend decides to come or bails at the last minute, no worries: you can add or remove stops during your trip as necessary.
"Your driver will automatically receive directions to each of the stops so you can sit back and relax," Uber Product Manager Don Stayner wrote in a blog post.
The app-based car service admitted that arriving to events as a group "hasn't always been easy with Uber." Until now, your options for doing that were to meet at one place and catch an Uber from there, or change your destination mid-trip. The new multiple stops feature should make things a lot easier.
"Whether you're heading to a costume party with friends, or a night out with your other half, you'll be able to arrive in one piece this Halloween weekend – and beyond – with the multiple stops feature," Stayner wrote.
Uber has been busy adding new features as of late, including in-app chat and the ability to request a ride for someone else. Earlier this year, Uber also added a tipping feature to appease frustrated drivers and save riders from fumbling with their wallets. Meanwhile, Uber is also facing some major challenges, including a ban in London and a federal investigation into its alleged use of spying software.
For more, check out our Uber Tips for a Smooth Rideshare.


Taking a play out of President Bush's book, the Recording Industry Association of America has developed a surge of its own, as it launched an escalated offensive this past week targeted at college students accused of downloading music illegally.
But this war isn't fought with troops; it's fought with lawsuits. The RIAA sent out 400 pre-litigation settlement letters to students at 13 schools and set up a Web site where students can settle their claims by paying a fine and promising never to illegally download music again before an official lawsuit is filed.
Also parallel to the war on terror, the organization also sent out letters to college and university presidents across the country asking for their cooperation in the ongoing war against file sharing. We can only hope they'll be as helpful foreign leaders have been in flushing out terrorists.
The RIAA's tactic is a blatant attempt at circumventing the U.S. judicial system by scaring the accused students into submission before a rightful trial and using them as an example to other students who think about downloading music, which is on scale with the U.S. administration's use of Guantanamo and war tribunals.
Yet another similarity between the RIAA's war on file sharing and the U.S. war on terror is in the effects on the law-abiding citizens. When you buy a RIAA-sanctioned album in the United States, you are bombarded with anti-piracy warnings and even malicious software preventing you from making full use of the music you purchased.
Likewise, U.S. government sanctions to prevent terrorism have regular citizens waiting in ridiculous lines at airports and borders, getting virtually strip-searched, wiretapped, video recorded and eventually being required to carry around a national identification card, basically giving up freedoms for a false sense of security.
Surely these entities could find a way to fight their battles without making major invasions into the lives of people who already obey the rules, but both groups remain uninterested in such measures.
While the Bush administration fought to be able to torture terrorism suspects, the RIAA fights to limit the fair use of digital media.
When these organizations treat everyone like a criminal, or even a possible criminal, they serve only to encourage the illegal behavior.
You'll never have to deal with anti-piracy warnings or copyright protection software if you download an album off of the Internet. And the war on terrorism definitely hasn't won the nation any friends.
If the RIAA isn't careful, it will be faced with a long and uphill battle that will only end up alienating future generations of music fans. Additionally, the United States must be careful not to arouse and embolden future generations of terrorists with its actions.
Furthermore, in both the RIAA's and the United States' current conflicts, victory can never be absolute, as the groups fight against an abstract idea. Whether it's music piracy or terrorism, you may be able to take down a few of the people that perform these actions, but you can never hope to completely terminate the actions.
There is one stark difference between the war on terror and the fight against music piracy, though. In the end, the United States has at least a benevolent cause for its actions in attempting to prevent people from getting hurt or killed.
On the other hand, the RIAA uses its guerilla tactics to terrify people who just want to listen to the new Justin Timberlake single, only to line the recording industry executives' pocketbooks and protect their market shares.


Interview from 1982 when Lynch was working on the Dune script, published in the adult comic book magazine Heavy Metal (Nothing to do with the music). The first part is an article by Lou Stathis, then follows the interview.
Many thanks to Dominic Kulcsar for providing the interview.
No, I'm sorry. There must be some mistake. The smiling, mild mannered guy sitting behind the desk across from me cannot be the same David Lynch who wrote/directed Eraserhead and The Elephant Man. No way. That David lynch undoubtedly resembles Eraserhead's Henry- short, dark, stoop shouldered, tense, scared, and furtive. This alleged David Lynch is any thing but those things. He's fairly tall, around six feet, with pale doughy skin, blond/brown/red hair and an innocently transparent air of guileless sincerity. No chance this well adjusted relaxed, and articulate individual could've conceived two such dark brooding bits of nightmare. But he insists. Would this guy lie?
David was born in 1946 in Missoula, Montana and spent the first eighteen years of hi life in succession of five different small-to-medium-sized American cities. He attended art school in Washington D.C. , Boston , and Philadelphia, studying painting, and began making short films while at Pennsylvania Academy of the Fine Arts. His third, a thirty-four-minute animated live/action featurette called "The Grandmother," won him a trio of film festival prizes. And paved the way for the American Film Institute- supported Eraserhead, inspired by his unpleasant stay in decaying Philadelphia, but filmed entirely in Los Angeles. Taking six years from conception to release, Eraserhead was Lynch's movie form beginning to end ( seven people did everything short of developing the emulsion) and is probably the premier underground/ independent American film of the seventies. It still plays the college and midnight circuits incessantly (Lynch notes proudly that all investors have been repaid, and he still receives regular royalty checks). Not bad for a strange, scarcely narrative, profoundly disturbing little film.
Within two years, Lynch found himself directing a major, studio-financed feature film. The Elephant Man, a marvelously realized study in compassion and human cruelty, garnered Lynch two Academy Award nominations, for best director and best screenplay adaptation. Currently he is at work on his fourth screenplay draft for Dino De Laurentis production of Dune at Universal Studios, which he is also slated to direct ( Alexandro Jodorowsky and Ridley Scott have both been there before him). He is excited and optimistic about the project.
I meet him in his office on the Universal lot. To my left , arranged on a brown leathered couch, are five stuffed Woody Woodpecker dolls ("My boys" he calls them, and reels off their names by way of introduction). Shapes cut from red construction paper are pinned in various locations on the walls. Opposite his desk in a waist-high row of colored pushpins, to which are attached strings trailing down to the floor, their ends tied around fist sized rocks. There is something of a self-conscious idiosyncrasy about the decor., but also a dead-pan humor of enforced contradiction, something I find echoed in Lynch's wry speech. I have absolutely no idea what to make of all of this.
No I had a very happy childhood. These things in Eraserhead come from somewhere unseen; it's not a surface kind of thing.
Meaning it's not drawn from your own life?
If its from my own life, I don't see it. It's from so far inside, hidden, that it can only come out in an idea, which kind of balloons out. I don't know where it comes from. My childhood was picket fences, blue skies, red flowers, and cherry trees - but then I would see millions of little ants swarming on the cherry tree, which had pitch oozing out of it. I noticed these little things but mostly what I saw was very happy. It was good times on our street- that's my life. When I first saw New York and Philadelphia, they made a huge impression on me because the contrast was so great. It hit me harder. I really saw it, and I really felt it - the fear was so great it was unbelievable. The things I saw were so foreign, it was like being in another world.
Yes, it's more of a reproductive fear, I think. A responsibility fear - Mel Brooks told me he saw in Eraserhead a tremendous fear of responsibility.
Yes, I would agree with that. I never really analyze too many things: I just go with feelings and moods. It's like an unspoken kind of logic.
So do you think that being in a place like Philadelphia when you were in the process of becoming an adult-going to college, getting married, etc.- made Eraserhead into what it is, your "Philadelphia" movie?
I'm sure. Everything around you goes in and swims around, and how it comes out is determined by your filter. Your filter is shaped through so many things in your being, in your head; that's why so much of the same material can go through different people and come out so differently in the end.
What sort of process do you go through to pull this sort of stuff up?
There's an original idea somewhere that's sort of a magnet, and it attracts ideas that will join up with it - sort of like a little solar system. They all swim about around this sun, which is the original idea, and pretty soon you've got a system going. And maybe something will swim through, but it won't really be part of it, so it'll keep on going and go away, because it didn't fit. And that's why Eraserhead is an honest picture- even though it isn't "normal" or explained, it goes by rules, and those rules were adhered to. You can feel an honesty and a logic to it. This takes a lot of concentration - you have to spend lots of time thinking about these ideas, capturing them, because they'll swim so deep you won't see them. They'll go away - you've got to dive down there and catch them, and once you catch them , you've got to look at them very carefully, because the way you see them the first time you'll forget about later on. You've got to make sure that you preserve the way you originally saw them - that's where the power of the idea is. Now I know that it's good to have rules of thought, but I don't think it's too good to analyze too much while you're flowing, because sometimes you can think too much. Later on when you look back at what you've done, it seems almost magical - there's so much power there and so many things that were right on, but there was no thinking.
Did you write an actual script for Eraserhead?
yes, it was twenty-one pages long. It wasn't a regular script at all, though; it was more of a diagram kind of thing to remind myself to do certain things. Even if I had scripted it out, it never would have been made in that way. So many things in a film like Eraserhead can't really be written down, and when you're forced to write things down, you end up making a different kind of film.
How did you go about assembling the film?
I went around finding people to work on the movie, to be in it. We started building sets and finding props, getting Henry dressed up, the whole thing.
Was any of it improvised?
No, I don't hate improvisation, but it sort of implies that you don't know what you want and you're going to fiddle around until you like something.
I don't know, but she's the light in Henry's life. We'd already shot the radiator, and when I got this idea, I ran back in.... and there it was, a little hole, perfect for her to live in. the idea came about in its entirety, and it fit perfectly with what we had done.
Do you think visually or verbally?
Yes, way more visual than verbal. It's hard for me to write a script - I've written several, but I'm not a writer. It's kind of a shame that we have to write things down - film is so much more than just words. It's sound and picture and sequences. I wish there was some other way to represent film, some better form of visual shorthand.
Do you think now that your working within the studio structure you can still make films that satisfy you?
Oh yeah. In the future I'd like to do abstract, absurd films, because I still get ideas like that. But I have to kind of , like, hold them now, and wait for the time to do them. Even on The Elephant Man, there were things in it that were abstract that had feelings, and a mood that I could really get into, and now on Dune, there are some incredible things, cinema things that I'm getting used to.
You not finding these impulses conflicting?
What's with the fascination for machinery?
I love factories, Industry, railroads, diners, anything industrial, I go for. This world unfortunately, really only exists in our minds - if we could go into this world, it would be unbelievable. I love going in there.
Both Eraserhead and Elephant Man have a frightened view of machinery - it's malevolent and threatening. Yet when you talk of it, you say you like it.
You see I like Bob's Big Boy- you don't know Bob's Big Boy, do you?
Bob's is a coffee shop and it's very clean. It's very normal, good food. And they've got a chocolate shake that's, like, the most. This is what I like, where I'd like to go -I'd like to go to Bob's, but in my mind I'd rather go into a factory world. It's too frightening to go there really, so we can only go there in the movies. I like clean well-lit places in my life, but when I sit down and start thinking, I can go to Philadelphia. It's like looking in, but if things get heavy, then you can leave. It makes you feel comfortable and happy, so you can think of other things and concentrate on ideas. If you're miserable you can't create.


Protest in New York against China's reelection to the UN Human Rights Council in 2009. Credit: Students for a Free Tibet.
The president's moves to replace the government and dissolve Parliament have been denounced as unconstitutional.
Freedom House conducted an online survey designed to explore the relationship between human rights and the rule of law and Kenya's fight against terrorism.
Freedom House supports the decision for the Organization for Security and Cooperation in Europe to use the Moscow Mechanism to hold Russia accountable for human rights abuses in Chechnya.


Welcome to the latest issue of Turning Points, please click here to read the latest news.
In this issue, we are pleased to feature stories from two of our assistive technology clients whose lives have been empowered thanks to our independent living solutions. Alongside this, we also highlight the revolutionary work of the team at the specialist diabetic clinic in Leeds and the pioneering developments with the Leeds Orthotic Contact Cast technique.


International artist, Falco, rose to stardum throughout the world and eventually in the US with his #1 hit "Rock Me Amadeus." Born in Austria, Falco saw his fan-base grow into 1990s with international hits until his untimely death at the age of 40.
Johann Hölzl aka Falco died at the age of 40 on February 6th in a car accident near Puerto Plata while vacationing in the resort area.
Falco's Greatest Hits was released.
VH1: 100 Greatest Songs of the 80's included "Rock Me Amadeus" at # 87.
Tracks: "Zuviel Hitze" - "Der Kommissar" - "Siebzehn Jahr" - "Auf Der Flucht" - "Ganz Wien" - "Mashine Brennt" - "Hinter Uns Die Sintflut" - "Nie Mehr Schule" - "Helden Von Huete" - "Einzelhaft"
Tracks: "Rock Me Amadeus" - "America" - "Tango In The Night" - "Munich Girls" - "Jeanny" - "Vienna Calling" - "Manner Des Westens - Any Kind Of Land" - "Nother Sweeter Than Arabia" - "Macho Macho" - "It's All Over Now Baby Blue"
Tracks: "Der Kommissar, Pt. 2" - "Rock Me Amadeus" (Club Remix) - "Jeanny, Pt. 1" - "Data de Groove" (Club Remix) - "Vienna Calling" - "Junge Romer" - "Wiener Blut" (Club Remix) - "Emotional" - "Coming Home (Jeanny, Pt. 2, One Year Later)" - "Falco Megamix" - "Sound Of Musik"


Viaduct - the best hosting service, ever?
I've recently signed up to Viaduct, a hosting service by the guys at aTech Media. I was very intrigued after using their last hosting service, Appli, and was upset when it was shut down.
It supports multiple languages such as Ruby, Node.js, Python and PHP with more coming soon.
Supports a number of different databases like MySQL, Postgres, Redis and more.
Easily setup "shared directories" allowing files to stored on Viaduct. They don't need to be stored on a cloud storage provider such as S3.
Setup web processes or workers with a few clicks. It also automatically detects if you have DelayedJob or Resque setup which is very neat!
Deploy from Git repositories as well as Mercurial with zip & FTP coming soon.
They also have an SMTP service meaning you don't have to pay extra for a service like Postmark.
Small applications are completely free! You get 1 worker process, 1 small/hobby database, 1GB storage and 3 shared directories for free.
A simple & beautiful web interface for managing your apps.
Useful graphs for showing number of requests, the speed of your app and the amount of bandwidth.
There are loads of features that Viaduct does better, or that Heroku doesn't have, to list here. Those are just some of them!
Seriously, you should try it out now!


DeLille Cellars Crushes It with 2014 Four Flags Cab Sauvignon - Write for Wine: It's Wine O'Clock Somewhere!Write for Wine: It's Wine O'Clock Somewhere!
The 2014 DeLille Cellars Four Flags Cabernet Sauvignon follows up the impressive 2013 vintage, and showcases the depth and structure resulting from Red Mountain grapes. Since its first vintage in 2010, executive winemaker Chris Upchurch has crafted a beautiful wine that becomes more and more powerful with each year.
The 2014 Four Flags is inky in color, full-bodied, balanced, intense, and savory, featuring aromas of cassis, spices and minerality, followed by layered flavors of dark fruits, licorice, spice and a touch of flint.
At $68 and a 93-95 barrel rating from Robert Parker's Wine Advocate, this lucious Cabernet Sauvignon more than rivals its counterparts in Napa Valley, where Cab is King. To illustrate this point, DeLille Cellars conducted a study of all Cabs rated 90+ across five vintages in Red Mountain and Napa Valley.
Of course, wine isn't all about scores and ratings, not by any means. But this chart shows the relationship of points and price for both wine regions — and showcases the beauty and value of Washington state wine compared to our neighbors to the south.
If you want a special-occasion wine, look no further than DeLille's 2014 Four Flags. Or if you want to pair a seductively rich Washington Cab with a summer barbecue, this wine is for you. Four Flags is drinking amazingly well now, but will be even better with a few years behind it.
We recently tasted the 2013 vintage at Northwest Wine Encounter at Semiahmoo Resort, and were fortunate to receive a sample of the 2014 vintage.
This entry was posted in Cabernet Sauvignon, Red Mountain, Washington, Wine, Woodinville and tagged Cabernet Sauvignon, Chris Upchurch, DeLille Cellars, Napa Valley, Washington wine, Washington wineries, wine, wineries, Woodinville by Margot. Bookmark the permalink.


Load testing software tests software products, websites, and servers by adding load pressure and measuring the response. Development teams use this software as a part of a larger software testing regimen to verify developed products, websites, and servers can handle the various stresses of day-to-day use, as well as high-impact uses (e.g., holiday shopping, enterprise application use, etc.). Load testing tools work well with load balancing software, often being integrated to stress points of impact during testing and then manage those stresses as they occur.
Load Testing reviews by real, verified users. Find unbiased ratings on user satisfaction, features, and price based on the most reviews available anywhere.
BlazeMeter is a 100% JMeter-compatible, self-service web load testing cloud.
Gatling is an open-source load & performance testing tool for web applications. Gatling integrates the DevOps lifecycle and comes with many official and community plugins for other developer tools (like the continuous integration tool Jenkins).
LoadUI Pro is a tool that allows developers and testers to conduct rapid and comprehensive performance testing for SOAP and REST APIs, test speed and scalability of new changes to APIs in minutes, as well as preview API performance behaviors before releasing to production environments.
LoadComplete is a desktop tool for load, stress, scalability testing of websites and web applications that works with both traditional HTML web sites and with Rich Internet Applications using modern web technologies like AJAX, ASP.NET, Java, Flash, Flex and Silverlight. The 'record and playpack' and 'visual programming' features enable to create powerful and flexible first load test within a few seconds.
Testable is an innovative distributed load testing and synthetic monitoring platform. Define a test with a variety of open-source tools and let Testable handle the scale, reporting, and analytics. Supports JMeter, Gatling, Locust, Node.js (including HTTP, websockets, Socket.io, and Engine.io), Webdriver.io, Selenium Java, Serenity BDD, PhantomJS, SlimerJS, record-and-replay, and HAR files. Load can be generated on our globally distributed AWS infrastructure, on premises using Docker, or by Testable automatically spinning up isolated on demand EC2 instances for each test using our AWS account or yours. Simulate as many virtual users as you can from the test runners without having to pay more. 1 m4.large can often generate 1000+ virtual users depending on the tool. Real-time results include percentiles, success analytics, and trend analysis for every single metric. Want to know how many concurrent users your environment can handle? Define your performance requirements and let Testable automatically figure it out. Track how that number changes across test runs like any other metric. Define your own KPIs and get alerted when a test fails to meet them. Results can be shared and customized to provide different views for different stakeholders. We also integrate with leading monitoring tools like NewRelic and CI solutions to seamlessly integrate load testing and monitoring into your software development lifecycle.
Automai's performance testing solution uses robot technology to give the most realistic tests possible. Robots access your applications from the front end just as real users do. Captures screenshots so you can act on failures. Easy record and play, or command selection scripting requires no coding, just knowledge of the application use. Intelligent engine recognizes images even if they change or move, or change color, adapting as real people do. This product is one part of Automai's Robotic Automation Platform which allows you to use the same scripts for performance testing, performance monitoring, automated testing, and running business processes with RPA , robotic process automation. Saves you time and money.
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It's that time of year again…. Your render may be looking a bit grubby and maybe there are a few stains? Autumn is the best time of year to clean down your render and kill that red or green algae before it takes hold. A wash down with some Alkem will kill the algae and give your render a chance to shine. A small hand vacuum pump and spray the walls with diluted Alkem from your local Rowebb depot (using suitable PPE obviously…) and just leave it to work its magic. By the Spring you will be able to have a look and see if you need to carry out any small repairs and maybe consider a coat of weather protection or a suitable paint. Remember to take advice from render professionals about weather protection products and paints – It is imperative that these products are suitable for your render. These products must be more breathable than the render it is applied to and they must be specifically designed for use with your render. Using the wrong products can lead to significant damage to your render so take advice before you act!


text:
Photo by Anupam Gupta | Mercury Staff
Molecule makes monumental impact
Editor's Note: Picture caption originally misidentified Tae-Kyung Lee as Jung-Mo Ahn.
A UTD professor and his team have developed a molecule that could benefit breast cancer patients who don't respond to current treatments anymore.
Jung-Mo Ahn, an associate professor of chemistry and biochemistry, and his team of researchers developed ERX-11, a molecule that works differently from molecules in other current breast cancer treatments. Their work was published on Aug. 8 in the online journal eLife.
Ahn said the current breast cancer therapies work for a while, but in time, tumor cells develop immunity against these methods.
"When people are undergoing treatment, their bodies produce lesser estrogen than what they used to," Ahn said. "Since estrogen is less, the tumor cells harvest as much as possible from them and mutate more number of proteins."
Breast cancer cells contain proteins called estrogen receptors. These receptors bind to the hormone estrogen and help tumor cells spread through the body. Current treatments involve one of two approaches – limiting estrogen production in the body or blocking estrogen molecules from binding to their receptors. The molecule ERX-11 prevents the proteins activated by the tumor cells from mutating neighboring proteins.
Ahn and his team started working on this idea around five years ago. They have been developing small molecules targeting protein-protein interactions from the start.
"Because protein-protein interactions deal with enormous surface areas, small molecules cannot compete with them," he said. "Tumor cells target the inside of cells which are protected by membranes. We have been working on creating small molecules that can cross the membrane and stop the tumor cells from doing further damage."
Ahn's research team, composed of research scientist Tae-Kyung Lee and chemistry graduate student Bikash Manandhar, helped with the molecule design and synthesis. They conducted the next phases of testing by collaborating with Ganesh Raj, a professor of urology and pharmacology at the Harold C. Simmons Comprehensive Cancer Center at UT Southwestern Medical Center, and Ratna Vadlamudi, a professor of obstetrics and gynecology at UT Health Science Center at San Antonio.
Ahn and his team initially researched prostate cancer, and around five years ago, started working on breast cancer.
"When we moved to researching breast cancer, initially the compounds, which worked in the case of prostate cancer, were not so effective," Lee said. "So, we designed a new one. ERX-11 is based on the structure of the molecule we developed for prostate cancer."
Undergraduate and graduate students helped Ahn and his team by testing the molecule's design at the cellular and animal level. Ahn said it is important to have students on the team because they bring a fresh perspective to the table.
Research scientist Tae-Kyung Lee speaks about ERX-11, a molecule his team developed over the past five years to improve breast cancer treatments. Photo by Anupam Gupta | Mercury Staff.
"Currently, I have 40 undergraduate students working in my lab, and about seven graduate students," Ahn said. "But this is not enough. Sometimes if you see things all the time, you may miss something. We need a fresh pair of eyes. Even though they are not direct contributors to the paper, their work has been helpful for us to get here."
Ahn's team of researchers and collaborators showed in their recently published paper that ERX-11 is much more effective in mitigating the growth of tumor cells. Lee said that despite the effectiveness, the molecule still needs to be refined.
"It's not easy," Lee said. "Several problems are yet to be solved. The first one is potency. The second is solubility. Practically, our molecule is not soluble in water. My ongoing effort is to improve the solubility of our compound."
Ahn and his team are looking at a five to 10 years' timeline to advance to further trials.
"We are in the discovery stage," Ahn said. "We are sort of closing the pre-clinical trial at this moment. We are testing and trying to prove that our molecule works on cells, on animals and maybe in the human tissue. If we keep going further, it could be a clinical trial someday. That's what we are actually pushing for right now."
cancer4 Cancer Research4 ERX-111 Jung-Mo Ahn1
UTD is implementing solutions, spreading awareness of resources for sexual assault
Donated sculpture finds home at UTD


text:
Carbonylation of epoxides
Carbonylation of epoxides involves the ring-expanding formal insertion of carbon monoxide into one of the C–O bonds of an epoxide. In reactions catalyzed by Lewis acid cobaltate complexes, simple epoxides afford β-lactones while hydroxyl-substituted epoxides may afford larger lactones. γ-Lactones and δ-lactones may be the major products in reactions of alkenyl epoxides catalyzed by iron, palladium, or rhodium.[1]
2 Mechanism and Stereochemistry
2.1 β-Lactones
2.2 Larger Lactones
3 Scope and Limitations
4 Synthetic Applications
5 Comparison to Other Methods
6 Experimental Conditions and Procedure
6.1 Typical Conditions
6.2 Example Procedure[4]
Although β-lactones are of great interest for their pharmaceutical properties, relatively few methods exist for the reliable synthesis of β-lactones. Ring-expanding carbonylation of epoxides is an atom economical and versatile method for construction of β-lactones, larger lactones, and other carbonyl-containing heterocycles (Eq. 1). Reactions catalyzed by Lewis acid cobaltate complexes exhibit stereospecifity and may be combined with stereocontrolled epoxidation to facilitate the rapid construction of lactones from simple starting materials.
Carbonylation of epoxides requires a metal catalyst to facilitate insertion of CO into one of the C–O bonds of the epoxide. Well-defined complexes containing a Lewis acid and the tetracarbonylcobaltate anion have emerged as useful catalysts for site-selective and stereospecific carbonylation to form β-lactones.[2] The Lewis acids in these catalysts are typically aluminum or chromium(III) cations coordinated by a salen or porphyrin ligand (Eq. 2).
The number of catalysts available for epoxide carbonylation is very large, and the scope of the reaction is consequently expansive. This page focuses exclusively on reactions that afford β-, γ-, and δ-lactones. Reactions that afford succinic anhydrides, 1,3-oxazinane-2,4-diones, and 1,3-oxathiolan-2-ones are described in greater detail in the corresponding Organic Reactions chapter.
Mechanism and Stereochemistry
β-Lactones
The generally accepted mechanism for reactions catalyzed by well defined Lewis acid cobaltate complexes begins with coordination of the epoxide to the Lewis acid followed by SN2-type opening of the epoxide at the less substituted carbon. Insertion of CO into the cobalt-carbon bond with coordination of a molecule of CO to cobalt affords a cobalt acyl complex, which is the resting state of the catalyst.[3] Addition-elimination regenerates the catalyst and forms the β-lactone product (Eq. 3). Reactions of monosubstituted epoxides generally yield the β-substituted β-lactone,[4] supporting the idea that opening of the epoxide occurs via an SN2 process.
Although 1,2-disubstituted epoxides typically yield mixtures of constitutional isomers, these substrates can serve as useful stereochemical probes. trans-1,2-Disubstituted epoxides yield cis products exclusively (Eq. 4),[5] suggesting that these reactions are stereospecific. Ring opening occurs with inversion of stereochemistry, again consistent with SN2-type attack by cobaltate.
Iron, palladium, and rhodium complexes mediate or catalyze the ring-expanding carbonylation of epoxides with unsaturated substituents, including alkenyl and aryl epoxides. These reactions involve intermediate π-allyl complexes,[6] which can be isolated from stoichiometric reactions with Fe2(CO)9. Oxidation of the diastereomeric complexes with ceric ammonium nitrate (CAN) affords a mixture of cis- and trans-β-lactones (Eq. 5).[7] In these reactions, insertion of CO into a metal-oxygen bond occurs, followed by reductive elimination to establish the new carbon-carbon bond.
Larger Lactones
Substrates containing hydroxyl groups proximal to the epoxide, such as glycidols and homoglycidols, may react to form γ- and δ-lactones respectively. The mechanisms of these reactions are analogous to the mechanism of β-lactone formation shown in Eq. 3, with a pendant hydroxyl group responsible for addition-elimination rather than the epoxide oxygen.[8] The selectivity for larger lactone formation over β-lactone formation depends on the catalyst used. Rearrangement of initially formed β-lactones to form larger lactones under these conditions has been ruled out.
Reactions of alkenyl epoxides catalyzed by palladium and iron may afford δ-lactones if reductive elimination occurs at the far end of the allylic ligand.[9]
Scope and Limitations
Epoxide carbonylation is catalyzed by many different types of metal complexes, and the structure of the catalyst and substitution pattern of the epoxide both affect the structure of the major product. This section focuses on reactions that afford four-, five-, and six-membered lactones and emphasizes the role of substrate structure in determining the product distribution of carbonylation reactions. More subtle details of catalyst structure are addressed in the corresponding Organic Reactions chapter.
Carbonylation reactions employing Lewis acid cobaltate catalysts and monosubstituted epoxides generally give the β-substituted lactone rather than the α-substituted lactone. SN2-type substitution at the less substituted carbon of the epoxide leads ultimately to the β-substituted lactone. Epoxides that can form stabilized carbocations upon ring opening may form the α-substituted isomer upon carbonylation. For example, aryl epoxides react via an SN1-type pathway to afford α-aryl-β-lactones (Eq. 6).[3]
Well defined Lewis acid cobaltate catalysts are more active than catalysts generated in situ and exhibit good functional group tolerance. Esters, amides, nitriles, halogens, acetals, and distant hydroxyl groups are well tolerated. Strongly Lewis basic functional groups such as amines interfere with carbonylations.
1,1-Disubstituted epoxides often form mixtures of isomeric β-lactone products in the presence of Lewis acid cobaltate catalysts (Eq. 7). SN1-type reactivity via a carbocation intermediate competes with the SN2-type reactivity characteristic of monosubstituted alkyl epoxides.
1,2-Disubstituted alkyl epoxides do not generally react with site selectivity. However, one recent report has identified catalysts that exhibit site selectivity in reactions of epoxides with substituents of different sizes.[10]
Cyclic epoxides sometimes represent an exception to the rule of stereochemical inversion in carbonylations with Lewis acid cobaltate catalysts, if the resulting β-lactone would possess considerable ring strain. For example, cis-cyclopentene oxide gives the cis-β-lactone product via a carbocation intermediate after very long reaction time. cis-Cyclohexene oxide is completely unreactive and cis-cyclooctene oxide forms the corresponding trans-β-lactone relatively rapidly (Eq. 8).[11]
The palladium complex Pd2(C4H7)2Cl2 catalyzes carbonylation of alkenyl epoxides; however this reaction is not always the major process that occurs (Eq. 9).[6] Reaction with the alcoholic solvent can lead to ring opening or β,γ-unsaturated ester formation.
Glycidols contain a hydroxyl group in the appropriate position to form γ-lactones. Because glycidols can also form β-lactones, a judicious choice of catalyst is critical to favor the γ-lactone. Substrates with substitution in the hydroxymethyl substituent tend to exhibit lower yields than glycidol itself. Co4(CO)12 has been identified as a catalyst for the selective formation of γ-lactones from glycidols (Eq. 10).[8] Dehydration of the resulting 3-hydroxy-δ-lactones affords butenolides, an important class of γ-lactones.
Ynolates generated in situ via treatment of diazo compounds with butyllithium and carbon monoxide react with epoxides to form γ-lactones (Eq. 11).[12] This reaction occurs with inversion at the carbon attacked by ynolate, but unselective protonation gives a mixture of diastereomeric α-silyl esters.
Homoglycidols can react analogously to glycidols to afford δ-lactones. Reactions employing Lewis acid cobaltate complexes give mixtures of β- and δ-lactones when homoglycidols are used as substrates, but the acidic cobalt tetracarbonyl hydride has been shown to selectively catalyze δ-lactone formation (Eq. 12).[13]
The iron carbonyl complexes Fe(CO)5 and Fe2(CO)9 promote the carbonylation of alkenyl epoxides to β- or δ-lactones. Substitution is well tolerated throughout the alkenyl epoxide, and selectivity for the δ-lactone can be achieved through careful choice of the catalyst (Eq. 13).[14]
Synthetic Applications
β-Lactones are synthetically valuable both as lipase inhibitors[15] and as monomers for biodegradable polyesters.[16] However, the β-lactone moiety presents a synthetic challenge because of its considerable ring strain and propensity to open under acidic or basic conditions. To survive a synthesis, β-lactones generally must be installed at a late stage. Epoxide carbonylation is an attractive method for the synthesis of β-lactones owing to the atom economy, functional group tolerance, and accessible starting materials of the transformation.
A prototypical example of the use of epoxide carbonylation for organic synthesis is found in a synthesis of (–)-valilactone.[7] Ring-expanding carbonylation using stoichiometric Fe2(CO)9 was followed by peptide coupling, deprotection of the amino group, and formylation. Although the yield of the carbonylation step was only 26%, this step was critical in establishing the β-lactone core of the target.
Comparison to Other Methods
Carbonylative ring expansion of epoxides is generally an efficient method for the synthesis of lactones. Nonetheless, a huge variety of methods exist for the synthesis of lactones, each with its own advantages and disadvantages. This section focuses on a limited number of popular alternatives for the synthesis of β-, γ-, and δ-lactones.
β-Lactones may be formed via ring closure of β-hydroxy carboxylic acids or β-haloacids. The latter methods have been superseded by the former, which are generally based on a Mitsunobu approach that inverts the configuration of the carbon bearing the hydroxyl group. Mitsunobu conditions can be problematic, however, as activation of the carboxylic acid group can compete with activation of the hydroxyl group.[17] Arenesulfonyl chlorides selectively activate the carboxylic acid.[18]
β-Lactones are the products of \[2+2\] cycloaddition of ketenes with aldehydes.[19] Highly enantioselective variants of this reaction have been developed, and cycloaddition is arguably the most efficient way to establish the β-lactone skeleton. Enantioselective reactions generally rely on chiral quinine or quinidine catalysts (Eq. 16) and exhibit remarkably high enantioselectivity.[20] However, generation of complex substituted ketenes is typically accomplished through dehydrohalogenation of acid chlorides, which may require harsh reaction conditions.
Because γ-lactones lack ring strain, a large number of methods exist for the synthesis of these five-membered heterocycles. Some useful methods include Mitsunobu reactions,[21] halolactonization,[22] acid-activating agents such as dicyclohexylcarbodiimide,[23] Baeyer-Villiger oxidations of cyclobutanones,[24] and desymmetrizing reductions of succinic anhydrides.[25]
One approach that is conceptually similar to glycidol carbonylation involves the enantioselective dihydroxylation of a β,γ-unsaturated ester followed by lactonization. 3-Hydroxy-γ-lactones are formed with high enantioselectivity and in excellent yield.
δ-Lactones may be synthesized via ring opening of an epoxide by a homoenolate equivalent followed by lactonization (Eq. 18).[26] In the example below, after deprotonation of the acidic α-carbon of the sulfonate and opening of the epoxide, the orthoester is unmasked to an ester and lactonization is facilitated by tosic acid. Subsequent elimination of sulfonate affords an unsaturated δ-lactone.
Experimental Conditions and Procedure
Typical Conditions
Carbonylations of epoxides are universally performed in environments free of water and oxygen to avoid catalyst decomposition and side reactions. Reactions may be prepared either in a drybox or using standard Schlenk techniques. Carbon monoxide is a highly toxic, odorless, and invisible gas, so these reactions should be conducted in a well-ventilated fume hood or box equipped with a CO detector. High pressures of CO (10-60 atm) are generally required to achieve selective carbonylation; at low pressures, isomerization of epoxides to ketones[27] or other side reactions may occur. A variety of different solvents have been used, as solvent can affect the relative rates of carbonylation and competing processes.
Example Procedure[4]
In a drybox, salphCr (182 mg, 0.200 mmol) was weighed into a 500-mL, oven-dried, three-neck round-bottomed flask with a magnetic stir bar. A dry, 50-mL addition funnel was attached, along with a stopper and a rubber septum. DME (9.0 mL) was drawn into a Gastight syringe while phenyl glycidyl ether (1.50 g, 10.0 mmol) was drawn into a separate syringe with 1.0 mL DME. The flask was removed to a fume hood where the flask was sparged with CO for 10 min before a double balloon of CO was attached to the flask using a needle to puncture the septum. The flask was then placed into an ice bath, the DME was added to the catalyst, and the mixture was stirred for 10 min. The epoxide solution was added dropwise at 0 °C via the addition funnel over the course of 30 min while stirring. After epoxide addition was complete, the ice bath was removed and the flask was allowed to warm to rt and was stirred for 24 h. The flask was vented in a fume hood and the reaction mixture was concentrated under vacuum to an oil. The crude oil was purified by chromatography through silica gel with CH2Cl2, and then was recrystallized from CH2Cl2/hexanes to afford 4-phenoxymethyl-2-propiolactone (1.5 g, 84%): mp 75–77 °C; IR (neat, NaCl) 1818 (C=O) cm–1; 1H NMR (CDCl3, 300 MHz) δ 7.31 (t, 3J = 7.9 Hz, 2H), 7.00 (t, 3J = 7.3 Hz, 1H), 6.92 (d, 3J = 8.2 Hz, 2H), 4.83 (dddd, 3J = 3.0, 4.4, 5.1, 9.5 Hz, 1H), 4.32 (dd, 2J = 11.1 Hz, 3J = 3.0 Hz, 1H), 4.19 (dd, 2J = 11.1 Hz, 3J = 4.2 Hz, 1H), 3.55 (d, 3J = 5.1 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 167.5, 158.1, 129.8, 121.8, 114.8, 68.5, 67.3, 40.0; HRMS (EI) m/z: calcd for C10H10O3, 178.0630; found, 178.0630.
↑ Kramer, J. W.; Rowley, J. M.; Coates, G. W. Org. React. 2015, 86, 1. (link)
↑ Getzler, Y. D. Y. L.; Mahadevan, V.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2002, 124, 1174. (link)
↑ a b Rowley, J. M.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2007, 129, 4948.
↑ a b Kramer, J. W.; Treitler, D. S.; Coates, G. W. Org. Synth. 2009, 86, 287.
↑ Kramer, J. W.; Lobkovsky, E. B.; Coates, G. W. Org. Lett. 2006, 8, 3709.
↑ a b Shimizu, I.; Maruyama, T.; Makuta, T.; Yamamoto, A. Tetrahedron Lett. 1993, 34, 2135.
↑ a b Bates, R. W.; Fernandez-Moro, R.; Ley, S. V. Tetrahedron 1991, 47, 9929.
↑ a b Brima, T. S. U.S. Patent 4968817 (1990).
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↑ Mulzer, M.; Coates, G. W. J. Org. Chem. 2014, ASAP. (link)
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↑ Kai, H.; Iwamoto, K.; Chatani, N.; Murai, S. J. Am. Chem. Soc. 1996, 118, 7634.
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↑ Zhu, C.; Shen, X.; Nelson, S. G. J. Am. Chem. Soc. 2004, 126, 5352.
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↑ Carretero, J. C.; Ghosez, L. Tetrahedron Lett. 1988, 29, 2059.
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