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  • Articles  (390)
  • Chemistry
  • Science and Culture
  • Science  (229)
  • PNAS - Proceedings of the National Academy of Sciences  (48)
  • Science. 199(4334): 1173-82.  (1)
  • Science. 200(4337): 21-7.  (1)
  • Science. 202(4364): 174-82.  (1)
  • Science. 203(4385): 1135-7.  (1)
  • Science. 204(4397): 1081-2.  (1)
  • Science. 206(4424): 1309-11.  (1)
  • Science. 207(4426): 90-2.  (1)
  • Science. 210(4468): 385-90.  (1)
  • Science. 211(4481): 491-3.  (1)
  • Science. 211(4487): 1131-6.  (1)
  • Science. 212(4496): 749-53.  (1)
  • Science. 213(4509): 724-31.  (1)
  • Science. 214(4518): 270-4.  (1)
  • Science. 214(4526): 1259-61.  (1)
  • Science. 214(4527): 1305-12.  (1)
  • Science. 217(4555): 166-9.  (1)
  • Science. 217(4564): 1040-2.  (1)
  • Science. 218(4576): 961-6.  (1)
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  • Articles  (390)
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  • 1
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    Value of a good science hack [Applied Physical Sciences] (2016)
    National Academy of Sciences
    Details
    Publication Date: 2016-07-21
    Description: Physicist Matt Bellis attended his first Science Hack Day in the fall of 2010, in Palo Alto, California. Like many scientists attending the event for the first time, Bellis was skeptical. “Hacking,” after all, is usually left to computer programmers. Matt Bellis (green shirt) takes part in the 2014 Science...
    Keywords: Science and Culture
    Print ISSN: 0027-8424
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  • 2
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    [Perspective] Molecular sieves for gas separation (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2016-07-08
    Description: Separation and purification are critical industrial processes for separating components of chemical mixtures, and these processes account for about half of industrial energy usage (1). Gas mixtures of compounds with very similar physical properties are particularly difficult to separate. On pages 137 and 141 of this issue, Cadiau et al. (2) and Cui et al. (3), respectively, show that microporous materials can be designed to have high adsorption capacity and selectivity for particular hydrocarbons, enabling energy-efficient separation. Author: Jerry Y. S. Lin
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 3
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    [Perspective] How to break down crystalline cellulose (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2016-05-27
    Description: Biomass-degrading microorganisms use lytic polysaccharide monooxygenase (LPMO) enzymes to help digest cellulose, chitin, and starch. By cleaving otherwise inaccessible crystalline cellulose chains, these enzymes provide access to hydrolytic enzymes. LPMOs are of interest to biotechnology because efficient depolymerization of cellulose is a major bottleneck for the production of biologically based chemicals and fuels. On page 1098 of this issue, Kracher et al. (1) compare LPMO-reducing substrates in fungi from different taxonomic groups and lifestyles, based on both biochemical and genomic evidence. The results provide insights into reductive activation of LPMO that are important for developing more efficient industrial enzymes for lignocellulose biorefineries. Author: Angel T. Martínez
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 4
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    Kirigami and technology cut a fine figure together [Science and Culture] (2016)
    National Academy of Sciences
    Details
    Publication Date: 2016-01-13
    Description: When pursuing a degree in fine arts 15 years ago, Matthew Shlian never dreamed that he would one day be the coauthor of scientific research papers on nanoengineering and solar power (1, 2). But, the Ann Arbor-based artist and designer was exactly that earlier this year. A collaboration between Shlian...
    Keywords: Science and Culture
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  • 5
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    [Editors' Choice] Engineering open structures using DNA (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2016-03-25
    Description: Author: Marc S. Lavine
    Keywords: Chemistry
    Print ISSN: 0036-8075
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 6
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    Charting the history of Western art with math [Science and Culture] (2015)
    National Academy of Sciences
    Details
    Publication Date: 2015-06-24
    Description: For more than a century, researchers have used statistics to study writing style in a sort of literary forensics technique called stylometry. In 1901, physicist T. C. Mendenhall famously measured word-length frequency in William Shakespeare’s works and reported that the writer’s style was awfully close to that of fellow writer...
    Keywords: Science and Culture
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  • 7
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    Making a pitch for female engineers [Science and Culture] (2015)
    National Academy of Sciences
    Details
    Publication Date: 2015-10-14
    Description: High school is going great for pretty, 15-year-old Emily, until she accidentally burns down the school gym during the science fair. As a result, Emily faces an ultimatum: get expelled or join the school’s Science and Engineering Club, which her popular friends brand the “social suicide club.” Emily chooses the...
    Keywords: Science and Culture
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  • 8
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    Modern {#x201C}cathedral{#x201D} offers artistic inspiration [Physics] (2016)
    National Academy of Sciences
    Details
    Publication Date: 2016-08-11
    Description: Grandeur is often associated with feats of architecture and engineering. It’s not often applied to scientific experiments. One notable exception is the Large Hadron Collider (LHC), a particle accelerator and collider complex at CERN, the European Organization for Nuclear Research, outside Geneva, Switzerland. Artist Jonathan Feldschuh was so fascinated with...
    Keywords: Science and Culture
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  • 9
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    Putting a game face on biomedical research [Computer Sciences] (2016)
    National Academy of Sciences
    Details
    Publication Date: 2016-06-15
    Description: In 2011, game developer David Edery shocked his collaborator Sandy Anderson, a mathematical oncologist, with a provocative question: “If I could kill the patient really quickly, would that be useful?” It sounds cruel, but is rather typical thinking for game developers. Edery was essentially asking: “Would you learn something if...
    Keywords: Science and Culture
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  • 10
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    Using fiction to make the case for basic research [Science and Culture] (2015)
    National Academy of Sciences
    Details
    Publication Date: 2015-04-08
    Description: What possesses a respected, retired scientist to take on the agonizing task of writing a novel and fighting to get it published? Author Joram Piatigorsky, an emeritus scientist from the National Institute of Health’s National Eye Institute, says quite simply that he had something important to say. In Jellyfish Have...
    Keywords: Science and Culture
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  • 11
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    Oppenheimer goes center stage [Science and Culture] (2015)
    National Academy of Sciences
    Details
    Publication Date: 2015-06-17
    Description: J. Robert Oppenheimer, ambitious leader of the Manhattan Project, struggled with intense ethical dilemmas. To continue to work on the atom bomb, he had to abandon his communist friends in order to prove to military monitors his loyalty to the US government. Later, Oppenheimer faced the moral implications of the...
    Keywords: Science and Culture
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  • 12
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    Science on-screen and behind the scenes [Science and Culture] (2015)
    National Academy of Sciences
    Details
    Publication Date: 2015-01-28
    Description: In 2009, a team of Hollywood producers from Marvel Studios approached The Science & Entertainment Exchange, a program of the National Academy of Sciences (NAS), for advice on using good science to make the movie Thor. The filmmakers, aware of Arthur C. Clarke’s maxim that “any sufficiently advanced technology is...
    Keywords: Science and Culture
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  • 13
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    High-stakes game of oil use [Science and Culture] (2013)
    National Academy of Sciences
    Details
    Publication Date: 2013-02-20
    Description: pnas;110/8/2685/UNFIG01F1unfig01Visitors to the Koshland Science Museum engage in a game of Catan: Oil Springs, where they must balance the use of natural resources such as oil against the risk of catastrophe.While commuters fought evening rush-hour traffic on the streets of downtown Washington, DC, visitors to the Koshland Science Museum of...
    Keywords: Science and Culture
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  • 14
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    Biomimetic buildings [Science and Culture] (2013)
    National Academy of Sciences
    Details
    Publication Date: 2013-02-13
    Description: pnas;110/7/2433/UNFIG01F1unfig01Image courtesy of Art Works for Change from the Nature's Toolbox: Biodiversity, Art and Invention exhibition. Lee C, Bios Design Collective. (2010) Dissipative System. Diamond ink jet print, 27×30 in.The more technology advances, the more there seems to be a basic human yearning to return to nature. This is reflected...
    Keywords: Science and Culture
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  • 15
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    Cartoons to better communicate science [Science and Culture] (2015)
    National Academy of Sciences
    Details
    Publication Date: 2015-09-23
    Description: Words often fail when teaching science. Although some scientific concepts lend themselves to easily articulated descriptions and definitions, others consist mostly of a language of symbols only decipherable by knowledgeable experts. Diagrams can help. However, some researchers and science educators believe another medium, known more for its entertainment value than...
    Keywords: Science and Culture
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  • 16
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    Quantum interference and diradicals [Chemistry] (2016)
    National Academy of Sciences
    Details
    Publication Date: 2016-01-27
    Description: An empirical observation of a relationship between a striking feature of electronic transmission through a π-system, destructive quantum interference (QI), on one hand, and the stability of diradicals on the other, leads to the proof of a general theorem that relates the two. Subject to a number of simplifying assumptions,...
    Keywords: Chemistry
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  • 17
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    Science icescapes [Science and Culture] (2014)
    National Academy of Sciences
    Details
    Publication Date: 2014-04-02
    Description: Scientists will go to the ends of the earth for data. They will drop themselves on a featureless ice sheet to measure a temperature or float down a mosquito-infested river for a few tablespoons of water. Seattle-based photographer Chris Linder follows them and uses his camera to bring science’s epic...
    Keywords: Science and Culture
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  • 18
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    Turning to wood [Science and Culture] (2014)
    National Academy of Sciences
    Details
    Publication Date: 2014-11-26
    Description: It was the late 1990s when Wolfgang Vogelbein’s father first introduced him to woodturning. The art form attracted him, and soon enough he stumbled on an old gray high school shop lathe that could be his for $500. Vogelbein’s interest continued to grow, he got a newer machine, and he...
    Keywords: Science and Culture
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  • 19
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    Representing Feynman [Science and Culture] (2014)
    National Academy of Sciences
    Details
    Publication Date: 2014-09-03
    Description: Fundamental to science and art, says Edward Tufte, is “intense seeing,” or seeing without the use of words. Widely known for his graphical depictions of statistical data, Tufte uses intense seeing to discover the meaning of large amounts of information, which he then shares by crafting elegant designs to represent...
    Keywords: Science and Culture
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  • 20
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    Capturing the world's oldest living things [Science and Culture] (2014)
    National Academy of Sciences
    Details
    Publication Date: 2014-12-17
    Description: Artist Rachel Sussman thought she’d have little trouble devising a list of the world’s oldest living things for a photography project. She merely needed to find the right sort of expert. Jomon Sugi, Japanese cedar #0704–002 (2,180–7,000 years old, Yakushima, Japan). Image courtesy of Rachel Sussman. Sussman first met with...
    Keywords: Science and Culture
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  • 21
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    High concept art and experiments [Science and Culture] (2015)
    National Academy of Sciences
    Details
    Publication Date: 2015-03-11
    Description: Around the same time that Roger Guillemin was conducting research that would eventually earn him a share of the 1977 Nobel Prize in Physiology or Medicine, he was also experimenting with using his laboratory computer to make works of art. This computer-rendered painting, Room With a View, is one of...
    Keywords: Science and Culture
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  • 22
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    Data visualization nurtures an artistic movement [Science and Culture] (2015)
    National Academy of Sciences
    Details
    Publication Date: 2015-02-26
    Description: In recent years, new ways of visualizing data and networks have had an enormous influence on many areas of research, allowing, for example, thousands of data points to depict clear trends in science citations or genomic patterns. But the impact of these methods has extended beyond areas of scientific inquiry:...
    Keywords: Science and Culture
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  • 23
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    Q&A with Roger Malina [Science and Culture] (2014)
    National Academy of Sciences
    Details
    Publication Date: 2014-12-31
    Description: Professional astronomer Roger Malina is helping to lead a PhD program that marries art and science at the University of Texas at Dallas. Malina details the endeavor’s manifold challenges and his own artistic influences. Roger Malina. Image courtesy of the University of Texas at Dallas. Q: Many of your early...
    Keywords: Science and Culture
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  • 24
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    Sculpting the apples of science [Science and Culture] (2014)
    National Academy of Sciences
    Details
    Publication Date: 2014-06-04
    Description: The porcelain objects in sculptor Jessica Rath’s project “Take Me to the Apple Breeder” look just like what they’re based on: apples. However, they’re apples far beyond the familiar varieties of the grocery store or farmer’s market. The hefty Deacon Jones is the size of a baby’s head. The Sunset...
    Keywords: Science and Culture
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  • 25
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    Protein structure paintings [Science and Culture] (2014)
    National Academy of Sciences
    Details
    Publication Date: 2014-03-19
    Description: When artist Steve Miller met Nobel Laureate Rod MacKinnon at Brookhaven National Laboratory in New York, MacKinnon was investigating protein structures: specifically, how potassium ions move across cell membranes. Miller became fascinated with the visual tools MacKinnon used to grapple with the problem: 3D computer models of proteins, graphical equations...
    Keywords: Science and Culture
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  • 26
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    Supersized viruses [Science and Culture] (2014)
    National Academy of Sciences
    Details
    Publication Date: 2014-04-16
    Description: On February 22, festival-goers at Melbourne’s dusk-to-dawn White Night celebration lined up in droves outside the State Library of Victoria for an intimate evening with herpes. And they got it, in a big way: Bobbling around on the 40-meter-diameter central dome on the ceiling of the library’s La Trobe Reading...
    Keywords: Science and Culture
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  • 27
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    Digital dome [Science and Culture] (2013)
    National Academy of Sciences
    Details
    Publication Date: 2013-11-27
    Description: The National Academy of Sciences has a history of engagement with artists and architects dating back to 1924 when its historic home opened on Constitution Avenue in Washington, DC. The Academy’s building committee, along with architect Bertram Grosvenor Goodhue, engaged a number of prominent artists of the time to adorn...
    Keywords: Science and Culture
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  • 28
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    Dissecting the Great Wave [Science and Culture] (2014)
    National Academy of Sciences
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    Publication Date: 2014-09-17
    Description: The Great Wave off Kanagawa, a 19th century woodcut by Japanese artist Hokusai, depicts oshiokuri-bune, or cargo boats, navigating a monstrously rough sea within sight of a snow-capped Mt. Fuji. The woodcut is among the best-known works of Japanese art, yet in the last few years scientists have argued that...
    Keywords: Science and Culture
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  • 29
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    Dangerous doilies [Science and Culture] (2014)
    National Academy of Sciences
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    Publication Date: 2014-08-13
    Description: Artist Laura Splan’s oeuvre has beauty and death, illness and medicine, science and fashion paired in artworks that provoke and challenge our notions and traditions. Splan studied biological sciences before settling on art, and methodical experimentation is integral to her artistic process. Her current exhibition of doilies created in the...
    Keywords: Science and Culture
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  • 30
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    Patent law. Natural substances and patentable inventions (2003)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 2003-05-31
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Demaine, Linda J -- Fellmeth, Aaron X -- New York, N.Y. -- Science. 2003 May 30;300(5624):1375-6.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉RAND, Santa Monica, CA 90401, USA. demaine@rand.org〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/12775825" target="_blank"〉PubMed〈/a〉
    Keywords: Aluminum Oxide ; Chemical Phenomena ; Chemistry ; Natural Science Disciplines ; Patents as Topic/*legislation & jurisprudence ; Plant Extracts ; Plant Roots ; Titanium ; United States
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 31
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    Chemical ecology: missed opportunities? (2002)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 2002-03-16
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Eisner, Thomas -- Berenbaum, May -- New York, N.Y. -- Science. 2002 Mar 15;295(5562):1973.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/11896239" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; Biochemical Phenomena ; *Biochemistry ; *Biological Factors/chemistry ; *Biology ; Chemical Phenomena ; Chemistry ; *Ecology ; Ecosystem ; *Molecular Biology ; Research Support as Topic ; United States
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  • 32
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    Characterization of a helical protein designed from first principles (1988)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1988-08-19
    Description: The question of how the primary amino acid sequence of a protein determines its three-dimensional structure is still unanswered. One approach to this problem involves the de novo design of model peptides and proteins that should adopt desired three-dimensional structures. A systematic approach was aimed at the design of a four-helix bundle protein. The gene encoding the designed protein was synthesized and the protein was expressed in Escherichia coli and purified to homogeneity. The protein was shown to be monomeric, highly helical, and very stable to denaturation by guanidine hydrochloride (GuHCl). Thus a globular protein has been designed that is capable of adopting a stable, folded structure in aqueous solution.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Regan, L -- DeGrado, W F -- New York, N.Y. -- Science. 1988 Aug 19;241(4868):976-8.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉E. I. du Pont de Nemours & Company, Central Research & Development Department, Wilmington, DE 19898.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/3043666" target="_blank"〉PubMed〈/a〉
    Keywords: Amino Acid Sequence ; Chemical Phenomena ; Chemistry ; Chromatography, Gel ; Escherichia coli/genetics ; Molecular Sequence Data ; Plasmids ; *Protein Conformation ; *Proteins/genetics
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    Sequence-specific peptide cleavage catalyzed by an antibody (1989)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1989-03-03
    Description: Monoclonal antibodies have been induced that are capable of catalyzing specific hydrolysis of the Gly-Phe bond of peptide substrates at neutral pH with a metal complex cofactor. The antibodies were produced by immunizing with a Co(III) triethylenetetramine (trien)-peptide hapten. These antibodies as a group are capable of binding trien complexes of not only Co(III) but also of numerous other metals. Six peptides were examined as possible substrates with the antibodies and various metal complexes. Two of these peptides were cleaved by several of the antibodies. One antibody was studied in detail, and cleavage was observed for the substrates with the trien complexes of Zn(II), Ga(III), Fe(III), In(III), Cu(II), Ni(II), Lu(III), Mg(II), or Mn(II) as cofactors. A turnover number of 6 x 10(-4) per second was observed for these substrates. These results demonstrate the feasibility of the use of cofactor-assisted catalysis in an antibody binding site to accomplish difficult chemical transformations.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Iverson, B L -- Lerner, R A -- New York, N.Y. -- Science. 1989 Mar 3;243(4895):1184-8.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Molecular Biology, Research Institute of Scripps Clinic, La Jolla, CA 92037.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2922606" target="_blank"〉PubMed〈/a〉
    Keywords: Amino Acid Sequence ; Animals ; *Antibodies, Monoclonal ; Antigens/immunology ; Binding Sites, Antibody ; Catalysis ; Chemical Phenomena ; Chemistry ; Cobalt/immunology/metabolism ; Glycine/metabolism ; Haptens/immunology ; Hydrogen-Ion Concentration ; Hydrolysis ; Immunization ; Metals/metabolism ; Mice ; Molecular Sequence Data ; Molecular Structure ; Oligopeptides/*metabolism ; Phenylalanine/metabolism ; Trientine/immunology
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    Left- or right-handed C-H bond activation (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-02-16
    Keywords: Chemistry
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  • 35
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    Comment on "Selective anaerobic oxidation of methane enables direct synthesis of methanol" (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-02-16
    Description: The comment and response concerning the report of oxidation of methane to methanol by water (Reports, 5 May 2017, p. 523) do not fully capture the implications of thermodynamic limitations. A nonisothermal process in which each cycle requires a large temperature swing and permits only substoichiometric methane conversion surely could not be carried out on any practical scale.
    Keywords: Chemistry
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  • 36
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    Response to Comment on "Selective anaerobic oxidation of methane enables direct synthesis of methanol" (2018)
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    In: Science
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    Publication Date: 2018-02-16
    Description: Labinger argues that stepwise reaction of methane with water to produce methanol and hydrogen will never be commercially feasible because of its substoichiometric basis with respect to the active site and the requirement of a large temperature swing. This comment is not touching any new ground, beyond describing the thermodynamic feasibility, thermal cycling, and the role of water as discussed previously. Most important, it does not have a solid numerical basis.
    Keywords: Chemistry
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    Silicon smooths the way to vinyl cations (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-07-27
    Keywords: Chemistry
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    Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-07-27
    Description: Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium–weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond–forming reactions, including carbon-hydrogen (C–H) insertion into unactivated sp 3 C–H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C–H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.
    Keywords: Chemistry
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    Separation of enantiomers by their enantiospecific interaction with achiral magnetic substrates (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-06-22
    Description: It is commonly assumed that recognition and discrimination of chirality, both in nature and in artificial systems, depend solely on spatial effects. However, recent studies have suggested that charge redistribution in chiral molecules manifests an enantiospecific preference in electron spin orientation. We therefore reasoned that the induced spin polarization may affect enantiorecognition through exchange interactions. Here we show experimentally that the interaction of chiral molecules with a perpendicularly magnetized substrate is enantiospecific. Thus, one enantiomer adsorbs preferentially when the magnetic dipole is pointing up, whereas the other adsorbs faster for the opposite alignment of the magnetization. The interaction is not controlled by the magnetic field per se, but rather by the electron spin orientations, and opens prospects for a distinct approach to enantiomeric separations.
    Keywords: Chemistry
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    Inspiration from a vitamin (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-06-29
    Keywords: Chemistry
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    Observation of the geometric phase effect in the H + HD -〉 H2 + D reaction (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-12-14
    Description: Theory has established the importance of geometric phase (GP) effects in the adiabatic dynamics of molecular systems with a conical intersection connecting the ground- and excited-state potential energy surfaces, but direct observation of their manifestation in chemical reactions remains a major challenge. Here, we report a high-resolution crossed molecular beams study of the H + HD -〉 H 2 + D reaction at a collision energy slightly above the conical intersection. Velocity map ion imaging revealed fast angular oscillations in product quantum state–resolved differential cross sections in the forward scattering direction for H 2 products at specific rovibrational levels. The experimental results agree with adiabatic quantum dynamical calculations only when the GP effect is included.
    Keywords: Chemistry
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    Photocatalytic upgrading of natural gas (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-08-17
    Keywords: Chemistry
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    Radically transforming light hydrocarbons (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-08-17
    Keywords: Chemistry
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    Stereodivergent synthesis of 1,4-dicarbonyls by traceless charge-accelerated sulfonium rearrangement (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-08-17
    Description: The chemistry of the carbonyl group is essential to modern organic synthesis. The preparation of substituted, enantioenriched 1,3- or 1,5-dicarbonyls is well developed, as their disconnection naturally follows from the intrinsic polarity of the carbonyl group. By contrast, a general enantioselective access to quaternary stereocenters in acyclic 1,4-dicarbonyl systems remains an unresolved problem, despite the tremendous importance of 2,3-substituted 1,4-dicarbonyl motifs in natural products and drug scaffolds. Here we present a broad enantioselective and stereodivergent strategy to access acyclic, polysubstituted 1,4-dicarbonyls via acid-catalyzed [3,3]-sulfonium rearrangement starting from vinyl sulfoxides and ynamides. The stereochemistry at sulfur governs the absolute sense of chiral induction, whereas the double bond geometry dictates the relative configuration of the final products.
    Keywords: Chemistry
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    Four varieties of carbonyl sandwich (2018)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 2018-08-17
    Keywords: Chemistry
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    Selective functionalization of methane, ethane, and higher alkanes by cerium photocatalysis (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-08-17
    Description: With the recent soaring production of natural gas, the use of methane and other light hydrocarbon feedstocks as starting materials in synthetic transformations is becoming increasingly economically attractive, although it remains chemically challenging. We report the development of photocatalytic C–H amination, alkylation, and arylation of methane, ethane, and higher alkanes under visible light irradiation at ambient temperature. High catalytic efficiency (turnover numbers up to 2900 for methane and 9700 for ethane) and selectivity were achieved using abundant, inexpensive cerium salts as photocatalysts. Ligand-to-metal charge transfer excitation generated alkoxy radicals from simple alcohols that in turn acted as hydrogen atom transfer catalysts. The mixed-phase gas/liquid reaction was adapted to continuous flow, enabling the efficient use of gaseous feedstocks in scalable photocatalytic transformations.
    Keywords: Chemistry
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    Hot lithium-oxygen batteries charge ahead (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-08-24
    Keywords: Chemistry
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    A preference for acids (2018)
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    Publication Date: 2018-08-24
    Keywords: Chemistry
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    18 electrons and counting (2018)
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    In: Science
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    Publication Date: 2018-08-31
    Keywords: Chemistry
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    Directional control of a processive molecular hopper (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-08-31
    Description: Intrigued by the potential of nanoscale machines, scientists have long attempted to control molecular motion. We monitored the individual 0.7-nanometer steps of a single molecular hopper as it moved in an electric field along a track in a nanopore controlled by a chemical ratchet. The hopper demonstrated characteristics desired in a moving molecule: defined start and end points, processivity, no chemical fuel requirement, directional motion, and external control. The hopper was readily functionalized to carry cargos. For example, a DNA molecule could be ratcheted along the track in either direction, a prerequisite for nanopore sequencing.
    Keywords: Chemistry
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    Unlocking P(V): Reagents for chiral phosphorothioate synthesis (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-09-21
    Description: Phosphorothioate nucleotides have emerged as powerful pharmacological substitutes of their native phosphodiester analogs with important translational applications in antisense oligonucleotide (ASO) therapeutics and cyclic dinucleotide (CDN) synthesis. Stereocontrolled installation of this chiral motif has long been hampered by the systemic use of phosphorus(III) [P(III)]–based reagent systems as the sole practical means of oligonucleotide assembly. A fundamentally different approach is described herein: the invention of a P(V)-based reagent platform for programmable, traceless, diastereoselective phosphorus-sulfur incorporation. The power of this reagent system is demonstrated through the robust and stereocontrolled synthesis of various nucleotidic architectures, including ASOs and CDNs, via an efficient, inexpensive, and operationally simple protocol.
    Keywords: Chemistry
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    Self-assembly of lattices with high structural complexity from a geometrically simple molecule (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-09-21
    Description: Here we report an anomalous porous molecular crystal built of C–H···N-bonded double-layered roof-floor components and wall components of a segregatively interdigitated architecture. This complicated porous structure consists of only one type of fully aromatic multijoint molecule carrying three identical dipyridylphenyl wedges. Despite its high symmetry, this molecule accomplishes difficult tasks by using two of its three wedges for roof-floor formation and using its other wedge for wall formation. Although a C–H···N bond is extremely labile, the porous crystal maintains its porosity until thermal breakdown of the C–H···N bonds at 202°C occurs, affording a nonporous polymorph. Though this nonporous crystal survives even at 325°C, it can retrieve the parent porosity under acetonitrile vapor. These findings show how one can translate simplicity into ultrahigh complexity.
    Keywords: Chemistry
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    Two ways out of an oxetane (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-09-28
    Keywords: Chemistry
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    Arenes and amides from a single source (2018)
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    Publication Date: 2018-09-28
    Keywords: Chemistry
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    Interrupted carbonyl-olefin metathesis via oxygen atom transfer (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-09-28
    Description: Some of the simplest and most powerful carbon-carbon bond forming strategies take advantage of readily accessible ubiquitous motifs: carbonyls and olefins. Here we report a fundamentally distinct mode of reactivity between carbonyls and olefins that differs from established acid-catalyzed carbonyl-ene, Prins, and carbonyl-olefin metathesis reaction paths. A range of epsilon, zeta-unsaturated ketones undergo Brønsted acid–catalyzed intramolecular cyclization to provide tetrahydrofluorene products via the formation of two new carbon-carbon bonds. Theoretical calculations and accompanying mechanistic studies suggest that this carbocyclization reaction proceeds through the intermediacy of a transient oxetane formed by oxygen atom transfer. The complex polycyclic frameworks in this product class appear as common substructures in organic materials, bioactive natural products, and recently developed pharmaceuticals.
    Keywords: Chemistry
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    Arylsulfonylacetamides as bifunctional reagents for alkene aminoarylation (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-09-28
    Description: Alkene aminoarylation with a single, bifunctional reagent is a concise synthetic strategy. We report a catalytic protocol for the addition of arylsulfonylacetamides across electron-rich alkenes with complete anti-Markovnikov regioselectivity and excellent diastereoselectivity to provide 2,2-diarylethylamines. In this process, single-electron alkene oxidation enables carbon-nitrogen bond formation to provide a key benzylic radical poised for a Smiles-Truce 1,5-aryl shift. This reaction is redox-neutral, exhibits broad functional group compatibility, and occurs at room temperature with loss of sulfur dioxide. As this process is driven by visible light, uses readily available starting materials, and demonstrates convergent synthesis, it is well suited for use in a variety of synthetic endeavors.
    Keywords: Chemistry
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    Activating plasmonic chemistry (2018)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 2018-10-05
    Keywords: Chemistry
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    Hot carriers reducing thermal barriers (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-05
    Keywords: Chemistry
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    Quantifying hot carrier and thermal contributions in plasmonic photocatalysis (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-05
    Description: Photocatalysis based on optically active, "plasmonic" metal nanoparticles has emerged as a promising approach to facilitate light-driven chemical conversions under far milder conditions than thermal catalysis. However, an understanding of the relation between thermal and electronic excitations has been lacking. We report the substantial light-induced reduction of the thermal activation barrier for ammonia decomposition on a plasmonic photocatalyst. We introduce the concept of a light-dependent activation barrier to account for the effect of light illumination on electronic and thermal excitations in a single unified picture. This framework provides insight into the specific role of hot carriers in plasmon-mediated photochemistry, which is critically important for designing energy-efficient plasmonic photocatalysts.
    Keywords: Chemistry
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    An acid inaccessible to aldol products (2018)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 2018-10-12
    Keywords: Chemistry
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    Iodine smooths the way to ketyl radicals (2018)
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    Publication Date: 2018-10-12
    Keywords: Chemistry
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    Ketyl radical reactivity via atom transfer catalysis (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-10-12
    Description: Single-electron reduction of a carbonyl to a ketyl enables access to a polarity-reversed platform of reactivity for this cornerstone functional group. However, the synthetic utility of the ketyl radical is hindered by the strong reductants necessary for its generation, which also limit its reactivity to net reductive mechanisms. We report a strategy for net redox-neutral generation and reaction of ketyl radicals. The in situ conversion of aldehydes to α-acetoxy iodides lowers their reduction potential by more than 1 volt, allowing for milder access to the corresponding ketyl radicals and an oxidative termination event. Upon subjecting these iodides to a dimanganese decacarbonyl precatalyst and visible light irradiation, an atom transfer radical addition (ATRA) mechanism affords a broad scope of vinyl iodide products with high Z -selectivity.
    Keywords: Chemistry
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    Confined acids catalyze asymmetric single aldolizations of acetaldehyde enolates (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-10-12
    Description: Reactions that form a product with the same reactive functionality as that of one of the starting compounds frequently end in oligomerization. As a salient example, selective aldol coupling of the smallest, though arguably most useful, enolizable aldehyde, acetaldehyde, with just one partner substrate has proven to be extremely challenging. Here, we report a highly enantioselective Mukaiyama aldol reaction with the simple triethylsilyl (TES) and tert -butyldimethylsilyl (TBS) enolates of acetaldehyde and various aliphatic and aromatic acceptor aldehydes. The reaction is catalyzed by recently developed, strongly acidic imidodiphosphorimidates (IDPi), which, like enzymes, display a confined active site but, like small-molecule catalysts, have a broad substrate scope. The process is scalable, fast, efficient (0.5 to 1.5 mole % catalyst loading), and greatly simplifies access to highly valuable silylated acetaldehyde aldols.
    Keywords: Chemistry
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    Breaking through the nitrogen ceiling (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-12-21
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-12-21
    Description: Single-molecule magnets (SMMs) containing only one metal center may represent the lower size limit for molecule-based magnetic information storage materials. Their current drawback is that all SMMs require liquid-helium cooling to show magnetic memory effects. We now report a chemical strategy to access the dysprosium metallocene cation [(Cp i Pr5 )Dy(Cp*)] + (Cp i Pr5 , penta-iso-propylcyclopentadienyl; Cp *, pentamethylcyclopentadienyl), which displays magnetic hysteresis above liquid-nitrogen temperatures. An effective energy barrier to reversal of the magnetization of U eff = 1541 wave number is also measured. The magnetic blocking temperature of T B = 80 kelvin for this cation overcomes an essential barrier toward the development of nanomagnet devices that function at practical temperatures.
    Keywords: Chemistry
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    Molecular mechanisms and forces involved in the adhesion and fusion of amphiphilic bilayers (1989)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1989-11-17
    Description: The surface forces apparatus technique was used for measuring the adhesion, deformation, and fusion of bilayers supported on mica surfaces in aqueous solutions. The most important force leading to the direct fusion of bilayers is the hydrophobic interaction, although the occurrence of fusion is not simply related to the force law between bilayers. Bilayers do not need to "overcome" some repulsive force barrier, such as hydration, before they can fuse. Instead, once bilayer surfaces come within about 1 nanometer of each other, local deformations and molecular rearrangements allow them to "bypass" these forces.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Helm, C A -- Israelachvili, J N -- McGuiggan, P M -- New York, N.Y. -- Science. 1989 Nov 17;246(4932):919-22.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemical and Nuclear Engineering, University of California, Santa Barbara 93106.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2814514" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Lipid Bilayers ; Models, Biological ; Models, Structural ; Phosphatidylcholines ; Phosphatidylethanolamines
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    "Chemzymes" mimic biology in miniature (1989)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1989-07-28
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Waldrop, M M -- New York, N.Y. -- Science. 1989 Jul 28;245(4916):354-5.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2756423" target="_blank"〉PubMed〈/a〉
    Keywords: *Catalysis ; Chemical Phenomena ; Chemistry ; *Enzymes ; Technology, Pharmaceutical
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    A base dispute (1990)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1990-08-03
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Waldrop, M M -- New York, N.Y. -- Science. 1990 Aug 3;249(4968):472-3.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2382127" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Information Systems ; Jurisprudence ; Societies, Scientific ; United States
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 69
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    Clathrate hydrate formation in amorphous cometary ice analogs in vacuo (1991)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1991-10-25
    Description: The presence of clathrate hydrates in cometary ice has been suggested to account for anomalous gas release at large radial distances from the sun as well as the retention of volatiles in comets to elevated temperatures. However, how clathrate hydrates can form in low-pressure environments, such as in cold interstellar molecular clouds, in the outer reaches of the early solar nebula, or in cometary ices, has been poorly understood. Experiments performed with the use of a modified electron microscope demonstrate that during the warming of vapor-deposited amorphous ices in vacuo, clathrate hydrates can form by rearrangements in the solid state. Phase separations and microporous textures that are the result of these rearrangements may account for a variety of anomalous cometary phenomena.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Blake, D -- Allamandola, L -- Sandford, S -- Hudgins, D -- Freund, F -- New York, N.Y. -- Science. 1991 Oct 25;254:548-51.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Planetary Biology Branch, Ames Research Center, Moffett Field, CA 94035, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/11538372" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; Crystallography ; Earth (Planet) ; Hydrocarbons/chemistry ; Ice/*analysis ; *Meteoroids ; Microscopy, Electron ; *Solar System
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    Molecular recognition and metal ion template synthesis (1989)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 1989-05-26
    Description: Methods for the design and synthesis of ligands intended to be specific for a metal ion have been a recent chemical development. This article describes how this process can be inverted so that the specifics of the coordination environment around the metal ion can be used as a template in large-scale ligand synthesis. The synthesis of macrobicyclic ligands for ferric ion has been accomplished by using active esters of catechol ligands in which catecholate coordination to iron is a prelude to the organic chemical reactions that link the coordination subunits together into one ligand system surrounding a central metal ion coordination site. The lanthanide(III) ions, which are among the most labile metal ions known, have coordination numbers of 8 or higher, and thus their encapsulation into a macrobicyclic structure is a challenging problem. Lanthanide amine complexes have been used as metal templates in the synthesis of such macrobicyclic lanthanide complexes. There is evidence that such a complex is inert to exchange in aqueous solution.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉McMurry, T J -- Raymond, K N -- Smith, P H -- New York, N.Y. -- Science. 1989 May 26;244(4907):938-43.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Radiation Oncology Branch, National Cancer Institute, Bethesda, MD 20892.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2658057" target="_blank"〉PubMed〈/a〉
    Keywords: Cations ; Chemical Phenomena ; Chemistry ; Iron/metabolism ; *Ligands ; Macromolecular Substances ; Metals/*metabolism ; Metals, Rare Earth/metabolism ; Molecular Structure ; Templates, Genetic
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    Polymer synthesis and organotransition metal chemistry (1989)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1989-02-17
    Description: Mechanistic and synthetic studies in organometallic chemistry have provided considerable insight into olefin metathesis and Ziegler-Natta polymerization. New homogeneous olefin metathesis catalysts based on high oxidation state transition metals have opened new opportunities in polymer synthesis by providing unprecedented control in ring-opening polymerization of cyclic alkenes. The recent development of living coordinative polymerization systems has led to the preparation of a number of new, interesting materials, including block copolymers, conducting polymers or precursors, and ionophoric polymeric substrates.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Grubbs, R H -- Tumas, W -- New York, N.Y. -- Science. 1989 Feb 17;243(4893):907-15.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉California Institute of Technology, Pasadena 91125.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2645643" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Organometallic Compounds ; *Polymers
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    Direct measurement of forces between linear polysaccharides xanthan and schizophyllan (1990)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1990-09-14
    Description: Direct osmotic stress measurements have been made of forces between helices of xanthan, an industrially important charged polysaccharide. Exponentially decaying hydration forces, much like those already measured between lipid bilayer membranes or DNA double helices, dominate the interactions at close separation. Interactions between uncharged schizophyllans also show the same kind of hydration force seen between xanthans. In addition to the practical possibilities for modifying solution and suspension properties through recognition and control of molecular forces, there is now finally the opportunity for theorists to relate macroscopic properties of a polymer solution to the microscopic properties that underlie them.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Rau, D C -- Parsegian, V A -- New York, N.Y. -- Science. 1990 Sep 14;249(4974):1278-81.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Laboratory of Biochemistry and Metabolism, National Institute of Diabetes and Digestive and Kidney Diseases, National Institues of Health, Bethesda, MD 20892.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2144663" target="_blank"〉PubMed〈/a〉
    Keywords: Carbohydrate Sequence ; Chemical Phenomena ; Chemistry ; Gels ; *Glycosaminoglycans ; Macromolecular Substances ; Molecular Sequence Data ; Osmosis ; *Polysaccharides, Bacterial ; *Sizofiran ; Solutions ; Viscosity
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    Common features of protein unfolding and dissolution of hydrophobic compounds (1990)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1990-02-02
    Description: Protein unfolding and the dissolution of hydrophobic compounds (including solids, liquids, and gases) in water are characterized by a linear relation between entropy change and heat capacity change. The same slope is found for various classes of compounds, whereas the intercept depends on the particular class. The feature common to these processes is exposure of hydrophobic groups to water. These observations make possible the assignment of the heat capacity change to hydrophobic solvation and lead to the description of protein stability in terms of a hydrophobic and a nonhydrophobic contribution. A general representation of protein stability is given by the heat capacity change and the temperature.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Murphy, K P -- Privalov, P L -- Gill, S J -- New York, N.Y. -- Science. 1990 Feb 2;247(4942):559-61.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry and Biochemistry, University of Colorado, Boulder 80309.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2300815" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Protein Denaturation ; *Proteins ; Thermodynamics
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    Interparticle collisions driven by ultrasound (1990)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1990-03-02
    Description: Ultrasound has become an important synthetic tool in liquid-solid chemical reactions, but the origins of the observed enhancements remained unknown. The effects of high-intensity ultrasound on solid-liquid slurries were examined. Turbulent flow and shock waves produced by acoustic cavitation were found to drive metal particles together at sufficiently high velocities to induce melting upon collision. A series of transition-metal powders were used to probe the maximum temperatures and speeds reached during such interparticle collisions. Metal particles that were irradiated in hydrocarbon liquids with ultrasound underwent collisions at roughly half the speed of sound and generated localized effective temperatures between 2600 degrees C and 3400 degrees C at the point of impact for particles with an average diameter of approximately 10 microns.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Doktycz, S J -- Suslick, K S -- New York, N.Y. -- Science. 1990 Mar 2;247(4946):1067-9.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉School of Chemical Sciences, University of Illinois, Urbana 61801.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2309118" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Metals ; Microscopy, Electron, Scanning ; Microspheres ; *Ultrasonics
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    Changes in mean concentration, phase shifts, and dissipation in a forced oscillatory reaction (1990)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 1990-01-12
    Description: Experiments are presented that confirm earlier predictions that the mode of supply of reactants to a nonlinear (bio)chemical reaction determines or controls concentrations at steady states far from equilibrium. The oxidation of nicotinamide adenine dinucleotide (NADH) catalyzed by the enzyme horseradish peroxidase with continuous input of oxygen was studied; NAD+ is continuously recycled to NADH through a glucose-6-phosphate dehydrogenase system. A comparison of steady-state concentrations is made with an oscillatory oxygen input and a constant input at the same average oxygen input for both modes. By varying the frequency and amplitude of the perturbation (O2 influx), the following may be changed: the average concentration of NADH; the Gibbs free energy difference delta G of the reactants and products at steady state; the average rate of the reaction; the phase relation between the oscillatory rate and delta G; and the dissipation. These results confirm the possibility of an "alternating current chemistry," of control and optimization of thermodynamic efficiency and dissipation by means of external variation of constraints in classes of nonlinear reactions and biological pumps, and of improvements of the yield in such reactions (heterogeneous catalysis, for example).〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Lazar, J G -- Ross, J -- New York, N.Y. -- Science. 1990 Jan 12;247(4939):189-92.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, Stanford University, CA 94305.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2294601" target="_blank"〉PubMed〈/a〉
    Keywords: Adenosine Triphosphate/metabolism ; Chemical Phenomena ; Chemistry ; Glucosephosphate Dehydrogenase/*metabolism ; Horseradish Peroxidase/*metabolism ; Kinetics ; NAD/*metabolism ; Oxidation-Reduction ; Oxygen/metabolism ; Peroxidases/*metabolism ; Thermodynamics
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    An antibody binding site on cytochrome c defined by hydrogen exchange and two-dimensional NMR (1990)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1990-08-17
    Description: The interaction of a protein antigen, horse cytochrome c (cyt c), with a monoclonal antibody has been studied by hydrogen-deuterium (H-D) exchange labeling and two-dimensional nuclear magnetic resonance (2D NMR) methods. The H-exchange rate of residues in three discontiguous regions of the cyt c polypeptide backbone was slowed by factors up to 340-fold in the antibody-antigen complex compared with free cyt c. The protected residues, 36 to 38, 59, 60, 64 to 67, 100, and 101, and their hydrogen-bond acceptors, are brought together in the three-dimensional structure to form a contiguous, largely exposed protein surface with an area of about 750 square angstroms. The interaction site determined in this way is consistent with prior epitope mapping studies and includes several residues that were not previously identified. The hydrogen exchange labeling approach can be used to map binding sites on small proteins in antibody-antigen complexes and may be applicable to protein-protein and protein-ligand interactions in general.〈br /〉〈br /〉〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3432411/" target="_blank"〉〈img src="https://static.pubmed.gov/portal/portal3rc.fcgi/4089621/img/3977009" border="0"〉〈/a〉   〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3432411/" target="_blank"〉This paper as free author manuscript - peer-reviewed and accepted for publication〈/a〉〈br /〉〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Paterson, Y -- Englander, S W -- Roder, H -- GM 31847/GM/NIGMS NIH HHS/ -- GM 35926/GM/NIGMS NIH HHS/ -- R01 GM031847/GM/NIGMS NIH HHS/ -- S07-RR-05415-28/RR/NCRR NIH HHS/ -- New York, N.Y. -- Science. 1990 Aug 17;249(4970):755-9.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Microbiology, University of Pennsylvania, Philadelphia 19104.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/1697101" target="_blank"〉PubMed〈/a〉
    Keywords: Antibodies, Monoclonal/immunology/metabolism ; Antigen-Antibody Complex ; *Binding Sites, Antibody ; Chemical Phenomena ; Chemistry ; Cytochrome c Group/*immunology ; Deuterium ; Epitopes/immunology ; Hydrogen/*metabolism ; Hydrogen Bonding ; Kinetics ; *Magnetic Resonance Spectroscopy ; Molecular Structure ; Protein Conformation
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    Manifest destiny at the Scripps Research Institute (1991)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1991-07-12
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Baskin, Y -- New York, N.Y. -- Science. 1991 Jul 12;253(5016):140-2.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/1853198" target="_blank"〉PubMed〈/a〉
    Keywords: *Academies and Institutes ; Biology ; California ; Chemical Phenomena ; Chemistry ; Research Support as Topic
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    Studies of unusual simple molecules by neutralization-reionization mass spectrometry (1990)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 1990-02-23
    Description: Reactive or unstable molecules are key intermediates in many important reactions, but can be difficult to prepare for experimental studies. Species with missing (:CH-OH) or extra (H3) substituents can often be formed conveniently in the gas phase by neutralizing a beam of a more stable ionic counterpart (CH = O+H, H3+). Reionization of the neutral after approximately 10(-6) seconds tests its stability, whereas its unimolecular chemistry can be probed by preparing it with different amounts of internal energy. The resulting neutral products are reionized and mass analyzed. Isomers are then characterized by ion dissociation and a third mass-analysis step. Many unusual molecules have been characterized with this technique, which can also be used to probe complex unimolecular chemistry, such as that of cyclobutadiene and ethylene oxide.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉McLafferty, F W -- GM-16609/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 1990 Feb 23;247(4945):925-9.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Cornell University, Baker Laboratory, Ithaca, NY 14853-1301.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2305261" target="_blank"〉PubMed〈/a〉
    Keywords: Butadienes ; Chemical Phenomena ; Chemistry ; Ethylene Oxide ; Free Radicals ; Hydrocarbons ; *Ions ; *Mass Spectrometry ; Methane/analogs & derivatives ; Molecular Structure ; Thermodynamics
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    Inhibition of FKBP rotamase activity by immunosuppressant FK506: twisted amide surrogate (1990)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1990-05-18
    Description: The immunosuppressive agents cyclosporin A and FK506 inhibit the transcription of early T cell activation genes. The binding proteins for cyclosporin A and FK506, cyclophilin and FKBP, respectively, are peptidyl-prolyl-cis-trans isomerases, or rotamases. One proposed mechanism for rotamase catalysis by cyclophilin involves a tetrahedral adduct of an amide carbonyl and an enzyme-bound nucleophile. The potent FKBP rotamase inhibitor FK506 has a highly electrophilic carbonyl that is adjacent to an acyl-pipicolinyl (homoprolyl) amide bond. Such a functional group would be expected to form a stabilized, enzyme-bound tetrahedral adduct. Spectroscopic and chemical evidence reveals that the drug interacts noncovalently with its receptor, suggesting that the alpha-keto amid of FK506 serves as a surrogate for the twisted amide of a bound peptide substrate.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Rosen, M K -- Standaert, R F -- Galat, A -- Nakatsuka, M -- Schreiber, S L -- GM-38627/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 1990 May 18;248(4957):863-6.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, Harvard University, Cambridge, MA 02138.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/1693013" target="_blank"〉PubMed〈/a〉
    Keywords: Amino Acid Isomerases/*antagonists & inhibitors ; Anti-Bacterial Agents/metabolism/*pharmacology ; Binding Sites ; Carrier Proteins/antagonists & inhibitors/metabolism ; Chemical Phenomena ; Chemistry ; Cloning, Molecular ; Cyclosporins/metabolism/pharmacology ; Escherichia coli/genetics ; Gene Expression ; *Immunosuppressive Agents ; Lymphocyte Activation ; Magnetic Resonance Spectroscopy ; Molecular Structure ; Peptidylprolyl Isomerase ; Recombinant Proteins ; T-Lymphocytes/immunology ; Tacrolimus
    Print ISSN: 0036-8075
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    At the crossroads of chemistry and immunology: catalytic antibodies (1991)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1991-05-03
    Description: Immunochemistry has historically focused on the nature of antigenicity and antibody-antigen recognition. However, in the last 5 years, the field of immunochemistry has taken a new direction. With the aid of mechanistic and synthetic chemistry, the vast network of molecules and cells of the immune system has been tapped to produce antibodies with a new function--catalytic antibodies. Because antibodies can be generated that selectively bind almost any molecule of interest, this new technology offers the potential to tailor-make highly selective catalysts for applications in biology, chemistry, and medicine. In addition, catalytic antibodies provide fundamental insight into important aspects of biological catalysis, including the importance of transition-state stabilization, proximity effects, general acid and base catalysts, electrophilic and nucleophilic catalysis, and strain.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Lerner, R A -- Benkovic, S J -- Schultz, P G -- New York, N.Y. -- Science. 1991 May 3;252(5006):659-67.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, Scripps Research Institute, La Jolla, CA 92037.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2024118" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; *Antibodies/chemistry/immunology/metabolism ; Antibodies, Monoclonal/immunology/metabolism ; Antibody Specificity ; Antigens/chemistry/immunology/metabolism ; Binding Sites, Antibody ; *Catalysis ; Chemical Phenomena ; Chemistry ; Haptens ; Hydrogen-Ion Concentration ; Hydrolysis ; Metals ; Molecular Conformation ; Recombinant Proteins ; Thermodynamics ; Zinc
    Print ISSN: 0036-8075
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    Evolution. Darwin for all seasons (2006)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 2006-07-22
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Szathmary, Eors -- New York, N.Y. -- Science. 2006 Jul 21;313(5785):306-7.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Institute of Biology, Eotvos University Budapest, and Collegium Budapest (Institute for Advanced Study), 2 Szentharomsag utca, H-1014 Budapest, Hungary. szathmary@colbud.hu〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/16857926" target="_blank"〉PubMed〈/a〉
    Keywords: *Biological Evolution ; Chemical Phenomena ; Chemistry ; Computational Biology ; Cooperative Behavior ; Cultural Evolution ; Exobiology ; Humans ; Language ; Models, Biological ; Models, Theoretical ; Molecular Biology ; Origin of Life ; *Research ; Selection, Genetic
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    Herve This profile. The joy of evidence-based cooking (2006)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 2006-11-25
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Enserink, Martin -- New York, N.Y. -- Science. 2006 Nov 24;314(5803):1235-6.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/17124302" target="_blank"〉PubMed〈/a〉
    Keywords: Chemistry ; *Cooking ; *Food ; France ; History, 20th Century ; History, 21st Century
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    Cyberinfrastructure for e-Science (2005)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 2005-05-10
    Description: Here we describe the requirements of an e-Infrastructure to enable faster, better, and different scientific research capabilities. We use two application exemplars taken from the United Kingdom's e-Science Programme to illustrate these requirements and make the case for a service-oriented infrastructure. We provide a brief overview of the UK "plug-and-play composable services" vision and the role of semantics in such an e-Infrastructure.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Hey, Tony -- Trefethen, Anne E -- New York, N.Y. -- Science. 2005 May 6;308(5723):817-21.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Engineering and Physical Sciences Research Council, Polaris House, North Star Avenue, Swindon SN2 1ET, UK.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/15879209" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; Combinatorial Chemistry Techniques ; *Computational Biology ; *Computer Communication Networks ; *Computing Methodologies ; Databases as Topic ; Graves Disease/genetics ; *Internet ; *Research ; *Software ; Williams Syndrome/genetics
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    Profile: Marina Protopopova (2004)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 2004-05-29
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Malakoff, David -- New York, N.Y. -- Science. 2004 May 28;304(5675):1283.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/15166364" target="_blank"〉PubMed〈/a〉
    Keywords: Biotechnology ; Career Choice ; Chemistry ; Emigration and Immigration ; History, 20th Century ; History, 21st Century ; Siberia ; United States
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    The class of 2005. United States: two scientists and a baby (2005)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 2005-10-22
    Description: If you trust the conventional wisdom, Amy Palmer and Alexis Templeton did a lot of things wrong in their job search. Then why did things turn out so right?〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Austin, Jim -- New York, N.Y. -- Science. 2005 Oct 21;310(5747):518-9.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/16239480" target="_blank"〉PubMed〈/a〉
    Keywords: *Career Choice ; *Career Mobility ; Chemical Phenomena ; Chemistry ; Education, Graduate ; *Faculty ; Microbiology ; *Research ; United States ; *Universities
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    [This Week in Science] Synthetic twists among lipids (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2016-04-29
    Description: Author: Jake Yeston
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    [This Week in Science] Temporarily caught in a bind (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2016-03-18
    Description: Author: Marc S. Lavine
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    [Perspective] Quantum dynamics in the smallest water droplet (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2016-03-18
    Description: Water plays a central role in scientific disciplines ranging from geology to astronomy to biology. Yet it is an extraordinarily dif cult liquid to understand because of its complex, ever-changing patterns of hydrogen bonds. Studies of small water clusters have provided important insights into the concerted hydrogen-bond motions that can occur in water. These studies are also crucial for developing an accurate potential function for simulating the properties of liquid water and ice (1). On page 1310 of this issue, Richardson et al. (2) provide evidence for a concerted type of motion in which two hydrogen bonds in a water cluster are broken simultaneously (see the figure). The results have implications for many areas of scientific study, including the chemistry of polar solvents, the conformations of proteins, and the dissolution of ions in minerals. Author: David C. Clary
    Keywords: Chemistry
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    [Editors' Choice] Beyond blank slates in the lab notebook (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2016-03-18
    Description: Author: Jake Yeston
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    [Perspective] Surprised by selectivity (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2016-03-04
    Description: Lower olefins, particularly ethylene (C2H4), propylene (C3H6), and butylene (C4H8), are important intermediates in the manufacture of products such as plastics, solvents, paints, and medicines. They are produced worldwide in amounts exceeding 200 million tons per year (see the photo) (1), mostly from crude oil. More recent approaches use methanol or synthesis gas (syngas; a mixture of carbon monoxide and hydrogen) as feedstocks, but capital investments are high and/or selectivities to lower olefins limited. A bifunctional catalyst reported by Jiao et al. on page 1065 of this issue (2) enables the direct conversion of synthesis gas to lower olefins with a surprisingly high selectivity. Author: Krijn P. de Jong
    Keywords: Chemistry
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    High-tech tries to reveal artistic motivations [Social Sciences] (2016)
    National Academy of Sciences
    Details
    Publication Date: 2016-05-25
    Description: One day in 1896, while working on his painting Why Are You Angry?, artist Paul Gauguin changed his mind. He painted over the doorway in a bamboo hut behind the irate-looking Tahitian woman and her companions, leaving it opaque black. Conservation scientist Francesca Casadio (Right) and Inge Fiedler (Left) at...
    Keywords: Science and Culture
    Print ISSN: 0027-8424
    Electronic ISSN: 1091-6490
    Topics: Biology , Medicine , Natural Sciences in General
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    Dancing with Pythagoras [Science and Culture] (2016)
    National Academy of Sciences
    Details
    Publication Date: 2016-03-24
    Description: To the steady beat of drums, three ballerinas pirouette and plié toward the center of a stage. Two make contact, embracing and spinning in apparent joy. The third does not reach them in time, and she trails away to one side, alone. A collaboration between an astrophysicist and a choreographer...
    Keywords: Science and Culture
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    How fish innards inspire art [Science and Culture] (2016)
    National Academy of Sciences
    Details
    Publication Date: 2016-04-13
    Description: Looking down a microscope at dead fish for eight months can change an artist’s perspective on nature—and even influence her art. Textile artist Annet Couwenberg discovered such anatomical insights first hand when, in the summer of 2014, she embarked on a stint in the laboratory as part of the Smithsonian...
    Keywords: Science and Culture
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    Terraforming a volcano, artfully [Agricultural Sciences] (2016)
    National Academy of Sciences
    Details
    Publication Date: 2016-04-20
    Description: From October 26 to November 12, 2010, Indonesia’s Mount Merapi blew its top in the volcano’s largest series of eruptions in decades. It spewed ash and lava rock thousands of meters into the air. Hundreds of thousands of villagers fled, abandoning their homes along with more than 1,000 ha of...
    Keywords: Science and Culture
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    Carbon nanotubes help nickel work in water (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-10-19
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Chiral Lewis acids integrated with single-walled carbon nanotubes for asymmetric catalysis in water (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-10-19
    Description: The development of highly reactive and stereoselective catalytic systems is required not only to improve existing synthetic methods but also to invent distinct chemical reactions. Herein, a homogenized combination of nickel-based Lewis acid–surfactant-combined catalysts and single-walled carbon nanotubes is shown to exhibit substantial activity in water. In addition to the enhanced reactivity, stereoselective performance and long-term stability were demonstrated in asymmetric conjugate addition reactions of aldoximes to furnish chiral nitrones in high yields with excellent selectivities. The practical and straightforward application of the designed catalysts in water provides an expedient, environmentally benign, and highly efficient pathway to access optically active compounds.
    Keywords: Chemistry
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    Steps to smaller rings (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-11-02
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Pinpointing the role of geometric phase (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-12-14
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Salt and iron ease the way to amines (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-10-26
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Catalytic palladium-oxyallyl cycloaddition (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-11-02
    Description: Exploration of intermediates that enable chemoselective cycloaddition reactions and expeditious construction of fused- or bridged-ring systems is a continuous challenge for organic synthesis. As an intermediate of interest, the oxyallyl cation has been harnessed to synthesize architectures containing seven-membered rings via (4+3) cycloaddition. However, its potential to access five-membered skeletons is underdeveloped, largely due to the thermally forbidden (3+2) pathway. Here, the combination of a tailored precursor and a Pd(0) catalyst generates a Pd-oxyallyl intermediate that cyclizes with conjugated dienes to produce a diverse array of tetrahydrofuran skeletons. The cycloaddition overrides conventional (4+3) selectivity by proceeding through a stepwise pathway involving a Pd-allyl transfer and ring closure sequence. Subsequent treatment of the (3+2) adducts with a palladium catalyst converts the heterocycles to the carbocyclic cyclopentanones.
    Keywords: Chemistry
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