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Organic chemistry*

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https://www.readbyqxmd.com/read/28103106/low-temperature-alkaline-ph-hydrolysis-of-oxygen-free-titan-tholins-carbonates-impact
#1
Coralie Brassé, Arnaud Buch, Patrice Coll, François Raulin
Titan, the largest moon of Saturn, is one of the key planetary objects in the field of exobiology. Its dense, nitrogen-rich atmosphere is the site of important organic chemistry. This paper focuses on the organic aerosols produced in Titan's atmosphere that play an important role in atmospheric and surface processes and in organic chemistry as it applies to exobiological interests. To produce reliable laboratory analogues of these aerosols, we developed, tested, and optimized a device for the synthesis of clean tholins...
January 2017: Astrobiology
https://www.readbyqxmd.com/read/28103032/-naked-lithium-cation-strongly-activated-metal-cations-facilitated-by-carborane-anions
#2
Yu Kitazawa, Ryo Takita, Kengo Yoshida, Atsuya Muranaka, Seijiro Matsubara, Masanobu Uchiyama
Experimental and spectroscopic studies revealed unprecedented reactivity of "naked" lithium cation with very weakly coordinating anions including carborane anions. The super-activated lithium cation has greatly enhanced Lewis acidic character, and mediates various organic reactions, such as carbonyl-ene reaction, NBS-bromination of unactivated aromatics, and Friedel-Crafts alkylation, that are not promoted by conventional lithium salts. Chemical robustness of the counter anion also plays an important role in the chemistry of strongly activated lithium cation...
January 19, 2017: Journal of Organic Chemistry
https://www.readbyqxmd.com/read/28103018/copper-oxygen-complexes-revisited-structures-spectroscopy-and-reactivity
#3
Courtney E Elwell, Nicole L Gagnon, Benjamin D Neisen, Debanjan Dhar, Andrew D Spaeth, Gereon M Yee, William B Tolman
A longstanding research goal has been to understand the nature and role of copper-oxygen intermediates within copper-containing enzymes and abiological catalysts. Synthetic chemistry has played a pivotal role in highlighting the viability of proposed intermediates and expanding the library of known copper-oxygen cores. In addition to the number of new complexes that have been synthesized since the previous reviews on this topic in this journal (Mirica, L. M.; Ottenwaelder, X.; Stack, T. D. P. Chem. Rev. 2004, 104, 1013-1046 and Lewis, E...
January 19, 2017: Chemical Reviews
https://www.readbyqxmd.com/read/28102692/de-novo-assembly-of-highly-substituted-morpholines-and-piperazines
#4
Pravin Patil, Rudrakshula Madhavachary, Katarzyna Kurpiewska, Justyna Kalinowska-Tłuścik, Alexander Dömling
The morpholine and piperazine with their remarkable physical and biochemical properties are popular heterocycles in organic and medicinal chemistry used in rational property design. However, in the majority of cases these rings are added to an existing molecule in a building block approach thus limiting their substitution pattern and diversity. Here we introduce a versatile de novo synthesis of the morpholine and piperazine rings using multicomponent reaction chemistry. The large scale amenable building blocks can be further substituted at up to four positions, making this a very versatile scaffold synthesis strategy...
January 19, 2017: Organic Letters
https://www.readbyqxmd.com/read/28102668/adventures-in-reactive-intermediate-chemistry-a-perspective-and-retrospective
#5
Robert A Moss
I review aspects of my research on reactive intermediates, specifically the physical organic chemistry of carbenes and carbocations. The topics treated include carbenoids, carbenic philicity, absolute rates of carbene/alkene additions, the diazirine exchange reaction and derived carbenes, carbene equilibria, carbocations from diazotates, and carbocations from alkoxychlorocarbenes. The essay concludes with observations on the protean nature of physical organic chemistry.
January 19, 2017: Journal of Organic Chemistry
https://www.readbyqxmd.com/read/28102364/indefinitely-stable-iron-iv-cage-complexes-formed-in-water-by-air-oxidation
#6
Stefania Tomyn, Sergii I Shylin, Dmytro Bykov, Vadim Ksenofontov, Elzbieta Gumienna-Kontecka, Volodymyr Bon, Igor O Fritsky
In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation...
January 19, 2017: Nature Communications
https://www.readbyqxmd.com/read/28101114/dietary-and-socio-demographic-determinants-of-serum-persistent-organic-pollutants-pops-levels-in-pregnant-women-in-tehran
#7
Bita Eslami, Batool Hossein-Rashidi, Kazem Naddafi, Noushin Rastkari, Abolghasem Djazayeri, Hossein Malekafzali
Objective: To determine the levels of Polychlorinated biphenyls (PCBs) and Polybrominateddiphenyl ethers (PBDEs) as persistent organic pollutants (POPs) in serum of primiparous women at the third trimester of pregnancy and identify the main determinants of POPs levels such as socio-demographic, lifestyle, and diet in Tehran. Materials and methods: One- hundred eighty five serum samples from two simultaneous case-control studies were collected from September 2013 until August 2015.Ten most abundant PCB congeners (International Union of Pure and Applied Chemistry (IUPAC) congeners 28, 52, 74, 99, 101, 118, 138, 153, 180 and 187) as well as eight PBDE congeners (IUPAC congeners 28, 47, 99, 100, 153, 154, 183 and 209)were analyzed by Gas Chromatography Mass Spectrometry (GC/MS)...
September 2016: Journal of Family & Reproductive Health
https://www.readbyqxmd.com/read/28100048/unanticipated-stickiness-of-%C3%AE-pinene
#8
Hilary M Chase, Junming Ho, Mary Alice Upshur, Regan J Thomson, Victor S Batista, Franz M Geiger
Hilary M. Chase1#, Junming Ho2#, Mary Alice Upshur1, Regan J. Thomson1, Victor S. Batista3, Franz M. Geiger1* 1Department of Chemistry, Northwestern University, Evanston, IL. 60208, United States; 2 Agency for Science, Technology and Research, Institute of High Performance Computing, 1 Fusionopolis Way #16-16 Connexis North, Singapore 138632; 3Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT. 06520, United States # These authors contributed equally to this work. *corresponding author: geigerf@chem...
January 19, 2017: Journal of Physical Chemistry. A
https://www.readbyqxmd.com/read/28099019/combined-molecular-dynamics-atoms-in-molecules-and-ir-studies-of-the-bulk-mono-fluoro-ethanol-and-bulk-ethanol-to-understand-the-role-of-organic-fluorine-in-hydrogen-bond-network
#9
Biswajit Biswas, Saptarsi Mondal, Prashant Chandra Singh
Presence of the fluorocarbon group in fluorinated alcohols makes them an important class of molecules which have diverse applications in the field of separation techniques, synthetic chemistry, polymer industry, and biology. In this paper, we have performed the density function theory calculation along with atom in molecule analysis, molecular dynamics simulation as well as IR measurements of the bulk mono fluoro-ethanol (MFE) and compared them with the bulk ethanol (ETH) in order to understand the effect of fluorocarbon group in the structure as well as hydrogen bond network of the bulk MFE...
January 18, 2017: Journal of Physical Chemistry. A
https://www.readbyqxmd.com/read/28097707/covalent-bond-formation-via-on-surface-chemistry
#10
REVIEW
Philipp Alexander Held, Harald Fuchs, Armido Studer
In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions...
January 18, 2017: Chemistry: a European Journal
https://www.readbyqxmd.com/read/28097044/study-on-the-single-dose-toxicity-of-shineumhur-pharmacopuncture-injected-into-the-muscles-of-rats
#11
Hohyun Jeong, Eunhye Cha, Jongcheol Lee, Seongjin Lee, Manyong Park, Dongwoung Kim, Bongkeun Song, Jongdeok Lee, Sungchul Kim
OBJECTIVES: This study was carried out to analyze the single dose toxicity of ShinEumHur (SEH) pharmacopuncture injected into the muscles of Sprague-Dawley rats. METHODS: The SEH pharmacopuncture was made in a clean room at the Korean Pharmacopuncture Institute (K-GMP). After the mixing process with sterile distilled water had been completed, the pH was controlled to between 7.0 and 7.5. All experiments were conducted at Biotoxtech, an institution authorized to perform non-clinical studies under the Good Laboratory Practice (GLP) regulations...
December 2016: Journal of Pharmacopuncture
https://www.readbyqxmd.com/read/28096422/hydrogen-isotope-fractionation-in-methane-plasma
#12
François Robert, Sylvie Derenne, Guillaume Lombardi, Khaled Hassouni, Armelle Michau, Peter Reinhardt, Rémi Duhamel, Adriana Gonzalez, Kasia Biron
The hydrogen isotope ratio (D/H) is commonly used to reconstruct the chemical processes at the origin of water and organic compounds in the early solar system. On the one hand, the large enrichments in deuterium of the insoluble organic matter (IOM) isolated from the carbonaceous meteorites are interpreted as a heritage of the interstellar medium or resulting from ion-molecule reactions taking place in the diffuse part of the protosolar nebula. On the other hand, the molecular structure of this IOM suggests that organic radicals have played a central role in a gas-phase organosynthesis...
January 17, 2017: Proceedings of the National Academy of Sciences of the United States of America
https://www.readbyqxmd.com/read/28094920/antifouling-thin-film-composite-membranes-by-controlled-architecture-of-zwitterionic-polymer-brush-layer
#13
Caihong Liu, Jongho Lee, Jun Ma, Menachem Elimelech
In this study, we demonstrate a highly antifouling thin-film-composite (TFC) membrane by grafting a zwitterionic polymer brush via atom-transfer radical-polymerization (ATRP), a controlled, environmentally benign chemical process. Initiator molecules for polymerization were immobilized on the membrane surface by bio-inspired catechol chemistry, leading to the grafting of a dense zwitterionic polymer brush layer. Surface characterization revealed that the modified membrane exhibits reduced surface roughness, enhanced hydrophilicity, and lower surface charge...
January 17, 2017: Environmental Science & Technology
https://www.readbyqxmd.com/read/28094525/photocatalytic-color-switching-of-transition-metal-hexacyanometalate-nanoparticles-for-high-performance-light-printable-rewritable-paper
#14
Wenshou Wang, Ji Feng, Yifan Ye, Fenglei Lyu, Yi-Sheng Liu, Jinghua Guo, Yadong Yin
Developing efficient photoreversible color switching systems for constructing rewritable paper is of significant practical interest owing to the potential environmental benefits including forest conservation, pollution reduction, and resource sustainability. Here we report that the color change associated with the redox chemistry of nanoparticles of Prussian blue and its analogues could be integrated with the photocatalytic activity of TiO2 nanoparticles to construct a class of new photoreversible color switching systems, which can be conveniently utilized for fabricating ink-free, light printable rewritable paper with various working colors...
January 17, 2017: Nano Letters
https://www.readbyqxmd.com/read/28094501/artificial-cells-synthetic-compartments-with-life-like-functionality-and-adaptivity
#15
Bastiaan C Buddingh', Jan C M van Hest
Cells are highly advanced microreactors that form the basis of all life. Their fascinating complexity has inspired scientists to create analogs from synthetic and natural components using a bottom-up approach. The ultimate goal here is to assemble a fully man-made cell that displays functionality and adaptivity as advanced as that found in nature, which will not only provide insight into the fundamental processes in natural cells but also pave the way for new applications of such artificial cells. In this Account, we highlight our recent work and that of others on the construction of artificial cells...
January 17, 2017: Accounts of Chemical Research
https://www.readbyqxmd.com/read/28092796/global-open-data-management-in-metabolomics
#16
REVIEW
Kenneth Haug, Reza M Salek, Christoph Steinbeck
Chemical Biology employs chemical synthesis, analytical chemistry and other tools to study biological systems. Recent advances in both molecular biology such as next generation sequencing (NGS) have led to unprecedented insights towards the evolution of organisms' biochemical repertoires. Because of the specific data sharing culture in Genomics, genomes from all kingdoms of life become readily available for further analysis by other researchers. While the genome expresses the potential of an organism to adapt to external influences, the Metabolome presents a molecular phenotype that allows us to asses the external influences under which an organism exists and develops in a dynamic way...
January 13, 2017: Current Opinion in Chemical Biology
https://www.readbyqxmd.com/read/28092430/optimal-reactivity-and-improved-self-healing-capability-of-structurally-dynamic-polymers-grafted-on-janus-nanoparticles-governed-by-chain-stiffness-and-spatial-organization
#17
Guoxi Xu, Zihan Huang, Pengyu Chen, Tianqi Cui, Xinghua Zhang, Bing Miao, Li-Tang Yan
Structurally dynamic polymers are recognized as a key potential to revolutionize technologies ranging from design of self-healing materials to numerous biomedical applications. Despite intense research in this area, optimizing reactivity and thereby improving self-healing ability at the most fundamental level pose urgent issue for wider applications of such emerging materials. Here, the authors report the first mechanistic investigation of the fundamental principle for the dependence of reactivity and self-healing capabilities on the properties inherent to dynamic polymers by combining large-scale computer simulation, theoretical analysis, and experimental discussion...
January 16, 2017: Small
https://www.readbyqxmd.com/read/28089687/stabilizing-effects-for-antibody-formulations-and-safety-profiles-of-cyclodextrin-polypseudorotaxane-hydrogels
#18
Taishi Higashi, Naoko Ohshita, Tatsunori Hirotsu, Yoshihito Yamashita, Keiichi Motoyama, Sawako Koyama, Ruriko Iibuchi, Takayuki Uchida, Shiuhei Mieda, Kenji Handa, Tomoaki Kimoto, Hidetoshi Arima
Antibodies often have poor physicochemical stability during storage and/or transport, which is a serious drawback for the development of antibody-based drugs. In this study, we prepared polypseudorotaxane (PPRX) hydrogels consisting of cyclodextrins (CyDs) and polyethylene glycol (PEG), and evaluated them as stabilizers for commercially available antibody-based drugs. α-CyD and γ-CyD formed PPRX hydrogels with PEG (MW 20,000 Da) in the presence of antibody-based drugs such as omalizumab, palivizumab, panitumumab, and ranibizumab...
January 12, 2017: Journal of Pharmaceutical Sciences
https://www.readbyqxmd.com/read/28088854/conjugated-covalent-organic-frameworks-via-michael-addition%C3%A2-elimination
#19
Malakalapalli Rajeswara Rao, Yuan Fang, Steven De Feyter, Dmitrii F Perepichka
Dynamic covalent chemistry enables self-assembly of reactive building blocks into structurally complex yet robust materials, such as Covalent Organic Frameworks (COFs). However, the synthetic toolbox used to prepare such materials, and thus the spectrum of attainable properties, is very limited. For π-conjugated COFs, the Schiff base condensation of aldehydes and amines is the only general dynamic reaction, but the resulting imine-linked COFs display only a moderate electron delocalization and are susceptible to hydrolysis, particularly in acidic conditions...
January 14, 2017: Journal of the American Chemical Society
https://www.readbyqxmd.com/read/28088631/an-esipt-based-two-photon-fluorescent-probe-detection-of-hydrogen-peroxide-in-live-cells-and-tissues
#20
Liyi Zhou, Yongbo Peng, Qianqian Wang, Qinlu Lin
A variety of diseases associated with human aging, which have a strong oxidative stress, but connecting age-related diseases and oxidative stress of the basic molecular mechanisms still insufficiently understood. Oxidative stress origins from the unregulated production of reactive oxygen species (ROS), and oxidative damaging to tissues and organs from subsequent oxidation-reduction chemistry by cellular mismanagement. In particular, H2O2 is a major by-product of ROS in live organisms and a common marker for oxidative stress, and its dynamic equilibrium can have various physiological and pathological consequences...
January 9, 2017: Journal of Photochemistry and Photobiology. B, Biology
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