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141.
Sara Bertuzzi Dr. Ana Gimeno Reyes Núñez-Franco Dr. Ganeko Bernardo-Seisdedos Sandra Delgado Dr. Gonzalo Jiménez-Osés Dr. Oscar Millet Prof. Dr. Jesús Jiménez-Barbero Dr. Ana Ardá 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15643-15653
The interaction of human galectin-1 with a variety of oligosaccharides, from di-(N-acetyllactosamine) to tetra-saccharides (blood B type-II antigen) has been scrutinized by using a combined approach of different NMR experiments, molecular dynamics (MD) simulations, and isothermal titration calorimetry. Ligand- and receptor-based NMR experiments assisted by computational methods allowed proposing three-dimensional structures for the different complexes, which explained the lack of enthalpy gain when increasing the chemical complexity of the glycan. Interestingly, and independently of the glycan ligand, the entropy term does not oppose the binding event, a rather unusual feature for protein-sugar interactions. CLEANEX-PM and relaxation dispersion experiments revealed that sugar binding affected residues far from the binding site and described significant changes in the dynamics of the protein. In particular, motions in the microsecond-millisecond timescale in residues at the protein dimer interface were identified in the presence of high affinity ligands. The dynamic process was further explored by extensive MD simulations, which provided additional support for the existence of allostery in glycan recognition by human galectin-1. 相似文献
142.
Dr. Sara Realista Janaína C. Almeida Sofia A. Milheiro Dr. Nuno A. G. Bandeira Dr. Luis G. Alves Dr. Filipe Madeira Prof. Dr. Maria José Calhorda Dr. Paulo N. Martinho 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(50):11670-11679
Three CoII octaazacryptates, with different substituents on the aromatic rings (Br, NO2, CCH), were synthesised and characterised. These and the already published non-substituted cryptate catalysed CO2 photoreduction to CO and CH4 under blue visible light at room temperature. Although CO was observed after short irradiation times and a large range of catalyst concentrations, CH4 was only observed after longer irradiation periods, such as 30 h, but with a small catalyst concentration (25 nm ). Experiments with 13C labelled CO2 showed that CO is formed and reacts further when the reaction time is long. The CCH catalyst is deactivated faster than the others and the more efficient catalyst for CH4 production is the one with Br. This reactivity trend was explained by an energy decomposition analysis based on DFT calculations. 相似文献
143.
Dr. Mahendra K. Sharma Dr. Sebastian Blomeyer Beate Neumann Dr. Hans-Georg Stammler Priv.-Doz. Dr. Rajendra S. Ghadwal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8249-8253
The first divinyldiarsenes [{(NHC)C(Ph)}As]2 (NHC=IPr 3 a , SIPr 3 b ; IPr=C{(NAr)CH}2; SIPr=C{(NAr)CH2}2; Ar=2,6-iPr2C6H3) are reported. Compounds 3 a and 3 b were prepared by the reduction of corresponding chlorides {(NHC)C(Ph)}AsCl2 (NHC=IPr 2 a , SIPr 2 b ) with Mg. Calculations revealed a small HOMO–LUMO energy gap of 3.86 ( 3 a ) and 4.24 eV ( 3 b ). Treatment of 3 a with (Me2S)AuCl led to the cleavage of the As=As bond to restore 2 a , which is expected to proceed via the diarsane [{(IPr)C(Ph)}AsCl]2 ( 4 ). Remarkably, 4 as well as 2 a can be selectively accessed on treatment of 3 a with an appropriate amount of C2Cl6. Moreover, 3 a readily reacts with PhEEPh (E=Se or Te) at room temperature to give {(IPr)C(Ph)}As(EPh)2 (E=Se 5 a ; Te 5 b ), revealing the cleavage of As=As and E−E bonds and the formation of As−E bonds. Such highly selective stepwise oxidation ( 3 a → 4 → 2 a ) and bond metathesis ( 3 a → 5 a , b ) reactions are unprecedented in main-group chemistry. 相似文献
144.
145.
Haoquan Li Dr. Helfried Neumann Prof. Dr. Matthias Beller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10050-10056
A benign and efficient palladium‐catalyzed aminocarbonylation reaction of allylic alcohols is presented. The generality of this novel process is demonstrated by the synthesis of β,γ‐unsaturated amides including aliphatic, cinnamyl, and terpene derivatives. The choice of ligand is crucial for optimal carbonylation processes: Whereas in most cases the combination of PdCl2 with Xantphos ( L6 ) gave best results, sterically hindered substrates performed better in the presence of simple triphenylphosphine ( L10 ), and primary anilines gave the best results using cataCXium® PCy ( L8 ). The reactivity of the respective catalyst system is significantly enhanced by addition of small amounts of water. Mechanistic studies and control experiments revealed a tandem allylic alcohol amination/C?N bond carbonylation reaction sequence. 相似文献
146.
147.
Multifunctional mesoporous silica nanoparticles in poly(ethylene‐co‐vinyl acetate) for transparent heat retention films 下载免费PDF全文
Md Abdul Mumin Kazi Farida Akhter Sara Dresser Sasha T. van Dinther Wei Wu Paul A. Charpentier 《Journal of Polymer Science.Polymer Physics》2015,53(12):851-859
Transparent inorganic‐polymer nanocomposite films are of tremendous current interest inemerging solar coverings including photovoltaic encapsulants and commercial greenhouse plastics, but suffer from significant radiative heat loss. This work provides a new and simple approach for controlling this heat loss by using mesoporous silica/quantum dot nanoparticles in poly(ethylene‐co‐vinyl acetate) (EVA) films. Mesoporous silica shells were grown on CdS‐ZnS quantum dot (QDs) cores using a reverse microemulsion technique, controlling the shell thickness. These mesoporous silica nanoparticles (MSNs) were then melt‐mixed with EVA pellets using a mini twin‐screw extruder and pressed into thin films of concentration variable controlled thickness. The results demonstrate that the experimental MSNs showed improved infrared and thermal wavebands retention in the EVA transparent films compared to commercial silica additives, even at lower concentrations. It was also found MSNs enhanced the quantum yield and photostability of the QDs, providing high visible light transmission and blocking of UV transmission of interest for next generation solar coatings. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 851–859 相似文献
148.
149.
Alexander M. Khenkin Gregory Leitus Lev Weiner Ronny Neumann 《Journal of Cluster Science》2014,25(3):687-693
The tri-rhenium(VI) capped Wells–Dawson polyoxometalate, [Re3P2W15O62]6– with quaternary ammonium cations was synthesized by reacting the trivacant lacunary species, [P2W15O56]12– with [ReOCl3(PPh3)2] in an organic solvent. Elemental analysis by thermogravimetry and inductively coupled plasma mass spectroctrometry confirmed the substitution of three rhenium atoms, single-crystal X-ray diffraction as well as infra red spectroscopy showed the complete Wells–Dawson structure. The presence of all three rhenium atoms in one cap is indicated by 31P nuclear magnetic resonance spectroscopy and the electron spin resonance spectrum shows that the tri-rhenium(V) species with three unpaired electrons is low spin, S = ½. 相似文献
150.
Claudia Curcio Silvia Brugiapaglia Sara Bulfamante Laura Follia Paola Cappello Francesco Novelli 《Molecules (Basel, Switzerland)》2021,26(6)
Pancreatic ductal adenocarcinoma (PDA) is one of the most lethal forms of human cancer, characterized by unrestrained progression, invasiveness and treatment resistance. To date, there are limited curative options, with surgical resection as the only effective strategy, hence the urgent need to discover novel therapies. A platform of onco-immunology targets is represented by molecules that play a role in the reprogrammed cellular metabolism as one hallmark of cancer. Due to the hypoxic tumor microenvironment (TME), PDA cells display an altered glucose metabolism—resulting in its increased uptake—and a higher glycolytic rate, which leads to lactate accumulation and them acting as fuel for cancer cells. The consequent acidification of the TME results in immunosuppression, which impairs the antitumor immunity. This review analyzes the genetic background and the emerging glycolytic enzymes that are involved in tumor progression, development and metastasis, and how this represents feasible therapeutic targets to counteract PDA. In particular, as the overexpressed or mutated glycolytic enzymes stimulate both humoral and cellular immune responses, we will discuss their possible exploitation as immunological targets in anti-PDA therapeutic strategies. 相似文献