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31.
Huijun Qian Hieu D. Nguyen Prof. Leiyang Lv Prof. Shuming Chen Prof. Zhiping Li 《Angewandte Chemie (International ed. in English)》2023,62(23):e202303271
Defluorinative manipulation of polyfluorinated molecules has shown great promise due to its granting of synthetic versatility to inert C−F bonds. The development of chemo-, stereo- and regioselective strategies to realize highly efficient formation of either the linear/branched or E/Z products from gem-difluorocyclopropanes (gem-F2CPs) is a challenging task. Herein, we have realized palladium/NHC-catalyzed fluoroallylation/annulation of hydrazones with gem-F2CPs that incorporate the hydrazone N2 moiety into the products. The thermodynamically unstable fluorinated E-allylation products with aryl ketone hydrazones were obtained for the first time, while the di-alkyl ketone hydrazones yielded the monofluorinated products with branched selectivity under similar reaction conditions. With aldehyde hydrazones, two kinds of pyrazoles were obtained via a defluorinative allylation/annulation cascade, in which different carbon atoms of gem-F2CPs could be incorporated into the pyrazole rings regiospecifically. DFT calculations revealed that the divergent selectivity was kinetically controlled and the final C−C bond formation proceeded through a 7-membered TS. 相似文献
32.
Tho Duc Khanh Nguyen Stefania Rabasco Alicia A. Lork Andre Du Toit Prof. Andrew G. Ewing 《Angewandte Chemie (International ed. in English)》2023,62(28):e202304098
We used correlative transmission electron microscopy (TEM) and nanoscale secondary ion mass spectrometry (NanoSIMS) imaging to quantify the contents of subvesicular compartments, and to measure the partial release fraction of 13C-dopamine in cellular nanovesicles as a function of size. Three modes of exocytosis comprise full release, kiss-and-run, and partial release. The latter has been subject to scientific debate, despite a growing amount of supporting literature. We tailored culturing procedures to alter vesicle size and definitively show no size correlation with the fraction of partial release. In NanoSIMS images, vesicle content was indicated by the presence of isotopic dopamine, while vesicles which underwent partial release were identified by the presence of an 127I-labelled drug, to which they were exposed during exocytosis allowing entry into the open vesicle prior to its closing again. Demonstration of similar partial release fractions indicates that this mode of exocytosis is predominant across a wide range of vesicle sizes. 相似文献
33.
Thuy An Trinh Thai Minh Duy Le Hien Thi-Thanh Nguyen Thanh Loc Nguyen Jaeyun Kim Dai Phu Huynh Doo Sung Lee 《Macromolecular bioscience》2023,23(11):2300221
Type 2 Diabetes Mellitus (T2D) is a chronic, obesity-related, and inflammatory disorder characterize by insulin resistance, inadequate insulin secretion, hyperglycemia, and excessive glucagon secretion. Exendin-4 (EX), a clinically established antidiabetic medication that acts as a glucagon-like peptide-1 receptor agonist, is effective in lowering glucose levels and stimulating insulin secretion while significantly reducing hunger. However, the requirement for multiple daily injections due to EX's short half-life is a significant limitation in its clinical application, leading to high treatment costs and patient inconvenience. To address this issue, an injectable hydrogel system is developed that can provide sustained EX release at the injection site, reducing the need for daily injections. In this study, the electrospray technique is examine to form EX@CS nanospheres by electrostatic interaction between cationic chitosan (CS) and negatively charged EX. These nanospheres are uniformly dispersed in a pH-temperature responsive pentablock copolymer, which forms micelles and undergoes sol-to-gel transition at physiological conditions. Following injection, the hydrogel gradually degraded, exhibiting excellent biocompatibility. The EX@CS nanospheres are subsequently released, maintaining therapeutic levels for over 72 h compared to free EX solution. The findings demonstrate that the pH-temperature responsive hydrogel system containing EX@CS nanospheres can be a promising platform for the treatment of T2D. 相似文献
34.
Tyler R. Priddy-Arrington Reagan E. Edwards Claire E. Colley Marissa M. Nguyen Tess Hamilton-Adaire Mary E. Caldorera-Moore 《Macromolecular bioscience》2023,23(6):2200505
In recent years, there has been an increased interest in injectable, in situ crosslinking hydrogels due to their minimally invasive application and ability to conform to their environment. Current in situ crosslinking chitosan hydrogels are either mechanically robust with poor biocompatibility and limited biodegradation due to toxic crosslinking agents or the hydrogels are mechanically weak and undergo biodegradation too rapidly due to insufficient crosslinking. Herein, the authors developed and characterized a thermally-driven, injectable chitosan-genipin hydrogel capable of in situ crosslinking at 37 °C that is mechanically robust, biodegradable, and maintain high biocompatibility. The natural crosslinker genipin is utilized as a thermally-driven, non-toxic crosslinking agent. The chitosan-genipin hydrogel's crosslinking kinetics, injectability, viscoelasticity, swelling and pH response, and biocompatibility against human keratinocyte cells are characterized. The developed chitosan-genipin hydrogels are successfully crosslinked at 37 °C, demonstrating temperature sensitivity. The hydrogels maintained a high percentage of swelling over several weeks before degrading in biologically relevant environments, demonstrating mechanical stability while remaining biodegradable. Long-term cell viability studies demonstrated that chitosan-genipin hydrogels have excellent biocompatibility over 7 days, including during the hydrogel crosslinking phase. Overall, these findings support the development of an injectable, in situ crosslinking chitosan-genipin hydrogel for minimally invasive biomedical applications. 相似文献
35.
Thao T. P. Nguyen Dr. Foad Raji Dr. Cuong V. Nguyen Dr. Ngoc N. Nguyen Prof. Anh V. Nguyen 《Chemphyschem》2023,24(23):e202300062
Surfactants are used to control the macroscopic properties of the air-water interface. However, the link between the surfactant molecular structure and the macroscopic properties remains unclear. Using sum-frequency generation spectroscopy and molecular dynamics simulations, two ionic surfactants (dodecyl trimethylammonium bromide, DTAB, and sodium dodecyl sulphate, SDS) with the same carbon chain lengths and charge magnitude (but different signs) of head groups interact and reorient interfacial water molecules differently. DTAB forms a thicker but sparser interfacial layer than SDS. It is due to the deep penetration into the adsorption zone of Br− counterions compared to smaller Na+ ones, and also due to the flip-flop orientation of water molecules. SDS alters two distinctive interfacial water layers into a layer where H+ points to the air, forming strong hydrogen bonding with the sulphate headgroup. In contrast, only weaker dipole-dipole interactions with the DTAB headgroup are formed as they reorient water molecules with H+ point down to the aqueous phase. Hence, with more molecules adsorbed at the interface, SDS builds up a higher interfacial pressure than DTAB, producing lower surface tension and higher foam stability at a similar bulk concentration. Our findings offer improved knowledge for understanding various processes in the industry and nature. 相似文献
36.
Multi‐Species Multi‐Channel (MSMC): An Ab Initio‐based Parallel Thermodynamic and Kinetic Code for Complex Chemical Systems 下载免费PDF全文
Multi‐Species Multi‐Channel (MSMC) is an ab initio parallel program to calculate thermodynamic quantities (e.g., , , , and , time‐dependent species profiles, and rate coefficients as functions of temperature and pressure for complex chemical reaction systems, which consist of multiple stable species and multiple reaction channels interconnecting them. Thermodynamic properties of the species involved are calculated using statistical mechanics with molecular information from electronic structure calculations. Temperature‐ and pressure‐dependent behaviors are rigorously characterized within the eigenpair master equation/Rice–Ramsperger–Kassel–Marcus (ME/RRKM) framework. Corrections, e.g., for hindered internal rotation and tunneling treatment, are included. With the implementation of an ultra‐high precision package and rigorous matrix setup, MSMC is able to correctly mimic real behaviors of different types of chemical systems. Different eigenpair‐based approaches to extract phenomenological/macroscopic rate coefficients are implemented for different applications. Moreover, a friendly and platform‐independent graphical‐user‐interface (GUI) is provided to facilitate the use of MSMC and the pre‐/postcalculation data visualization/analysis on the fly. The program can be freely downloaded at https://sites.google.com/site/msmccode/ . 相似文献
37.
Synthesis of Inorganic Structural Isomers By Diffusion‐Constrained Self‐Assembly of Designed Precursors: A Novel Type of Isomerism 下载免费PDF全文
Marco Esters Matti B. Alemayehu Zachary Jones Dr. N. T. Nguyen Dr. Michael D. Anderson Corinna Grosse Prof. Saskia F. Fischer Prof. David C. Johnson 《Angewandte Chemie (International ed. in English)》2015,54(4):1130-1134
The structure of precursors is used to control the formation of six possible structural isomers that contain four structural units of PbSe and four structural units of NbSe2: [(PbSe)1.14]4[NbSe2]4, [(PbSe)1.14]3[NbSe2]3[(PbSe)1.14]1[NbSe2]1, [(PbSe)1.14]3[NbSe2]2[(PbSe)1.14]1[NbSe2]2, [(PbSe)1.14]2[NbSe2]3[(PbSe)1.14]2[NbSe2]1, [(PbSe)1.14]2[NbSe2]2[(PbSe)1.14]1[NbSe2]1[(PbSe)1.14]1[NbSe2]1, [(PbSe)1.14]2[NbSe2]1[(PbSe)1.14]1[NbSe2]2[(PbSe)1.14]1[NbSe2]1. The electrical properties of these compounds vary with the nanoarchitecture. For each pair of constituents, over 20 000 new compounds, each with a specific nanoarchitecture, are possible with the number of structural units equal to 10 or less. This provides opportunities to systematically correlate structure with properties and hence optimize performance. 相似文献
38.
Organocatalyzed Asymmetric Conjugate Addition of Heteroaryl and Aryl Trifluoroborates: a Synthetic Strategy for Discoipyrrole D 下载免费PDF全文
Jiun‐Le Shih Thien S. Nguyen Prof. Jeremy A. May 《Angewandte Chemie (International ed. in English)》2015,54(34):9931-9935
Bis‐heteroaryl or bis‐aryl stereocenters were formed by an organocatalytic enantioselective conjugate addition using the respective trifluoroborate salts as nucleophiles. Control studies suggested that fluoride dissociation is necessary in the anhydrous conditions. This strategy is applicable to the synthesis of discoipyrrole D, an inhibitor of BR5 fibroblast migration. 相似文献
39.
Ji Min Kim Loc Nguyen Mary Frances Barr Michael Morabito Damien Stringer J. Helen Fitton Kelly A. Mowery 《Analytica chimica acta》2015
The use of polyanion and polycation-sensitive membrane electrodes to detect five different preparations of fucoidan is described. Unlike linear polyanionic molecules previously measured with polymer membrane-based electrochemical sensors, fucoidans from marine brown algae are all highly branched, sulfated polysaccharides with varying charge densities and structures, depending on the species of seaweed, method of extraction used and extent of purification. When tridodecylmethylammonium (TDMA) was used as the ion-exchanger, a large, non-equilibrium EMF response was observed over a concentration range of 0.5–50 μg mL−1 fucoidan. Fucoidan was also measured by titration with polycationic protamine, using a dinonylnaphthalene sulfonate (DNNS)-doped membrane electrode as the potentiometric endpoint detector. Potentiometric titration was used to determine the binding ratio between protamine and fucoidan at the neutralization endpoint for each fucoidan preparation. This binding ratio was then used to successfully determine the fucoidan content of commercially available nutritional supplements. Fucoidan was also measured in undiluted blood serum, demonstrating that this method may be applicable for measuring fucoidan for clinical applications. 相似文献
40.