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71.
Xiang‐Gao Meng Chun‐Shan Zhou Li Wang Chang‐Lin Liu 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):o667-o670
5‐Sulfosalicylic acid (5‐SSA) and 3‐aminopyridine (3‐APy) crystallize in the same solvent system, resulting in two kinds of 1:1 proton‐transfer organic adduct, namely 3‐aminopyridinium 3‐carboxy‐4‐hydroxybenzenesulfonate monohydrate, C5H7N2+·C7H5O6S−·H2O or 3‐APy·5‐SSA·H2O, (I), and the anhydrous adduct, C5H7N2+·C7H5O6S− or 3‐APy·5‐SSA, (II). Both compounds have extensively hydrogen‐bonded three‐dimensional layered polymer structures, with interlayer homo‐ and heterogeneous π–π interactions in (I) and (II), respectively. 相似文献
72.
Two new coordination polymers of PbII complexes with bridging 4,4′‐[(1E)‐ethane‐1,2‐diyl]bis[pyridine] (ebp), thiocyanato, and acetato ligands, [Pb(μ‐SCN)2(μ‐ebp)1.5]n ( 1 ) and {[Pb(μ‐OAc)(μ‐ebp)](ClO4)}n ( 2 ), were synthesized and characterized by elemental analysis, FT‐IR, 1H‐ and 13C‐NMR, thermal analysis, and single‐crystal X‐ray diffraction. In 1 , the Pb2+ ions are doubly bridged by both the ebp and the SCN− ligands into a two‐dimensional polymeric network. The seven‐coordinate geometry around the Pb2+ ion in 1 is a distorted monocapped trigonal prism, in which the Pb2+ ions have a less‐common holodirected geometry. In 2 , the Pb2+ ions are bridged by AcO− ligands forming linear chains, which are also further bridged by the neutral ebp ligands into a two‐dimensional polymeric framework. The Pb2+ ions have a five‐coordinate geometry with two N‐atoms from two ebp ligands and three O‐atoms of AcO−. Although ClO acts as a counter‐ion, it also makes weak interactions with the Pb2+ center. The arrangement of the ligands in 2 exhibits hemidirected geometry, and the coordination gap around the Pb2+ ion is possibly occupied by a configurationally active lone pair of electrons. 相似文献
73.
AbstractPoria cocos is an edible medicinal mushroom with the effects of inducing diuresis, excreting dampness, invigorating the spleen and tranquilizing the mind. The triterpenoids of Poria cocos as the main active ingredients have shown health benefits of the central nervous system of the human body. Accordingly, this study aimed at further understanding the antidepressant-like effect and a potential mechanism of the triterpenoids extracts from Poria cocos (TPC). As a result, the TPC significantly ameliorated depression-like behaviors on chronic unpredictable mild stress (CUMS) rats, and restored the levels of brain-derived neurotrophic factor and nerve growth factor in the hippocampus of rats. Gut microiota analysis revealed that TPC could increase the biodiversity and markedly regulate the relative abundance of [Prevotella], Allobaculum and Ochrobactrum of CUMS rats. The cecal contents metabolomics pointed to thirteen biomarkers associated with TPC antidepressant effect, which involved in primary bile acid biosynthesis, taurine and hypotaurine metabolism, arginine and proline metabolism. Correlation analysis further showed that there was a strong correlation relationship between the gut microbiota and the cecal contents metabolites, especially compounds involved in energy metabolism, inflammation and immunity. In conclusion, TPC showed a potential antidepressant effect, which was possibly mediated the gut microbiota and cecal contents metabolism. 相似文献
74.
Yaohao Li Xiaoyang Guan Patrick K. Chaffey Yuan Ruan Bo Ma Shiying Shang Michael E. Himmel Gregg T. Beckham Hai Long Zhongping Tan 《Chemical science》2020,11(34):9262
Improved understanding of the effect of protein glycosylation is expected to provide the foundation for the design of protein glycoengineering strategies. In this study, we examine the impact of O-glycosylation on the binding selectivity of a model Family 1 carbohydrate-binding module (CBM), which has been shown to be one of the primary sub-domains responsible for non-productive lignin binding in multi-modular cellulases. Specifically, we examine the relationship between glycan structure and the binding specificity of the CBM to cellulose and lignin substrates. We find that the glycosylation pattern of the CBM exhibits a strong influence on the binding affinity and the selectivity between both cellulose and lignin. In addition, the large set of binding data collected allows us to examine the relationship between binding affinity and the correlation in motion between pairs of glycosylation sites. Our results suggest that glycoforms displaying highly correlated motion in their glycosylation sites tend to bind cellulose with high affinity and lignin with low affinity. Taken together, this work helps lay the groundwork for future exploitation of glycoengineering as a tool to improve the performance of industrial enzymes.Improved understanding of the effect of protein glycosylation is expected to provide the foundation for the design of protein glycoengineering strategies.The cell walls of terrestrial plants primarily comprise the polysaccharides cellulose, hemicellulose, and pectin, as well as the heterogeneous aromatic polymer, lignin. In nature, carbohydrates derived from plant polysaccharides provide a massive carbon and energy source for biomass-degrading fungi, bacteria, and archaea, which together are the primary organisms that recycle plant matter and are a critical component of the global carbon cycle. Across the various environments in which these microbes break down lignocellulose, a few known enzymatic and chemical systems have evolved to deconstruct polysaccharides to soluble sugars.1–6 These natural systems are, in several cases, being evaluated for industrial use to produce sugars for further conversion into renewable biofuels and chemicals.From an industrial perspective, overcoming biomass recalcitrance to cost-effectively produce soluble intermediates, including sugars for further upgrading remains the main challenge in biomass conversion. Lignin, the evolution of which in planta provided a significant advantage for terrestrial plants to mitigate microbial attack, is now widely recognized as a primary cause of biomass recalcitrance.7 Chemical and/or biological processing scenarios of lignocellulose have been evaluated8 and several approaches have been scaled to industrial biorefineries to date. Many biomass conversion technologies overcome recalcitrance by partially or wholly removing lignin from biomass using thermochemical pretreatment or fractionation. This approach enables easier polysaccharide access for carbohydrate-active enzymes and/or microbes. There are however, several biomass deconstruction approaches that employ enzymes or microbes with whole, unpretreated biomass.9,10 In most realistic biomass conversion scenarios wherein enzymes or microbes are used to depolymerize polysaccharides, native or residual lignin remains.11,12 It is important to note that lignin can bind and sequester carbohydrate-active enzymes, which in turn can affect conversion performance.13Therefore, efforts aimed at improving cellulose binding selectivity relative to lignin have emerged as major thrusts in cellulase studies.14–25 Multiple reports in the past a few years have made exciting new contributions to our collective understanding of how fungal glycoside hydrolases, which are among the most well-characterized cellulolytic enzymes given their importance to cellulosic biofuels production, bind to lignin from various pretreatments.15,17 Taken together, these studies have demonstrated that the Family 1 carbohydrate-binding modules (CBMs) often found in fungal cellulases are the most relevant sub-domains for non-productive binding to lignin,15,17,20,26 likely due to the hydrophobic face of these CBMs that is known to be also responsible for cellulose binding (Fig. 1).27Open in a separate windowFig. 1Model of glycosylated CBM binding the surface of a cellulose crystal. Glycans are shown in green with oxygen atoms in red, tyrosines known to be critical to binding shown in purple, and disulfide bonds Cys8–Cys25 and Cys19–Cys35 in yellow.Furthermore, several studies have been published recently using protein engineering of Family 1 CBMs to improve CBM binding selectivity to cellulose with respect to lignin. Of particular note, Strobel et al. screened a large library of point mutations in both the Family 1 CBM and the linker connecting the catalytic domain (CD) and CBM.21,22 These studies demonstrated that several mutations in the CBM and one in the linker led to improved cellulose binding selectivity compared to lignin. The emerging picture is that the CBM-cellulose interaction, which occurs mainly as a result of stacking between the flat, hydrophobic CBM face (which is decorated with aromatic residues) and the hydrophobic crystal face of cellulose I, is also likely the main driving force in the CBM-lignin interaction given the strong potential for aromatic–aromatic and hydrophobic interactions.Alongside amino acid changes, modification of O-glycosylation has recently emerged as a potential tool in engineering fungal CBMs, which Harrison et al. demonstrated to be O-glycosylated.28–31 In particular, we have revealed that the O-mannosylation of a Family 1 CBM of Trichoderma reesei cellobiohydrolase I (TrCel7A) can lead to significant enhancements in the binding affinity towards bacterial microcrystalline cellulose (BMCC).30,32,33 This observation, together with the fact that glycans have the potential to form both hydrophilic and hydrophobic interactions with other molecules, led us to hypothesize that glycosylation may have a unique role in the binding selectivity of Family 1 CBMs to cellulose relative to lignin and as such, glycoengineering may be exploited to improve the industrial performance of these enzymes. To test this hypothesis, in the present study, we systematically probed the effects of glycosylation on CBM binding affinity for a variety of lignocellulose-derived cellulose and lignin substrates and investigated routes to computationally predict the binding properties of different glycosylated CBMs. 相似文献
75.
Yiming Mo Yanfei Guan Pritha Verma Jiang Guo Mike E. Fortunato Zhaohong Lu Connor W. Coley Klavs F. Jensen 《Chemical science》2021,12(4):1469
With recent advances in the computer-aided synthesis planning (CASP) powered by data science and machine learning, modern CASP programs can rapidly identify thousands of potential pathways for a given target molecule. However, the lack of a holistic pathway evaluation mechanism makes it challenging to systematically prioritize strategic pathways except for using some simple heuristics. Herein, we introduce a data-driven approach to evaluate the relative strategic levels of retrosynthesis pathways using a dynamic tree-structured long short-term memory (tree-LSTM) model. We first curated a retrosynthesis pathway database, containing 238k patent-extracted pathways along with ∼55 M artificial pathways generated from an open-source CASP program, ASKCOS. The tree-LSTM model was trained to differentiate patent-extracted and artificial pathways with the same target molecule in order to learn the strategic relationship among single-step reactions within the patent-extracted pathways. The model achieved a top-1 ranking accuracy of 79.1% to recognize patent-extracted pathways. In addition, the trained tree-LSTM model learned to encode pathway-level information into a representative latent vector, which can facilitate clustering similar pathways to help illustrate strategically diverse pathways generated from CASP programs.Tree-structured long short-term memory neural model learns to understand the retrosynthesis design strategies from patent-extracted retrosynthetic pathway data. 相似文献
76.
Cheng-Hua DengChuan-Jin Guan Man-Hua ShenCheng-Xue Zhao 《Journal of fluorine chemistry》2002,116(2):109-115
Some newly synthesized fluorinated nitroxides, such as t-butyl perfluoroalkyl nitroxides ButN(O) Rf (Rf=CF3, 5; C2F5, 6; n-C3F7, 7) and s-butyl perfluoroacyl nitroxides BusN(O) CORf (Rf=CF3, 9; n-C3F7, 10) have been employed as ESR probes of solvation in different common organic solvents. In aprotic solvents, the measured aN values for each of the nitroxyl probes show a linear correlation with the cybotactic polar solvent parameters ET (Dimroth) and Z (Kosowar), i.e. aN=bET+c, and aN=b′Z+c′. The physical significance for the slope (b or b′), the slope×ET or slope×Z, the extrapolated intercept on aN axis, c or c′, are linked, respectively, to the sensitivity of a specific nitroxide toward solvation, the magnitude of the overall solvation effect on the aN value, and the intrinsic aN value of each nitroxide in the ideal gaseous state. The intercept on the aN axis may also serve as a new measure of electronegativity for perfluoroalkyl groups, CF3, C2F5, n-C3F7, and perfluoroacyl groups, CF3CO, n-C3F7CO. In protic solvents, i.e. alcohols and carboxylic acids, however, aN values of all the probes, kept almost no change with the increase in ET and Z. Furthermore, the plots of aN versus non-cybotactic solvent constants, such as dipolar moment (μ) and dielectric constant (ε), all show random variations. 相似文献
77.
78.
Hui Jin Yan-bing Hou Xian-guo Meng Feng Teng 《高分子科学》2006,(6):553-558
In this paper, photoexcitation processes in the bilayer devices based on inorganic materials and poly(N-vinylcarbazole) (PVK) were investigated. In order to clarify the roles of inorganic materials in photoconductive properties of bilayer devices, TiO2 and ZnS were chosen to combine with PVK. A model for generation of photocurrent (Iph) in single layer device of PVK was obtained. It is deduced that the recombination rate constant (Pcomb) and the ionization rate constant (y) ofexcitons should be considered as the most important factors for Iph. For inorganic materials (TiO2 or ZnS)/PVK bilayer devices, in reverse bias of-4 V, the photocurrent of 115 mA/cm^2 in the TiO2/PVK device was observed, but the photocurrent in the ZnS/PVK device was only 10 mA/cma under the illumination light of 340 nm and the light intensity of 14.2 mW/cm^2. The weaker photocurrent is attributed to the absorption of ZnS within UV region and the energy offset at the interface between PVK and ZnS, which impedes the transport of charge carriers. 相似文献
79.
Acta Mathematica Sinica, English Series - The main purpose of this article is to study the calculating problem of the sixth power mean of the two-term exponential sums, and give an interesting... 相似文献
80.
In this paper, we are interested in the regularity estimates of the nonnegative viscosity super solution of the $β$−biased infinity Laplacian equation $$∆^β_∞u = 0,$$ where $β ∈ \mathbb{R}$ is a fixed constant and $∆^β_∞u := ∆^N_∞u + β|Du|,$ which arises from the random game named biased tug-of-war. By studying directly the $β$−biased infinity Laplacian equation, we construct the appropriate exponential cones as barrier functions to establish a key estimate. Based on this estimate, we obtain the Harnack inequality, Hopf boundary point lemma, Lipschitz estimate and the Liouville property etc. 相似文献