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991.
To understand the substitution effects of 3-aminomethyl-pyridine on the reaction equilibrium, the interactions between a series of 3-aminomethyl-pyridine derivatives and peroxovanadium(V) complex [OV(O2)2(D2O)]?/[OV(O2)2(HOD)]? in solution were explored by the combined use of multinuclear (1H, 13C, and 51V) magnetic resonance spectroscopy together with HSQC in 0.15 M NaCl ionic medium for mimicking the physiological conditions. Some direct NMR data are given for the first time. The relative reactivity among the 3-aminomethyl-pyridine derivative ligands are N-(pyridin-3-ylmethyl)acetamide (1) ≈ N-(pyridin-3-ylmethyl)propionamide (2) > N-(pyridin-3-ylmethyl)pivalamide (3) > t-butyl(pyridin-3-ylmethyl)carbamate (4). The competitive coordination results in the formation of a series of new six-coordinate peroxovanadium species [OV(O2)2L]? (L = 1–4). The results of density functional calculations indicated that the solvation effects play an important role in these reactions, providing a reasonable explanation on the relative reactivity of the 3-aminomethyl-pyridine derivatives. 相似文献
992.
Metalloproteins have inspired chemists for many years to synthesize artificial catalysts that mimic native enzymes.As a complementary approach to studying native enzymes or making synthetic models,biosynthetic approach using small and stable proteins to model native enzymes has offered advantages of incorporating non-covalent secondary sphere interactions under physiological conditions.However,most biosynthetic models are restricted to natural amino acids.To overcome this limitation,incorporating unnatural amino acids into the biosynthetic models has shown promises.In this review,we summarize first synthetic,semisynthetic and biological methods of incorporates unnatural amino acids(UAAs)into proteins,followed by progress made in incorporating UAAs into both native metalloproteins and their biosynthetic models to fine-tune functional properties beyond native enzymes or their variants containing natural amino acids,such as reduction potentials of azurin,O_2 reduction rates and percentages of product formation of HCO models in Mb,the rate of radical transport in ribonucleotide reductase(RNR)and the proton and electron transfer pathways in photosystemⅡ(PSⅡ).We also discuss how this endeavour has allowed systematic investigations of precise roles of conserved residues in metalloproteins,such as Metl21 in azurin,Tyr244 that is cross-linked to one of the three His ligands to CuB in HCO,Tyr122,356,730 and 731 in RNR and TyrZ in PSⅡ.These examples have demonstrated that incorporating UAAs has provided a new dimension in our efforts to mimic native enzymes and in providing deeper insights into structural features responsible high enzymatic activity and reaction mechanisms,making it possible to design highly efficient artificial catalysts with similar or even higher activity than native enzymes. 相似文献
993.
Five saturated α-branched fatty acids, also known as Guerbet acids, including α-propylhexyl acid (G 1 ), α-butylhexyl acid (G 2 ), α-propyloctyl acid (G 3 ), α-butyloctyl acid (G 4 ), and α-hexyloctyl acid (G 5 ), were synthesized in high yields by four-step reaction. Colorless, almost odorless, and oily products were obtained with high purity, whose structures were confirmed by GC, 1H/13C NMR, and ESI–MS characterization. G 1 , G 3 , and G 4 had pour points lower than ?60 °C, while G 2 and G 5 showed higher pour points (?42 °C and 6 °C, respectively) because of their molecular symmetry. Considering the low-temperature properties, G 1 , G 3 , G 4 , and even G 2 held great potential applications in the lubricant and oilfield. 相似文献
994.
Photochemical sensing of NO(2) with SnO(2) nanoribbon nanosensors at room temperature 总被引:7,自引:0,他引:7
995.
Jia‐Xiang Yang Yu‐Peng Tian Qing‐Liang Liu Yong‐Shu Xie Hoong‐Kun Fun Suchada Chantrapromma Ibrahim Abdul Razak 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(1):m43-m44
In the title compound, [Fe(C5H5)(C16H12N3OS)], the 8‐aminoquinoline and acylthiourea moieties are almost planar. There are two perpendicular arrangements of the molecules in the crystal with slightly different conformations. The two cyclopentadienyl rings in each molecule are parallel and eclipsed. 相似文献
996.
997.
Lin C Wang Y Lai Y Yang W Jiao F Zhang H Ye S Zhang Q 《Colloids and surfaces. B, Biointerfaces》2011,83(2):285-375
Biodegradable poly(lactic-co-glycolic acid) (PLGA)/carboxyl-functionalized multi-walled carbon nanotube (c-MWCNT) nanocomposites were successfully prepared via solvent casting technique. Rat bone marrow-derived mesenchymal stem cells (MSCs) were employed to assess the biocompatibility of the nanocomposites in vitro. Scanning electron microscopy (SEM) observations revealed that c-MWCNTs gave a better dispersion than unmodified MWCNTs in the PLGA matrix. Surface properties were determined by means of static contact angle, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) analysis. The presence of c-MWCNTs increased the mechanical properties of the nanocomposites. Seven-week period in vitro degradation test showed the addition of c-MWCNTs accelerated the hydrolytic degradation of PLGA. In addition, SEM proved that the cells could adhere to and spread on films via cytoplasmic processes. Compared with control groups, MSCs cultured onto PLGA/c-MWCNT nanocomposites exhibited better adhesion and viability and also displayed significantly higher production levels of alkaline phosphatase (ALP) over 21 days culture. These results demonstrated that c-MWCNTs modified PLGA films were beneficial for promoting cell growth and inducing MSCs to differentiate into osteoblasts. This work presented here had potential applications in the development of 3-D scaffolds for bone tissue engineering. 相似文献
998.
Selective fast pyrolysis of biomass impregnated with ZnCl2: Furfural production together with acetic acid and activated carbon as by-products 总被引:1,自引:0,他引:1
Qiang Lu Zhi Wang Chang-qing Dong Zhi-fei Zhang Ying Zhang Yong-ping Yang Xi-feng Zhu 《Journal of Analytical and Applied Pyrolysis》2011,91(1):273-279
Fast pyrolysis of biomass materials impregnated with ZnCl2 offered a promising way to obtain a liquid product rich in furfural (FF) and acetic acid (AA), and the pyrolytic solids could be used as the precursors to prepare activated carbons (ACs). In this study, a lab-scale fast pyrolysis set was designed and used for the quantitative production of the three chemicals. The maximum FF was produced from the corncob impregnated with at least 15 wt% ZnCl2 and at the pyrolysis temperature around 340 °C, with the yield of more than 8 wt% compared with only 0.49 wt% from the raw corncob. Meanwhile, AA of around 4 wt% could be obtained. The content of the FF and AA was over 50 wt% and 25 wt% on the water-free basis of the pyrolytic liquids. In addition, ACs were prepared from the pyrolytic solids, and they exhibited similar properties as those prepared from direct activation of ZnCl2-impregnated biomass materials. 相似文献
999.
An Ylide Transformation of Rhodium(I) Carbene: Enantioselective Three‐Component Reaction through Trapping of Rhodium(I)‐Associated Ammonium Ylides by β‐Nitroacrylates 下载免费PDF全文
Xiaochu Ma Dr. Jun Jiang Siying Lv Wenfeng Yao Yang Yang Dr. Shunying Liu Dr. Fei Xia Prof. Dr. Wenhao Hu 《Angewandte Chemie (International ed. in English)》2014,53(48):13136-13139
The chiral RhI–diene‐catalyzed asymmetric three‐component reaction of aryldiazoacetates, aromatic amines, and β‐nitroacrylates was achieved to obtain γ‐nitro‐α‐amino‐succinates in good yields and with high diastereo‐ and enantioselectivity. This reaction is proposed to proceed through the enantioselective trapping of RhI‐associated ammonium ylides by nitroacrylates. This new transformation represents the first example of RhI‐carbene‐induced ylide transformation. 相似文献
1000.
Structures of Chlorinated Fullerenes,IPR C96Cl20 and Non‐classical C94Cl28 and C92Cl32: Evidence of the Existence of Three New Isomers of C96 下载免费PDF全文
Prof. Dr. Shangfeng Yang Tao Wei Song Wang Dr. Ilya N. Ioffe Prof. Dr. Erhard Kemnitz Prof. Dr. Sergey I. Troyanov 《化学:亚洲杂志》2014,9(11):3102-3105
Chlorination of various HPLC fractions of C96 with a mixture of VCl4 and SbCl5 at 340–360 °C and single‐crystal X‐ray diffraction study of the products led to the identification of three new IPR isomers of C96. The C96(175) isomer forms a stable chloride, C96(175)Cl20, while chlorides of two other new isomers, C96(114) and C96(80), undergo cage shrinkage yielding C94(NC1)Cl28 and C96(NC2)Cl32 with non‐classical (NC) cages. These two NC chlorides contain, respectively, one and two heptagons flanked by pairs of fused pentagons and are stabilized by chlorine attachment to the emerging pentagon–pentagon junctions. Thus, the number of the experimentally confirmed C96 isomers has reached nine, which corroborates the empirical rule that the C6n fullerenes exhibit particularly rich isomerism. 相似文献