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81.
Jun Liu Kelton A. Schleyer Tyrel L. Bryan Changjian Xie Gustavo Seabra Yongmei Xu Arjun Kafle Chao Cui Ying Wang Kunlun Yin Benjamin Fetrow Paul K. P. Henderson Peter Z. Fatland Jian Liu Chenglong Li Hua Guo Lina Cui 《Chemical science》2021,12(1):239
Heparanase (HPA) is a critical enzyme involved in the remodeling of the extracellular matrix (ECM), and its elevated expression has been linked with diseases such as various types of cancer and inflammation. The detection of heparanase enzymatic activity holds tremendous value in the study of the cellular microenvironment, and search of molecular therapeutics targeting heparanase, however, no structurally defined probes are available for the detection of heparanase activity. Here we present the development of the first ultrasensitive fluorogenic small-molecule probe for heparanase enzymatic activity via tuning the electronic effect of the substrate. The probe exhibits a 756-fold fluorescence turn-on response in the presence of human heparanase, allowing one-step detection of heparanase activity in real-time with a picomolar detection limit. The high sensitivity and robustness of the probe are exemplified in a high-throughput screening assay for heparanase inhibitors.Heparanase, a critical enzyme involved in the remodeling of the extracellular matrix, activates a disaccharide probe HADP to give a strong fluorescence signal. 相似文献
82.
Bistatic scattering by arbitrarily shaped objects with rough surface at optical and infrared frequencies 总被引:2,自引:0,他引:2
The scattering cross sections for arbitrarily shaped dielectric objects with rough surface are determined for optical and infrared frequencies using the Kirchhoff approximation. The formula of the coherent scattering cross section is derived, and numerical method of incoherent scattering cross section is given. As a specific example, the infrared laser scattering cross sections of rough spheres are calculated at 1.06 m. 相似文献
83.
XPS定量分析及其在CdTe(Ⅲ)面识别化学物种中的应用 总被引:3,自引:0,他引:3
我们用谱仪能量传输函数修正的相对原子灵敏度因子获得了XPS定量数据。通过将定量结果与结合能的化学位移相结合的方法,分析了CdTe表面的两个氧化过程,结果表明,机械抛光样品表面的构成是:66%CdTe,28.9%的Cd(OH)2和5.1%TeOx(X>2),而经化学抛光的表面构成是∶84.4%的TdTeO4和15.6%TeOx(X>1)。 相似文献
85.
Xuejun Cui Shuangling Zhong Haitao Zhang Qiang Gu Junfeng Li Hongyan Wang 《先进技术聚合物》2007,18(7):544-548
Polytetrafluoroethylene (PTFE)‐polyacrylate core–shell nanoparticles were produced by using PTFE micropowder and acrylate via seeded emulsion polymerization in the presence of fluorosurfactant. The properties of emulsion under various polymerization conditions were investigated and optimized. The chemical composition of the PTFE‐polyacrylate nanoparticles was characterized by Fourier‐transform infrared spectrometry (FTIR). The particle size and core–shell structure of the resulting PTFE‐polyacrylate nanoparticles were confirmed by transmission electron microscopy (TEM). Wettability of the PTFE‐polyacrylate core–shell particles was higher than the pristine PTFE. The formation of this kind of PTFE‐polyacrylate core–shell nanoparticles could improve the compatibility of PTFE with other materials because PTFE is covered by polyacrylate shell, which make them promising in various fields. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
86.
A dicyano-containing [Fe(bpb)(CN)2]- building block has been employed for the synthesis of cyano-bridged heterometallic Ni(II)-Fe(III) complexes. The presence of steric bpb(2-) ligand around the iron ion results in the formation of low-dimensional species: five are neutral NiFe2 trimers and three are one-dimensional (1D). The structure of the 1D complexes consists of alternating [NiL]2+ and [Fe(bpb)(CN)2]- generating a cyano-bridged cationic polymeric chain and the perchlorate as the counteranion. In all complexes, the coordination geometry of the nickel ions is approximately octahedral with the cyano nitrogen atoms at the trans positions. Magnetic studies of seven complexes show the presence of ferromagnetic interaction between the metal ions through the cyano bridges. Variable temperature magnetic susceptibility investigations of the trimeric complexes yield the following J(NiFe) values (based on the spin exchange Hamiltonian H = -2J(NiFe) S(Ni) (S(Fe(1)) + S(Fe(2))): J(NiFe) = 6.40(5), 7.8(1), 8.9(2), and 6.03(4) cm(-1), respectively. The study of the magneto-structural correlation reveals that the cyanide-bridging bond angle is related to the strength of magnetic exchange coupling: the larger the Ni-N[triple bond]C bond angle, the stronger the Ni- - -Fe magnetic interaction. One 1D complex exhibits long-range antiferromagnetic ordering with T(N) = 3.5 K. Below T(N) (1.82 K), a metamagnetic behavior was observed with the critical field of approximately 6 kOe. The present research shows that the [Fe(bpb)(CN)2]- building block is a good candidate for the construction of low-dimensional magnetic materials. 相似文献
87.
The role of tunneling for two proton-transfer steps in the reactions catalyzed by triosephosphate isomerase (TIM) has been studied. One step is the rate-limiting proton transfer from Calpha in the substrate to Glu 165, and the other is an intrasubstrate proton transfer proposed for the isomerization of the enediolate intermediate. The latter, which is not important in the wild-type enzyme but is a useful model system because of its simplicity, has also been examined in the gas phase and in solution. Variational transition-state theory with semiclassical ground-state tunneling was used for the calculation with potential energy surface determined by an AM1 method specifically parametrized for the TIM system. The effect of tunneling on the reaction rate was found to be less than a factor of 10 at room temperature; the tunneling becomes more important at lower temperature, as expected. The imaginary frequency (barrier) mode and modes that have large contributions to the reaction path curvature are localized on the atoms in the active site, within 4 A of the substrate. This suggests that only a small number of atoms that are close to the substrate and their motions (e.g., donor-acceptor vibration) directly determine the magnitude of tunneling. Atoms that are farther away influence the effect of tunneling indirectly by modulating the energetics of the proton transfer. For the intramolecular proton transfer, tunneling was found to be most important in the gas phase, to be similar in the enzyme, and to be the smallest in water. The major reason for this trend is that the barrier frequency is substantially lower in solution than in the gas phase and enzyme; the broader solution barrier is caused by the strong electrostatic interaction between the highly charged solute and the polar solvent molecules. Analysis of isotope effects showed that the conventional Arrenhius parameters are more useful as experimental criteria for determining the magnitude of tunneling than the widely used Swain-Schaad exponent (SSE). For the primary SSE, although values larger than the transition-state theory limit (3.3) occur when tunneling is included, there is no clear relationship between the calculated magnitudes of tunneling and the SSE. Also, the temperature dependence of the primary SSE is rather complex; the value of SSE tends to decrease as the temperature is lowered (i.e., when tunneling becomes more significant). For the secondary SSE, the results suggest that it is more relevant for evaluating the "coupled motion" between the secondary hydrogen and the reaction coordinate than the magnitude of tunneling. Although tunneling makes a significant contribution to the rate of proton transfer, it appears not to be a major aspect of the catalysis by TIM at room temperature; i.e., the tunneling factor of 10 is "small" relative to the overall rate acceleration by 10(9). For the intramolecular proton transfer, the tunneling in the enzyme is larger by a factor of 5 than in solution. 相似文献
88.
Huang WL Cui SH Liang KM Gu SR Yuan ZF 《Journal of colloid and interface science》2002,246(1):129-134
Silica xerogels were prepared by thermal drying wet gels in an electric oven (70 degrees C) after certain duration of ambient drying, and the relevant effect is investigated on the mesopore structures and surface fractal dimensions of the resultant xerogels. The silica gels were derived from a hydrochloric acid-catalyzed TEOS (tetraethylorthaosilicate) system, and both magnetic stirring and ultrasonic vibration were adopted during sol preparation. The percentage mesoporosity and surface fractal dimensions are evaluated using image analysis methods, based on FE-SEM (field emission gun-scanning electron microscopy) images. The results show that the mesoporosity of the resultant xerogels decreases with the duration of ambient drying for samples prepared using magnetic stirring and low-intensity ultrasonic vibration, while samples subjected to high-intensity ultrasound show a somewhat reverse trend. Samples prepared with magnetic stirring have almost constant surface fractal dimensions (nearly 3), irrespective of the ambient drying before thermal drying. The surface fractal dimensions of samples prepared using ultrasound increase with the duration of ambient drying. 相似文献
89.
The synthesis of some new N‐[1‐(2,5‐dichlorophenyl)‐5‐methyl‐1,2,3‐triazol‐4‐yl]‐carbamic acid ester derivatives are reported in this paper. The yielded products 6a‐l were confirmed by Elemental analyses, NMR, MS, and IR spectra. 相似文献
90.
Theoretical insights into the mechanism of acetylcholinesterase-catalyzed acylation of acetylcholine
Acylation of acetylcholine (ACh) catalyzed by acetylcholinesterase (AChE) has been studied using high-level theoretical calculations on a model system that mimics the reaction center of the enzyme, and compared with uncatalyzed acylation reaction. The geometries of all the intermediates and transition states, activation energies, and solvent effects have been calculated. The calculations predict simultaneous formation of two short-strong hydrogen bonds (SSHB) in the rate-determining transition state structures [the first SSHB involves the hydrogen atom of Ser-200 (H(s)) and another involves the hydrogen atom of His-440 (H(h))]. In the intermediate states, the H-bond corresponding to H(h) involves SSHB, whereas the one corresponding to H(s) does not. 相似文献