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排序方式: 共有842条查询结果,搜索用时 15 毫秒
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Helio G. Bonacorso Francieli M. Libero Fábio M. Luz Maiara C. Moraes Susiane Cavinatto Felipe S. Stefanello Melissa B. Rodrigues Nilo Zanatta Marcos A.P. Martins 《Tetrahedron letters》2017,58(40):3827-3830
This work reports the synthesis of a series of (1H-1,2,3-triazol-4-yl)carbohydrazides (2), which were obtained from 4-trichloroacetyl-1H-1,2,3-triazoles (1). Triazoles 1 were synthesized by 1,3-dipolar cycloaddition reaction, starting from 4-alkoxy-1,1,1-trichloroalk-3-en-2-ones and benzyl azides and easily (15 min) converted to 2 by reaction with hydrazine hydrate (73–82% yield). Carbohydrazides 2 proved to be a versatile building block for constructing a series of fluorinated heterocycles analogous to rufinamide, i.e., 1H-1,2,3-triazol-4-yl-1,3,4-oxadiazoles, a pyrrole derivative, and a 2-pyrazoline, through [4+1]–, [1+4]–, and [3+2]–cyclocondensation reactions, respectively. Finally, and according to the Lipinski’s rule of five, 2,6-difluorobenzylated 1,2,3-triazoles can be considered as potential candidates for further biological activity assays. 相似文献
75.
1,3-Dipolar cycloadditions of 2-thio-3-chloroacrylamides with nitrile oxides and nitrones is described. A series of novel isoxazolines are isolated from the nitrile oxide cycloadditions, whilst the isoxazolines generated from the nitrone cycloadditions undergo further ring opening to yield piperidines. 相似文献
76.
Hill MP Carroll EC Vang MC Addington TA Toney MD Larsen DS 《Journal of the American Chemical Society》2010,132(47):16953-16961
The mechanisms of pyridoxal 5'-phosphate (PLP)-dependent enzymes require substrates to form covalent "external aldimine" intermediates, which absorb light strongly between 410 and 430 nm. Aspartate aminotransferase (AAT) is a prototypical PLP-dependent enzyme that catalyzes the reversible interconversion of aspartate and α-ketoglutarate with oxalacetate and glutamate. From kinetic isotope effects studies, it is known that deprotonation of the aspartate external aldimine C(α)-H bond to give a carbanionic quinonoid intermediate is partially rate limiting in the thermal AAT reaction. We show that excitation of the 430-nm external aldimine absorption band increases the steady-state catalytic activity of AAT, which is attributed to the photoenhancement of C(α)-H deprotonation on the basis of studies with Schiff bases in solution. Blue light (250 mW) illumination gives an observed 2.3-fold rate enhancement for WT AAT activity, a 530-fold enhancement for the inactive K258A mutant, and a 58600-fold enhancement for the PLP-Asp Schiff base in water. These different levels of enhancement correlate with the intrinsic reactivities of the C(α)-H bond in the different environments, with the less reactive Schiff bases exhibiting greater enhancement. Time-resolved spectroscopy, ranging from femtoseconds to minutes, was used to investigate the nature of the photoactivation of C(α)-H bond cleavage in PLP-amino acid Schiff bases both in water and bound to AAT. Unlike the thermal pathway, the photoactivation pathway involves a triplet state with a C(α)-H pK(a) that is estimated to be between 11 and 19 units lower than the ground state for the PLP-Val Schiff base in water. 相似文献
77.
Simas ER Gehlen MH Pinto MF Siqueira J Misoguti L 《The journal of physical chemistry. A》2010,114(47):12384-12390
Polyfluorene end-capped with N-(2-benzothiazole)-1,8-naphthalimide (PF-BNI) is a highly fluorescent material with fluorescence emission modulated by solvent polarity. Its low energy excited state is assigned as a mixed configuration state between the singlet S(1) of the fluorene backbone (F) with the charge transfer (CT) of the end group BNI. The triexponential fluorescence decays of PF-BNI were associated with fast energy migration to form an intrachain charge-transfer (ICCT) state, polyfluorene backbone decay, and ICCT deactivation. Time-resolved fluorescence anisotropy exhibited biexponential relaxation with a fast component of 12-16 ps in addition to a slow one in the range 0.8-1.4 ns depending on the solvent, showing that depolarization occurs from two different processes: energy migration to form the ICCT state and slow rotational diffusion motion of end segments at a longer time. Results from femtosecond transient absorption measurements agreed with anisotropy decay and showed a decay component of about 16 ps at 605 nm in PF-BNI ascribed to the conversion of S(1) to the ICCT excited state. From the ratio of asymptotic and initial amplitudes of the transient absorption measurement, the efficiency of intrachain ICCT formation is estimated in 0.5, which means that, on average, half of the excited state formed in a BNI-(F)(n)-BNI chain with n = 32 is converted to its low energy intrachain charge-transfer (ICCT) state. 相似文献
78.
Nathan A. Lacher Qian Wang Rachel K. Roberts Heidi J. Holovics Serdar Aykent Michael R. Schlittler Melissa R. Thompson Charles W. Demarest 《Electrophoresis》2010,31(3):448-458
A CGE method for monitoring the disulfide isomer distribution characteristic of IgG2 MAbs is presented. Disulfide heterogeneity of MAbs has been studied using various chromatographic and electrophoretic methods. Although CGE operates using a different selectivity mechanism from that of sorption chromatographic techniques, similar trends are present in the data, which allow the CGE method to be used as a complementary method for studying disulfide isomer distribution. This article focuses on the optimization of a capillary‐based gel electrophoresis method that can be used to support antibody development including bioprocess optimization, antibody characterization, release, and formulation stability assessment. 相似文献
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80.
Stefan Louw Frédéric Lynen Melissa Hanna-Brown Pat Sandra 《Journal of chromatography. A》2010,1217(4):514-521
Recently, hydrophilic interaction chromatography (HILIC) has emerged as a valuable orthogonal tool to reversed-phase liquid chromatography (RP-LC) as it allows for resolution of highly polar ionisable compounds. The relationships between separation efficiency, column length and speed of analysis for 4.6 mm ID × 5 μm silica particle columns in HILIC are demonstrated using kinetic plots. The kinetic plots constructed for conventional pressure systems operating at 350 bar and at 30 °C and 80 °C are confirmed using experimental data for different column lengths. Efficiencies of more than 130,000 theoretical plates could be achieved by connecting up to six columns of 25 cm. As expected, a significant gain in analysis speed without loss of efficiency could be obtained by operating at 80 °C compared to 30 °C. The advantages of using long columns in HILIC in combination with elevated column temperature for the pharmaceutical industry are illustrated using test mixtures comprised of commercially available ionisable compounds (including some containing functional groups with potential genotoxic typical structural alerts) as well as real polar ionisable pharmaceuticals. 相似文献