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91.
Myriam E. Rodriguez Ping Zhang Kashif Azizuddin Grace B. Delos Santos Song-mao Chiu Liang-yan Xue Jeffery C. Berlin Xinzhan Peng Hongqiao Wu Minh Lam Anna-Liisa Nieminen Malcolm E. Kenney Nancy L. Oleinick 《Photochemistry and photobiology》2009,85(5):1189-1200
The phthalocyanine photosensitizer Pc 4 has been shown to bind preferentially to mitochondrial and endoplasmic reticulum membranes. Upon photoirradiation of Pc 4-loaded cells, membrane components, especially Bcl-2, are photodamaged and apoptosis, as indicated by activation of caspase-3 and cleavage of poly(ADP-ribose) polymerase, is triggered. A series of analogs of Pc 4 were synthesized, and the results demonstrate that Pcs with the aminopropylsiloxy ligand of Pc 4 or a similar one on one side of the Pc ring and a second large axial ligand on the other side of the ring have unexpected properties, including enhanced cell uptake, greater monomerization resulting in greater intracellular fluorescence and three-fold higher affinity constants for liposomes. The hydroxyl-bearing axial ligands tend to reduce aggregation of the Pc and direct it to lysosomes, resulting in four to six times more killing of cells, as defined by loss of clonogenicity, than with Pc 4. Whereas Pc 4-PDT photodamages Bcl-2 and Bcl-xL, Pc 181-PDT causes much less photodamage to Bcl-2 over the same dose–response range relative to cell killing, with earlier cleavage of Bid and slower caspase-3-dependent apoptosis. Therefore, within this series of photosensitizers, these hydroxyl-bearing axial ligands are less aggregated than is Pc 4, tend to localize to lysosomes and are more effective in overall cell killing than is Pc 4, but induce apoptosis more slowly and by a modified pathway. 相似文献
92.
Victor Ryzhov Adrian K. Y. Lam Richard A. J. O’Hair 《Journal of the American Society for Mass Spectrometry》2009,20(6):985-995
In this work, we describe two different methods for generating protonated S-nitrosocysteine in the gas phase. The first method
involves a gas-phase reaction of protonated cysteine with t-butylnitrite, while the second method uses a solution-based transnitrosylation reaction of cysteine with S-nitrosoglutathione
followed by transfer of the resulting S-nitrosocysteine into the gas phase by electrospray ionization mass spectrometry (ESI-MS).
Independent of the way it was formed, protonated S-nitrosocysteine readily fragments via bond homolysis to form a long-lived
radical cation of cysteine (Cys•+), which fragments under collision-induced dissociation (CID) conditions via losses in the following relative abundance order:
•COOH ≫ CH2S > •CH2SH-H2S. Deuterium labeling experiments were performed to study the mechanisms leading to these pathways. DFT calculations were
also used to probe aspects of the fragmentation of protonated S-nitrosocysteine and the radical cation of cysteine. NO loss
is found to be the lowest energy channel for the former ion, while the initially formed distonic Cys•+ with a sulfur radical site undergoes proton and/or H atom transfer reactions that precede the losses of CH2S, •COOH, •CH2SH, and H2S. 相似文献
93.
HV Nguyen R Kannengießer W Stahl 《Physical chemistry chemical physics : PCCP》2012,14(33):11753-11758
Conformational studies with quantum chemical methods yielded for the most stable conformer of triethyl amine a propeller-like structure belonging to the point group C(3), which corresponds to an oblate top. The microwave spectrum of this conformer with (14)N hyperfine splitting of all rotational transitions was assigned and molecular parameters were determined. The rotational constants were found to be A = B = 2.314873978(11) GHz, the (14)N quadrupole coupling constant χ(cc) = -5.2444(07) MHz. The observed spectrum could be reproduced within experimental accuracy. The standard deviation of a global fit with 48 rotational transitions is 1.5 kHz. The propeller-like structure seems to be energetically favorable and therefore also typical for related systems like triethyl phosphine, triisopropyl amine, tri-n-propyl amine, and tri-tert-butyl amine. Furthermore, the rotational transitions of two isotopologues, (13)C(2) and (13)C(5), could be measured in natural abundance and fitted with an excellent standard deviation. The C rotational constants could be determined to be 1.32681(96) GHz and 1.32989(18) GHz for the (13)C(2) and (13)C(5) isotopologues, respectively. 相似文献
94.
External forces are increasingly recognized as major regulators of cellular structure and function, yet the underlying mechanism by which cells sense forces and transduce them into intracellular biochemical signals and behavioral responses ('mechanotransduction') is largely undetermined. To aid in the mechanistic study of mechanotransduction, herein we devised a cell stretching device that allowed for quantitative control and real-time measurement of mechanical stimuli and cellular biomechanical responses. Our strategy involved a microfabricated array of silicone elastomeric microposts integrated onto a stretchable elastomeric membrane. Using a computer-controlled vacuum, this micropost array membrane (mPAM) was activated to apply equibiaxial cell stretching forces to adherent cells attached to the microposts. Using the mPAM, we studied the live-cell subcellular dynamic responses of contractile forces in vascular smooth muscle cells (VSMCs) to a sustained static equibiaxial cell stretch. Our data showed that in response to a sustained cell stretch, VSMCs regulated their cytoskeletal (CSK) contractility in a biphasic manner: they first acutely enhanced their contraction to resist rapid cell deformation ('stiffening') before they allowed slow adaptive inelastic CSK reorganization to release their contractility ('softening'). The contractile response across entire single VSMCs was spatially inhomogeneous and force-dependent. Our mPAM device and live-cell subcellular contractile measurements will help elucidate the mechanotransductive system in VSMCs and thus contribute to our understanding of pressure-induced vascular disease processes. 相似文献
95.
Zhou YP Zhang M Li YH Guan QR Wang F Lin ZJ Lam CK Feng XL Chao HY 《Inorganic chemistry》2012,51(9):5099-5109
A series of mononuclear gold(I) acetylide complexes with urea moiety, R'(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(4)-4-R (R' = cyclohexyl, R = NO(2) (2a), CF(3) (2b), Cl (2c), H (2d), CH(3) (2e), (t)Bu (2f), OCH(3) (2g); R' = phenyl, R = NO(2) (3a), OCH(3) (3b); R' = 4-methoxyphenyl, R = H (4a), OCH(3) (4b)), have been synthesized and characterized. The crystal structures of Ph(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(4)-4-NO(2) (3a) and (4-CH(3)OC(6)H(4))(3)PAuC≡CC(6)H(4)-4-NHC(O)NHC(6)H(5) (4a) have been determined by X-ray diffraction. Complexes 2a-2g, 3b, and 4a-4b show intense luminescence both in the solid state and in degassed THF solution at 298 K. Anion binding properties of complexes 2a-2g, 3a-3b, and 4a-4b have been studied by UV-vis and (1)H NMR titration experiments. In general, the log K values of 2a-2g with the same anion in THF depend on the substituent R on the acetylide ligand of 2a-2g: R = NO(2) (2a) > CF(3) (2b) ≥ Cl (2c) > H (2d) > CH(3) (2e) ≈ (t)Bu (2f) ≥ OCH(3) (2g). Complex 2a with NO(2) group shows the dramatic color change toward F(-) in DMSO, which provides an access of naked eye detection of F(-). 相似文献
96.
Zhao Q Lam YH Kheirabadi M Xu C Houk KN Schafmeister CE 《The Journal of organic chemistry》2012,77(10):4784-4792
Derivatives of 4-hydroxyproline with a series of hydrophobic groups in well-defined orientations have been tested as catalysts for the aldol reactions. All of the modified proline catalysts carry out the intermolecular aldol reaction in water and provide high diastereoselectivity and enantioselectivity. Modified prolines with aromatic groups syn to the carboxylic acid are better catalysts than those with small hydrophobic groups (1a is 43.5 times faster than 1f). Quantum mechanical calculations provide transition structures, TS-1a(water) and TS-1f(water), that support the hypothesis that a stabilizing hydrophobic interaction occurs with 1a. 相似文献
97.
A chemo-electro-mechanical multi-field model, termed the multi-effect-coupling pH-electric-stimuli (MECpHe) model, has been
developed to simulate the response behavior of smart hydrogels subject to pH and electric voltage coupled stimuli when the
hydrogels are immersed in a pH buffer solution subject to an externally applied electric field. The MECpHe model developed
considers multiphysics effects and formulates the fixed charge density with the coupled buffer solution pH and electric voltage
effects, expressed by a set of nonlinear partial differential governing equations. The model can be used to predict the hydrogel
displacement and the distributive profiles of the concentrations of diffusive ionic species and the electric potential and
the fixed charge density in both the hydrogels and surrounding solution. After validation of the model by comparison of current
numerical results with experiment data extracted from the literature, one-dimensional steady-state simulations were carried
out for equilibrium of the smart hydrogels subject to pH and electric coupled stimuli. The effects of several important physical
conditions, including the externally applied electric voltage, on the distributions of the concentrations of diffusive ionic
species, the electric potential, the fixed charge density, and the displacement of the hydrogel strip were studied in detail.
The effects of the ionic strength on the bending deformation of the hydrogels under the solution pH and electric voltage coupled
stimuli are also discussed. 相似文献
98.
This paper presents the development of a highly precise and accurate analytical method for the determination of three matrix-bound
pyrethroids, namely, cypermethrin, permethrin, and bifenthrin, using an isotope dilution gas chromatography/mass spectrometry
technique. Identification of the analytes was confirmed under selective ion monitoring mode by the presence of two dominant
ion fragments within specific time windows and matching of relative ion intensities of the ions concerned in samples and calibration
standards. Quantitation was based on the measurement of concentration ratios of the natural and isotope analogues in the sample
and calibration blends. Intraday and interday repeatabilities of replicate analyses of the pyethroids in an apple juice sample
were below 0.5%. The expanded relative uncertainty ranged from 3 to 6%, which was significantly lower than the range obtained
using internal or external calibration methods. As a labeled analogue is not available for bifenthrin, bifenthrin was determined
using labeled cis-permethrin as the internal standard. The results were counterchecked by a gas chromatography-electron capture detection technique
using PCB 209 as the internal standard. The method developed was applied to a recent pilot study organized by CCQM and the
results were consistent with those of other participants. 相似文献
99.
The microwave spectra of the natural substance coumarin, a planar aromatic molecule with the specific scent of maibowle, a popular fruit punch served in spring and early summer, were recorded using a molecular jet Fourier transform microwave spectrometer working in the frequency range from 4.0 to 26.5 GHz. The rotational constants and centrifugal distortion constants were determined with high precision, reproducing the spectra to experimental accuracy. The spectra of all singly-substituted 13C and 18O isotopologues were observed in their natural abundances to determine the experimental heavy atom substitution rs and semi-experimental equilibrium reSE structures. The experimental bond lengths and bond angles were compared to those obtained from quantum chemical calculations and those of related molecules reported in the literature with benzene as the prototype. The alternation of the C−C bond lengths to the value of 1.39 Å found for benzene reflects the localization of π electrons in coumarin, where the benzene ring and the lactone-like chain −CH=CH−(C=O)−O− are fused. The large, negative inertial defect of coumarin is consistent with out-of-plane vibrations of the fused rings. 相似文献
100.
Lam WH Jia G Lin Z Lau CP Eisenstein O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2775-2782
Theoretical calculations on the metathesis process, [Tp(PH3)MR(eta 2-H[bond]CH3)] --> [Tp(PH3)M(CH3)(eta 2-H[bond]R)] (M=Fe, Ru, and Os; R=H and CH3), have been systematically carried out to study their detailed reaction mechanisms. Other than the one-step mechanism via a four-center transition state and the two-step mechanism through an oxidative addition/reductive elimination pathway, a new one-step mechanism, with a transition state formed under oxidative addition, has been found. Based on the intrinsic reaction coordinate calculations, we found that the trajectories of the transferring hydrogen atom in the metathesis processes studied are similar to each other regardless of the nature of reaction mechanisms. 相似文献