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81.
Summary: The influence of number‐average molecular weight ranging from 1.4 · 104 to 1.2 · 106 g/mol on the thermal behaviour of polytetrafluoroethylene (PTFE) has been studied. Samples have been prepared by radiation‐induced degradation of commercial PTFE. The molecular weight has been calculated using end‐group concentration determined by infrared (IR) spectroscopy and 19F solid‐state nuclear magnetic resonance (NMR) spectroscopy. Melting and crystallisation heats were investigated by differential scanning calorimetry (DSC). The results have been discussed with respect to quantitative relationships between number‐average molecular weight and heat of crystallisation of PTFE described in the literature. The molecular weight calculated from Suwa's equation, which is often used in the literature, has been found to be too low.
82.
E. Monflier H. Bricout F. Hapiot S. Tilloy A. Aghmiz A.M. Masdeu‐Bult 《Advanced Synthesis \u0026amp; Catalysis》2004,346(4):425-431
The effect of methylated cyclodextrins on the RhH(CO)(TPPTS)3 complex in hydroformylation conditions [50 atm of CO/H2 (1/1) and 80 °C] has been investigated by high‐pressure 31P{1H} NMR spectroscopy. In the presence of methylated β‐cyclodextrin, the equilibria between the rhodium species lie in favor of phosphine low‐coordinated rhodium species. The formation of a stable inclusion complex between this cyclodextrin and the trisulfonated triphenylphosphine ligand (TPPTS) was found to be the key to understanding the displacement of the equilibria. Indeed, the methylated α‐cyclodextrin which does not interact with the TPPTS and the methylated γ‐cyclodextrin which can weakly bind to the TPPTS have no and a very low effect on the equilibria, respectively. These results explain for the first time why a decrease in the normal to branched aldehydes ratio is always observed when cyclodextrins are used as mass‐transfer agents in aqueous biphasic hydroformylation processes. 相似文献
83.
Linking chemical reactivity and protein precipitation to structural characteristics of foliar tannins 总被引:22,自引:0,他引:22
Tannins influence ecosystem function by affecting decomposition rates, nutrient cycling, and herbivory. To determine the role of tannins in ecological processes, it is important to quantify their abundance and understand how structural properties affect reactivity. In this study, purified tannins from the foliage of nine species growing in the pygmy forest of the northern California coast were examined for chemical reactivity, protein precipitation capacity (PPC), and structural characteristics (13C NMR). Reactivity of purified tannins varied among species 1.5-fold for the Folin total phenol assay, and 7-fold and 3-fold, respectively, for the acid butanol and vanillin condensed tannin assays. There was about a 5-fold difference in PPC. Variation in chemical reactivity and PPC can be largely explained by differences in structural characteristics of the tannins determined by 13C NMR. In particular, the condensed versus hydrolyzable tannin content, as well as the hydroxylation pattern of the B-ring and stereochemistry at the C-2–C-3 position appear to influence reactivity. Due to the large differences in chemical reactivity among species, it is necessary to use a well-characterized purified tannin from the species of interest to convert assay values to concentrations. Our results suggest that structural characteristics of tannins play an important role in regulating their reactivity in ecological processes. 相似文献
84.
85.
The triad-level sequence analysis of poly(ethylene/1,4-cyclohexanedimethylene terephthalate) copolymer was reported in a solvent system of o-chlorophenol/deuterated chloroform mixture (50/50 v/v) at 80 °C using 600 MHz 1H NMR. The well-resolved alcoholic CH2 proton peak of the glycol units was observed, which made the detailed sequence analysis possible. The peaks of the cis- and trans-forms of the 1,4-cyclohexanedimethylene glycol units were split into the triad sequence in the chain and could be assigned by a comparison of the spectra with those of homopolymers and by an additional two-dimensional heteronuclear multiple bond correlation observation. The triad sequence distributions centered on 1,4-cyclohexanedimethylene glycol units were determined, which was independent of the cis- and trans-forms of the units and controlled according to Bernoullian statistics. 相似文献
86.
Bassarello C Cimino P Bifulco G Boger DL Smith JA Chazin WJ Gomez-Paloma L 《Chembiochem : a European journal of chemical biology》2003,4(11):1188-1193
We report the NMR solution structure of (+)-CPI-indole (CPI, 1,2,8,8a-tetrahydrocyclopropa[c]pyrrolo[3,2-e]indol-4(5H)-one), an agent belonging to the CC-1065/duocarmycin family of antitumor compounds. This (+)-CPI-indole structure is covalently bound to d(G(1)ACTAATTGTC(11))-d(G(12)TCAATTAGTC(22)), a synthetic DNA duplex containing a high-affinity binding site. The three-dimensional structure has been determined by several cycles of restrained molecular dynamics calculations with a total of 563 NMR-derived constraints, both in vacuo and by using the generalized Born solvent continuum model. In-depth analysis of the structure of this ligand-DNA complex led to a detailed knowledge of the bound state conformation of the CPI-indole, the most simplified agent related to CC-1065 and duocarmycins, the parent members of a family of extremely potent antitumor compounds. Comparison of the CPI-indole bound conformation with those previously found for (+)-duocarmycin SA (DSA), its unnatural enantiomer (-)-DSA, and the demethoxylated analogue (+)-DSI in their DNA complexes provided additional evidence of the tight correlation between the catalytic effect exerted by DNA on the alkylation reaction and the extent of angular twist between the two planar heteroaromatic subunits of these agents. Additionally, comparison of the structural features of the DNA-bound state of a "naked" ligand, such as CPI-indole, with those of various other duocarmycin agents provided useful information for the interpretation of the observed effects on chemical reactivity of the different substitution patterns at the hemispheres of these types of complex. 相似文献
87.
Two types of alinite cements, Mg-alinite and Zn-alinite, were synthesized using the reagent grade chemicals. Their hydration behavior was compared with ordinary Portland cement (OPC) using impedance spectroscopy (IS) and 29Si nuclear magnetic resonance (NMR) spectroscopy. The bulk resistance in the IS spectra and the intensity ratio of the hydrous (Q1 and Q2) to anhydrous (Q0) phases in the NMR spectra were estimated as the extent of hydration. The results obtained from both techniques were consistent each other. Mg-alinite had a comparable hydration rate to OPC and Zn-alinite exhibited faster hydration kinetics than Mg-alinite. 相似文献
88.
Escaja N Gómez-Pinto I Rico M Pedroso E González C 《Chembiochem : a European journal of chemical biology》2003,4(7):623-632
The structures and stabilities of cyclic DNA octamers of different sequences have been studied by NMR and CD spectroscopy and by restrained molecular dynamics. At low oligonucleotide concentrations, some of these molecules form stable monomeric structures consisting of a short stem of two base pairs connected by two mini-loops of two residues. To our knowledge, these dumbbell-like structures are the smallest observed to date. The relative stabilities of these cyclic dumbbells have been established by studying their melting transitions. Dumbbells made up purely of GC stems are more stable than those consisting purely of AT base pairs. The order of the base pairs closing the loops also has an important effect on the stabilities of these structures. The NMR data indicate that there are significant differences between the solution structures of dumbbells with G-C base pairs in the stem compared to those with A-T base pairs. In the case of dumbbells with G-C base pairs, the residues in the stem form a short segment of a BDNA helix stabilized by two Watson-Crick base pairs. In contrast, in the case of d, the stem is formed by two A-T base pairs with the glycosidic angles of the adenine bases in a syn conformation, most probably forming Hoogsteen base pairs. Although the conformations of the loop residues are not very well defined, the thymine residues at the first position of the loop are observed to fold back into the minor groove of the stem. 相似文献
89.
This work examines the correlation between the 1H‐NMR T2 relaxation constant and the mechanical properties of aged crosslinked polyolefin cable insulation. T2 experiments on unswollen samples could not differentiate between unaged and highly aged materials; all exhibited 1H T2 constants of approximately 0.5 ms. To accentuate the effects of aging, samples were swollen in various solvents. Unaged samples had T2 values of approximately 15 ms in good solvents. With thermal aging, T2 values decreased as the ultimate tensile elongation decreased. However, the correlation between T2 and elongation differed for samples irradiated with high‐energy radiation and for materials aged above versus below the crystalline melting temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2578–2582, 2003 相似文献
90.
Bernhard Blümich Vladimir Anferov Sophia Anferova Martin Klein Radu Fechete 《大分子材料与工程》2003,288(4):312-317
A special unilateral NMR sensor has been designed for investigations of thin samples with a thickness of less than 1 mm and of surface effects of polymers. For use with the bar‐magnet NMR‐MOUSE®, the so‐called “crazy coil” is introduced with a low penetration depth. It is a flat meander coil etched on a printed circuit board with wiggles in the conductors. The design of the new coil and FEM simulations of the B 1 field are presented. Different applications are discussed by means of illustrative examples. They are the detection of surface damage in rubber samples, the swelling and drying of a latex membrane exposed to cyclohexane vapor mimicking a chemical sensor, and the drying of a thin sprayed adhesive layer.