全文获取类型
收费全文 | 316903篇 |
免费 | 2726篇 |
国内免费 | 1243篇 |
专业分类
化学 | 152782篇 |
晶体学 | 4393篇 |
力学 | 16380篇 |
综合类 | 2篇 |
数学 | 57919篇 |
物理学 | 89396篇 |
出版年
2020年 | 1764篇 |
2019年 | 2036篇 |
2018年 | 12533篇 |
2017年 | 12303篇 |
2016年 | 9694篇 |
2015年 | 3387篇 |
2014年 | 4149篇 |
2013年 | 11395篇 |
2012年 | 11631篇 |
2011年 | 19994篇 |
2010年 | 11920篇 |
2009年 | 12250篇 |
2008年 | 15253篇 |
2007年 | 17429篇 |
2006年 | 8541篇 |
2005年 | 9024篇 |
2004年 | 8409篇 |
2003年 | 8061篇 |
2002年 | 7078篇 |
2001年 | 7410篇 |
2000年 | 5601篇 |
1999年 | 4331篇 |
1998年 | 3699篇 |
1997年 | 3687篇 |
1996年 | 3470篇 |
1995年 | 3241篇 |
1994年 | 3016篇 |
1993年 | 3085篇 |
1992年 | 3344篇 |
1991年 | 3389篇 |
1990年 | 3190篇 |
1989年 | 3155篇 |
1988年 | 3217篇 |
1987年 | 3084篇 |
1986年 | 2980篇 |
1985年 | 4031篇 |
1984年 | 4184篇 |
1983年 | 3435篇 |
1982年 | 3789篇 |
1981年 | 3683篇 |
1980年 | 3562篇 |
1979年 | 3594篇 |
1978年 | 3810篇 |
1977年 | 3624篇 |
1976年 | 3829篇 |
1975年 | 3403篇 |
1974年 | 3527篇 |
1973年 | 3841篇 |
1972年 | 2344篇 |
1971年 | 1793篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Copolymers of acrylic acid, methyl methacrylate and glycidyl methacrylate have been synthesized and converted into cross-linked hydrophilic membranes by successive treatments with heat, alkali solution and acidic solution. The copolymerization was carried out in solution using tetrahydrofuran and p-dioxane as solvents. The polymer was obtained as a clear viscous solution at yields of approximately 95%. The polymerization was stopped before gelation took place. This gelation resulted from the reaction of epoxy and carboxylic groups of the polymeric chain. The polymerization time ranged from 3.5 to 7 hr depending on the content of the glycidyl methacrylate in the feed. The monomer mixture consisted of 25–45 mol% of acrylic acid, 40–70 mol% of methyl methacrylate and 2.5–15 mol% of glycīdyl methacrylate. With increasing content of acrylic acid, the membranes became soft and elastic; with decreasing content, they became brittle and hydrophobic. The swelling of the cured polymeric film increased with increase in the acrylic acid content of the monomer mixture and decreased with increasing glycidyl methacrylate content. Dialysis runs were conducted with sodium chloride, urea and a series of ethylene glycols with molecular weights up to 600. The permeability coefficients through the membranes for the ethylene glycols were similar to those through a commercial cellulose membrane (Cuprophane). The permeability proportional to . The membranes showed very low permeabilities to sodium chloride compared with those of commercial nonionic membranes. This appears to be due to the ionic exclusion mechanisms expected for ion exchange membranes. 相似文献
992.
A. J. Blotcky E. P. Rack R. R. Recker J. A. Leffler S. Teitelbaum 《Journal of Radioanalytical and Nuclear Chemistry》1978,43(2):381-388
A destructive neutron activation analysis procedure was developed for determining trace aluminum content in bone. It was found
that soil contamination can influence the aluninum bone levels in prehistoric bone specimens. These maximum aluninum content
values for prehistoric bone are larger than those of modern bone and comparable to aluminum levels present in bone from renal
patients. 相似文献
993.
J R J Delben D R Chaves P D Candelorio A A S T Delben 《Journal of Thermal Analysis and Calorimetry》2006,83(2):411-414
New glasses have been synthesized in the system ZrF46BaF26PrF3. Glasses were prepared by conventional fusion method and the
vitreous domain was established. For vitreous samples the thermal stability
parameters were determined, so that the best compositions could be selected
according to a compromise between high glass forming ability and thermal stability
vs. crystallization. 相似文献
994.
A pressure-assisted capillary chromatography-mass spectrometry method based on the use of a monolithic octadecylsilica (ODS) capillary is proposed for the determination of aliphatic amines. A 25 mM citric acid buffer containing 10% methanol is used as running electrolyte. Separation is achieved by simultaneously applying a capillary electrophoresis (CE) voltage of 13 kV and an overimposed pressure of 8 bar. The use of pressure is required to ensure stable electrospray conditions. Analysis times are reduced by using a capillary column consisting of a 30 cm long monolithic silica capillary column bound with ODS and a fused-silica capillary column also 30 cm long. The proposed method was successfully applied to the determination of low-molecular-weight aliphatic amines in tap and river water. The analysis of real samples requires cleanup and preconcentration, which can be performed automatically by inserting a minicolumn in the replenishment system of the commercial instrument. 相似文献
995.
No satisfactory high-performance liquid chromatographic (HPLC) method is currently available for the separation of the major dideoxyribonucleosides (ddNs) and their derivatives. A method involving HPLC has been developed for the separation of five major ddNs [ddA, ddC, ddI, azT and 2',3'-dideoxy-2',3'-didehydrothymidine (d4T)]. Elution of the common and modified components of DNA was also examined under the selected separation conditions of HPLC. The elution characteristics of these compounds were studied using serum plasma samples spiked with ddN derivatives. In addition, capillary electrophoresis (CE) was investigated for the separation of ddNs and their derivatives. Picomolar amounts of the five major ddNs and the metabolic product of azT [5'-O-glucuronide-3'-azido-3'-deoxythymidine (Glo-azT)] were satisfactorily resolved in 10 min by using a modification of CE. The spectral properties of the ddNs were characterized under different pH conditions and compared with those of their parent deoxyribonucleosides (dNs) because these compounds are commonly measured in HPLC by their spectral properties. The spectra of ddC and ddT derivatives resemble very closely those of dC and dT, but those of ddA and ddI differ to some extent from their parent dNs. The HPLC method was extensively examined for satisfactory resolutions of these compounds. For example, an isocratic elution method, although simple, failed to resolve these compounds and ion-pair chromatography did not offer any advantage. Gradient elution involving buffered solutions and increasing amounts of an organic modifier yielded satisfactory results. Methanol appeared to be the organic modifier of choice. A reversed-phase matrix with smaller than octadecyl alkyl chains did not produce the necessary interactions. Uniform spherical beads of smaller diameter produced superior resolutions. The separation of these compounds on three commercially available columns is discussed. The separation of human plasma samples spiked with dideoxynucleoside derivatives by HPLC was accomplished in ca. 16 min. The presence of the dNs did not interfere in their separations. 相似文献
996.
S.D. Morley D.E. Jackson M.R. Saunders J.G. Vinter 《Journal of computational chemistry》1992,13(6):693-703
A hybrid conformational search algorithm (DMC) is described that combines a modified form of molecular dynamics with Metropolis Monte Carlo sampling, using the COSMIC(90) force field. Trial configurations are generated by short bursts of high-temperature dynamics in which the initial kinetic energy is focused into single bond rotations or alternatively into “corner-flapping” motions in ring systems. Constant temperature and simulated annealing search protocols have been applied to the conformational analysis of several model hydrocarbons (cyclopentane, cyclohexane, cycloheptane, cyclooctane, cycloheptadecane, decane, and tetradecane), and the performance compared with conventional molecular dynamics and Monte Carlo sampling methods. Optimum Metropolis sampling temperatures have been determined and range from 1000–2000 K for acyclic molecules to 3000 K for cyclic systems. Simulated annealing runs are most successful at locating the global minimum when cooling slowing from these optimum temperatures. 相似文献
997.
Summary Nineteen analogs of the dopaminergic neurotoxin N-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) have been used as probes to study the structural parameters that influence MAO-catalyzed oxidation. In this study, the efficiency of enzyme-catalyzed substrate oxidation was found to be unrelated to parameters such as the ionization potential, dipole moment, net atomic charge at C5 and the dihedral angle between the phenyl ring and the tetrahydropyridine moiety. Conformational analysis revealed that substitution at the C2 position of MPTP yields atropisomers. It is suggested that one of these atropisomers would be either inactive or substantially less active than the other. Therefore, the relative oxidative efficiency and toxicity of these compounds reported earlier may have been significantly underestimated. Based on the conformational analysis and other data, a rudimentary model of the MAO substrate site has been developed which partially explains the substrate specificities of MAO A and MAO B.Each substrate binding site can be divided into two regions, (a) an amine-binding pocket (for the tetrahydropyridine moiety), and (b) a bulky substituent region (for the phenyl group and its substituents). The length of the substrate binding site (measured along the long axis of MPTP) is approximately 8.5 Å, and the width of the amine-binding pocket is approximately 2.5 Å (from C3 to C5). The bulky substituent region contains a central area for binding the phenyl group of MPTP. This central area is flanked by two hydrophobic pockets, P2 and P3. In MAO A, the pocket P2-A is oriented 45–135° relative to the plane of the tetrahydropyridine moiety, with a radius of 3.1 Å from C2 of the phenyl ring. The radius of a similar but smaller pocket, P2-B, in MAO B, is approximately 2.7 Å. In MAO B, the pocket P3-B (radius 2.36 Å from C3) is larger than a similar pocket P3-A (radius 1.70 Å from C3) in MAO A. The foregoing characterization suggests that differences in the size and topography of both of the substituent pockets play an important role in determining the substrate specificities of these two isozymes. 相似文献
998.
R J Perchalski 《Journal of chromatography. A》1978,145(1):97-103
A previously published procedure for the gas chromatographic analysis of carbamazepine has been modified and expanded to allow simultaneous determination of phenylethylmalonamide, a metabolite of primidone. Internal standards that closely resemble each compound are used, and derivatives are made by reaction with dimethylformamide dimethylacetal. This change of internal standard for carbamazepine and the use of a commercial, pretested column-packing material eliminate the major pitfalls of the original method. 相似文献
999.
Diffusion of organic vapors at low concentrations in glassy PVC, polystyrene, and PMMA 总被引:1,自引:0,他引:1
Diffusion coefficients of various C1 to C6 organic vapors, at concentrations 0.5 wt. percent, have been determined by gravimetric sorption rate measurements on emulsion and suspension-polymerized powder samples of PVC, polystyrene, and PMMA. Fickian diffusion kinetics were observed at the lowest concentrations, with a second-stage, relaxation-controlled sorption appearing at higher concentrations. In conjunction with published data for diffusivities of fixed gases in these polymers, the results indicate that diffusivity decreases exponentially, and that diffusion activation energy (ED) increases linearly, with increasing diameter of “spherical” penetrant molecules (e.g., the noble gases, CH4, SF6, CCl4, and neopentane). Much of the observed scatter in these correlations is attributable to uncertainty in the molecular diameters. For C4 and larger n-alkanes and other elongated or flattened molecules, diffusivities are higher, and ED lower, than for spherical molecules of similar molar volume. This finding suggests that anisometric molecules are oriented and move along their long axes during diffusion through the glassy polymer matrix. Correlations of diffusivities with molecular dimensions suggests that transport of anisometric molecules is governed by a diameter smaller than the mean (equivalent sphere) diameter but larger than the minimum dimension of their extended-chain conformation. Among the three polymers studied, diffusivity of each penetrant, at a given temperature, decreases in the order polystyrene> PVC ≥ PMMA. 相似文献
1000.
Cotton-linter pulps, wood pulps and several filter papers have been evaluated as substrates for room-temperature phosphorescence. A variety of chemical treatments of one filter paper is discussed in terms of reducing the background phosphorescence of the cellulose and in evaluating possible trace contaminants in cotton fibres. In order to account for uniformity of filter paper used in room temperature phosphorescence, a final evaluation of several different lots of one type of filter paper is presented. 相似文献