全文获取类型
收费全文 | 1506篇 |
免费 | 79篇 |
国内免费 | 10篇 |
专业分类
化学 | 1151篇 |
晶体学 | 11篇 |
力学 | 21篇 |
数学 | 221篇 |
物理学 | 191篇 |
出版年
2024年 | 2篇 |
2023年 | 14篇 |
2022年 | 55篇 |
2021年 | 46篇 |
2020年 | 25篇 |
2019年 | 27篇 |
2018年 | 26篇 |
2017年 | 15篇 |
2016年 | 54篇 |
2015年 | 60篇 |
2014年 | 53篇 |
2013年 | 97篇 |
2012年 | 107篇 |
2011年 | 136篇 |
2010年 | 85篇 |
2009年 | 79篇 |
2008年 | 120篇 |
2007年 | 86篇 |
2006年 | 73篇 |
2005年 | 92篇 |
2004年 | 72篇 |
2003年 | 44篇 |
2002年 | 39篇 |
2001年 | 16篇 |
2000年 | 16篇 |
1999年 | 14篇 |
1998年 | 14篇 |
1997年 | 7篇 |
1996年 | 18篇 |
1995年 | 10篇 |
1994年 | 12篇 |
1993年 | 9篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 6篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 6篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1974年 | 3篇 |
1968年 | 2篇 |
1959年 | 1篇 |
1956年 | 1篇 |
排序方式: 共有1595条查询结果,搜索用时 15 毫秒
41.
Classical parameters obtained from surface tension technique coupled to small angle X-ray scattering (SAXS) measurements gave support to investigate conformational changes in the bovine serum albumin (BSA)-sodium dodecyl sulfate (SDS) complexes, as well as the size of the micelle-like clusters distributed along the polypeptide chain. The studied systems were composed of 1 wt% of BSA in the absence and presence of increasing SDS molar concentration up to 80 mM, under experimental conditions of low ionic strength and pH 5.40. At SDS concentrations below the critical aggregation concentration (cac) of 2.2 mM, SAXS results indicate that the detergent does not modify the native protein conformation. However, the beginning of protein unfolding, evidenced by SAXS through an increase in the values of radius of gyration Rg and protein maximum dimension Dmax, is coincident with the onset of SDS cooperative binding to BSA identified by the first breakpoint in the surface tension-SDS profile. Further SDS addition leads to the formation of micelle-like aggregates randomly distributed along the unfolded polypeptide chain, consistent to a necklace and bead model. The SAXS data also demonstrate that the SDS micelles grow in size up to 50 mM detergent. At 50 mM surfactant, the micelles stop growing. This concentration is near the BSA saturation binding by SDS measured by dialyzes and indicated by the second breakpoint in surface tension-SDS profile. The SAXS and surface tension data are also consistent with the formation of free micelles in equilibrium with BSA-SDS complexes for surfactant amount above the saturation. 相似文献
42.
The inhibition performance of five azomethine derivatives such as: 1-(4-Methyloxy phenylimino)-1-(phenylhydrazono)-propan-2-one (SB1), 1-(4-Methylphenylimino)-1-(phenylhydrazono) propan-2-one (SB2), 1-(phenylimino)-1(phenylhydrazono)-propan-2-one (SB3), 1-(4-Bromo phenylimino)-1(phenylhydrazono)-propan-2-one (SB4) and 1-(4-Chlorophenylimino)-1(phenylhydrazono) -propan-2-on (SB5) as corrosion inhibitors for mild steel in sulfuric acid 0.5 ?M were investigated using different methods. All experimental results demonstrate that these compounds are eficients inhibitors. The inhibition efficiencies () increase with inhibitors concentration. At 7.5 10?5 ?M, the was 97.27%, 96.31%, 94.23%, 93.19 and 91.64% for SB1, SB2, SB3, SB4 and SB5, respectively. The potentiodynamic polarization results indicated that all the studied inhibitors act as mixed type. The adsorption process on mild steel surface obeyed Langmuir isotherm. The associated activation parameters and thermodynamic have been calculated and discussed. The adsorbed film formed on the metal surface was characterized by SEM and EDX. 相似文献
43.
We present a deep-bed aerosol filtration model that can be used to estimate the efficiency of sintered granular membrane filters in the region of the most penetrating particle size. In this region the capture of submicrometer aerosols, much smaller than the filter pore size, takes place mainly via Brownian diffusion and direct interception acting in synergy. By modeling the disordered sintered grain packing of such filters as a simple cubic lattice, and mapping the corresponding 3D connected pore volume onto a discrete cylindrical pore network, the efficiency of a granular filter can be estimated, using new analytical results for the efficiency of cylindrical pores. This model for aerosol penetration in sintered granular filters includes flow slip and the kinetics of particle capture by the pore surface. With a unique choice for two parameters, namely the structural tortuosity and effective kinetic coefficient of particle adsorption, this semiempirical model can account for the experimental efficiency of a new class of "high-efficiency particulate air" ceramic membrane filters as a function of particle size over a wide range of filter thickness and texture (pore size and porosity) and operating conditions (face velocity). 相似文献
44.
Alberto Plaza Ciro Balestrieri Giuseppe Bifulco Arafa Hamed Sonia Piacente 《Tetrahedron》2005,61(31):7470-7480
Eight new 14,15-secopregnane glycosides, namely argelosides C-J, possessing two ketal functions involved in three five-membered rings, have been isolated from the hairy seeds of Solenostemma argel. Their structures have been established by MS and NMR experiments, combined with quantum mechanical calculations of the 13C chemical shifts for the interpretation of the experimental data. On the basis of the obtained results, the structures of argelosides A and B have been revised. Additionally, the effect of these compounds on the VEGF-induced in Kaposi's sarcoma cell proliferation was evaluated. Results indicated that all the compounds reduced the cell proliferation in a dose-dependent manner. 相似文献
45.
Ilieva S Galabov B Musaev DG Morokuma K Schaefer HF 《The Journal of organic chemistry》2003,68(4):1496-1502
The aminolysis of esters is a basic organic reaction considered as a model for the interaction of carbonyl group with nucleophiles. In the present computational study the different possible mechanistic pathways of the reaction are reinvestigated by applying higher level electronic structure theory, examining the general base catalysis by the nucleophile, and a more comprehensive study the solvent effect. Both the ab initio QCISD/6-31(d,p) method and density functional theory at the B3LYP/6-31G(d) level were employed to calculate the reaction pathways for the simplest model aminolysis reaction between methylformate and ammonia. Solvent effects were assessed by the PCM method. The results show that in the case of noncatalyzed aminolysis the addition/elimination stepwise mechanism involving two transition states and the concerted mechanism have very similar activation energies. However, in the case of catalyzed aminolysis by a second ammonia molecule the stepwise mechanism has a distinctly lower activation energy. All transition states in the catalyzed aminolysis are 10-17 kcal/mol lower than those for the uncatalyzed process. 相似文献
46.
Katya Arishtirova Barbara Pawelec Rodimir N. Nikolov J. L. G. Fierro Sonia Damyanova 《Reaction Kinetics and Catalysis Letters》2007,91(2):241-248
The effect of Pt/Ni ratio on the surface properties and catalytic behavior of bimetallic PtNi catalysts for reforming of methane
with CO2 was studied. The TPR, FTIR of adsorbed CO and XPS data showed that introduction of a small amount of Pt (0.3 – 0.5 wt.%)
into the Ni catalyst leads to a decrease of the NiO size, its easy reduction and a uniform distribution of the nickel metal
particles. 相似文献
47.
Maria V. Encinas Carlos M. Previtali Sonia G. Bertolotti Miguel G. Neumann 《Photochemistry and photobiology》1995,62(1):65-70
Abstract—
The reactions of the excited states of safranine T with aliphatic amines have been studied in methanol and acetonitrile. Quenching of the singlet and triplet states occurs by different mechanisms. Whereas the former excited state is quenched by a charge-transfer mechanism, the triplet state is quenched through proton transfer from the excited dye to the amine. This process leads to the unprotonated form of the dye in the triplet state, which is later quenched by amines to form the corresponding semireduced species. The monoprotonated triplet also undergoes self-quenching in both solvents (k = 1.2 × 108 M -1 s-1 ). 相似文献
The reactions of the excited states of safranine T with aliphatic amines have been studied in methanol and acetonitrile. Quenching of the singlet and triplet states occurs by different mechanisms. Whereas the former excited state is quenched by a charge-transfer mechanism, the triplet state is quenched through proton transfer from the excited dye to the amine. This process leads to the unprotonated form of the dye in the triplet state, which is later quenched by amines to form the corresponding semireduced species. The monoprotonated triplet also undergoes self-quenching in both solvents (k = 1.2 × 10
48.
Sonia M AlessoZhanru Yu David PearsPaul A Worthington Richard W.A LukeMark Bradley 《Tetrahedron》2003,59(36):7163-7169
The preparation, characterisation and application of a series of non-grafted polystyrene (PS) resins containing a styrenic methoxypoly(ethylene glycol) (MPEG) derivative is presented. These novel PS-MPEG resins were designed to balance swelling and solvation with improved handling. The monomer, 1-[2-(2-methoxyethoxy)ethoxy]-4-vinyl-benzene, contained an inert phenyl ether linkage designed to provide broad chemical compatibility and stability, yet imparting all the favourable properties of the PEG group into the new resin, whilst maintaining a high loading capacity. The synthetic performance of the new resins compared very favourably to those of TentaGel™, ArgoGel™ and aminomethyl PS. 相似文献
49.
Sonia Bacca 《Few-Body Systems》2013,54(7-10):903-909
The electromagnetic probe is a very valuable tool to study the dynamics of few nucleons. It can be very helpful in shedding light on the not yet fully understood three-nucleon forces. We present an update on the theoretical studies of electromagnetic induced reactions, such as photo-disintegration and electron scattering off 4He. We will show that they potentially represent a tool to discriminate among three-nucleon forces. Then, we will discuss the charge radius and the nuclear electric polarizability of the 6He halo nucleus. 相似文献