全文获取类型
收费全文 | 483篇 |
免费 | 16篇 |
专业分类
化学 | 366篇 |
力学 | 1篇 |
数学 | 25篇 |
物理学 | 107篇 |
出版年
2023年 | 11篇 |
2022年 | 19篇 |
2021年 | 17篇 |
2020年 | 14篇 |
2019年 | 13篇 |
2018年 | 13篇 |
2017年 | 7篇 |
2016年 | 20篇 |
2015年 | 13篇 |
2014年 | 17篇 |
2013年 | 47篇 |
2012年 | 33篇 |
2011年 | 29篇 |
2010年 | 22篇 |
2009年 | 17篇 |
2008年 | 32篇 |
2007年 | 22篇 |
2006年 | 24篇 |
2005年 | 23篇 |
2004年 | 26篇 |
2003年 | 17篇 |
2002年 | 12篇 |
2001年 | 8篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1992年 | 1篇 |
1991年 | 4篇 |
1989年 | 3篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1982年 | 1篇 |
1981年 | 8篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1975年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有499条查询结果,搜索用时 0 毫秒
101.
Malay Patra Larissa S. Eichenberger Gregor Fischer Jason P. Holland 《Angewandte Chemie (International ed. in English)》2019,58(7):1928-1933
Monoclonal antibodies (mAbs), immunoglobulin fragments, and other proteins are important scaffolds in the development of radiopharmaceuticals for diagnostic immuno‐positron emission tomography (immuno‐PET) and targeted radioimmunotherapy (RIT). Conventional methods for radiolabelling proteins with metal ions such as 68Ga, 64Cu, 89Zr, and 90Y require multi‐step procedures involving pre‐purification, functionalisation with a chelate, and subsequent radiolabelling. Standard coupling chemistries are time‐consuming, difficult to automate, and involve synthesis, isolation, and storage of an intermediate, new molecular entity (the conjugated mAb) whose biochemical properties can differ from those of the parent protein. To circumvent these issues, we developed a photoradiochemical approach that uses fast, chemoselective, light‐induced protein modification under mild conditions with novel metal‐ion‐binding chelates derivatised with aryl azide (ArN3) groups. Experiments show that one‐pot photochemical conjugation and radiolabelling of formulated mAbs can be achieved in <20 min. 相似文献
102.
Germanium oxide nanofilaments (GNFs) have been synthesized under ambient conditions from the gas phase using germanium tetrachloride as a precursor. Non-crystalline GNFs synthesized by this procedure are 1–10 μm in length and 80–110 nm in diameter applying Droplet Assisted Growth and Shaping (DAGS) Chemistry. The relative humidity has been adjusted at various values in order to demonstrate the crucial role of humidity in the gas phase for the nanofilament synthesis. The novel GNFs show a strong luminescence emission in the ultra-violet and light blue region. In addition, a self-cleaning and superhydrophobic properties could be introduced in the luminescent GNF nanofilaments by simple treatment with silane molecules. 相似文献
103.
Shiran Aharon Dr. Shanti Gopal Patra Prof. Dr. Dan Meyerstein Dr. Eyal Tzur Dr. Dror Shamir Dr. Yael Albo Prof. Dr. Ariela Burg 《Chemphyschem》2023,24(22):e202300517
The Na3[Ru2(μ-CO3)4] complex is acting as a water oxidation catalyst in a homogeneous system. Due to the significance of heterogeneous systems and the effect of bicarbonate on the kinetic, we studied the bicarbonate effect on the heterogeneous electrocatalyst by entrapping the Na3[Ru2(μ-CO3)4] complex in a sol-gel matrix. We have developed two types of sol-gel electrodes, which differ by the precursor, and are demonstrating their stability over a minimum of 200 electrochemical cycles. The pH increases affected the currents and kcat for both types of electrodes, and their hydrophobicity, which was obtained from the precursor type, influenced the electrocatalytic process rate. The results indicate that NaHCO3 has an important role in the catalytic activity of the presented heterogeneous systems; without NaHCO3, the diffusing species is probably OH−, which undergoes diffusion via the Grotthuss mechanism. To the best of our knowledge, this is the first study to present a simple and fast one-step entrapment process for the Na3[Ru2(μ-CO3)4] complex by the sol-gel method under standard laboratory conditions. The results contribute to optimizing the WSP, ultimately helping expand the usage of hydrogen as a green and more readily available energy source. 相似文献
104.
Oxovanadium(IV) complexes [VO(salmet)(B)] (1-3) and [VO(saltrp)(B)] (4-6), where salmet and saltrp are N-salicylidene-l-methionate and N-salicylidene-l-tryptophanate, respectively, and B is a N,N-donor heterocyclic base (viz. 1,10-phenanthroline (phen, 1, 4), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 2, 5), and dipyrido[3,2-a:2',3'-c]phenazine (dppz, 3, 6)) are prepared and characterized and their DNA binding and photoinduced DNA cleavage activity studied. Complexes 1, 2, and 4 are structurally characterized by single-crystal X-ray crystallography. The molecular structure shows the presence of a vanadyl group in the VO3N3 coordination geometry. The dianionic alpha-amino acid Schiff base acts as a tridentate O,N,O-donor ligand in a meridional binding mode. The N,N-donor heterocyclic base displays a chelating mode of bonding with a N-donor site trans to the oxo group. The complexes show a d-d band in the range of 680-710 nm in DMF with a shoulder near 840 nm. They exhibit an irreversible oxidative cyclic voltammetric response near 0.8 V assignable to the V(V)/V(IV) couple and a quasi-reversible V(IV)/V(III) redox couple near -1.1 V vs SCE in DMF-0.1 M TBAP. The complexes show good binding propensity to calf thymus DNA giving binding constant values in the range from 5.2 x 10(4) to 7.2 x 10(5) M(-1). The binding site size, thermal melting, and viscosity data suggest DNA surface and/or groove binding nature of the complexes. The complexes show poor "chemical nuclease" activity in the dark in the presence of 3-mercaptopropionic acid or hydrogen peroxide. The dpq and dppz complexes show efficient DNA cleavage activity on irradiation with UV-A light of 365 nm via a mechanistic pathway involving formation of singlet oxygen as the reactive species. They also show significant DNA cleavage activity on photoexcitation in red light (>750 nm) by (1)O2 species. Observation of red-light-induced cleavage of DNA is unprecedented in the vanadium chemistry. The DNA cleavage activity is metal promoted as the ligands or vanadyl sulfate alone are cleavage inactive on photoirradiation at these wavelengths. 相似文献
105.
Selective separation of pyrite and galena from mixture of the two minerals was achieved through interaction with cells and metabolic products from a culture of Paenibacillus polymyxa. Adsorption of cells and metabolic products onto minerals and electrokinetic studies of minerals after interaction with cells and metabolic products were carried out to examine the resulting surface modification on the mineral surfaces. Flocculation and flotation techniques were successfully applied in the selective separation of minerals after bacterial interaction. The effect of varying conditions for production of extracellular polysaccharides and protein provided an insight into the possible mechanism involved in microbially induced flocculation and flotation of pyrite and galena. 相似文献
106.
Amali AJ Singh S Rangaraj N Patra D Rana RK 《Chemical communications (Cambridge, England)》2012,48(6):856-858
Counter-ion condensation of Poly(L-Lysine) in the presence of pyranine-3 generates spherical coacervates, which then template the assembly of silica nanoparticles to form microcapsule structures that dynamically control the optical ratiometric sensing of both the change in pH and release of the probe molecule. 相似文献
107.
Patra D El Khoury E Ahmadieh D Darwish S Tafech RM 《Photochemistry and photobiology》2012,88(2):317-327
Recent increase and wider use of ionic liquids (ILs) for various applications has drawn attention to their toxicological consequence on human health. The present study explores effects of three different kinds of widely used ILs, such as 1‐methyl‐3‐octylimidazolium chloride, 1‐buytl‐3‐methyl imadazolium tetrafluoroborate and 1‐benzyl‐3‐methyl imidazolium tetrafluoroborate, on liposome properties of 1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphocholine (DPPC) by applying curcumin as molecular probe. Fluorescence intensity of curcumin is reported as a novel rotor which is sensitive to viscosity and thus the fluidity of the solvent. It follows a linear relationship of log fluorescence vs viscosity as proposed by Förster–Hoffmann equation. Curcumin binds strongly to liposome. At low concentration, the lipophilic drug curcumin does not appreciably influence the phase transition temperature of DPPC but as concentration reaches high levels significantly depresses the phase transition temperature. ILs diminish membrane fluidity. 1‐methyl‐3‐octylimidazolium chloride disorders membrane properties by lowering the phase transition as is observed for higher concentration of curcumin, but 1‐buytl‐3‐methyl imidazolium tetrafluoroborate and 1‐benzyl‐3‐methyl imidazolium tetrafluoroborate do not modify phase transition temperature perceptibly; rather they broaden the phase transition at low molar concentration ratio. The three different kinds of ILs under study behave similarly at a high IL:DPPC ratio (1:2), while they behave differently at lower ratios (1:10–1:5). 相似文献
108.
The paper deals with the interaction between three Griffith cracks propagating under antiplane shear stress at the interface of two dissimilar infinite elastic half-spaces. The Fourier transform technique is used to reduce the elastodynamic problem to the solution of a set of integral equations which has been solved by using the finite Hilbert transform technique and Cooke’s result. The analytical expressions for the stress intensity factors at the crack tips are obtained. Numerical values of the interaction effect have been computed for and results show that interaction effects are either shielding or amplification depending on the location of each crack with respect to other and crack tip spacing. 相似文献
109.
In the present paper an isotropic sample of air-dried elastoidin has been studied considering it to be a non-ideal two-phase densely packed system after the theories by Vonk [1]. The relevant important physical parameters obtained for the sample areE, the width of the transition layer,D, the average periodicity transverse to the layers, S/V, the specific inner surface
1 and
2, the volume fraction of two phases, i. e. matter and void,l
1 andl
2 the transversal lengths,l
r, the range of inhomogeneity,l
c, the length of coherence and 2E/D, the volume fraction of the transition layer. The values ofE obtained by two approches as given by Vonk [1] and Ruland [2] show but a small difference indicating the correctness of the analysis. 相似文献
110.