全文获取类型
收费全文 | 3805篇 |
免费 | 216篇 |
国内免费 | 12篇 |
专业分类
化学 | 2809篇 |
晶体学 | 8篇 |
力学 | 141篇 |
数学 | 480篇 |
物理学 | 595篇 |
出版年
2023年 | 38篇 |
2022年 | 65篇 |
2021年 | 81篇 |
2020年 | 87篇 |
2019年 | 85篇 |
2018年 | 72篇 |
2017年 | 58篇 |
2016年 | 126篇 |
2015年 | 110篇 |
2014年 | 144篇 |
2013年 | 178篇 |
2012年 | 301篇 |
2011年 | 342篇 |
2010年 | 151篇 |
2009年 | 146篇 |
2008年 | 283篇 |
2007年 | 246篇 |
2006年 | 242篇 |
2005年 | 236篇 |
2004年 | 198篇 |
2003年 | 117篇 |
2002年 | 134篇 |
2001年 | 37篇 |
2000年 | 28篇 |
1999年 | 31篇 |
1998年 | 15篇 |
1997年 | 28篇 |
1996年 | 32篇 |
1995年 | 16篇 |
1994年 | 24篇 |
1993年 | 23篇 |
1992年 | 26篇 |
1990年 | 18篇 |
1989年 | 13篇 |
1988年 | 12篇 |
1987年 | 8篇 |
1986年 | 11篇 |
1985年 | 23篇 |
1984年 | 21篇 |
1983年 | 15篇 |
1982年 | 18篇 |
1981年 | 22篇 |
1980年 | 14篇 |
1979年 | 18篇 |
1978年 | 18篇 |
1977年 | 19篇 |
1976年 | 14篇 |
1975年 | 16篇 |
1974年 | 16篇 |
1973年 | 8篇 |
排序方式: 共有4033条查询结果,搜索用时 0 毫秒
131.
Vincent Remusat Thierry Terme Armand Gellis Pascal Rathelot Patrice Vanelle 《Journal of heterocyclic chemistry》2004,41(2):221-225
A new heterocyclic bioreductive bis‐alkylating agent, 2,3‐bis(chloromethyl)benzo[g]quinoxaline‐5,10‐dione, was prepared in a four‐steps synthesis. It was shown to react under electron transfer conditions with 2‐nitropropane anion by an bis‐SRN1 mechanism to give three C‐alkylation products in excellent yields. Extension of this bis‐SRN1 reaction to various nitronate or malonate anions and S‐centered anions led to a new class of potentially active benzo[g]quinoxaline‐5,10‐dione derivatives. 相似文献
132.
Ning Fang Vincent Chan Kai-Tak Wan Hai-Quan Mao Kam W. Leong 《Colloids and surfaces. B, Biointerfaces》2002,25(4):347-362
High-resolution reflection interference contrast microscopy (HR-RICM) was developed for probing the deformation and adhesion of phospholipid vesicles induced by colloidal forces on solid surfaces. The new technique raised the upper limit of the measured membrane–substrate separation from 1 to 4.5 μm and improved the spatial resolution of the heterogeneous contact zones. It was applied to elucidate the effects of wall thickness, pH and osmotic stress on the non-specific adhesion of giant unilamellar vesicles (ULV) and multilamellar vesicles (MLV) on fused silica substrates. By simultaneous cross-polarization light microscopy and HR-RICM measurements, it was observed that ULV with the wall thickness of a single bilayer would be significantly deformed in its equilibrium state on the substrate as the dimension of its adhesive–cohesive zone was 29% higher than the theoretical value of a rigid sphere with the same diameter. Besides, electrostatic interaction was shown as a significant driving force for vesicle adhesions since the reduction in pH significantly increased the degree of deformation of adhering ULV and heterogeneity of the adhesion discs. The degree of MLV deformation on the solid surfaces was significantly less than that of ULV. When the wall thickness of vesicle increased, the dimension of contact zone was reduced dramatically due to the increase of membrane bending modulus. Most important, the adhesion strength of colloidal adhesion approached that of specific adhesion. Finally, the increase of osmotic stress led to the collapse of adhering vesicles on the non-deformable substrate and raised the area of adhesive contact zone. To interpret these results better, the equilibrium deformation of adhering vesicle was modeled as a truncated sphere and the adhesion energy was calculated with a new theory. 相似文献
133.
Xu Zhao Sarah E. Cleary Ceren Zor Nicole Grobert Holly A. Reeve Kylie A. Vincent 《Chemical science》2021,12(23):8105
Heterogeneous biocatalytic hydrogenation is an attractive strategy for clean, enantioselective C X reduction. This approach relies on enzymes powered by H2-driven NADH recycling. Commercially available carbon-supported metal (metal/C) catalysts are investigated here for direct H2-driven NAD+ reduction. Selected metal/C catalysts are then used for H2 oxidation with electrons transferred via the conductive carbon support material to an adsorbed enzyme for NAD+ reduction. These chemo-bio catalysts show improved activity and selectivity for generating bioactive NADH under ambient reaction conditions compared to metal/C catalysts. The metal/C catalysts and carbon support materials (all activated carbon or carbon black) are characterised to probe which properties potentially influence catalyst activity. The optimised chemo-bio catalysts are then used to supply NADH to an alcohol dehydrogenase for enantioselective (>99% ee) ketone reductions, leading to high cofactor turnover numbers and Pd and NAD+ reductase activities of 441 h−1 and 2347 h−1, respectively. This method demonstrates a new way of combining chemo- and biocatalysis on carbon supports, highlighted here for selective hydrogenation reactions.Heterogeneous chemo-bio catalytic hydrogenation is an attractive strategy for clean, enantioselective C X reduction. 相似文献
134.
We consider information-theoretic bounds on the expected generalization error for statistical learning problems in a network setting. In this setting, there are K nodes, each with its own independent dataset, and the models from the K nodes have to be aggregated into a final centralized model. We consider both simple averaging of the models as well as more complicated multi-round algorithms. We give upper bounds on the expected generalization error for a variety of problems, such as those with Bregman divergence or Lipschitz continuous losses, that demonstrate an improved dependence of on the number of nodes. These “per node” bounds are in terms of the mutual information between the training dataset and the trained weights at each node and are therefore useful in describing the generalization properties inherent to having communication or privacy constraints at each node. 相似文献
135.
Manal Diab Ana Mateo Joumada El Cheikh Zeinab El Hajj Mohamed Haouas Alireza Ranjbari Vincent Gurineau David Touboul Nathalie Leclerc Emmanuel Cadot Daoud Naoufal Carles Bo Sbastien Floquet 《Molecules (Basel, Switzerland)》2022,27(22)
Herein we report the synthesis of a new class of compounds associating Keggin and Dawson-type Polyoxometalates (POMs) with a derivative of the anionic decahydro-closo-decaborate cluster [B10H10]2− through aminopropylsilyl ligand (APTES) acting as both a linker and a spacer between the two negatively charged species. Three new adducts were isolated and fully characterized by various NMR techniques and MALDI-TOF mass spectrometry, notably revealing the isolation of an unprecedented monofunctionalized SiW10 derivative stabilized through intramolecular H-H dihydrogen contacts. DFT as well as electrochemical studies allowed studying the electronic effect of grafting the decaborate cluster on the POM moiety and its consequences on the hydrogen evolution reaction (HER) properties. 相似文献
136.
Lin Jiang Pauline M.G.van Deursen Hadi Arjmandi-Tash Liubov A.Belyaeva Haoyuan Qi Jiao He Vincent Kofman Longfei Wu Valery Muravev Ute Kaiser Harold Linnartz Emiel J.M.Hensen Jan P.Hofmann Grégory F.Schneider 《中国科学:化学(英文版)》2021,(6):1047-1056
Graphene as a two-dimensional material is prone to hydrocarbon contaminations,which can significantly alter its intrinsic electrical properties.Herein,we implem... 相似文献
137.
Thorbjrn Vincent Snderby Zahra Najarzadeh Daniel Erik Otzen 《Molecules (Basel, Switzerland)》2022,27(13)
Functional amyloid is produced by many organisms but is particularly well understood in bacteria, where proteins such as CsgA (E. coli) and FapC (Pseudomonas) are assembled as functional bacterial amyloid (FuBA) on the cell surface in a carefully optimized process. Besides a host of helper proteins, FuBA formation is aided by multiple imperfect repeats which stabilize amyloid and streamline the aggregation mechanism to a fast-track assembly dominated by primary nucleation. These repeats, which are found in variable numbers in Pseudomonas, are most likely the structural core of the fibrils, though we still lack experimental data to determine whether the repeats give rise to β-helix structures via stacked β-hairpins (highly likely for CsgA) or more complicated arrangements (possibly the case for FapC). The response of FuBA fibrillation to denaturants suggests that nucleation and elongation involve equal amounts of folding, but protein chaperones preferentially target nucleation for effective inhibition. Smart peptides can be designed based on these imperfect repeats and modified with various flanking sequences to divert aggregation to less stable structures, leading to a reduction in biofilm formation. Small molecules such as EGCG can also divert FuBA to less organized structures, such as partially-folded oligomeric species, with the same detrimental effect on biofilm. Finally, the strong tendency of FuBA to self-assemble can lead to the formation of very regular two-dimensional amyloid films on structured surfaces such as graphite, which strongly implies future use in biosensors or other nanobiomaterials. In summary, the properties of functional amyloid are a much-needed corrective to the unfortunate association of amyloid with neurodegenerative disease and a testimony to nature’s ability to get the best out of a protein fold. 相似文献
138.
139.
Predoana Luminita Atkinson Irina Karaj Dániel Attila Odhiambo Vincent Otieno Bakos László Péter Nagyné Kovács Teodóra Pandele-Cusu Jeanina Petrescu Simona Rusu Adriana Szilágyi Imre M. Pokol György Zaharescu Maria 《Journal of Thermal Analysis and Calorimetry》2021,143(4):2893-2900
Journal of Thermal Analysis and Calorimetry - In the literature data, several papers reported the synthesis by various chemical or physical methods of the SrCu2O2 (SCO) having possible applications... 相似文献
140.
Dr. Oumaïma Gharbi Dr. Mai T. T. Tran Prof. Mark E. Orazem Dr. Bernard Tribollet Dr. Mireille Turmine Dr. Vincent Vivier 《Chemphyschem》2021,22(13):1371-1378
The different contributions of the interfacial capacitance are identified in the case of passive materials or thin protective coatings deposited on the electrode surface. The method is based on a graphical analysis of the EIS results to determine both the passive-film capacitance in the high-frequency domain and the double-layer capacitance in the low-frequency domain. The proposed analysis is shown to be independent of the physicochemical origins of the frequency dispersion of the interfacial capacitances which results, from an analysis point of view of the experimental results, in the use of a constant-phase element However, for a correct evaluation of the thin-film properties such as its thickness, the high-frequency data must be corrected for the double-layer contribution. In particular, it is shown that if the double-layer capacitance gives a frequency-dispersed response, it is necessary to correct the high-frequency part for the double-layer constant-phase elements. This is first demonstrated on synthetic data and then used for the determination of the thickness of thin oxide film formed on Al in neutral pH solution. 相似文献