全文获取类型
收费全文 | 2356篇 |
免费 | 84篇 |
国内免费 | 23篇 |
专业分类
化学 | 1455篇 |
晶体学 | 7篇 |
力学 | 44篇 |
数学 | 399篇 |
物理学 | 558篇 |
出版年
2023年 | 9篇 |
2022年 | 12篇 |
2021年 | 28篇 |
2020年 | 38篇 |
2019年 | 29篇 |
2018年 | 30篇 |
2017年 | 36篇 |
2016年 | 61篇 |
2015年 | 59篇 |
2014年 | 61篇 |
2013年 | 121篇 |
2012年 | 186篇 |
2011年 | 177篇 |
2010年 | 125篇 |
2009年 | 111篇 |
2008年 | 160篇 |
2007年 | 164篇 |
2006年 | 167篇 |
2005年 | 203篇 |
2004年 | 138篇 |
2003年 | 124篇 |
2002年 | 115篇 |
2001年 | 19篇 |
2000年 | 23篇 |
1999年 | 15篇 |
1998年 | 15篇 |
1997年 | 15篇 |
1996年 | 33篇 |
1995年 | 17篇 |
1994年 | 17篇 |
1993年 | 19篇 |
1992年 | 11篇 |
1991年 | 5篇 |
1990年 | 8篇 |
1989年 | 12篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 12篇 |
1984年 | 10篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 10篇 |
1980年 | 5篇 |
1979年 | 7篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1973年 | 5篇 |
1972年 | 3篇 |
1970年 | 2篇 |
排序方式: 共有2463条查询结果,搜索用时 92 毫秒
981.
制备了两种非手性PNNP型钌配合物Ru(BF4)2P2N2(3a,P2N2=N,N'-双-[邻-(二苯基膦)苯哑甲基]乙二胺)和Ru(BF4)2P2H4(3b,P2N2H4=N,N'-双-[邻-(二苯基膦)苯甲基]乙二胺),并以(R)-苯乙醇的消旋化为探针反应,分别考察了添加剂、溶剂、催化剂用量及温度等对两种钌配合物催化反应的影响,得到了较理想的反应条件,即4%3a,2 mL甲苯,lequiv.Ag2O,70℃下,在氮气保护下反应12 h.反应结果发现钌配合物3a可以较好地催化仲醇的消旋化,其中(R)-和(S)-苯乙醇消旋化反应后,ee都为58%;另外(S)-对甲基苯乙醇和(S)-对氟苯乙醇消旋化反应后,ee值分别为85%和71%.并初步试探了以苯乙醇为探针底物,钌配合物结合脂肪酶Candida antarctica催化的动态动力学拆分. 相似文献
982.
Honora K. Smith Paul R. Harper Chris N. Potts Ann Thyle 《European Journal of Operational Research》2009
In this research, we consider the planning of community health schemes by non-governmental or faith-based organisations in rural areas of developing countries, from both top-down and ground level viewpoints. We conclude that both types of planning approach are valid and necessary for sustainability of such developments. With top-down planning in mind, we describe our hierarchical models especially designed for location of community health facilities, with objectives pertaining to both efficiency and equity of provision. As an additional case study, we present modelling of the location of a maximal number of self-sustainable primary healthcare workers in a rural region of India. 相似文献
983.
Chris S.K. Mak Qing Yun Leung Wai Kin Chan Aleksandra B. Djuriši? 《Journal of organometallic chemistry》2009,694(17):2770-2776
A series of sublimable substituted chlorotricarbonyl bis(phenylimino)acenaphthene rhenium(I) complexes was synthesized and used in the fabrication of photovoltaic devices. The hole and electron carrier mobilities of these complexes are in the order of 10−3 to 10−4 cm2 V−1 s−1. Heterojunction devices with CuPc/complex/C60 (CuPc = copper phthalocyanine) as the active layer and bulk heterojunction devices with complex:C60 as the active layer were fabricated. The rhenium complexes function as photosensitizer in the devices, and exhibit optical absorption in the region between 500 and 550 nm within which other components in the device do not absorb. Other devices with hole transport materials, exciton blocking materials, and different active layer thickness were also fabricated. Variation of substitution groups in the ligand did not show significant difference in device performance. The best power conversion efficiency of the devices was measured to be 1.29% under illumination of AM1.5 simulated solar light. 相似文献
984.
985.
986.
Choi KY Matsuda YH Nojiri H Kortz U Hussain F Stowe AC Ramsey C Dalal NS 《Physical review letters》2006,96(10):107202
We report pulsed field magnetization and ESR experiments on a {Cu3} nanomagnet, where antiferromagnetically coupled Cu(2+) (S = 1/2) ions form a slightly distorted triangle. The remarkable feature is the observation of a half step magnetization, hysteresis loops, and an asymmetric magnetization between a positive and a negative field in a fast sweeping external field. This is attributed to an adiabatic change of magnetization. The energy levels determined by ESR unveil that the different mixing nature of a spin chirality of a total S = 1/2 Kramers doublet by virtue of Dzyaloshinskii-Moriya interactions is decisive for inducing half step magnetization. 相似文献
987.
In this rapid communication we describe an exciting platform technology that promises to fundamentally address two underlying
constraints of modern assays and immunoassays, namely sensitivity and rapidity. By combining the use of Metal-enhanced Fluorescence
(MEF) with low power microwave heating (Mw), we can significantly increase the sensitivity of surface assays as well as >95%
kinetically complete the assay within a few seconds. This technology is subsequently likely to find significant importance
in certain clinical assays, such as in the clinical assessment of myoglobin, where both the assay rapidity and sensitivity
are paramount for the assessment and treatment of acute myocardial infarction. 相似文献
988.
Wahl EH Fidric B Rella CW Koulikov S Kharlamov B Tan S Kachanov AA Richman BA Crosson ER Paldus BA Kalaskar S Bowling DR 《Isotopes in environmental and health studies》2006,42(1):21-35
Recent measurements of carbon isotopes in carbon dioxide using near-infrared, diode-laser-based cavity ring-down spectroscopy (CRDS) are presented. The CRDS system achieved good precision, often better than 0.2 per thousand, for 4% CO2 concentrations, and also achieved 0.15-0.25 per thousand precision in a 78 min measurement time with cryotrap-based pre-concentration of ambient CO2 concentrations (360 ppmv). These results were obtained with a CRDS system possessing a data rate of 40 ring-downs per second and a loss measurement of 4.0 x 10(-11) cm(-1) Hz(-1/2). Subsequently, the measurement time has been reduced to under 10 min. This standard of performance would enable a variety of high concentration (3-10%) isotopic measurements, such as medical human breath analysis or animal breath experiments. The extension of this ring-down to the 2 microm region would enable isotopic analysis at ambient concentrations, which, combined with the small size, robust design, and potential for frequent measurements at a remote site, make CRDS technology attractive for remote atmospheric measurement applications. 相似文献
989.
Aaron G Filler Garth T Whiteside Mark Bacon Martyn Frederickson Franklyn A Howe Miri D Rabinowitz Alan J Sokoloff Terrence W Deacon Chris Abell Raj Munglani John R Griffiths B Anthony Bell Andrew ML Lever 《BMC neuroscience》2010,11(1):1-26
Background
Targeted delivery of pharmaceutical agents into selected populations of CNS (Central Nervous System) neurons is an extremely compelling goal. Currently, systemic methods are generally used for delivery of pain medications, anti-virals for treatment of dermatomal infections, anti-spasmodics, and neuroprotectants. Systemic side effects or undesirable effects on parts of the CNS that are not involved in the pathology limit efficacy and limit clinical utility for many classes of pharmaceuticals. Axonal transport from the periphery offers a possible selective route, but there has been little progress towards design of agents that can accomplish targeted delivery via this intraneural route. To achieve this goal, we developed a tripartite molecular construction concept involving an axonal transport facilitator molecule, a polymer linker, and a large number of drug molecules conjugated to the linker, then sought to evaluate its neurobiology and pharmacological behavior.Results
We developed chemical synthesis methodologies for assembling these tripartite complexes using a variety of axonal transport facilitators including nerve growth factor, wheat germ agglutinin, and synthetic facilitators derived from phage display work. Loading of up to 100 drug molecules per complex was achieved. Conjugation methods were used that allowed the drugs to be released in active form inside the cell body after transport. Intramuscular and intradermal injection proved effective for introducing pharmacologically effective doses into selected populations of CNS neurons. Pharmacological efficacy with gabapentin in a paw withdrawal latency model revealed a ten fold increase in half life and a 300 fold decrease in necessary dose relative to systemic administration for gabapentin when the drug was delivered by axonal transport using the tripartite vehicle.Conclusion
Specific targeting of selected subpopulations of CNS neurons for drug delivery by axonal transport holds great promise. The data shown here provide a basic framework for the intraneural pharmacology of this tripartite complex. The pharmacologically efficacious drug delivery demonstrated here verify the fundamental feasibility of using axonal transport for targeted drug delivery. 相似文献990.
Aysegül Turupcu Matthias Diem Assoc. Prof. Lorna J. Smith Prof. Dr. Chris Oostenbrink 《Chemphyschem》2019,20(11):1527-1537
A powerful conformational searching and enhanced sampling simulation method, and unbiased molecular dynamics simulations have been used along with NMR spectroscopic observables to provide a detailed structural view of O-glycosylation. For four model systems, the force-field parameters can accurately predict experimental NMR observables (J couplings and NOE's). This enables us to derive conclusions based on the generated ensembles, in which O-glycosylation affects the peptide backbone conformation by forcing it towards to an extended conformation. An exception is described for β-GalNAc-Thr where the α content is increased and stabilized via hydrogen bonding between the sugar and the peptide backbone, which was not observed in the rest of the studied systems. These observations might offer an explanation for the evolutionary preference of α-linked GalNAc glycosylation instead of a β link. 相似文献