全文获取类型
收费全文 | 3649篇 |
免费 | 108篇 |
国内免费 | 28篇 |
专业分类
化学 | 2444篇 |
晶体学 | 16篇 |
力学 | 119篇 |
数学 | 448篇 |
物理学 | 758篇 |
出版年
2021年 | 20篇 |
2020年 | 47篇 |
2019年 | 34篇 |
2018年 | 28篇 |
2017年 | 19篇 |
2016年 | 63篇 |
2015年 | 38篇 |
2014年 | 58篇 |
2013年 | 143篇 |
2012年 | 179篇 |
2011年 | 251篇 |
2010年 | 99篇 |
2009年 | 89篇 |
2008年 | 179篇 |
2007年 | 195篇 |
2006年 | 193篇 |
2005年 | 228篇 |
2004年 | 178篇 |
2003年 | 177篇 |
2002年 | 136篇 |
2001年 | 52篇 |
2000年 | 47篇 |
1999年 | 30篇 |
1998年 | 27篇 |
1997年 | 48篇 |
1996年 | 60篇 |
1995年 | 41篇 |
1994年 | 39篇 |
1993年 | 38篇 |
1992年 | 33篇 |
1991年 | 41篇 |
1990年 | 48篇 |
1989年 | 47篇 |
1988年 | 40篇 |
1987年 | 36篇 |
1986年 | 32篇 |
1985年 | 64篇 |
1984年 | 46篇 |
1983年 | 43篇 |
1982年 | 43篇 |
1981年 | 53篇 |
1980年 | 51篇 |
1979年 | 46篇 |
1978年 | 64篇 |
1977年 | 53篇 |
1976年 | 35篇 |
1975年 | 47篇 |
1974年 | 21篇 |
1973年 | 49篇 |
1970年 | 16篇 |
排序方式: 共有3785条查询结果,搜索用时 15 毫秒
1.
Low-flow chromatography has a rich history of innovation but has yet to reach widespread implementation in bioanalytical applications. Improvements in pump technology, microfluidic connections, and nano-electrospray sources for MS have laid the groundwork for broader application, and innovation in this space has accelerated in recent years. This article reviews the instrumentation used for nano-flow LC, the types of columns employed, and strategies for multidimensionality of separations, which are key to the future state of the technique to the high-throughput needs of modern bioanalysis. An update of the current applications where nano-LC is widely used, such as proteomics and metabolomics, is discussed. But the trend toward biopharmaceutical development of increasingly complex, targeted, and potent therapeutics for the safe treatment of disease drives the need for ultimate selectivity and sensitivity of our analytical platforms for targeted quantitation in a regulated space. The selectivity needs are best addressed by mass spectrometric detection, especially at high resolutions, and exquisite sensitivity is provided by nano-electrospray ionization as the technology continues to evolve into an accessible, robust, and easy-to-use platform. 相似文献
2.
Brandon C. Presley Marisol S. Castaneto Barry K. Logan Susan A. Jansen-Varnum 《Biomedical chromatography : BMC》2020,34(9):e4884
FUB-AMB, an indazole carboxamide synthetic cannabinoid recreational drug, was one of the compounds most frequently reported to governmental agencies worldwide between 2016 and 2019. It has been implicated in intoxications and fatalities, posing a risk to public health. In the current study, FUB-AMB was incubated with human liver microsomes (HLM) to assess its metabolic fate and stability and to determine if its major ester hydrolysis metabolite (M1) was present in 12 authentic forensic human blood samples from driving under the influence of drug cases and postmortem investigations using UHPLC–MS/MS. FUB-AMB was rapidly metabolized in HLM, generating M1 that was stable through a 120-min incubation period, a finding that indicates a potential long detection window in human biological samples. M1 was identified in all blood samples, and no parent drug was detected. The authors propose that M1 is a reliable marker for inclusion in laboratory blood screens for FUB-AMB; this metabolite may be pharmacologically active like its precursor FUB-AMB. M1 frequently appears in samples in which the parent drug is undetectable and can point to the causative agent. The results suggest that it is imperative that synthetic cannabinoid laboratory assay panels include metabolites, especially known or potential pharmacologically active metabolites, particularly for compounds with short half-lives. 相似文献
3.
Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities 下载免费PDF全文
Guillaume G. Hedir A. Pitto‐Barry Andrew P. Dove Rachel K. O'Reilly 《Journal of polymer science. Part A, Polymer chemistry》2015,53(23):2699-2710
Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710 相似文献
4.
5.
Mengjie Liu Te‐Chun Chu Agnes Jocher Mica C. Smith Istvan Lengyel William H. Green 《国际化学动力学杂志》2021,53(1):27-42
Using Reaction Mechanism Generator (RMG), we have automatically constructed a detailed mechanism for acetylene pyrolysis, which predicts formation of polycyclic aromatic hydrocarbons (PAHs) up to pyrene. To improve the data available for formation pathways from naphthalene to pyrene, new high‐pressure limit reaction rate coefficients and species thermochemistry were calculated using a combination of electronic structure data from the literature and new quantum calculations. Pressure‐dependent kinetics for the CH potential energy surface calculated by Zádor et al. were incorporated to ensure accurate pathways for acetylene initiation reactions. After adding these new data into the RMG database, a pressure‐dependent mechanism was generated in a single RMG simulation which captures chemistry from C to C. In general, the RMG‐generated model accurately predicts major species profiles in comparison to plug‐flow reactor data from the literature. The primary shortcoming of the model is that formation of anthracene, phenanthrene, and pyrene are underpredicted, and PAHs beyond pyrene are not captured. Reaction path analysis was performed for the RMG model to identify key pathways. Notable conclusions include the importance of accounting for the acetone impurity in acetylene in accurately predicting formation of odd‐carbon species, the remarkably low contribution of acetylene dimerization to vinylacetylene or diacetylene, and the dominance of the hydrogen abstraction CH addition (HACA) mechanism in the formation pathways to all PAH species in the model. This work demonstrates the improved ability of RMG to model PAH formation, while highlighting the need for more kinetics data for elementary reaction pathways to larger PAHs. 相似文献
6.
7.
Cyanide Bridged Platinum-Iron Complexes as Cisplatin Prodrug Systems: Design and Computational Study
Dr. Ariela W. Kaspi-Kaneti Srijana Bhandari Dr. Alexander Schubert Prof. Songping D. Huang Prof. Barry D. Dunietz 《Chemphyschem》2021,22(1):106-111
The potential role of cyanide-bridged platinum-iron complexes as an anti-cancer Pt(IV) prodrug is studied. We present design principles of a dual-function prodrug that can upon reduction dissociate and release concurrently six cisplatin units and a ferricyanide anion per prodrug unit. The prodrug molecule is a unique complex of hepta metal centers consisting of a ferricyanide core with six Pt(IV) centers each bonded to the Fe(III) core through a cyano ligand. The functionality of the prodrug is addressed through density functional theory (DFT) calculations. 相似文献
8.
Adam I. Green Dr. Fruzsina Hobor Dr. Christopher P. Tinworth Dr. Stuart Warriner Prof. Andrew J. Wilson Prof. Adam Nelson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(47):10682-10689
Protein–protein interactions (PPIs) provide a rich source of potential targets for drug discovery and biomedical science research. However, the identification of structural-diverse starting points for discovery of PPI inhibitors remains a significant challenge. Activity-directed synthesis (ADS), a function-driven discovery approach, was harnessed in the discovery of the p53/hDM2 PPI. Over two rounds of ADS, 346 microscale reactions were performed, with prioritisation on the basis of the activity of the resulting product mixtures. Four distinct and novel series of PPI inhibitors were discovered that, through biophysical characterisation, were shown to have promising ligand efficiencies. It was thus shown that ADS can facilitate ligand discovery for a target that does not have a defined small-molecule binding site, and can provide distinctive starting points for the discovery of PPI inhibitors. 相似文献
9.
Isomotive dielectrophoresis (isoDEP) is a unique DEP geometrical configuration where the gradient of the field-squared () is constant. IsoDEP analyzes polarizable particles based on their magnitude and direction of translation. Particle translation is a function of the polarizability of both the particles and suspending medium, the particles’ size and shape, and the frequency of the electric field. However, other electrokinetics act on the particles simultaneously, including electrothermal hydrodynamics. Hence, to maximize the DEP force relative to over electrokinetic forces, design parameters such as microchannel geometry, fabrication materials, and applied electric field must be properly tuned. In this work, scaling law analyses were developed to derive design rules, relative to particle diameter, to reduce unwanted electrothermal hydrodynamics relative to DEP-induced particle translation. For a particle suspended in 10 mS/m media, if the channel width and height are below ten particle diameters, the electrothermal-driven flow is reduced by ∼500 times compared to a channel that is 250 particles diameters in width and height. Replacing glass with silicon as the device's underlying substrate for an insulative-based isoDEP reduces the electrothermal induced flow approximately 20 times less. 相似文献
10.
Nonlinear Dynamics - We investigate the control of friction-induced vibration in a precision motion stage under the effect of the LuGre friction dynamics. We consider a lumped parameter model of... 相似文献