全文获取类型
收费全文 | 16590篇 |
免费 | 503篇 |
国内免费 | 38篇 |
专业分类
化学 | 8761篇 |
晶体学 | 133篇 |
力学 | 421篇 |
数学 | 3352篇 |
物理学 | 4464篇 |
出版年
2022年 | 111篇 |
2021年 | 211篇 |
2020年 | 239篇 |
2019年 | 257篇 |
2018年 | 296篇 |
2017年 | 304篇 |
2016年 | 595篇 |
2015年 | 541篇 |
2014年 | 637篇 |
2013年 | 1150篇 |
2012年 | 858篇 |
2011年 | 995篇 |
2010年 | 670篇 |
2009年 | 554篇 |
2008年 | 697篇 |
2007年 | 586篇 |
2006年 | 548篇 |
2005年 | 343篇 |
2004年 | 383篇 |
2003年 | 323篇 |
2002年 | 323篇 |
2001年 | 222篇 |
2000年 | 265篇 |
1999年 | 192篇 |
1998年 | 200篇 |
1997年 | 177篇 |
1996年 | 184篇 |
1995年 | 170篇 |
1994年 | 151篇 |
1993年 | 167篇 |
1992年 | 155篇 |
1991年 | 131篇 |
1990年 | 146篇 |
1989年 | 125篇 |
1988年 | 139篇 |
1987年 | 142篇 |
1986年 | 127篇 |
1985年 | 176篇 |
1984年 | 189篇 |
1983年 | 128篇 |
1982年 | 146篇 |
1981年 | 164篇 |
1980年 | 154篇 |
1979年 | 155篇 |
1978年 | 153篇 |
1977年 | 148篇 |
1976年 | 164篇 |
1975年 | 164篇 |
1974年 | 157篇 |
1973年 | 120篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Effects of Quantum Nuclear Delocalisation on NMR Parameters from Path Integral Molecular Dynamics
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Martin Dračínský Dr. Paul Hodgkinson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2201-2207
The influence of nuclear delocalisation on NMR chemical shifts in molecular organic solids is explored using path integral molecular dynamics (PIMD) and density functional theory calculations of shielding tensors. Nuclear quantum effects are shown to explain previously observed systematic deviations in correlations between calculated and experimental chemical shifts, with particularly large PIMD‐induced changes (up to 23 ppm) observed for carbon atoms in methyl groups. The PIMD approach also enables isotope substitution effects on chemical shifts and J couplings to be predicted in excellent agreement with experiment for both isolated molecules and molecular crystals. An approach based on convoluting calculated shielding or coupling surfaces with probability distributions of selected bond distances and valence angles obtained from PIMD simulations is used to calculate isotope effects. 相似文献
992.
Back Cover: Chemical Preparation of Graphene Materials Results in Extensive Unintentional Doping with Heteroatoms and Metals (Chem. Eur. J. 48/2014)
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
993.
Phase‐Transfer‐Catalysed Synthesis of Pyrroloindolines and Pyridoindolines by a Hydrogen‐Bond‐Assisted Isocyanide Cyclization Cascade
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Peter C. Knipe Dr. Matija Gredičak Artiom Cernijenko Dr. Robert S. Paton Dr. Martin D. Smith 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(11):3005-3009
A cascade reaction that generates pyrrolo‐ and pyridoindoline motifs from isocyanide precursors under phase‐transfer conditions is described. This transformation proceeds at room temperature in the presence of a quaternary ammonium catalyst and base to generate functionalized products containing an all‐carbon quaternary stereocentre. Quantum chemical calculations demonstrated that intramolecular general acid catalysis plays a key accelerating role through stabilization of developing charge in the transition state, and that the reaction is best described as a 5‐endo dig cyclization, rather than an anionic 6π electrocyclization. Investigations employing chiral phase‐transfer catalysts have given promising selectivities to date. 相似文献
994.
Constrained‐Geometry Bisphosphazides Derived from 1,8‐Diazidonaphthalene: Synthesis,Spectroscopic Characteristics,Structural Features,and Theoretical Investigations
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Julius F. Kögel Nuri C. Abacılar Felicia Weber Dr. Benjamin Oelkers Dr. Klaus Harms Dr. Borislav Kovačević Prof. Dr. Jörg Sundermeyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):5994-6009
Investigations on the Staudinger reaction between 1,8‐diazidonaphthalene and phosphorous(III) building blocks, a key step in the synthesis of superbasic bisphosphazene proton sponges, yielded a set of bisphosphazides with a constrained geometry 1,8‐disubstituted naphthalene backbone. This compound class has attracted our interest not only due to their surprisingly high stability, but in particular because of their theoretically predicted basicity in the range of their bisphosphazene analogues that can be referred to the constrained geometry interaction of two highly basic nitrogen atoms. Eleven new bisphosphazides bearing simple P‐amino groups as well as P‐guanidino substituents, azaphosphatrane moieties, P2 building blocks, or chiral P‐amino substituents derived from L ‐proline are presented. They were studied concerning their spectroscopic properties and partly also their chromophoric and structural features. In the case of the pyrrolidino‐substituted TPPN(2N2) (TPPN=1,8‐bis(trispyrrolidinophosphazenyl)naphthalene), the stepwise nitrogen elimination is investigated theoretically and experimentally, which led to the isolation and structural characterization of TPPN(1N2) bearing a phosphazide and a phosphazene functionality in one molecule. Attempts to protonate the obtained bisphosphazides and to prove the computationally predicted pKBH+ values through NMR titration reactions resulted in their decay, which again was rationalized by theoretical calculations. Altogether we present the so far most extensive spectroscopic, structural and theoretical investigation of constrained geometry bisphosphazides and their Brønsted and Lewis basic properties. 相似文献
995.
Jelena Vasiljević Brigita Tomšič Ivan Jerman Boris Orel Gregor Jakša Barbara Simončič 《Cellulose (London, England)》2014,21(4):2611-2623
This research aimed to prepare cotton fibres with novel multifunctional water- and oil-repellent, antibacterial, and flame-retardant properties. A three-component equimolar sol mixture, which included 1H,1H,2H,2H-perfluorooctyltriethoxysilane, 3-(trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride, and P,P-diphenyl-N-(3-(trimethoxysilyl)propyl) phosphinic amide, was applied to the cotton fabric using the sol–gel process. The presence of the coating on the cotton fibres was confirmed by Fourier transform-infrared spectroscopy and X-ray photoelectron spectroscopy. The functional properties of the coated cotton fabric were determined from liquid contact angle measurements and antibacterial activity, burning behaviour, and thermo-oxidative stability studies. The results demonstrate that a unique, compatible, and uniform organic-inorganic hybrid polymer network was formed on the fabric surface, which preserved its simultaneous hydrophobic (water contact angle of 135 ± 2°), oleophobic (n-hexadecane contact angle of 117 ± 1°), and bactericidal (bacterial reduction of 100 %) properties and incorporated the enhanced thermo-oxidative stability of the modified cellulose fibres. 相似文献
996.
In Situ Synthesis of Alkenyl Tetrazines for Highly Fluorogenic Bioorthogonal Live‐Cell Imaging Probes
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Haoxing Wu Dr. Jun Yang Dr. Jolita Šečkutė Prof. Neal K. Devaraj 《Angewandte Chemie (International ed. in English)》2014,53(23):5805-5809
In spite of the wide application potential of 1,2,4,5‐tetrazines, particularly in live‐cell and in vivo imaging, a major limitation has been the lack of practical synthetic methods. Here we report the in situ synthesis of (E)‐3‐substituted 6‐alkenyl‐1,2,4,5‐tetrazine derivatives through an elimination–Heck cascade reaction. By using this strategy, we provide 24 examples of π‐conjugated tetrazine derivatives that can be conveniently prepared from tetrazine building blocks and related halides. These include tetrazine analogs of biological small molecules, highly conjugated buta‐1,3‐diene‐substituted tetrazines, and a diverse array of fluorescent probes suitable for live‐cell imaging. These highly conjugated probes show very strong fluorescence turn‐on (up to 400‐fold) when reacted with dienophiles such as cyclopropenes and trans‐cyclooctenes, and we demonstrate their application for live‐cell imaging. This work provides an efficient and practical synthetic methodology for tetrazine derivatives and will facilitate the application of conjugated tetrazines, particularly as fluorogenic probes for live‐cell imaging. 相似文献
997.
Back Cover: Assessment of DNA Binding to Human Rad51 Protein by using Quartz Crystal Microbalance and Atomic Force Microscopy: Effects of ADP and BRC4‐28 Peptide Inhibitor (ChemPhysChem 17/2014)
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
998.
Substitution of chloride in [PtCl(bpma)]+ and [PtCl(gly-met-S,N,N)], where bpma is bis(2-pyridylmethyl)amine and gly-met-S,N,N is glycyl-l-methionine, was studied as a function of the entering nucleophile concentration and temperature. Reactions between the platinum(II) complexes and thiourea (TU), iodides (I?), and nitrites(III) (NO 2 ? ) were carried out in aqueous solutions using conventional UV-VIS spectrophotometry. Suitable ionic conditions were reached by an addition of 0.1 M NaClO4 and 0.01 M NaCl (to suppress hydrolysis). The second-order rate constants, k 2, for the studied reactions with NO 2 ? varied between 0.036–0.038 M?1 s?1, and for the reactions with TU between 0.095–1.06 M?1 s?1, respectively. The reaction between TU and the [PtCl(bpma)]+ ion is ten times faster than that of the [PtCl(gly-met-S,N,N)] complex. An analysis of the activation parameters, ΔH ≠ and ΔS ≠, for the selected reactions clearly shows their associative nature. 相似文献
999.
Katarína Kráľová František Šeršeň Matúš Peško Karel Waisser Lenka Kubicová 《Chemical Papers》2014,68(1):46-52
5-Bromo-(Br-PBA) and 3,5-dibromo-2-hydroxy-N-phenylbenzamides (Br2-PBA) inhibited photosynthetic electron transport (PET) and their inhibitory efficiency depended on the compound lipophilicity as well as on the electronic properties of the R substituent in the N-phenyl moiety. Br-PBA showed higher PET inhibiting activity than Br2-PBA with the same R substituent. The most effective inhibitors in the tested series were the derivatives with R = 3-F (Br-PBA; IC50 = 4.3 μmol dm?3) and R = 3-Cl (Br2-PBA; IC50 = 8.6 μmol dm?3). Bilinear dependence of the PET inhibiting activity on the lipophilicity of the compounds as well as on the Hammett constant, σ, of the R substituent was observed for both investigated series. Using EPR spectroscopy it was found that the site of action of the tested compounds in the photosynthetic apparatus is situated on the donor side of PS 2, in D· or in the Z·/D· intermediates. Interaction of the studied compounds with chlorophyll a and aromatic amino acids present in the pigment-protein complexes mainly in photosystem 2 was documented by fluorescence spectroscopy. 相似文献
1000.
Two perpendicular projections of rising bubbles were observed in counter-current downstream diverging flow. Evidently, the bubbles did not enter the boundary layer at the channel wall and a plug liquid flow assumption was acceptable in our experimental equipment. This confirmed that the experiment was appropriate for simulation of bubble rises in a quiescent liquid column. Recent data obtained by a high-speed camera permitted recording over a period of 60 s. Image analysis by a tailor-made program provided a time-series of quantities related to the position, size, and shape of bubbles. In addition to determination of the aspect ratio of the equivalent oblate ellipsoid, deviation from this shape was investigated in respect of the difference between the bubble’s centre of mass and the geometrical centre of bubble projection. Autocorrelation of the data indicated that the bubble inclination oscillated harmonically with a frequency of 5–10 Hz; cross correlation showed that the horizontal shift of the centre of mass, as well as the horizontal velocity, increased with increasing bubble inclination, and the vertical shift of the centre of mass increased with an increases in the absolute value of the bubble inclination. There is no significant phase shift in the oscillation of these quantities. The bulky bottom side of the bubbles is in accordance with the model of bubble oscillation induced by instability of the equilibrium of gravity and surface tension forces. The oscillation frequency dependence on surface forces (Eötvös number) is evident, while viscosity does not play a significant role in low-viscosity liquids. Therefore, vortex-shedding is more likely to be an effect of the oscillation and not its cause. 相似文献