全文获取类型
收费全文 | 10188篇 |
免费 | 554篇 |
国内免费 | 43篇 |
专业分类
化学 | 7558篇 |
晶体学 | 51篇 |
力学 | 176篇 |
数学 | 1536篇 |
物理学 | 1464篇 |
出版年
2023年 | 79篇 |
2022年 | 109篇 |
2021年 | 154篇 |
2020年 | 235篇 |
2019年 | 200篇 |
2018年 | 149篇 |
2017年 | 124篇 |
2016年 | 416篇 |
2015年 | 381篇 |
2014年 | 405篇 |
2013年 | 491篇 |
2012年 | 679篇 |
2011年 | 718篇 |
2010年 | 516篇 |
2009年 | 418篇 |
2008年 | 662篇 |
2007年 | 590篇 |
2006年 | 552篇 |
2005年 | 567篇 |
2004年 | 476篇 |
2003年 | 345篇 |
2002年 | 324篇 |
2001年 | 165篇 |
2000年 | 148篇 |
1999年 | 154篇 |
1998年 | 121篇 |
1997年 | 168篇 |
1996年 | 119篇 |
1995年 | 112篇 |
1994年 | 110篇 |
1993年 | 105篇 |
1992年 | 94篇 |
1991年 | 70篇 |
1990年 | 47篇 |
1989年 | 80篇 |
1988年 | 60篇 |
1987年 | 39篇 |
1986年 | 37篇 |
1985年 | 51篇 |
1984年 | 53篇 |
1983年 | 27篇 |
1982年 | 52篇 |
1981年 | 32篇 |
1980年 | 28篇 |
1979年 | 31篇 |
1978年 | 28篇 |
1977年 | 28篇 |
1976年 | 19篇 |
1975年 | 31篇 |
1973年 | 24篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
61.
Sc3N@C68 is assigned to isomer Sc3N@C68:6140 on the grounds of relative energies, geometrical data, and its 13C NMR pattern. Sc3N@C68:6140 is an endohedral fullerene where each Sc atom is coordinated to the center of an equatorial pentalene unit. Static and dynamic computer simulations explain the different point groups observed in NMR and X-ray experiments. Computed and experimental 13C NMR pattern are in close agreement except for one low-intensity signal. The competing isomer Sc3N@C68:6275 is found to be 409 kJ/mol less stable and shows a different 13C NMR pattern. 相似文献
62.
Nidetzky Bernd Griessler Richard Weinhausel Andreas Haltrich Dietmar Kulbe Klaus D. 《Applied biochemistry and biotechnology》1997,(1):159-172
Some important process properties of α-l,4-D-ghican phosphorylases isolated from the bacteriumCorynebacterium callunae and potato tubers (Solatium tuberosum) were compared. Apart from minor differences in their stability and specificity (represented by the maximum degree of maltodextrin
conversion) and a 10-fold higher affinity of the plant phosphorylase for maltodextrin (K
M of 1.3 g/L at 300 mM of orthophosphate), the performances of both enzymes in a continuous ultrafiltration membrane reactor
were almost identical. Product synthesis was carried out over a time course of 300–400 h in the presence or absence of auxiliary
pullulanase (increasing the accessibility of the glucan substrate for phosphorolytic attack up to 15–20%). The effect of varied
dilution rate and reaction temperature on the resulting productivities was quantitated, and a maximum operational temperature
of 40°C was identified. 相似文献
63.
Andreas Charalambous 《Analytica chimica acta》2005,547(1):53-58
This work is an investigation into the utility of bismuth-film electrodes (BiFEs) for the determination of indium in the presence of cadmium and lead by square wave anodic stripping voltammetry (SWASV). The purpose of this study was to demonstrate that, after judicious choice of the associated chemical and instrumental conditions, it is possible to achieve satisfactory separation of the relevant stripping peak and, thus, to determine simultaneously trace concentrations of cadmium, lead and indium. It was conclusively demonstrated that a BiFE performed better than the equivalent mercury-film electrode (MFE) in this particular application. 相似文献
64.
65.
Luise Unger 《manuscripta mathematica》1986,57(1):1-31
Let
be the path algebra for some representation-infinite quiver
over some field k. There exists a bound
such that mI is faithful for all indecomposable injective
-modules I and all
, and such that there exists an indecomposable injective
-module J satisfying that
J is not faithful, denotes the Auslander-Reiten-translation. Let m() be the maximum of the
taken over all possible orientations of the underlying graph . In this article we determine the bounds m() for representation-infinite quivers
for which is a tree. 相似文献
66.
67.
Enantiomerically pure iridium complexes with phosphino‐ and (phosphinooxy)‐substituted N‐heterocyclic carbene (NHC) ligands were synthesized. Investigation of their electronic properties showed a similar trans influence of the phosphino (or phosphinooxy) and the NHC units. The complexes were tested in iridium‐catalyzed hydrogenation. While low conversions were observed with unfunctionalized olefins, the catalysts proved to be suitable for hydrogenation of the α,β‐unsaturated ester 20 , allylic alcohol 21 , and imine 22 . The enantioselectivities were, however, moderate. 相似文献
68.
Both, dielectric continuum solvation models as well as surface or group based methods using polarity and lipophilicity parameters have been proven to be useful tools for the analysis of solvation and partition questions. For the first time, COSMO-RS provides an integrated theory, which combines the aspects of continuum solvation and surface interactions, and which ends up with chemical potentials of molecules in almost arbitrary solvents and mixtures. Due to its sound theoretical basis, COSMO-RS does not only provide a new quantitative access to solvation and partition properties in well defined solvents, but it also opens a novel view and gives a better understanding of the general problem of solvation. Finally, this allows for a generalisation of COSMO-RS to sophisticatedphysiological partition problems involving as complex phases as blood, brain, or cell membranes. The use of COSMO-RS for drug discovery and design is demonstrated by applications to blood-brain partition coefficients, and water solubility. 相似文献
69.
Spikmans V Lane SJ Leavens B Manz A Smith NW 《Rapid communications in mass spectrometry : RCM》2002,16(14):1377-1388
A system is presented that demonstrates the principle of on-line and on-chip post-column derivatisation reactions in micro-high-performance liquid chromatography (micro-HPLC) hyphenated to electrospray time-of-flight mass spectrometry (ESI-TOFMS). In this micro-HPLC-chip-MS set-up, the analytes are separated using gradient micro-HPLC and subsequently derivatised on-chip and detected. One of the major limitations of MS detection is its dependency on the degree of ionisation, which is widely variable and compound-specific. Optimising and controlling the degree of ionisation in a simple manner would allow MS detection to be truly generic. One way of achieving this is by pre-ionisation of analytes using simple derivatisation procedures that are both rapid and quantitative. Performing this in situ on the system described here overcomes issues of sample handling and efficiency losses when time-consuming "bench chemistry" is necessary prior to analysis. The power of the system is demonstrated by the separation of primary and secondary amines, which are subsequently derivatised with a positively charged phosphonium complex and detected in an enhanced manner. Typically, molecular cations (M(+)) are detected showing that the ionisation process is dominated by the phosphonium species, leading to more constant ionisation for a variety of compounds. In addition, stable isotopically labelled ((12)C/(13)C)-phosphonium reagent is used for the reactions, allowing for inherent signal/noise (S/N) improvement and automated data processing using cluster analysis. A similar reaction scheme is used for the derivatisation of ketones and aldehydes, also demonstrating dramatic increases in sensitivity, especially with increasing temperature. Minimal loss in chromatographic fidelity in terms of retention times is observed by the introduction of the micromixer chip into the system. Optimal flow rates in micro-HPLC and ESI-MS are compatible with flow rates for the chip as well as a multitude of in-line optical detectors including UV and fluorescence. In addition, the micromixer chip can be positioned pre-column if preferred. The system is robust, easily fully automated and applicable to a wide variety of reactions. The system has a major advantage in its simple robust connection to the "normal scale" outside world. 相似文献
70.
Walter Purcell Andreas Roodt Stephen S. Basson Johann G. Leipoldt 《Transition Metal Chemistry》1990,15(3):239-241
Summary The crystal structure of the tetraethylammonium salt of [ReO(H2O)(CN)4]– has been determined from threedimensional x-ray diffraction data. The light blue crystals are monoclinic, space group P21/m witha=8.760(1),b=9.518(5),c=11.718(1) Å, =102.63(1)o with two molecules per unit cell. The final R value using 2009 observed reflections and anisotropic thermal parameters for all the non-hydrogen atoms was 0.038. The [ReO(H2O)(CN)4]– ion has a distorted octahedral geometry with the rhenium atom displaced by 0.30 Å out of the plane formed by the four carbon atoms of the cyano ligands towards the oxo ligand. Bond distances: Re=O=1.667(8), Re–OH2=2.142(7) and Re–C (average)=2.11(1) Å. 相似文献