全文获取类型
收费全文 | 3956篇 |
免费 | 87篇 |
国内免费 | 32篇 |
专业分类
化学 | 2587篇 |
晶体学 | 31篇 |
力学 | 115篇 |
数学 | 662篇 |
物理学 | 680篇 |
出版年
2022年 | 26篇 |
2021年 | 37篇 |
2020年 | 43篇 |
2019年 | 37篇 |
2018年 | 30篇 |
2017年 | 25篇 |
2016年 | 56篇 |
2015年 | 62篇 |
2014年 | 63篇 |
2013年 | 190篇 |
2012年 | 179篇 |
2011年 | 192篇 |
2010年 | 112篇 |
2009年 | 96篇 |
2008年 | 201篇 |
2007年 | 181篇 |
2006年 | 218篇 |
2005年 | 191篇 |
2004年 | 155篇 |
2003年 | 126篇 |
2002年 | 148篇 |
2001年 | 60篇 |
2000年 | 41篇 |
1999年 | 57篇 |
1998年 | 63篇 |
1997年 | 55篇 |
1996年 | 48篇 |
1995年 | 42篇 |
1994年 | 51篇 |
1993年 | 56篇 |
1992年 | 40篇 |
1991年 | 45篇 |
1990年 | 46篇 |
1989年 | 39篇 |
1988年 | 38篇 |
1987年 | 32篇 |
1986年 | 34篇 |
1985年 | 56篇 |
1984年 | 69篇 |
1983年 | 58篇 |
1982年 | 60篇 |
1981年 | 72篇 |
1980年 | 47篇 |
1979年 | 37篇 |
1978年 | 58篇 |
1977年 | 52篇 |
1976年 | 62篇 |
1975年 | 50篇 |
1974年 | 52篇 |
1973年 | 39篇 |
排序方式: 共有4075条查询结果,搜索用时 10 毫秒
91.
Douglas O. Spry Anita R. Bhala Wayne A. Spitzer Noel D. Jones John K. Swartzendruber 《Tetrahedron letters》1984,25(24):2531-2534
The major product from the thermolysis and photolysis of C(3)-azido cephem 2 is the ring expanded 1,4,6-thiadiazepine azetidinone. 相似文献
92.
Subhash Deshmukh Wayne P. Hess 《Journal of photochemistry and photobiology. A, Chemistry》1994,80(1-3):17-21
Jet-cooled phosphorus trichloride, carbon tetrachloride, chloroform and molecular chlorine are photodissociated in the UV wavelength range 235–238 nm. Chlorine atom photofragments Cl (2P3/2) and Cl* (2P1/2) are detected via resonance-enhanced (2+1) ionization throughout the 232–238 nm wavelength region. The relative Cl* yields, φ*=[Cl*]/([Cl]+[Cl*]), are measured for both 35Cl and 37Cl isotopes using the two-photon atomic transitions at 235.3 nm for Cl and 237.8 nm for Cl*. Preliminary results indicate that the Cl* yields are different for the two isotopes for some of the precursors. In addition, we obtained the two-photon oscillator strength of the Cl transition at 237.7 nm relative to the Cl* transition at 237.8 nm. The advantage of using the two-photon Cl transition at 237.7 nm for quantum yield measurements is discussed. 相似文献
93.
Nguyen Huyen Rao A. Madhusudhan Phillips J. B. John Vijay T. Reed Wayne F. 《Applied biochemistry and biotechnology》1991,(1):843-853
We describe a technique to modify protein solubility and optimize enzyme activity in reversed micellar solutions. The technique
is based on the ability of hydrates of natural gas to form in the micro-aqueous phase. Clathrate hydrates are crystalline
inclusions of water and gas, and their formation in bulk water has traditionally been studied with relevance to natural gas
recovery. We have found that hydrates can form in the environment of the microaqueous pools of reversed micelles, and that
their extent of formation can be well controlled through the thermodynamic variables of temperature and pressure. Additionally,
formation of hydrates affects the size and aggregation number of the micelles, and thus influences the solubility and conformation
of encapsulated proteins. We demonstrate how the concept can be used in two applications: (i) protein extraction into reversed
micelles and subsequent recovery, and (ii) optimization of enzyme activity in reversed micelles. 相似文献
94.
MNDO and AMI calculations, including configuration interactions, were performed on cycloheptatriene (2), 1,6-methano[10]annulene (3), and the tautomeric elassovalenes (4), (5), and (6). The goal of this study is to examine these systems and assess indicators of the importance of through space (homoaromatic) interactions. It is established that the two-center energy partitioning terms are capable of detecting favorable (negative two-center term) through space interactions. In cases of cyclic conjugation (homoconjugation), it is also shown that the inclusion of CI is necessary. 相似文献
95.
This paper reports the results of the interlaboratory peer validation study of AOAC Peer-Verified Method (PVM) 1:2,000 for the determination of niacin in infant formula by solid-phase extraction/liquid chromatography. We have used a Data Quality Objectives (DQO) approach to address not only method variability and robustness but also accuracy of data through the use of an appropriate reference material in conjunction with the interlaboratory validation study. Our DQO included the following: (1) statistical agreement of analytical results and quantitative recovery between 2 collaborating laboratories; (2) the repeatability relative standard deviation (RSDr) values and the HORRAT (Horwitz ratio) obtained (1.07), which satisfied the criteria of the Horwitz "limits of acceptability" at the analyte level present; (3) validation of lack of interference; and (4) accuracy agreement within assigned values for a certified reference material. National Institute of Standards and Technology Standard Reference Material (NIST SRM) 1846 Infant Formula, with a certified value of 63.3 +/- 7.6 microg/g for niacin content, was used as a test material for collaborative study and accuracy assessment. Niacin values obtained by the originating laboratory were 59.7 +/- 4.0 microg/g (95% confidence interval [CI] = 1.4 microg/g with a relative standard deviation [RSD] of 6.7%) and by the peer laboratory were 56.6 +/- 6.6 microg/g (95% CI = 4.1 microg/g, with an RSD of 11.7%). Statistical evaluation using the means equivalence test showed that nicotinic acid values obtained by the peer laboratory were equivalent to those values obtained by the originating laboratory. Linear calibration curves and quantitative recovery were obtained. Integration of the PVM process with a readily available certified reference material gives the user confidence in the accuracy of the data generated by the method through traceability to the reference material used. 相似文献
96.
In an effort to build effective photovoltaic cells based on porphyrin-functionalised polythiophenes we have focused on synthetic routes to three monomer types. By controlling the geometric structure of the monomer, oxidation of these materials should produce polymers with different architectural structures, and as a result, different opto-electronic properties. Employing Wittig protocols allowed access to monomers in which the porphyrin moiety is connected to the beta-position of the thiophene via an alkene linkage. In addition, monomers were constructed using porphyrin condensation methods to afford alpha-thiophene meso-substituted porphryins. Another set of monomers was also prepared via porphyrin condensation routes, but instead utilising beta-formylthiophenes. By utilising different formyloligothiophenes we were able to generate a series of monomers that can be used to control the loading of the porphyrin in the polythiophene matrix. 相似文献
97.
Detection of phosphoproteins on electroblot membranes using a small-molecule organic fluorophore 总被引:1,自引:0,他引:1
A new formulation of the small-molecule organic fluorophore, Pro-Q Diamond dye, has been developed that permits rapid and simple detection of phosphoproteins directly on polyvinylidene difluoride (PVDF) or nitrocellulose membranes (electroblots). Protein samples are first separated by electrophoresis and then electroblotted to membranes, stained and destained, in an analogous manner as typically performed with Amido Black or Ponceau S dye staining of total protein profiles. After staining, blots are imaged using any of a variety of laser-based gel scanners, xenon-arc lamp-based gel scanners or charge-coupled device (CCD) camera-based imaging devices equipped with UV trans- or epi-illumination. The uncomplicated and reliable staining protocol delivers results in as little as 1 h and the limit of detection for the stain is typically 2-4 ng of phosphoprotein with a linear dynamic range of approximately 15-fold. Compared with traditional radiolabeling and antibody-based approaches, the new method offers significant advantages, including avoidance of radioactivity, no need for expensive antibodies, no requirement for blocking unoccupied sites on the membrane with protein or detergent solutions, no sequence context-specific binding to phosphorylated amino acid residues and the ability to analyze the native, steady-state phosphorylation of proteins obtained directly from tissue specimens or body fluids. Pro-Q Diamond dye binds directly and exclusively to the phosphate moiety, allowing it to detect the broadest spectrum of phosphorylated proteins possible. The stain binds noncovalently to phosphoproteins and is thus fully compatible with matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS) or Edman sequencing. The blot stain is also compatible with standard colorimetric, fluorogenic, and chemiluminescent detection techniques employed in immunoblotting. 相似文献
98.
Donald R. McLaughlin Charles F. Bender Henry F. Schaefer III 《Theoretical chemistry accounts》1972,25(4):352-359
Ab initio calculations including electron correlation are reported for the water and methylene molecules as a function of geometry. A large contracted gaussian basis set is used and the multiconfiguration wave functions, optimized by the iterative natural orbital procedure, include 277 and 617 configurations for H2O and CH2 respectively. The method of selecting configurations, yielding first-order wave functions, is discussed in some detail. For H2O, the SCF geometry is r=0,942 Å, =105,8°, the correlated result is r=0,968 Å, =103,2°, and the experimental r=0,957 Å, =104,5°. The water stretching force constants, in millidynes/Å, are 8,72 (SCF), 8,75 (CI), and 8,4 (experiment). Bending force constants are 0,88 (SCF), 0,83 (CI), and 0,76 (experiment). For methylene the SCF geometry is r=1,072 Å, =129,5°, while the result from first-order wave functions is r=1,088 Å, =134°. The predicted CH2 force constants are 6,16 (SCF) and 6,13 (CI) for stretching and 0,44 (SCF) and 0,33 (CI) for bending.
Work performed under the auspices of the U.S. Atomic Energy Commision.
Supported by the grants from the Research Corporation and the University of California Committee on Research. 相似文献
Zusammenfassung Es wird über ab intito-Rechnungen mit Berücksichtigung der Elektronenkorrelation berichtet, die an Wasser- und Methylenmolekülen als Funktion der Geometrie durchgeführt worden sind. Dazu benutzt man einen großen kontrahierten Gauß-Basissatz. Die Multikonfigurationswellenfunktionen, die unter Benutzung von natürlichen Orbitalen nach der iterativen Prozedur optimiert werden, enthalten für H2O 277 Konfigurationen und für CH2 617. Die Auswahlmethode, die zu Wellenfunktionen 1. Ordnung führt, wird diskutiert. Im Falle des Wassers erhält man die SCF-Geometrie zu r=0,942 Å, =105,8°, das korrelierte Resultat ist: r=0,968 Å, =103,2° und das experimentelle r=0,957 Å, =104,5°. Für Wasser ergeben sich die Valenzkraftkonstanten (in Millidyn Å–1) 8,72 (SCF), 8,75 (CI) und 8,4 (Experiment). Die Deformationskonstanten sind 0,88 (SCF), 0,83 (CI) und 0,76 (Experiment). Im Falle des Methylens ist die SCF-Geometrie r=1,072 Å, =129,5°, während man mit Wellenfunktionen 1. Ordnung r=1,088 Å und =134° erhält. Die CH2-Kraftkonstanten werden für die Valenzschwingung zu 6,16 (SCF) und 6,13 (CI) bzw. für die Deformationsschwingung zu 0,44 (SCF) und 0,33 (CI) vorausgesagt.
Work performed under the auspices of the U.S. Atomic Energy Commision.
Supported by the grants from the Research Corporation and the University of California Committee on Research. 相似文献
99.
Digrazia Philip M. Blackburn James W. Bienkowski Paul R. Hilton Barry Reed Gregory D. King J. M. Henry Sayler Gary S. 《Applied biochemistry and biotechnology》1990,(1):237-252
An experimental and mathematical method is developed for the microbial systems analysis of polyaromatic hydrocarbon (PAH)-degrading
mixed cultures in PAH-contaminated “town gas” soil systems. Frequency response is the primary experimental and data analysis
tool used to probe the structure of these complicated systems. The objective is to provide a fundamental protocol for evaluating
the performance of specific mixed microbial cultures on specific soil systems by elucidating the salient system variables
and their interactions. Two well-described reactor systems, a constant volume stirred tank reactor (CSTR) and a plug flow
differential volume reactor, are used in order to remove performance effects that are related to reactor type as opposed to
system structure. These two reactor systems are well-defined systems that can be described mathematically and represent the
two extremes of one potentially important system variable, macroscopic mass transfer. The experimental and mathematical structure
of the protocol is described, experimental data is presented, and data analysis is demonstrated for the stripping, sorption,
and biodegradation of napththalene. 相似文献
100.
Rzepa HS 《Organic letters》2005,7(21):4637-4639
[structure: see text] B3LYP and KMLYP/6-31G(d) calculations predict a double-helical and chiral conformation of [14]annulene with the topological properties of a double-twist M?bius band as highly aromatic; its energy with respect to the known Hückel-aromatic conformation is predicted to be stabilized by suitable ring substitution. 相似文献