全文获取类型
收费全文 | 1052篇 |
免费 | 13篇 |
国内免费 | 11篇 |
专业分类
化学 | 675篇 |
晶体学 | 3篇 |
力学 | 29篇 |
数学 | 190篇 |
物理学 | 179篇 |
出版年
2022年 | 4篇 |
2021年 | 6篇 |
2019年 | 5篇 |
2017年 | 4篇 |
2016年 | 8篇 |
2015年 | 12篇 |
2014年 | 16篇 |
2013年 | 55篇 |
2012年 | 42篇 |
2011年 | 45篇 |
2010年 | 29篇 |
2009年 | 30篇 |
2008年 | 40篇 |
2007年 | 39篇 |
2006年 | 49篇 |
2005年 | 56篇 |
2004年 | 46篇 |
2003年 | 32篇 |
2002年 | 45篇 |
2001年 | 24篇 |
2000年 | 10篇 |
1999年 | 21篇 |
1998年 | 21篇 |
1997年 | 21篇 |
1996年 | 20篇 |
1995年 | 14篇 |
1994年 | 21篇 |
1993年 | 21篇 |
1992年 | 11篇 |
1991年 | 12篇 |
1990年 | 17篇 |
1988年 | 9篇 |
1987年 | 11篇 |
1986年 | 13篇 |
1985年 | 16篇 |
1984年 | 22篇 |
1983年 | 24篇 |
1982年 | 12篇 |
1981年 | 20篇 |
1980年 | 16篇 |
1979年 | 11篇 |
1978年 | 21篇 |
1977年 | 22篇 |
1976年 | 14篇 |
1975年 | 16篇 |
1974年 | 18篇 |
1973年 | 8篇 |
1972年 | 9篇 |
1968年 | 7篇 |
1966年 | 3篇 |
排序方式: 共有1076条查询结果,搜索用时 15 毫秒
51.
Selenomethionine contents of NIST wheat reference materials 总被引:1,自引:0,他引:1
Values of the total selenium and selenomethionine (Semet) content of four wheat-based reference materials have been obtained by gas chromatography-stable isotope dilution mass spectrometry methods. The total Se method is an established one, and the results obtained with it are consistent with previously-assigned values. The Semet method (previously reported by our laboratory) is based on reaction with CNBr. Our data indicate that the four wheat samples (wheat gluten, durum wheat, hard red spring wheat, and soft winter wheat), though having a 30-fold range in total Se content, all have about 45% of their total Se values in the form of selenomethionine. Investigation of the CNBr-based method suggests that additional experiments are needed to verify that all selenomethionine in the wheat samples is accounted for, but also indicates that the values obtained are within 15% of the true values. As the form in which Se occurs in foods and dietary supplements is important from a nutritional perspective, adding information about Se speciation to total Se values in appropriate reference materials makes these materials more valuable in relevant analytical work. 相似文献
52.
53.
We demonstrate the application of a modified form of the configurational-bias algorithm for the simulation of chain molecules on the second-nearest-neighbor-diamond lattice. Using polyethylene and poly(ethylene-oxide) as model systems we show that the present configurational-bias algorithm can increase the speed of the equilibration by at least a factor of 2-3 or more as compared to the previous method of using a combination of single-bead and pivot moves along with the Metropolis sampling scheme [N. Metropolis, A. W. Rosenbluth, M. N. Rosenbluth, A. H. Teller, and E. Teller, J. Chem. Phys. 21, 1087 (1953)]. The increase in the speed of the equilibration is found to be dependent on the interactions (i.e., the polymer being simulated) and the molecular weight of the chains. In addition, other factors not considered, such as the density, would also have a significant effect. The algorithm is an extension of the conventional configurational-bias method adapted to the regrowth of interior segments of chain molecules. Appropriate biasing probabilities for the trial moves as outlined by Jain and de Pablo for the configurational-bias scheme of chain ends, suitably modified for the interior segments, are utilized [T. S. Jain and J. J. de Pablo, in Simulation Methods for Polymers, edited by M. Kotelyanskii and D. N. Theodorou (Marcel Dekker, New York, 2004), pp. 223-255]. The biasing scheme satisfies the condition of detailed balance and produces efficient sampling with the correct equilibrium probability distribution of states. The method of interior regrowth overcomes the limitations of the original configurational-bias scheme and allows for the simulation of polymers of higher molecular weight linear chains and ring polymers which lack chain ends. 相似文献
54.
Fabrication and thermal analysis of submicron silver tubes prepared from electrospun fiber templates
Submicron silver tubes have been synthesized by a polymer-based template approach. Two different approaches to metallization, electroless deposition and exchange plating, were evaluated within the template approach. Silver films with average thickness approximately 50-100 nm were deposited on polycarbonate fibers approximately 400 nm in diameter by each technique, resulting in tubes with a diameter between 450 and 500 nm after thermal degradation of core fibers. These nanomaterials were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and scanning thermal microscopy. The thermal conductivity of the silver submicron tubes was found to differ depending on the method of preparation, with tubes from electroless plating possessing relative thermal conductivity values that were 1 order of magnitude higher than that from exchange plating, 3000 W/m x K and 660 W/m x K, respectively. Interestingly, these results indicate that silver submicron tubes possess higher thermal conductivity than the bulk metal. This observation is discussed in the context of the continuous conduction path of the tubes and their high surface area-to-volume ratio. 相似文献
55.
Dwyer JT Holden J Andrews K Roseland J Zhao C Schweitzer A Perry CR Harnly J Wolf WR Picciano MF Fisher KD Saldanha LG Yetley EA Betz JM Coates PM Milner JA Whitted J Burt V Radimer K Wilger J Sharpless KE Hardy CJ 《Analytical and bioanalytical chemistry》2007,389(1):37-46
This article illustrates the importance of having analytical data on the vitamin and mineral contents of dietary supplements
in nutrition studies, and describes efforts to develop an analytically validated dietary supplement ingredient database (DSID)
by a consortium of federal agencies in the USA. Preliminary studies of multivitamin mineral supplements marketed in the USA
that were analyzed as candidates for the DSID are summarized. Challenges are summarized, possible future directions are outlined,
and some related programs at the Office of Dietary Supplements, National Institutes of Health are described. The DSID should
be helpful to researchers in assessing relationships between intakes of vitamins and minerals and health outcomes. 相似文献
56.
Updated estimates of the selenomethionine content of four NIST wheat reference materials have been obtained by use of a revised
gas chromatography–stable-isotope dilution mass spectrometric method. The revised method makes use of digestion with methanesulfonic
acid, which enables more complete recovery of endogenous selenomethionine than was previously achieved by overnight denaturing
treatment in 0.1 mol L−1 HCl. The NIST wheat reference materials each contain approximately 55% of their total Se content as selenomethionine. Information
about forms of Se in reference materials adds value to these materials in Se speciation studies. Estimates of selenomethionine
content are also provided for other wheat samples, including several grown under conditions of exposure to high Se levels.
These samples also contain approximately 55% of their total Se content as selenomethionine. The consistent level of 55% of
total selenium occurring in the form of selenomethionine when the total selenium content varies by a factor of 500 is suggestive
of an active mechanism of incorporation of selenium into wheat grain.
Figure Selenomethionine content of wheat samples 相似文献
57.
Stir bar sorptive extraction based on restricted access material for the direct extraction of caffeine and metabolites in biological fluids 总被引:2,自引:0,他引:2
A biocompatible stir bar sorptive extraction (SBSE) device was prepared using an alkyl-diol-silica (ADS) restricted access material (RAM) as the SBSE coating. The RAM-SBSE bar was able to simultaneously fractionate the protein component from a biological sample, while directly extracting caffeine and its metabolites, overcoming the present disadvantages of direct sampling in biological matrices by SBSE, such as fouling of the extraction coating by proteins. Desorption of the analytes was performed by stirring the bar in a water/ACN mixture (3/1, v/v) and subsequently reconcentrating the sample solution in water to enable HPLC-UV analysis to be performed. The limit of detection, based on a signal to noise ratio of 3, for caffeine was 25 ng/mL in plasma. The method was confirmed to be linear over the range of 0.5-100 microg/mL of caffeine with an average linear coefficient (R2) value of 0.9981. The injection repeatability and intra-assay precision of the method were evaluated over ten injections, resulting in a %RSD of approximately 8%. The RAM-SBSE device was robust (>50 extraction in plasma without significant signal loss) and simple to use, providing many direct extractions and subsequent determination of caffeine and its metabolites in biological fluids. In contrast to existing sample preparation methods for the analysis of caffeine and selected metabolites in biological fluids, this feasibility study using a biocompatible SBSE approach was advantageous in terms of simplifying the sample preparation procedures. 相似文献
58.
Harding WW Tidgewell K Schmidt M Shah K Dersch CM Snyder J Parrish D Deschamps JR Rothman RB Prisinzano TE 《Organic letters》2005,7(14):3017-3020
[reaction: see text] Two new neoclerodane diterpenes, salvinicins A (4) and B (5), were isolated from the dried leaves of Salvia divinorum. The structures of these compounds were elucidated by spectroscopic techniques, including (1)H and (13)C NMR, NOESY, HMQC, and HMBC. The absolute stereochemistry of these compounds was assigned on the basis of single-crystal X-ray crystallographic analysis of salvinicin A (4) and a 3,4-dichlorobenzoate derivative of salvinorin B. 相似文献
59.
Total synthesis of polycavernoside A, a lethal toxin of the red alga Polycavernosa tsudai 总被引:1,自引:0,他引:1
Blakemore PR Browder CC Hong J Lincoln CM Nagornyy PA Robarge LA Wardrop DJ White JD 《The Journal of organic chemistry》2005,70(14):5449-5460
[structure: see text] Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)-3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-zeta-hydroxy-alpha,beta-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%. 相似文献
60.
Roucoules V Fail CA Schofield WC Teare DO Badyal JP 《Langmuir : the ACS journal of surfaces and colloids》2005,21(4):1412-1415
A substrate-independent method has been devised for ring formation at solid surfaces. This entails the aminolysis reaction of allylamine with maleic anhydride pulsed plasma polymer films to yield terminal alkene groups at the surface. Subsequent exposure to 1,3-cyclohexadiene leads to a Diels-Alder type (4 + 2) cycloaddition reaction to give a mixture of endo- and exo-bicyclo[2.2.2]oct-2-ene rings. 相似文献