全文获取类型
收费全文 | 3533篇 |
免费 | 60篇 |
国内免费 | 13篇 |
专业分类
化学 | 1908篇 |
晶体学 | 24篇 |
力学 | 97篇 |
数学 | 520篇 |
物理学 | 1057篇 |
出版年
2021年 | 27篇 |
2020年 | 25篇 |
2019年 | 29篇 |
2018年 | 22篇 |
2017年 | 32篇 |
2016年 | 43篇 |
2015年 | 62篇 |
2014年 | 61篇 |
2013年 | 182篇 |
2012年 | 136篇 |
2011年 | 165篇 |
2010年 | 96篇 |
2009年 | 61篇 |
2008年 | 196篇 |
2007年 | 168篇 |
2006年 | 153篇 |
2005年 | 163篇 |
2004年 | 107篇 |
2003年 | 117篇 |
2002年 | 101篇 |
2001年 | 93篇 |
2000年 | 85篇 |
1999年 | 30篇 |
1998年 | 39篇 |
1997年 | 38篇 |
1996年 | 66篇 |
1995年 | 71篇 |
1994年 | 61篇 |
1993年 | 57篇 |
1992年 | 49篇 |
1991年 | 55篇 |
1990年 | 50篇 |
1989年 | 27篇 |
1988年 | 38篇 |
1987年 | 22篇 |
1986年 | 34篇 |
1985年 | 49篇 |
1984年 | 39篇 |
1983年 | 35篇 |
1982年 | 42篇 |
1981年 | 53篇 |
1980年 | 43篇 |
1979年 | 56篇 |
1978年 | 44篇 |
1977年 | 65篇 |
1976年 | 56篇 |
1975年 | 48篇 |
1974年 | 40篇 |
1973年 | 55篇 |
1972年 | 22篇 |
排序方式: 共有3606条查询结果,搜索用时 0 毫秒
131.
Anandkumar R. Kannurpatti Karin J. Anderson Jay W. Anseth Christopher N. Bowman 《Journal of Polymer Science.Polymer Physics》1997,35(14):2297-2307
Crosslinked polymer networks are used in a wide variety of applications. To use these materials effectively, a fundamental understanding of their structural evolution and the relationship between material properties and structure is essential. In this article, a novel technique employing “iniferters,” i.e., living radical polymerizations, to photopolymerize these networks is utilized to study the property and structural evolution of these highly desirable materials. Living radical polymerizations are used in this work since this technique avoids the problem of carbon radical trapping encountered while using conventional initiators. Dynamic mechanical measurements are performed on highly crosslinked methacrylate networks to glean information regarding their structural heterogeneity. By performing these measurements on homopolymerized samples at various stages of the reaction and on copolymerized samples of multifunctional methacrylates, the mechanical properties are characterized as a function of double bond conversion and comonomer composition. From such analyses, with respect to both temperature and frequency, quantitative conclusions regarding the structure of the networks are drawn. This effort is aimed at exploiting the living radical polymerizations initiated by p-xylylene bis(N,N-diethyl dithiocarbamate) (XDT), to study the mechanical property evolution and structural heterogeneity of crosslinked polymers which is nearly impossible otherwise. Polymers examined in this study include networks formed by homopolymerization of diethylene glycol dimethacrylate (DEGDMA) and polyethylene glycol 600 dimethacrylate (PEG600DMA) as well as copolymers of DEGDMA and PEG600DMA. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2297–2307, 1997 相似文献
132.
Ighor C. Barreto Anderson S. de Almeida Jos G. Sena Filho 《Molecules (Basel, Switzerland)》2021,26(21)
Sesquiterpenes (SS) are secondary metabolites formed by the bonding of 3 isoprene (C5) units. They play an important role in the defense and signaling of plants to adapt to the environment, face stress, and communicate with the outside world, and their evolutionary history is closely related to their physiological functions. This review considers their presence and extensively summarizes the 156 sesquiterpenes identified in Vitex taxa, emphasizing those with higher concentrations and frequency among species and correlating with the insecticidal activities and defensive responses reported in the literature. In addition, we classify the SS based on their chemical structures and addresses cyclization in biosynthetic origin. Most relevant sesquiterpenes of the Vitex genus are derived from the germacredienyl cation mainly via bicyclogermacrene and germacrene C, giving rise to aromadrendanes, a skeleton with the highest number of representative compounds in this genus, and 6,9-guaiadiene, respectively, indicating the production of 1.10-cyclizing sesquiterpene synthases. These enzymes can play an important role in the chemosystematics of the genus from their corresponding routes and cyclizations, constituting a new approach to chemotaxonomy. In conclusion, this review is a compilation of detailed information on the profile of sesquiterpene in the Vitex genus and, thus, points to new unexplored horizons for future research. 相似文献
133.
Plastic microchannels (4.5 cm long) fabricated from an etched glass master were tested for high-resolution single-stranded DNA analysis. Using replaceable denaturing linear polyacrylamide as sieving matrix, one-color separation of a fragment sizing standard with single-base resolution (R > 0.5) was achieved up to 275 bases. Two-color sizing analysis of four loci short tandem repeat (STR) allelic ladder (CSF1PO, TPOX, TH01, vWA) with single-base resolution (R = 0.62) on TH01 alleles 9.3 (198 bp) and 10 (199 bp) was demonstrated. An average standard deviation of +/- 0.06 bp and +/-0.11 bp in sizing 32 alleles of the CTTv ladder was attained between runs and between channels, respectively. Four-color sequencing separation of a terminator sequencing standard showed a base-calling accuracy of 99.1% out to 320 bases in 13 min. 相似文献
134.
135.
An interlaboratory study was performed on behalf of the Food Standards Agency to evaluate the effectiveness of an affinity column cleanup liquid chromatographic (LC) method for the determination of ochratoxin A in a variety of dried fruit at European regulatory limits. To ensure homogeneity before analysis, laboratory samples are normally slurried with water in the ratio of 5 parts fruit to 4 parts water, and test materials in this form were used in the study. The test portion was extracted with acidified methanol. The extract was filtered, diluted with phosphate-buffered saline, and applied to an affinity column. The column was washed and ochratoxin A was eluted with methanol. Ochratoxin A was quantified by reversed-phase LC. The use of post-column pH shift to enhance the fluorescence of ochratoxin A by the addition of 1.1 M ammonia solution to the column eluant is optional. Determination was by fluorescence. Currants, sultanas, raisins, figs, and mixed fruit (comprising dried pineapple, papaya, sultanas, prunes, dates, and banana chips), both naturally contaminated and blank (very low level), were sent to 24 collaborators in 7 European countries. Participants were asked to spike test portions of all test samples at a level equivalent to 5 ng/g ochratoxin A. Average recoveries ranged from 69 to 74%. Based on results for 5 naturally contaminated test samples (blind duplicates) the relative standard deviation for repeatability (RSDr) ranged from 4.9 to 8.7%, and the relative standard deviation for reproducibility (RSDR) ranged from 14 to 28%. The method showed acceptable within- and between-laboratory precision for all 5 matrixes, as evidenced by HORRAT values <1.3. 相似文献
136.
The following pyrethrin and pyrethroid pesticides were determined in urine and water matrixes by liquid chromatography with diode array detection (LC-DAD): pyrethrin I, pyrethrin II, tetramethrin, baythroid, bifenthrin, fenvalerate, phenothrin, allethrin, resmethrin, cis-permethrin, and trans-permethrin. In addition, 3-phenoxybenzyl alcohol, a metabolite of various pyrethroids, was also successfully determined by the analytical method. The matrix extraction was simple, inexpensive, and fast, using only sodium chloride and acetonitrile. The acetonitrile extract was filtered and analyzed by LC-DAD. The method detection limits for the pyrethrin pesticides in 5 mL urine were determined to range from 0.002 to 0.04 microg/mL, depending on the individual pyrethrin. Recoveries from spiked tap water ranged from 77 to 96%; recoveries from urine ranged from 80 to 117%. This method is especially well-suited to clinical investigations, in which rapid analysis of forensic samples is often required. 相似文献
137.
Reaction of alpha-P(2)W(15)O(56)(12-) and Fe(III) in a saturated NaCl solution produces a trisubstituted Wells-Dawson structure with three low-valent metals, alpha-(Fe(III)Cl)(2)(Fe(III)OH(2))P(2)W(15)O(59)(11-) (1). Dissolution of this species into 1 M NaBr (Br(-) is non-coordinating) gives the triaquated species alpha-(Fe(III)OH(2))(3)P(2)W(15)O(59)(9-) (2). Ionic strength values of 1 M or greater are necessary to avoid decomposition of 1 or 2 to the conventional sandwich-type complex, alpha beta beta alpha-(Fe(III)OH(2))(2)Fe(III)(2)(P(2)W(15)O(56))(2)(12-) (3). If the pH is greater than 5, a new triferric sandwich, alpha alpha beta alpha-(NaOH(2))(Fe(III)OH(2))Fe(III)(2)(P(2)W(15)O(56))(2)(14-) (4), forms rather than 3. Like the previously reported Wells-Dawson-derived sandwich-type structures with three metals in the central unit ([TM(II)Fe(III)(2)(P(2)W(15)O(56))(P(2)TM(II)(2)W(13)O(52))],(16-) TM = Cu, Co), this complex has a central alpha-junction and a central beta-junction. Thermal studies suggest that 4 is more stable than 3 over a wide range of temperatures and pH values. The intrinsic Jahn-Teller distortion of d-electron-containing metal ions incorporated into the external sites of the central multi-metal unit impacts the stoichiometry of their incorporation (with a consequent change in the inter-POM-unit connectivity, where POM = polyoxometalate). Reaction of non-distorting Ni(II) with the diferric lacunary sandwich-type POM alpha alpha alpha alpha-(NaOH(2))(2)Fe(III)(2)(P(2)W(15)O(56))(2)(16-) (5) produces alpha beta beta alpha-(Ni(II)OH(2))(2)Fe(III)(2)(P(2)W(15)O(56))(2)(14-) (6), a Wells-Dawson sandwich-type structure with two Ni(II) and two Fe(III) in the central unit. All structures are characterized by (31)P NMR, IR, UV-vis, magnetic susceptibility, and X-ray crystallography. Complexes 4 and 6 are highly selective and effective catalysts for the H(2)O(2)-based epoxidation of alkenes. 相似文献
138.
Garner P Anderson JT Cox PB Klippenstein SJ Leslie R Scardovi N 《The Journal of organic chemistry》2002,67(17):6195-6209
The development of an effective chiral auxiliary for hydroxyalkyl radicals is delineated. Both the 2-tetrahydropyranyl (THP) and tri-O-benzyl-2-deoxy-alpha-D-glucopyranosyl (GLU) auxiliaries resulted in diastereoselective radical additions to methyl acrylate at -78 degrees C (ds = 6/1 and 11/1, respectively). The developing stereochemistry at the radical center was completely under auxiliary control. Correlation experiments showed that the D-GLU auxiliary led to attack on the radical Si-face. The selectivity of these radical additions dropped-off considerably when the more reactive 2-nitropropene trap was employed. Computational studies suggested that the observed facial selectivity was due primarily to entropic factors in the transition state but that a smaller temperature-dependent enthalpic contribution was also involved. It was hypothesized that incorporation of a quaternary center at C-6 (THP numbering) would restore the facial selectivity with more reactive radical traps by restricting the orientations available to the incoming alkene. In the event, the trans-6-tert-butyltetrahydropyranyl (tBu-THP) auxiliary resulted in very good diastereoselection with 2-nitropropene (ds = 35/1 at -78 degrees C, 15/1 at 0 degrees C, and 8/1 at RT) as did the tri-O-benzyl-6,6-dimethyl-2-alpha-D-deoxyglucopyranosyl (diMe-GLU) auxiliary during additions to ethyl alpha-trifluoroacetoxyacrylate (ds = 10/1 at 0 degrees C). A protocol for recovery of the sugar-derived chiral auxiliaries was also established. This work sets the stage for the development of a novel approach to 1, 3, 5.(2n + 1) polyols based on iterative radical homologation as well as the application of these pyranosidic auxiliaries to other synthetically important reactions. 相似文献
139.
Anderson PE Badlani RN Mayer J Mabrouk PA 《Journal of the American Chemical Society》2002,124(35):10284-10285
This contribution reports the first synthesis of conducting polymers (CPs), specifically, polyaniline (PAn) and polypyrrole (PPy), in supercritical carbon dioxide (scCO2). CPs synthesized electrochemically in scCO2 were characterized with cyclic voltammetry (CV), four-point probe conductivity, scanning electron microscopy (SEM), and UV-vis spectroscopy. Preliminary data indicate that CPs synthesized by this method exhibit novel morphology and high conductivity comparable to that synthesized by traditional methods. 相似文献
140.
Craig M. Anderson Garrett Brown Matthew W. Greenberg David Yu Nellie Bowen Rahma Ahmed Melissa Yost-Bido Alina Wray 《Tetrahedron letters》2019,60(43):151156
Several thiophene-based N^C ligands were synthesized. Strategically, a bromide was incorporated on the 2-position of the thiophene ring. When allowed to react with the platinum tetramethyl dimer, [Pt2Me4(µ-SMe2)2], platinum(IV) platinacycles were formed by oxidative addition of the C(sp2)-X bond. These platinum(IV) compounds were characterized by NMR and HRMS. The platinum (IV) compounds were subsequently subjected to thermolysis. A series of reactions occurred, including selective C-C reduction elimination and selective C-H oxidative addition, giving mixtures of platinum(II) products with varying degrees of regioselectivity. 相似文献