全文获取类型
收费全文 | 942篇 |
免费 | 12篇 |
国内免费 | 2篇 |
专业分类
化学 | 511篇 |
晶体学 | 28篇 |
力学 | 60篇 |
数学 | 94篇 |
物理学 | 263篇 |
出版年
2022年 | 6篇 |
2021年 | 11篇 |
2020年 | 11篇 |
2019年 | 11篇 |
2018年 | 6篇 |
2016年 | 12篇 |
2014年 | 13篇 |
2013年 | 35篇 |
2012年 | 34篇 |
2011年 | 38篇 |
2010年 | 25篇 |
2009年 | 11篇 |
2008年 | 42篇 |
2007年 | 48篇 |
2006年 | 44篇 |
2005年 | 59篇 |
2004年 | 52篇 |
2003年 | 32篇 |
2002年 | 31篇 |
2001年 | 27篇 |
2000年 | 16篇 |
1998年 | 8篇 |
1996年 | 16篇 |
1995年 | 9篇 |
1994年 | 14篇 |
1993年 | 9篇 |
1992年 | 20篇 |
1991年 | 14篇 |
1990年 | 18篇 |
1989年 | 13篇 |
1988年 | 13篇 |
1987年 | 11篇 |
1986年 | 15篇 |
1985年 | 20篇 |
1984年 | 14篇 |
1983年 | 13篇 |
1982年 | 8篇 |
1981年 | 19篇 |
1980年 | 9篇 |
1979年 | 9篇 |
1978年 | 9篇 |
1977年 | 9篇 |
1976年 | 6篇 |
1975年 | 9篇 |
1974年 | 15篇 |
1973年 | 10篇 |
1971年 | 7篇 |
1970年 | 7篇 |
1969年 | 8篇 |
1967年 | 6篇 |
排序方式: 共有956条查询结果,搜索用时 31 毫秒
11.
Abe F Amidei D Apollinari G Atac M Auchincloss P Baden AR Bamberger A Barbaro-Galtieri A Barnes VE Bedeschi F Behrends S Belforte S Bellettini G Bellinger J Bensinger J Beretvas A Berge JP Bertolucci S Bhadra S Binkley M Blair R Blocker C Booth AW Brandenburg G Brown D Buckley E Byon A Byrum KL Campagnari C Campbell M Carey R Carithers W Carlsmith D Carroll JT Cashmore R Cervelli F Chadwick K Chiarelli G Chinowsky W Cihangir S Clark AG Connor D Contreras M Cooper J Cordelli M Crane D Curatolo M 《Physical review letters》1989,63(7):720-723
12.
Five new thiophene imides having the structures C4H3SC(O)N(H)C(O)R (where R=Me, Et, Pr, t-Bu, 1-4) and C4H3SCH2C(O)N(H)C(O)CH35 have been prepared. Control over the orientation of the carbonyl groups was achieved by the introduction of a bulky group in the terminal position of the side chain, and molecular modeling calculations indicated that the energy difference between the ct and tt conformations is small. The acidity of 1-4 decreases from Me to t-Bu, and, although 1-4 will not undergo oxidative polymerization, the introduction of a single spacer CH2 group allows 5 to polymerize. 相似文献
13.
14.
15.
Jianfu Ding Futian Liu Mei Li Michael Day Ming Zhou 《Journal of polymer science. Part A, Polymer chemistry》2002,40(23):4205-4216
The polycondensation of decafluorobenzophenone with hexafluorobisphenol A was modified by the addition of a molecular sieve dehydrating apparatus to the refluxing reaction system. This modification promoted the polymerization and enabled the reactions to be conducted in milder conditions and completed in a shorter time, thereby depressing side reactions such as branching and crosslinking. The resulting fluorinated poly(arylene ether ketone)s (FPAEK) were free of gel particles and possessed the designed molecular weights. This modified procedure was also suitable for introducing crosslinkable pentafluorostyrene (FSt) moieties into the polymers at the chain ends and/or inside the chain with the vinyl group of FSt being pendant. The resulting FSt containing fluorinated poly(arylene ether ketone)s (FPAEK‐FSt) can then be thermally crosslinked at 100 °C in the presence of 1% benzoyl peroxide (BPO) or at 250 °C without any initiator. The glass‐transition temperatures (Tg's) of FPAEK increased with increasing molecular weight and leveled off at about 147 °C for the polymer with a number‐average molecular weight of 18,600 Da, whereas the values were not apparently affected by the addition of FSt units. However, crosslinking of the FPAEK‐FSt resulted in an approximate 30 °C increase of the Tg. Spin‐coating FPAEK‐FSt onto silicon wafers followed by crosslinking gave films with excellent thermal stability, physical strength, and adhesion to the substrate as well as good reproducibility in terms of film preparation and optical properties. The refractive index and birefringence of the films measured at a wavelength of 1.55 μm were 1.502 and 2.5 × 10?3, respectively. © 2002 Government of Canada. Exclusive worldwide publication rights in the article have been transferred to Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4205–4216, 2002 相似文献
16.
Akutsu H Akutsu-Sato A Turner SS Le Pevelen D Day P Laukhin V Klehe AK Singleton J Tocher DA Probert MR Howard JA 《Journal of the American Chemical Society》2002,124(42):12430-12431
Normal state conductivity and superconductivity together with bulk magnetic susceptibility and magnetization measurements have been measured for two molecular charge-transfer salts: beta' '-(ET)4[(H3O)Ga(C2O4)3]G (ET = bis(ethylenedithio)tetrathiafulvalene, G = pyridine for compound I and nitrobenzene for compound II). With the exception of the included guest molecules (G) the crystal structures are almost identical. Both show minima in their electrical transport at 130 K for I and at 160 K for II, but at lower temperatures their behaviors differ markedly. The resistance of I reaches a maximum at 50 K with a further small peak at 2 K and possible superconductivity only below 2 K, whereas that of II increases continuously down to 7.5 K, where an abrupt transition to a superconducting state occurs. 相似文献
17.
The interactions of [Pt(en)Cl(ACRAMTU-S)](NO3)2 (PT-ACRAMTU, en = ethane-1,2-diamine, ACRAMTU = 1-[2-(acridin-9-ylamino)ethyl]-1,3-dimethylthiourea) with adenine in DNA have been studied using a combination of analytical and high-resolution structural methods. For the first time, a cytotoxic platinum(II) complex has been demonstrated to form adducts in the minor groove of DNA through platination of the adenine-N3 endocyclic nitrogen. An acidic depurination assay was developed that allowed the controlled and selective (pH 2, 60 degrees C, 12 h) release of platinum-modified adenine from drug-treated nucleic acid samples. From the digested mixtures, three adducts were isolated by semipreparative reverse phase high-performance liquid chromatography and studied by electrospray ionization mass spectrometry (in-line LC-MS), variable-pH 1H NMR spectroscopy, and, where applicable, X-ray crystallography. The three species were identified as the N7 (A-I), N3 (A-II), and N1 (A-III) linkage isomers of [Pt(en)(ACRAMTU-S)(adenine)]3+ (A). Incubations carried out with the single- and double-stranded model sequences, d(TA)5 and d(TA)15, as well as native DNA indicate that the adduct profiles (A-I:A-II:A-IIIratios) are sensitive to the nature of the nucleic acid template. A-II was found to be a double-strand specific adduct. The crystal structure of this adduct has been determined, providing ultimate evidence for the N3 connectivity of platinum. A-II crystallizes in the triclinic space group P in the form of centrosymmetric dimers, {[Pt(en)(ACRAMTU-S)(adenine-N3)]2}6+. The cations are stabilized by a combination of adenine-adenine base pairing (N6...N1 2.945(5) A) and mutual acridine-adenine base stacking. Tandem mass spectra and 1H chemical shift anomalies indicate that this type of self-association is not merely a crystal packing effect but persists in solution. The monofunctional platination of adenine at its N7, N3, and N1 positions in a significant fraction of adducts breaks a longstanding paradigm in platinum-DNA chemistry, the requirement for nucleophilic attack of guanine-N7 as the principal step in cross-link formation. The biological consequences and potential therapeutic applications of the unique base and groove recognition of PT-ACRAMTU are discussed. 相似文献
18.
The performance of an integrated capillary electrophoresis system with a novel split-flow sample injection mechanism and special high sensitivity UV absorbance detector is described. Sample introduction into the capillary is accomplished with a standard HPLC-type microliter syringe. The injected sample is divided proportionally between the separation capillary and an adjustable splitvent. The volume of sample introduced into the capillary can be manipulated by varying the length or the i.d. of the splitvent tubing; or the volume of sample injected. Data are presented showing reproducibility of retention time, peak height, and peak area; minimum detectability; and operation at short UV wavelengths. 相似文献
19.
Wipf P Coleman CM Janjic JM Iyer PS Fodor MD Shafer YA Stephenson CR Kendall C Day BW 《Journal of combinatorial chemistry》2005,7(2):322-330
Cascade reactions of internal and terminal alkynes, zirconocene hydrochloride, dimethylzinc, and phosphinoyl imines (prepared in one step from aldehydes and diphenylphosphinoyl amide) lead to allylic phosphinoyl amides after aqueous workup. Microwave acceleration allows the completion of this one-pot reaction sequence in 10 min. These allylic amides can be converted into a variety of derivatives, including carbamates and sulfonamides, or reacted prior to workup with diiodomethane to give novel C-cyclopropylalkylamides. A solution-phase "libraries from libraries" approach was used to generate an intermediate 20-member library which was subsequently expanded to a 100-member library by a series of N-functionalizations. The biological activity was evaluated in an assay for competitive binding to the estrogen receptor (ERalpha), revealing three potent lead compounds of a new structural type. 相似文献
20.
Accelerator mass spectrometry (AMS) was used to measure 237Np in environmental water samples extracted from Irish Sea sediments. The samples were of limited volume (approximately 700 ml) and of low activity (0.06-0.79 mBq l-1; 2.30-30.3 pg l-1). AMS proved to have the required sensitivity for measuring these samples, and was in principle capable of measuring much smaller amounts, as low as 0.4 microBq (3.9 x 10(7) atoms). However, the background level in the procedural blanks showed that there was a systematic low level 237Np contamination of each sample, arising from the 239Np yield monitor used in the separations procedure, which effectively increased the detection limit of these analyses. 相似文献