全文获取类型
收费全文 | 1953篇 |
免费 | 80篇 |
国内免费 | 19篇 |
专业分类
化学 | 1423篇 |
晶体学 | 24篇 |
力学 | 16篇 |
数学 | 168篇 |
物理学 | 421篇 |
出版年
2023年 | 13篇 |
2021年 | 18篇 |
2020年 | 32篇 |
2019年 | 41篇 |
2018年 | 18篇 |
2017年 | 20篇 |
2016年 | 53篇 |
2015年 | 36篇 |
2014年 | 41篇 |
2013年 | 104篇 |
2012年 | 95篇 |
2011年 | 123篇 |
2010年 | 64篇 |
2009年 | 76篇 |
2008年 | 129篇 |
2007年 | 112篇 |
2006年 | 124篇 |
2005年 | 117篇 |
2004年 | 86篇 |
2003年 | 99篇 |
2002年 | 77篇 |
2001年 | 35篇 |
2000年 | 44篇 |
1999年 | 23篇 |
1998年 | 28篇 |
1997年 | 17篇 |
1996年 | 16篇 |
1995年 | 16篇 |
1994年 | 14篇 |
1993年 | 12篇 |
1992年 | 16篇 |
1991年 | 18篇 |
1990年 | 17篇 |
1989年 | 12篇 |
1988年 | 18篇 |
1987年 | 17篇 |
1986年 | 10篇 |
1985年 | 22篇 |
1984年 | 25篇 |
1983年 | 17篇 |
1982年 | 22篇 |
1981年 | 28篇 |
1980年 | 17篇 |
1979年 | 17篇 |
1978年 | 14篇 |
1977年 | 14篇 |
1975年 | 11篇 |
1974年 | 11篇 |
1973年 | 14篇 |
1972年 | 15篇 |
排序方式: 共有2052条查询结果,搜索用时 484 毫秒
31.
The negative chemical ionization mass spectra of representative perfluorinated alkanes, cycloalkanes, ethers and tertiary amines have been examined, using Ar at about 0.5 torr as the reagent gas. The compounds chosen are typical of those under study as components of fluorochemical emulsion blood substitutes. Many such PFC's, particularly those with cyclic or branched structures, give intense molecular ions; most give simple spectra with a few major fragment ions at high mass, in marked contrast to the EI spectra which are dominated by m/e 69 (CF3+) and 131 (C3F5+) of no value for structure elucidation. NCI-GC/MS is more sensitive than conventional EI-GC/MS and promises to be more generally useful for structure determination. Specific examples from the various classes will be presented, and their NCI and EI mass spectra compared. 相似文献
32.
Ono K Yoshida A Saito N Fujishima T Honzawa S Suhara Y Kishimoto S Sugiura T Waku K Takayama H Kittaka A 《The Journal of organic chemistry》2003,68(19):7407-7415
Six novel 2-substituted analogues of 1alpha,25-dihydroxy-19-norvitamin D(3), 6a,b-8a,b, were efficiently synthesized utilizing (-)-quinic acid as the A-ring precursor. The C2-modified A-rings were prepared as 4-alkylated (3R,5R)-3,5-dihydroxycyclohexanones 12-15 from (-)-quinic acid based on radical allylation at the C4 position of methyl (-)-quinicate. The new type of the CD-ring coupling partner 23 was synthesized from 25-hydroxy Grundmann's ketone 19 to apply to the modified Julia olefination to construct a diene unit between the A-ring and the CD-ring. The coupling yields, including a deprotection step, were 47-62%. After the separation of the diastereomers based on C2 stereochemistry, the structure (2alpha or 2beta) was determined by (1)H NMR experiments and compared to DeLuca's 2-methyl- and 2-ethyl-1alpha,25-dihydroxy-19-norvitamin D(3). Thus, the synthesized 2alpha-(3-hydroxypropyl)-1alpha,25-dihydroxy-19-norvitamin D(3) (8a) showed almost the same potency in binding to the bovine thymus vitamin D receptor (VDR) as the natural hormone 1, while its beta-isomer 8b had only a 3% affinity. Both 2alpha-allyl- and 2alpha-propyl-1alpha,25-dihydroxy-19-norvitamin D(3) (6a and 7a) and their 2beta-analogues (6b and 7b) possessed a weak affinity for the VDR. The strong VDR ligand 8a was ca. 36-fold more potent in induction of HL-60 cell differentiation than 1, and interestingly, even the weaker ligand 8b showed a 6.7-fold higher potency in the cell differentiation activity than that of 1. 相似文献
33.
Moisture of several ppm in hydrogen chloride gas has been accurately determined by a new method using the Karl Fischer reagent, which hitherto had a limitation in accuracy because of a partial reaction with hydrogen chloride when direct titration was employed.The moisture in the sample gas was collected in a cold trap kept at about ?80 °C while the hydrogen chloride gas passed through and the frozen moisture was dissolved by pyridine-methanol (1:1) solvent. a KF Reagent of factoe: 0.35 mg H2O/ml.Titration by the Karl Fischer reagent having the equivalency factor of, e.g., 0.5 mg H2O/ml was carried out and the concentration of the moisture was calculated from the sample volume used. 相似文献
34.
Solid sampling technique for direct detection of condensed tannins in bark by matrix-assisted laser desorption/ionization mass spectrometry 总被引:2,自引:0,他引:2
Ishida Y Kitagawa K Goto K Ohtani H 《Rapid communications in mass spectrometry : RCM》2005,19(5):706-710
A novel method for the direct analysis of condensed tannin components in bark was developed on the basis of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) combined with a simple solid sampling technique. The MALDI mass spectra obtained from the wood (bark) powder sample clearly showed a series of peaks corresponding to the sodium ion adducts of condensed tannin oligomers up to around m/z 3000. The results indicate that the condensed tannins in the bark sample used in this work mostly consist of combinations of flavan-3-ol units such as profisetinidin (PF), prorobinetinidin (PR) and prodelphinidin (PD), at least up to 10-mers (m/z approximately 3000). 相似文献
35.
The nitro group in tertiary or secondary aliphatic nitro compounds is replaced by hydrogen or deuterium on treatment with tributyltin hydride or tributyltin deuteride, respectively. 相似文献
36.
A cationic CpRu(II) complex in combination with quinaldic acid shows high reactivity and chemoselectivity for the catalytic deprotection of hydroxyl groups protected as allyl ethers. The catalyst operates in alcoholic solvents without the need for any additional nucleophiles, satisfying the practical requirements of operational simplicity, safety, and environmental friendliness. The wide applicability of this deprotection strategy to a variety of multifunctional molecules, including peptides and nucleosides, may provide new opportunities in protective group chemistry. [structure: see text] 相似文献
37.
Yasushi Mizobe Reiko Ono Yasuzo Uchida Masanobu Hidai Meguru Tezuka Suehiro Moue Atsuhiko Tsuchiya 《Journal of organometallic chemistry》1980,204(3):377-385
Diazoalkane complexes of type [MF(NNCRR′)(dpe)2][BF4] (M = Mo or W; dpe = Ph2PCH2CH2PPh2), which are easily derived from bis(dinitrogen) complexes [M(N2)2(dpe)2], undergo consecutive one- and two-electron oxidations and reductions under voltammetric conditions at a platinum electrode. The ESR spectra of the species generated by the controlled potential electrolysis show that primary oxidation occurred on the metal atom (M = Mo) and reduction on the two nitrogen atoms in the diazoalkane ligands (M = Mo or W). 相似文献
38.
Masahiro Manabe Asako Tokunaga Hideo Kawamura Hajime Katsuura Masaki Shiomi Koichi Hiramatsu 《Colloid and polymer science》2002,280(10):929-935
In the micellar solution of SDS, the partition coefficient (Kx) of following branched alkanols at infinite dilution was determined by applying a differential conductivity method: the alkanols used were i-CmH2m+1OH (m=4-9, i=1-5) in which the position of OH group (i) shifts from an end to the center of a hydrocarbon chain. The method provides two significant quantities, d!/dXam and dCsf/dCaf in addition to Kx. The following results have been obtained. (1) The dependence of Kx on i indicates that the hydrophobicity of alkanol is weakened with increasing i, whereas the increase in m strengthens the hydrophobicity. (2) The degree of counterion disossiation of micelles (!) is accelerated by the solubilized alkanols in micelles (mole fraction: Xam) and the acceleration rate, d!/dXam (=0.17), depends on neither m nor i. (3) In the bulk water, the monomerically dissolved alkanols (concentration: Caf) depresses the concentration of free monomer surfactant (Csf), and the depressing rate, dCsf/dCaf, in micellar solution is identical with the corresponding quantity, ((CMC/(Ca)o at CMC. 相似文献
39.
When heated with sodium ethoxide in ethanol 7-methylidenebicyclo[3.3.1]nonan-3-endo-ol (endo- 1 ) is converted into 1-methyl-2-oxa-adamantane ( 3 ). This reaction involves nucleophilic addition of a hydroxy group to an unactivated olefinic bond. Formation of the cyclic ether 3 also takes place when endo- 1 is heated in aqueous ethanol. This electrophilic addition is strongly catalysed by weak acids and suppressed by weak bases. These unusual reactions proceed more slowly with 7-methylbicyclo[3.3.1]non-6-en-3-endo-ol (endo- 2 ) and can be ascribed to a proximity effect. This follows from the IR . and NMR . spectra of endo- 1 and endo- 2 which show strong intramolecular hydrogen (OH-π) bonding. The unsaturated endo- and exo-alcohols 1 and 2 , respectively, undergo only exo-complexation with silver ion. 相似文献
40.
Dipping versus spraying: exploring the deposition conditions for speeding up layer-by-layer assembly
Izquierdo A Ono SS Voegel JC Schaaf P Decher G 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7558-7567
Polyelectrolyte film fabrication by successive spraying of polycation and polyanion solutions is described and compared to classic dipping. The poly(styrenesulfonate)/poly(allylamine) system is examined in detail. The influence of various parameters such as spraying time, polyelectrolyte concentration, and effect of film drying during multilayer construction is investigated. It is found that film deposition by spraying is easily controlled and very reliable. The thickness of the multilayers grows linearly with the number of deposition cycles similarly to what is observed when dipping substrates or when polyelectrolyte solutions flow over a surface. The assembly of films is very fast and leads to films with small surface roughness as estimated by atomic force microscopy and X-ray reflectometry. Spray deposition allows achieving regular multilayer growth even under conditions for which dipping fails to produce homogeneous films (e.g., extremely short contact times). Moreover, because drainage constantly removes a certain quantity of the excess material arriving at the surface, one can even skip the rinsing step and, thus, speed up even further the whole buildup process. 相似文献