全文获取类型
收费全文 | 2623篇 |
免费 | 47篇 |
国内免费 | 16篇 |
专业分类
化学 | 1537篇 |
晶体学 | 16篇 |
力学 | 50篇 |
数学 | 492篇 |
物理学 | 591篇 |
出版年
2021年 | 28篇 |
2020年 | 35篇 |
2019年 | 19篇 |
2018年 | 22篇 |
2017年 | 19篇 |
2016年 | 45篇 |
2015年 | 40篇 |
2014年 | 46篇 |
2013年 | 114篇 |
2012年 | 100篇 |
2011年 | 102篇 |
2010年 | 69篇 |
2009年 | 52篇 |
2008年 | 106篇 |
2007年 | 111篇 |
2006年 | 111篇 |
2005年 | 110篇 |
2004年 | 107篇 |
2003年 | 78篇 |
2002年 | 64篇 |
2001年 | 40篇 |
2000年 | 29篇 |
1999年 | 18篇 |
1998年 | 21篇 |
1997年 | 22篇 |
1996年 | 46篇 |
1995年 | 39篇 |
1994年 | 35篇 |
1993年 | 39篇 |
1992年 | 42篇 |
1991年 | 25篇 |
1990年 | 20篇 |
1989年 | 20篇 |
1988年 | 22篇 |
1987年 | 19篇 |
1986年 | 24篇 |
1985年 | 31篇 |
1984年 | 38篇 |
1983年 | 19篇 |
1982年 | 42篇 |
1981年 | 30篇 |
1980年 | 43篇 |
1979年 | 41篇 |
1978年 | 38篇 |
1977年 | 42篇 |
1976年 | 47篇 |
1975年 | 46篇 |
1974年 | 40篇 |
1973年 | 27篇 |
1971年 | 21篇 |
排序方式: 共有2686条查询结果,搜索用时 15 毫秒
31.
Simple two-parameter Hückel and Pitzer equations were used for the calculation of the activity coefficients of aqueous hydrochloric acid at 25°C up to a molality of 2.0 mol-kg–1. The data obtained by Harned and Ehlers(12,13) from galvanic cells without liquid junction were used in the analysis and the parameters obtained were compared to those obtained from all reliable data presented in the literature for HCl at this temperature. A good agreement between the parameters was always observed. The activity coefficients obtained by the new equations were compared to those suggested by Robinson and Stokes,(8) Hamer and Wu,(1) and Pitzer and Mayorga,(9) and good agreement was also found. The data from the most important literature data sets for HCl were also predicted using the new activity coefficient equations, and the magnitude of the resulting errors was close to the precision of the measurements, the errors forming an almost random pattern for all data sets. 相似文献
32.
S. Patzer N.L. Arthur P. Potzinger H.Gg. Wagner 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):2543-227
The photolysis of Me6Si2 at 206 nm results in two main decomposition processes: simple Si---Si bond breaking with a quantum yield of Φ = 0.21 ± 0.03, and Me3SiH elimination with the concomitant formation of Me2SiCH2 with Φ = 0.18 ± 0.01. There is also a minor decomposition channel with a very small quantum yield, Φ = (5.6 ± 0.2) × 10−3, which results in the formation of Me4Si and Me2Si. The main fate of the excited Me6Si2 molecule produced during photolysis is stabilization by collisional deactivation. The end products observed indicate that the reaction pathways followed by the main intermediates, Me3Si and Me2SiCH2, are the same as those found in the photolysis of Me4Si (Ahmed et al., J. Photochem. Photobiol. A: Chem. 86 (1995) 33). 相似文献
33.
Bergen HR Abraham RS Johnson KL Bradwell AR Naylor S 《Biomedical chromatography : BMC》2004,18(3):191-201
Primary systemic amyloidosis (AL) is characterized by the overproduction of immunoglobulin light chain proteins by a monoclonal, terminally differentiated B-lymphocyte or plasma cell clone. The free immunoglobulin light chains are deposited in an abnormal conformation as amyloid in a variety of organs in the body. The mechanism of amyloid formation is not well understood, but appears to be associated with some form of cleavage of the immunoglobulin light chain with subsequent aggregate formation. In an attempt to characterize the structure of amyloid-forming light chain proteins we developed an on-line immunoaffinity purification and subsequent characterization of free kappa and free lambda immunoglobulin light chains by electrospray ionization mass spectrometry. The methodology is totally automated and requires 20 micro L of serum. Mass spectral analysis of Bence Jones proteins under non-denaturing conditions was also utilized to examine the tertiary and quaternary structure of light chain proteins and clearly shows covalent dimer formation of lambda type light chain. This type of on-line assay may prove helpful in elucidating distinguishing features capable of discriminating AL from benign monoclonal gammopathies of undetermined significance as well as diagnosing AL. 相似文献
34.
Decroos K Vincken JP Heng L Bakker R Gruppen H Verstraete W 《Journal of chromatography. A》2005,1072(2):185-193
A novel method utilizing high-performance liquid chromatography (HPLC) with evaporative light scattering detection (ELSD) and electrospray ionisation mass spectrometry (ESI-MS) was developed for the analysis of soyasaponins, a divers group of triterpenic compounds with one or two sugar side chains, occurring in soy. Group A soyasaponins in different degrees of acetylation, as well as group B soyasaponins in both their 2,3-dihydro-2,5-dihydroxy-6-methyl-4H-pyran-4-one (DDMP)-conjugated and non-conjugated forms could be separated and quantified using authentic soyasaponin standards, in one single run. The method was tested by the determination of the soyasaponin content and composition of eight soygerm samples of different origin. Differences in the composition and the degree of acetylation of the group A soyasaponins were observed among these samples. The group B soyasaponins showed much less variability and they were mainly present in their DDMP-conjugated form. 相似文献
35.
Arthur A. Santilli Dong Han Kim Stephen V. Wanser 《Journal of heterocyclic chemistry》1972,9(2):309-313
Eighteen novel pyrimido[4,5-e][1,4]oxazepin-5-ones were prepared directly via the reaction of either ethyl 4-chloro-2-phenyl-5-pyrimidinecarboxylate (Ia) or ethyl 4-chloro-2-m-chlorophenyl-5-pyrimidinecarboxylate (Ib) with a variety of substituted 2-(alkylamino)ethanols. A typical example was the preparation of 8,9-dihydro-9-methyl-2-phenylpyrimido[4,5-e][1,4]-oxazepin-5(7H)-one (IIa) from the reaction of Ia with 2-(methylamino)ethanol. Hydrolytic cleavage of the lactone ring in IIa with sodium hydroxide solution, followed by acidification with hydrochloric acid afforded 4-[(2-hydroxyethyl)methylamino]-2-phenyl-5-pyrimidinecarboxylic acid (IV). Reactions of IIa with concentrated ammonium hydroxide or hydrazine also caused cleavage of the lactone ring, giving the corresponding amide (V) or hydrazide (VI), respectively. Structural assignments were supported by infrared and nuclear magnetic resonance spectra. 相似文献
36.
Exposure of ent-kaura-2,16-dien-19-ol (1) or its succinate (2) to resuspended mycelia of G. fujikuroi has produced a complex mixture of acids which after methylation gave the esters of two C19 (24) and (30) and five C20 gibberellins (4, 11, 20, 32 and 33). The triester (32) and the lactone ester (24) have been prepared before from the esters of gibberellin A13 (8) and gibberellin A4 (26) respectively. The structures of the other metabolites were assigned on spectroscopic data and by chemical transformations. Thus the lactone diester (4) has been converted to the known keto triester (6). The epoxide (11) has been related to gibberellin A14 (14) and the aldehyde (33) has been related to gibberellin A13 trimethyl ester (8) by way of the triol (34). Selective de-epoxidation of the 16,17-epoxy function in diepoxides has provided a route from the dienes (20 and 24) to the epoxides (11 and 30) respectively, but not from the ester of gibberellin A5 (23) to that of gibberellin A6 (29). On the other hand the latter can be obtained by epoxidation of gibberellin A5 methyl ester trifluoroacetate. Backfeeding experiments carried out with the epoxy diacid (12), the diene diacid (21) and the derived diol (39) indicate pathways connecting the various metabolites. The natural gibberellins A5 and A6 were shown to be formed in some of the backfeeding experiments. 相似文献
37.
Arthur A. Santilli Dong Han Kim Stephen V. Wanser 《Journal of heterocyclic chemistry》1971,8(3):445-453
A novel method for the preparation of esters and amides of thieno[2,3-d]pyrimidine-6-carb-oxylic acids was described. A typical example was the direct formation of ethyl 5-amino-2-methylthiothieno[2,3-d]pyrimidine-6-earboxylate(IIIa) from 4-chloro-2-methylthio-5-pyrimidine-carbonitrile (Ia) and ethyl mercaptoacetate in refluxing ethanol containing sodium carbonate. Displacement of the methylthio group in IIIa by various amines gave the corresponding amino derivatives. The reactions of IIIa and related compounds with acetylating agents such as acetic anhydride or chloroacetyl chloride gave various products. Treatment of 5-carbethoxy-4-chloro-2-phenylpyrimidine(IV) with methyl mercaptoacetate afforded the dechloro intermediate diester Va, which cyclized on reaction with sodium ethoxide to form methyl 5-hydroxy-2-phenylthieno-[2,3-d]pyrimidine-6-carboxylate (Vla). The synthesis was expanded to include the preparation of various new 2,4,5-trisubstituted thieno[2,3-d]pyrimidine-6-carboxylic acid esters and amides (Charts I-V). 相似文献
38.
Scoles L Sterenberg BT Udachin KA Carty AJ 《Chemical communications (Cambridge, England)》2002,(4):320-321
Reaction of the aminophosphinidene complex [Ru5(CO)15(mu 4-PNPri2)] 1 with [PPN][NO2] (PPN = Ph3P=N=PPh3) led to the mixed nitrosyl/phosphinidene cluster complex [PPN][Ru5(CO)13(mu-NO)(mu 4-PNPri2)] 2 which is transformed into the novel nitrene/phosphinidene cluster [Ru5(CO)10(mu-CO)2(mu 3-CO)(mu 4-NH)(mu 3-PNPri2)] 3 via treatment with triflic acid. 相似文献
39.
Kihachiro Takahara Masahide Sasaki Arthur J. Tomisek Samuel Natelson 《Microchemical Journal》1974,19(3):319-329
A reagent is developed for increasing the sensitivity of the direct o-toluidine procedure for glucose so that the reaction may be carried out at temperatures as low as 37 °C.The sensitivity is achieved by eliminating all water from the system, except for a minute percentage introduced with the samples and by using a high boric acid concentration. Under these conditions protein does not precipitate and lipids remain dissolved. At 55 °C, interference from bilirubin at a concentration of 20 mg/100 ml is 3.5%.Blood may be collected with sodium fluoride since it does not interfere in the procedure. The rate of color development is slower for aqueous standards than it is for serum at the lower temperatures. This may be corrected by preparing the standards in a 6% albumin solution.Results obtained by applying the reagent with the continuous flow system of analysis (Technicon), and with the discrete sample analyzers, Beckman DSA, Lars Jungberg Autolab (Sweden), Robot Chemist, and RaBA (Japan) are reported.The reagent is useful as a spray reagent for sugar identification on thin-layer chromatography plates. Heating at different temperatures permits the differentiation between certain sugars with similar Rf values. 相似文献
40.
Single p-toluic acid pendant groups were attached to 1,4,7,10,13-pentaazacyclopentadecane (15aneN5) and 1,4,8,11-tetraazacyclotetradecane (cyclam) to prepare bifunctional reagents for radiolabeling monoclonal antibodies with (64,67)Cu. The ligands are 1,4,7,10,13-pentaazacyclopentadecane-1-(alpha-1,4-toluic acid) (PCBA) and 1,4,8,11-tetraazacyclotetradecane-1-(alpha-1,4-toluic acid) (CPTA). For the parent macrocycles and their pendant arm derivatives, the 1:1 Cu(2+) complexes dissociate only below pH 2. At pH 0.0 and 25 degrees C the CPTA-Cu complex has a half-life toward complete dissociation of 24 days. A new approach was developed for the estimation of the Cu(2+) stability constant for the kinetically robust CPTA. All other formation constants were determined at 25.0 degrees C with batch spectrophotometric techniques. Potentiometric titrations were used to determine the protonation constants of the macrocyclic ligands as well as of the metal chelates. The protonation constants, stability constants, and pM's are discussed in terms of both molecular mechanics calculations and the ligands' potential applicability as copper(II) radiopharmaceuticals. 相似文献