全文获取类型
收费全文 | 3606篇 |
免费 | 161篇 |
国内免费 | 10篇 |
专业分类
化学 | 2656篇 |
晶体学 | 33篇 |
力学 | 30篇 |
数学 | 169篇 |
物理学 | 569篇 |
无线电 | 320篇 |
出版年
2023年 | 21篇 |
2022年 | 23篇 |
2021年 | 44篇 |
2020年 | 65篇 |
2019年 | 51篇 |
2018年 | 47篇 |
2017年 | 27篇 |
2016年 | 83篇 |
2015年 | 100篇 |
2014年 | 111篇 |
2013年 | 144篇 |
2012年 | 230篇 |
2011年 | 230篇 |
2010年 | 139篇 |
2009年 | 145篇 |
2008年 | 244篇 |
2007年 | 256篇 |
2006年 | 230篇 |
2005年 | 227篇 |
2004年 | 203篇 |
2003年 | 140篇 |
2002年 | 128篇 |
2001年 | 72篇 |
2000年 | 61篇 |
1999年 | 32篇 |
1998年 | 42篇 |
1997年 | 27篇 |
1996年 | 41篇 |
1995年 | 38篇 |
1994年 | 32篇 |
1993年 | 27篇 |
1992年 | 29篇 |
1991年 | 37篇 |
1990年 | 30篇 |
1989年 | 23篇 |
1988年 | 26篇 |
1987年 | 17篇 |
1986年 | 28篇 |
1985年 | 35篇 |
1984年 | 32篇 |
1983年 | 19篇 |
1982年 | 22篇 |
1981年 | 24篇 |
1980年 | 26篇 |
1979年 | 14篇 |
1978年 | 21篇 |
1977年 | 25篇 |
1975年 | 17篇 |
1974年 | 15篇 |
1973年 | 16篇 |
排序方式: 共有3777条查询结果,搜索用时 15 毫秒
71.
72.
Synthesis and characterization of 6-O-acyl-2-O-alpha-D-glucopyranosyl-L-ascorbic acids with a branched-acyl chain 总被引:3,自引:0,他引:3
We previously reported the chemical synthesis of a series of novel monoacylated vitamin C derivatives, 6-O-acyl-2-O-alpha-D-glucopyranosyl-L-ascorbic acids (6-Acyl-AA-2G) possessing a straight-acyl chain of varying length from C(4) to C(18), as effective skin antioxidants. In this paper, we describe branched type of 6-Acyl-AA-2G derivatives (6-bAcyl-AA-2G) synthesized by use of a 2-branched-chain fatty acid anhydride as an acyl donor. The stability of 6-bAcyl-AA-2G in neutral solution was much higher than that of 6-Acyl-AA-2G, while they were susceptible to enzymatic hydrolysis for exerting vitamin C effect. These branched derivatives as well as 6-Acyl-AA-2G increased the radical scavenging activity against 1, 1-diphenyl-2-picrylhydrazyl and the lipophilicity in octanol/water-partitioning systems with increasing length of their acyl group. In addition, the 6-bAcyl-AA-2G derivative with an acyl chain of C(12), 6-bDode-AA-2G had the excellent solubility to various solvents, suggesting easy handling in cosmetic use. These characteristics of 6-bAcyl-AA-2G may be available for skin care application as an effective antioxidant. 相似文献
73.
We report herein a practical synthesis of 4'-thiothymidine (15) and appropriately protected 2'-deoxy-4'-thiocytidine (16), -thioadenosine (27), and -thioguanosine (29) derivatives, substrates for the synthesis of 4'-thioDNA, from the corresponding 4'-thioribonucleosides. 2'-deoxy-4'-thiopyrimidine nucleosides were synthesized using a radical reaction of the corresponding 2'-alpha-bromo derivatives, which were prepared via 2,2'-O-anhydro derivatives. 2'-deoxy-4'-thiopurine nucleosides were synthesized using the same radical reaction of the corresponding 2'-beta-bromo derivatives. 相似文献
74.
Nishinaga T Yamazaki D Stahr H Wakamiya A Komatsu K 《Journal of the American Chemical Society》2003,125(24):7324-7335
Novel cyclopentadienyl (Cp)-alkali metal complexes 1-M and 2-M (M = Li, Na, K), in which the Cp ring is annelated with two bicyclo[2.2.2]octene units and substituted with a phenyl group for 1 and a tert-butyl group for 2, were synthesized, and their structures and dynamic behaviors were investigated by means of X-ray crystallography, dynamic (13)C NMR, and DFT calculations. The X-ray crystallography results indicated that 1-Li, 1-Na, and 2-Na form monomeric contact ion pairs (CIP) with three THF molecules coordinated to the metal atom. Also, in THF-d(8), all of the 1-M and 2-M form monomeric CIP in the ground state. However, variable-temperature (13)C NMR measurements of 1-M and 2-M in THF-d(8) demonstrated dynamic behavior in which the metal ion exchanges positions between the upper and lower faces of the Cp ring. From a study of the concentration dependence of the dynamic behavior, the exchange was found to proceed principally as an intramolecular process at concentration ranges lower than 0.2 M. The experimentally observed deltaG values for the intramolecular exchange process for all the 1-M and 2-M (except for 2-Li, whose intramolecular process was too slow to observe) were found to be quite similar in THF-d(8) solution and to fall within the range of 12-14 kcal mol(-)(1). Within this range, a tendency was observed for the deltaG values to increase as the size of the metal decreased. Theoretical calculations (B3LYP/6-31G(d)) afforded considerably large values as the gas-phase dissociation energy for 1-M (162.7 kcal mol(-)(1) for M = Li; 131.6 kcal mol(-)(1) for M = Na; 110.9 kcal mol(-)(1) for M = K) and for 2-M (170.0 kcal mol(-)(1) for M = Li; 137.5 kcal mol(-)(1) for M = Na; 115.4 kcal mol(-)(1) for M = K). These values should be compensated for by a decrease in the solvation energies for the metal ions with increasing size, as exemplified by the calculated solvation energy for M(+)(Me(2)O)(4), which serves as a model for metal ions solvated with four molecules of THF (-122.9 kcal mol(-)(1) for M = Li; -94.7 kcal mol(-)(1) for M = Na; -67.7 kcal mol(-)(1) for M = K). This compensation results in a small difference in the overall energy for dissociation of 1-M or 2-M in ethereal solutions, thus supporting the similar deltaG values observed for the intramolecular metal exchange. 相似文献
75.
Mori M Saito N Tanaka D Takimoto M Sato Y 《Journal of the American Chemical Society》2003,125(19):5606-5607
Novel alkenylative cyclization of enyne was developed using Cp*RuCl(cod) under ethylene gas at room temperature. 相似文献
76.
77.
Shinsaku Fujita 《Journal of mathematical chemistry》2003,33(2):113-143
Molecules of ligancy 4 that have been derived from an allene, an ethylene, a tetrahedral, and a square-planar skeleton have been investigated to show that their symmetries are dually and distinctly controlled by point groups and permutation groups. Insomuch as the point-group symmetry was exhibited to control the chirality/achirality of a molecule, sphericity in a molecule, and enantiomeric relationship between molecules [S. Fujita, J. Am. Chem. Soc. 112 (1990) 3390], the permutation-group symmetry has been now clarified to control the stereogenicity of a molecule, tropicity in a molecule, and diastereomeric relationship between molecules. To characterize permutation groups, proper and improper permutations have been defined by comparing proper and improper rotations. Thereby, such permutation groups are classified into stereogenic and astereogenic ones. After a coset representation (CR) of a permutation group has been ascribed to an orbit (equivalence class), the tropicity of the orbit has been defined in term of the global stereogenicity and the local stereogenicity of the CR. As a result, the conventional stereogenicity has now been replaced by the concept local stereogenicity of the present investigation. The terms homotropic, enantiotropic, and hemitropic are coined and used to characterize prostereogenicity. Thus, a molecule is defined as being prostereogenic if it has at least one enantiotropic orbit. Since this definition has been found to be parallel with the definition of prochirality, relevant concepts have been discussed with respect to the parallelism between stereogenicity and chirality in order to restructure the theoretical foundation of stereochemistry and stereoisomerism. The derivation of the skeletons has been characterized by desymmetrization due to the subduction of CRs. The Cahn–Ingold–Prelog (CIP) system has been discussed from the permutational point of view to show that it specifies diastereomeric relationships only. The apparent specification of enantiomeric relationships by the CIP system has been shown to stem from the fact that diastereomeric relationships and enantiomeric ones overlap occasionally in case of tetrahedral molecules. 相似文献
78.
Allyl 2-pyridyl sulfide or allyl phenyl sulfone on treatment with n-butyllithium in tetrahyrofuran followed by tri-n-butylstannylmethyl iodide () afforded directly the 1,3-diene in good yield. 相似文献
79.
An epoxy-group-containing polymer chain was grafted onto the hollow-fiber form of a porous polyethylene membrane by the immersion of the electron beam-irradiated trunk polymer in glycidyl methacrylate diluted with methanol and 1-butanol. The epoxy group density ranged from 8.5 to 13.4 mol per kg of the trunk polymer. Subsequently, the epoxy groups produced were converted into sulfonic acid and diethylamino groups. The density of -SOH and -N(C2H5), groups was 0.40 and 2.2 mol per kg of the product. respectively. The polymer brush, defined as a polymer chain extending from the surface of a pore toward the interior of the pore, was evaluated from the determination of an equilibrium binding capacity of hen egg lysozyme (HEL) and bovine serum albumin (BSA). The polymer brush prepared in 1-butanol was found to be longer than that prepared in methanol from the determinations of liquid permeability and protein adsorptivity. The proteins were bound to the polymer brush prepared in 1-butanol, followed by the functionalization, at higher degrees of multilayer binding: about 30 for HEL and 6 for BSA. 相似文献
80.
Takashi Fujita Takao Yoshioka 《Journal of polymer science. Part A, Polymer chemistry》1982,20(6):1639-1647
Copolymerization of N-oxyl biradical with α-chloro-p-xylylene was carried out by varying the feed ratio of α,α′-dichloro-p-xylene which was the precursor of α-chloro-p-xylylene. The structures of the obtained copolymers were determined spectroscopically. The results that the N-oxyl attacked the carbon-bearing chlorine atom of α-chloro-p-xylylene suggest a nucleophilic reactivity of N-oxyl radical. The copolymerization process was also discussed. 相似文献