全文获取类型
收费全文 | 1927篇 |
免费 | 49篇 |
国内免费 | 6篇 |
专业分类
化学 | 1345篇 |
晶体学 | 21篇 |
力学 | 29篇 |
数学 | 112篇 |
物理学 | 475篇 |
出版年
2021年 | 17篇 |
2020年 | 17篇 |
2019年 | 26篇 |
2018年 | 22篇 |
2016年 | 31篇 |
2015年 | 29篇 |
2014年 | 36篇 |
2013年 | 86篇 |
2012年 | 78篇 |
2011年 | 102篇 |
2010年 | 51篇 |
2009年 | 58篇 |
2008年 | 89篇 |
2007年 | 102篇 |
2006年 | 104篇 |
2005年 | 109篇 |
2004年 | 93篇 |
2003年 | 80篇 |
2002年 | 97篇 |
2001年 | 30篇 |
2000年 | 28篇 |
1999年 | 34篇 |
1998年 | 26篇 |
1997年 | 18篇 |
1996年 | 22篇 |
1995年 | 25篇 |
1994年 | 25篇 |
1993年 | 19篇 |
1992年 | 27篇 |
1991年 | 17篇 |
1990年 | 11篇 |
1989年 | 17篇 |
1988年 | 21篇 |
1987年 | 16篇 |
1986年 | 22篇 |
1985年 | 21篇 |
1984年 | 34篇 |
1983年 | 19篇 |
1982年 | 20篇 |
1981年 | 27篇 |
1980年 | 21篇 |
1979年 | 30篇 |
1978年 | 13篇 |
1977年 | 20篇 |
1976年 | 18篇 |
1975年 | 27篇 |
1974年 | 27篇 |
1973年 | 19篇 |
1972年 | 19篇 |
1965年 | 12篇 |
排序方式: 共有1982条查询结果,搜索用时 234 毫秒
111.
Cadmium sulfide (CdS) nanoclusters were prepared by a freeze drying method from two types of cadmium carboxylates. One was cadmium methacrylates that were part of poly(methyl methacrylate) (PMMA) ionomer. The other was cadmium acetates that were dispersed in PMMA. X-ray diffraction was mainly used to study the formation and the size of nanoclusters. The size of CdS made from the ionomer was 0.9 nm, whereas that from the composite of cadmium acetate and PMMA was 2 nm. This was consistent with the size difference of the precursors of CdS: i.e., Cd carboxylate nanoclusters (ionic aggregates) were smaller in the ionomer than in the PMMA mixture, because ionic groups in the ionomer were constrained due to their connectivity to backbone chains and thus forming smaller ionic aggregates. Once stabilized, however, CdS nanocluster sizes were unchanged despite thermal treatments at up to 220 °C for 24 h for both systems. Structural transformations from a freeze dried cadmium carboxylate powder, to a CdS-containing powder, and to a heat-treated CdS-containing sample are speculated for both types of systems. 相似文献
112.
Masanori Miura Takanori Koike Tsukasa Ishihara Fukushi Hirayama Shuichi Sakamoto Minoru Okada 《合成通讯》2013,43(24):3809-3820
A one‐pot synthetic procedure for 2,2′‐disubstituted biaryls was developed via a Suzuki cross‐coupling reaction of aryl triflates in a biphasic solvent system. The effects of various bases and solvents were investigated. Results showed that the Na2CO3–toluene/H2O combination gave the highest yields. 相似文献
113.
Makoto Hatakeyama Takako Mashiko Hisanao Hazama Kunio Awazu Masanori Tachikawa 《International journal of quantum chemistry》2013,113(2):125-129
To investigate the correlation between the wavelength dependence of ionization threshold fluence of target molecule in matrix‐assisted laser desorption/ionization by infrared (IR) laser and the IR absorption spectrum of matrix molecule, we have analyzed the IR absorption spectra of four matrix molecules using density functional theory and correlated ab initio molecular orbital method. The calculated IR absorption spectra of the isolated molecules showed more qualitative correlation with the wavelength dependence of ionization threshold fluence than those of the solid state structures. We can consider that a portion of matrix molecules lost the ordered crystal structure and that the transition to the diluted or isolated state occurred at the early process of IR laser irradiation. © 2012 Wiley Periodicals, Inc. 相似文献
114.
A mechanistic study was carried out for the asymmetric Michael addition reaction of malonates to enones catalyzed by a primary amino acid lithium salt to elucidate the origin of the asymmetric induction. A primary β-amino acid salt catalyst, O-TBDPS β-homoserine lithium salt, exhibited much higher enantioselectivity than that achieved with the corresponding catalysts derived from α- and γ-amino acids for this reaction. Detailed studies of the transition states with DFT calculations revealed that the lithium cation and carboxylate group of the β-amino acid salt catalyst have important roles in achieving high enantioselectivity in the Michael addition reaction of malonates to enones. 相似文献
115.
Yutaka Kubota Yuri Kaneda Kazuhiro Haraguchi Mirei Mizuno Hiroshi Abe Satoshi Shuto Takayuki Hamasaki Masanori Baba Hiromichi Tanaka 《Tetrahedron》2013
The key glycosyl donor for the target molecule 12 was prepared by two-step sequences; (1) acetalization of tert-butyldimethylsilyloxyacetaldehyde with 3-bromopropanediol, (2) DBN-initiated β-elimination of the resulting 2-(tert-butyldimethylsilyloxy)methyl-4-bromomethyl-1,3-dioxolane 11. Electrophilic glycosidation between 12 and silylated pyrimidine nucleobase proceeded efficiently to provide a mixture of β- and α-anomers of the respective glycosides 14 and 15. Tin radical-mediated reduction of the bromomethyl functional group of 14 and 15 gave protected 4′-C-methyl-dioxorane uracil- 16 and thymine nucleoside 17. The respective cytosine nucleoside 18 was synthesized from 16. De-silylation of 4′-methyl-1′,3′-dioxolane pyrimidine nucleosides 16–18 gave the target molecules. Evaluation of the anti-HIV-1 activity of the β- and α-anomers of the novel 4′-C-methyl-1′,3′-dioxolane nucleosides 22β,α–24β,α revealed that none of the nucleoside derivatives possess anti-viral activity against HIV-1 and show cytotoxicity against MT-4 cells at 100 μM. 相似文献
116.
Masashi Daido Yukio Kawashima Masanori Tachikawa 《Journal of computational chemistry》2013,34(28):2403-2411
The structure of Watson–Crick‐type adenine‐thymine and guanine‐cytosine pairs has been studied by hybrid Monte Carlo (HMC) and path integral hybrid Monte Carlo (PIHMC) simulations with the use of semiempirical PM6‐DH+ method in the gas phase. We elucidated the nuclear quantum effect and temperature dependency on the hydrogen‐bonded moiety of base pairs. It was shown that the contribution of nuclear quantum effect on the hydrogen‐bonded structure is significant not only at low temperature 150 K but also at temperature as high as 450 K. The relative position of hydrogen‐bonded proton between two heavy atoms and the nuclear quantum nature of the proton are also shown. Furthermore, we have applied principal component analysis to HMC and PIHMC simulations to analyze the nuclear quantum effect on intermolecular motions. We found that the ratio of Buckle mode (lowest vibrational mode from normal mode analysis) decreases due to the nuclear quantum effect, whereas that of Propeller mode (second lowest vibrational mode) increases. In addition, nonplanar structures of base pairs were found to become stable due to the nuclear quantum effect from two‐dimensional free energy landscape along Buckle and Propeller modes. © 2013 Wiley Periodicals, Inc. 相似文献
117.
Abstract Anomeric O-alkylation of mannopyranoses with various protecting groups was investigated using mannose derivatives and 2,3-O-isopropylidene-l-O-trifluoro-methanesulfonyl-D-glycerol (1) as alkylating agent. Generally, in polar solvents higher α/β ratios were obtained than in nonpolar solvents. Sterically demanding protecting groups at the 6-O-position and polar solvents led to higher yields. Reactivity differences were explained by different complex formation. Based on these results mannopyranosyl-α(1-4) glucopyranosides 26 and 27 were synthesized using mannose derivatives 5 and 6 having a 6-O-(p-methoxyphenyl)diphenylmethyl group and galactosyl trifluoromethane-sulfonate 24 or nonafluorobutanesulfonate (nonaflate) 25, respectively, as alkylating agents. 相似文献
118.
Jun‐ichi Tamura Akihiro Yamaguchi Junko Tanaka Yuko Nishimura 《Journal of carbohydrate chemistry》2013,32(2):61-82
We have synthesized, for the first time, the partial sequence of the betaglycan composed of the tetraosyl hexapeptide, which was directly usable as a probe for enzymatic glycosyl transfer. Stepwise elongation afforded the corresponding tetraosyl trichloroacetimidate. The common glycosyl dipeptide:[β‐d‐GlcA‐(1→3)‐β‐d‐Gal‐(1→3)‐β‐d‐Gal‐(1→4)‐β‐d‐Xyl‐(1→O)‐Ser‐Gly] was synthesized by glycosylation of the corresponding tetraosyl trichloroacetimidate and Ser‐Gly moiety. The glycosyl dipeptide was coupled with other core peptide parts in solution phase and on a solid support. These glycosyl hexapeptides were then transformed into the desired target compounds. 相似文献
119.
Keisuke Kinomura Masahiro Tamura Tetsuo Oga Hideo Okai 《Journal of carbohydrate chemistry》2013,32(2):229-241
Abstract To confirm the potential usefulness of amino acid residues as protecting groups for sugar hydroxyls, methyl 2,3-di-O-glycyl-α-D-glucopyranoside (5) and methyl 4,6-di-O-glycyl-2,3-di-O-methyl-α-D-gluco-pyranoside (7) were synthesized as reference compounds. Conditions were then established for the removal of these aminoacyl groups from the sugar molecules. The reference compounds were easily prepared by condensation of methyl α-D-glucopyranoside derivatives with N-protected glycine in the presence of dicyclohexyl-carbodiimide (DCC). The aminoacyl groups were removed by alkaline treatment, as were conventional acyl groups and also with ease by enzymatic hydrolysis using Pronase E. Conventional ester and ether protecting groups are not removed by such enzymatic treatment. Removal of aminoacyl group from sugar moieties on a practical scale is also described. 相似文献