全文获取类型
收费全文 | 1067篇 |
免费 | 12篇 |
专业分类
化学 | 784篇 |
晶体学 | 10篇 |
力学 | 8篇 |
数学 | 127篇 |
物理学 | 150篇 |
出版年
2021年 | 7篇 |
2019年 | 6篇 |
2016年 | 14篇 |
2015年 | 11篇 |
2014年 | 12篇 |
2013年 | 49篇 |
2012年 | 36篇 |
2011年 | 33篇 |
2010年 | 31篇 |
2009年 | 30篇 |
2008年 | 59篇 |
2007年 | 57篇 |
2006年 | 47篇 |
2005年 | 61篇 |
2004年 | 40篇 |
2003年 | 49篇 |
2002年 | 64篇 |
2001年 | 12篇 |
2000年 | 13篇 |
1999年 | 12篇 |
1998年 | 13篇 |
1997年 | 19篇 |
1996年 | 16篇 |
1995年 | 8篇 |
1994年 | 14篇 |
1993年 | 5篇 |
1992年 | 17篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 7篇 |
1988年 | 11篇 |
1987年 | 16篇 |
1986年 | 13篇 |
1985年 | 19篇 |
1984年 | 31篇 |
1983年 | 11篇 |
1982年 | 31篇 |
1981年 | 26篇 |
1980年 | 21篇 |
1979年 | 17篇 |
1978年 | 12篇 |
1977年 | 16篇 |
1976年 | 16篇 |
1975年 | 21篇 |
1974年 | 8篇 |
1973年 | 7篇 |
1972年 | 5篇 |
1971年 | 6篇 |
1968年 | 4篇 |
1966年 | 5篇 |
排序方式: 共有1079条查询结果,搜索用时 15 毫秒
91.
Transformation of arctiin to estrogenic and antiestrogenic substances by human intestinal bacteria 总被引:2,自引:0,他引:2
Xie LH Ahn EM Akao T Abdel-Hafez AA Nakamura N Hattori M 《Chemical & pharmaceutical bulletin》2003,51(4):378-384
After anaerobic incubation of arctiin (1) from the seeds of Arctium lappa with a human fecal suspension, six metabolites were formed, and their structures were identified as (-)-arctigenin (2), (2R,3R)-2-(3',4'-dihydroxybenzyl)-3-(3",4"-dimethoxybenzyl)butyrolactone (3), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3",4"-dimethoxybenzyl)butyrolactone (4), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3"-hydroxy-4"-methoxybenzyl)butyrolactone (5), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3",4"-dihydroxybenzyl)butyrolactone (6), and (-)-enterolactone (7) by various spectroscopic means including two dimensional (2D)-NMR, mass spectrometry, and circular dichroism. A possible metabolic pathway was proposed on the basis of their structures and the time course of the transformation. Enterolactones obtained from the biotransformation of arctiin and secoisolariciresinol diglucoside (SDG, from the seeds of Linum usitatissium) by human intestinal bacteria were proved to be enantiomers, with the (-)-(2R,3R) and (+)-(2S,3S) configurations, respectively. Compound 6 showed the most potent proliferative effect on the growth of MCF-7 human breast cancer cells in culture among 1 and six metabolites, while it showed inhibitory activity on estradiol-mediated proliferation of MCF-7 cells at a concentration of 10 microM. These results indicate that the transformation of 1 by intestinal flora might be essential for the manifestation of the estrogenic and antiestrogenic activity of 1. 相似文献
92.
Zhang ZB Fujiki M Motonaga M McKenna CE 《Journal of the American Chemical Society》2003,125(26):7878-7881
The chiral ordering in aggregated poly(3-alkylthiophene) can be controlled by a metal salt-dependent doping-dedoping process. Enhancement or reduction in the chiral anisotropy factor depends on the doping level, such that doping driven by polymer-metal salt interactions, and dedoping driven by aggregate formation must be balanced in order to achieve maximal chiral ordering. This phenomenon provides a new basis to control chiral arrangement in conjugated polymer aggregates, relying solely on doping, and thus avoiding tedious modification of side-chain or main-chain structures. 相似文献
93.
Kazuhiko Kandori Kazunao Hayashi Masaki Matsukawa Masao Fukusumi Yoshiaki Morisada 《Colloid and polymer science》2010,288(10-11):1071-1079
The shape and porosity of hematite particles, produced from a forced hydrolysis reaction of acidic FeCl3 solution, were controlled by using Pluronics as nonionic surfactants (0–4 wt.%). Pluronics possess a nominal formula of (PEO) x –(PPO) y –(PEO) x . The effect of Pluronics with low hydrophilicity (PEO contents were less than 50 mol%) was small and provided spherical particles the same as that of the system without Pluronics (control system). However, Pluronics with higher hydrophilicity (PEO contents were over 50 mol%) gave ellipsoidal hematite particles. This effect on the particle morphology was enhanced by an increase in their molecular weight. On the other hand, the Pluronics possessing an opposite nominal formula [(PPO) x –(PEO) y –(PPO) x ] exhibited no effect on the particle shape; it only depressed phase transformation from ?-FeOOH to hematite. Not only the morphology but also the pore size of hematite particles was controlled from nonporous to mesoporous by using Pluronics. The N2 adsorption experiment and t-plot curve analysis revealed that the hematite particles changed from mesoporous to microporous by an increase in the concentration of Pluronics. On the other hand, in the presence of very low amounts of Pluronics molecules (0.1 wt.%), nonporous hematite particles were produced via strong aggregation of PN particles by their hydrogen bonding between hydroxyl and PEO or PPO groups. The dynamic light scattering measurement for the system with Pluronics clarified the existence of polynuclear (PN) particles with a hydrodynamic particle diameter (D a) of ca. 40 nm after these were aged for 6 h. The size of PN particles remained constant at ca. 40 nm during aging time of 12 h~3 days, but the scattering intensity was decreased. This decrease in the scattering intensity reveals that the number of PN particles is reduced by aggregation. The transmission electron microscope, inductively coupled plasma atomic emission spectroscopy, and total organic carbon analysis measurements employed on the systems produced for ellipsoidal particles elucidated that the formation of ellipsoidal hematite particles is attributed to the adsorption of Pluronics on the surfaces of PN and growing hematite particles. 相似文献
94.
Makoto Obata Noriko Matsuura Kazunori Mitsuo Hiroki Nagai Keisuke Asai Masafumi Harada Shiho Hirohara Masao Tanihara Shigenobu Yano 《Journal of polymer science. Part A, Polymer chemistry》2010,48(3):663-670
A novel methacrylate monomer bearing 5,10,15,20‐tetraphenylporphyrinato palladium(II) (PdTPP) (monomer 1a ) was synthesized and copolymerized with isobutyl methacrylate (IBM) and 2,2,2‐trifluoroethyl methacrylate (TFEM) to give poly (IBM‐co‐TFEM) bearing PdTPP (copolymer 2a ) as a dye‐conjugated oxygen‐permeable polymer for pressure‐sensitive paint applications. The introduction of PdTPP into copolymer 2a was confirmed by UV–vis spectroscopy and extended X‐ray absorption fine structure analysis. The Stern–Volmer plots of the copolymer 2a and a mixture of PdTPP and poly(IBM‐co‐TFEM) both showed downward curvature, unlike that of the platinum complex analogue (copolymer 2b ) previously reported. The plots were successfully fitted with a two‐site model to give two distinct Stern–Volmer constants (KSV1 and KSV2) and the partition ratio f1. Interestingly, the f1 values for the copolymer 2a were almost constant at about 0.98, whereas those of the mixture of PdTPP and poly(IBM‐co‐TFEM) increased from 0.889 to 0.967 as the temperature was increased. This finding suggests that there are two distinct microheterogeneities, one temperature‐dependent and the other temperature‐independent, in the mixture of PdTPP and poly(IBM‐co‐TFEM). The dye‐conjugation approach effectively eliminates the temperature‐dependent, but not the temperature‐independent microheterogeneity. The luminescence decays of copolymers 2a and 2b and the corresponding mixtures in the absence of oxygen indicated that the temperature‐dependent microheterogeneity involves an oxygen diffusion process, whereas the temperature‐independent one appears to be inherent nature in PdTPP. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 663–670, 2010 相似文献
95.
Akagi M Omae D Tamura Y Ueda T Kumashiro T Urata H 《Chemical & pharmaceutical bulletin》2002,50(6):866-868
L-Ribose was synthesized by a simple four-step method with overall yield of 76.3% from a protected L-arabinose derivative, which is a compatible intermediate for the synthesis of L-deoxyribose. The key step of this strategy is the Swern oxidation and subsequent stereoselective reduction accompanied by inversion of the 2-hydroxy group of protected L-arabinose. 相似文献
96.
97.
Four new iridoid glycosides, named L-phenylalaninosecologanin (1), 7-O-(4-beta-D-glucopyranosyloxy-3-methoxybenzoyl)secologanolic acid (2), 6'-O-(7alpha-hydroxyswerosyloxy)loganin (3) and (Z)-aldosecologanin (5), were isolated, together with a known one, newly named (E)-aldosecologanin (4), from the stems and leaves of Lonicera japonica. Their structures were established on the basis of chemical and spectral data. 相似文献
98.
The reaction of N-aryl-substituted ketenimines with N,N-disubstituted cyanamides or (MeS)2C=N-CN under high pressure afforded 4-(N,N-disubstituted amino) or 4-(MeS)2C=N-substituted quinazoline derivatives, respectively. These products were formed by [4+2] cycloaddition between the aza-diene moieties of the N-arylsubstituted ketenimines and cyano groups. A 4-(unsubstituted amino)quinazoline derivative was synthesized by hydrolysis of the latter product. 相似文献
99.
Yoshiyuki Goh Takao Iijima Masao Tomoi 《Journal of polymer science. Part A, Polymer chemistry》2002,40(15):2702-2716
Novel quaternary ammonium bis(2‐oxybenzoyloxy)borate salts ( 1a – 1c ) or quaternary ammonium bis(1,2‐benzenedioxy)borate salts ( 2a and 2b ) with tetra‐n‐butylammonium (TBA+), tetra‐n‐octylammonium (TOA+), or bis(triphenylphosphoranylidene)ammonium (PNP+) cations were synthesized as latent catalysts of epoxy/phenol–novolac resins by the complexation between boric acid and salicylic acid or catechol, followed by neutralization with quaternary ammonium hydroxide. Polyaddition reactions of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐bisphenol F (44BPF) or bisphenol F (BPF‐D) with the ammonium borates were investigated as model reactions of epoxy/phenol–novolac resin systems with respect to the thermal latency and storage stability of the catalyst. The polyaddition of DGEBA/44BPF with 1a – 1c in diglyme at 150 °C for 6 h proceeded up to 85–96% conversions and gave polymers with number‐average molecular weights of 4180–10,500, whereas the polyaddition at 80 °C for 6 h gave less than 8% conversions. However, the polyaddition with 2a containing TBA+ cation proceeded to only a 32% conversion at 150 °C for 6 h in diglyme and to a 64% conversion even at 180 °C for 6 h in triglyme and only gave low molecular weight oligomers, and no reaction proceeded in the polyaddition at 80 °C. However, polyaddition with 2b containing PNP+ cation proceeded up to a 96% conversion at 150 °C for 6 h in diglyme and gave a higher molecular weight polymer with a number‐average molecular weight of 8050, whereas the polyaddition at 80 °C for 6 h gave only a 5% conversion. The catalytic activity of ammonium borates 1a – 1c and 2a and 2b depended on the borate anion structure: 1a and 1c with bis(2‐oxybenzoyloxy)borate anion revealed higher activity than 2a and 2b with bis(1,2‐benzenedioxy)borate anion, respectively. In comparison with tetra‐n‐butylammonium bromide (TBAB) as a conventional ammonium salt or tetra‐n‐butylammonium tetrakis(benzoyloxy)borate (TBA‐TBB), 1a – 1c and 2b revealed better thermal latency. The catalytic activity of ammonium borates also depended on the bulkiness of the ammonium cation, and the order of activity was 1c (PNP+) > 1b (TOA+) ≧ 1a (TBA+) and 2b (PNP+) > 2a (TBA+). The storage stability of DGEBA/BPF‐D with the ammonium borate catalysts 1a – 1c and 2a and 2b in bulk at 40 °C was much better than that with TBAB and TBA‐TBB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2702–2716, 2002 相似文献
100.