全文获取类型
收费全文 | 3112篇 |
免费 | 108篇 |
国内免费 | 12篇 |
专业分类
化学 | 2438篇 |
晶体学 | 27篇 |
力学 | 31篇 |
数学 | 144篇 |
物理学 | 592篇 |
出版年
2023年 | 14篇 |
2022年 | 21篇 |
2021年 | 28篇 |
2020年 | 35篇 |
2019年 | 50篇 |
2018年 | 36篇 |
2017年 | 26篇 |
2016年 | 64篇 |
2015年 | 63篇 |
2014年 | 66篇 |
2013年 | 136篇 |
2012年 | 132篇 |
2011年 | 231篇 |
2010年 | 101篇 |
2009年 | 121篇 |
2008年 | 223篇 |
2007年 | 205篇 |
2006年 | 173篇 |
2005年 | 177篇 |
2004年 | 164篇 |
2003年 | 147篇 |
2002年 | 124篇 |
2001年 | 50篇 |
2000年 | 51篇 |
1999年 | 40篇 |
1998年 | 31篇 |
1997年 | 26篇 |
1996年 | 47篇 |
1995年 | 28篇 |
1994年 | 32篇 |
1993年 | 30篇 |
1992年 | 26篇 |
1991年 | 23篇 |
1990年 | 23篇 |
1989年 | 20篇 |
1988年 | 21篇 |
1987年 | 26篇 |
1986年 | 27篇 |
1985年 | 48篇 |
1984年 | 49篇 |
1983年 | 21篇 |
1982年 | 39篇 |
1981年 | 30篇 |
1980年 | 22篇 |
1979年 | 36篇 |
1978年 | 20篇 |
1977年 | 29篇 |
1976年 | 21篇 |
1975年 | 19篇 |
1973年 | 23篇 |
排序方式: 共有3232条查询结果,搜索用时 15 毫秒
71.
Koji Ishizu Satoru Minematsu Takashi Fukutomi 《Journal of polymer science. Part A, Polymer chemistry》1990,28(5):1091-1099
We have studied the structural changes on poly(2-hydroxyethyl methacrylate) (PHEMA)/polystyrene (PS) blends by means of phase growth of microheterophase pattern on a template surface composed of poly[2-hydroxyethyl methacrylate (HEMA)-g-styrene (S)] graft copolymer (lamellar shape). The PS macromonomer was synthesized by free radical polymerization of S monomer initiated by a functional initiator [2,2'-azobis(2-(2-imidazolin-2-yl)propane: VA-061] in the presence of a degradative chain transfer agent, followed by an end-capping reaction with p-chloromethylstyrene (CMS). Poly(HEMA-g-S) graft copolymers were prepared by free radical copolymerization of these vinylbenzyl-terminated PS macromonomers with HEMA comonomer. 相似文献
72.
Yasuhide Yukawa Hisao Morisaki Kiyoshi Tsuji Seung-Geon Kim Takashi Ando 《Tetrahedron letters》1981,22(51):5187-5190
The behavior of ion pairs in the trifluoroacetolysis of 2-arylethyl arenesulfonates was studied by means of tracer techniques with deuterium and oxygen-18. 相似文献
73.
Akira Ando 《Journal of fluorine chemistry》2005,126(5):765-770
Treatment of 2-chloro-3,3-difluoroprop-2-en-1-ol derivatives (2) with methanesulfonyl chloride in the presence of a base did not give the expected esters but 2-chloro-1,1-difluoroprop-2-enyl methanesulfonates (4) through a novel [3,3] sigmatropic rearrangement. Reaction of 4 with diethylzinc in the presence of tetrakis(triphenylphosphine) palladium gave 1-alkyl- or 1-aryl-2-chloro-3-fluoropenta-1,3-dienes in moderate to good yields through a CC bond formation followed by dehydrofluorination. 相似文献
74.
J Holinej H Y Ando J W Snow 《Journal of chemical information and computer sciences》1989,29(4):233-236
Buffer changes and certain drugs cause temperature shifts, amplitude changes, and transition broadening in the differential scanning calorimetric (DSC) analysis of erythrocyte membranes. However, it has been difficult to interpret and quantitate these shifts and changes because the scans are composed of multiple overlapping transitions and because more than one transition may be simultaneously affected. An empirical approach has been developed by using Gaussian modeling to resolve these calorimetric transitions. Data analysis was carried out on a microcomputer using a nonlinear regression program (PCNONLIN) to fit the data scans. These results show that changes in the calorimetric scans of erythrocyte membranes due to alterations in the buffer environment, such as pH and osmolarity, can be resolved by fitting the data scans with the proposed mathematical model and optimizing the resolution parameters with PCNONLIN. In addition, resolution uncovered hidden characteristics that may not have been readily evident. Under certain conditions, for example, apparent transition shifts were shown to actually be amplitude changes and transition broadening. Determination of the limitations and validity of this method was accomplished with simulation studies. This technique offers a simple means for fitting overlapping DSC transitions by use of a commercially available nonlinear regression program that can be run on a microcomputer. 相似文献
75.
Koji Konomi He-Sheng Li† Norihito Kuno Masaki Furuya‡ 《Photochemistry and photobiology》1993,58(6):852-857
Abstract Treatment of imbibed embryonic axes taken from seeds of Pisum sativum with N-phenylimide S-23142, a herbicide that has been suggested to inhibit protoporphyrin synthesis, or with N -methyl mesoporphyrin IX, an inhibitor of the iron chelatase for heme, resulted in a significant decrease in the amount of spectrophotometrically detectable phytochromc in the axes in both cases. However, the amount of immunochemically detectable phytochrome was not affected by either treatment. If S-23142 inhibits the synthesis of protoporphyrin IX in pea, it appears that the conversion of protoporphyrinogen IX to protoporphyrin IX is involved in the biosynthesis of the phytochrome chromophore. The conversion of protoporphyrin IX to heme (Fe-protoporpbyrin) also appears to be a step in the biosynthesis of the chromophore, since N -methyl mesoporphyrin IX prevented the synthesis of spectrophotometrically detectable phytochrome but did not affect the magnesium chelatase activity required for the synthesis of chlorophyll in pea embryonic axes. The results suggest that protoporphyrinogen IX, protoporphyrin IX and heme are intermediates in the biogenesis of the phytochromc chromophore. The pathway to phytochromobilin might become fixed after protoporphyrin IX, being directed toward the Fe branch for heme rather than to the Mg branch for chlorophyll. 相似文献
76.
Poly(ethylene oxide-)-poly(1, 1-dimethyl-2, 2-dihexyldisilene) block copolymers (PEO-b-PMHS) were synthesized by the anionic polymerization of masked disilenes initiated with the potassium alkoxide of poly(ethylene glycol). The block copolymer self-assembled into polymer micelles in water accompanied by a transition in the polysilane conformation. 相似文献
77.
The most widely used method for qualitative and quantitative analysis of carbonyl compounds is the 2,4-dinitrophenylhydrazine method through the formation of 2,4-dinitrophenylhydrazone derivatives. However, this method may cause an analytical error because 2,4-dinitrophenylhydrazones have both E- and Z-stereoisomers. Purified aldehyde-2,4-dinitrophenylhydrazone demonstrated only the E-isomer. However under UV irradiation and the addition of acid, both E- and Z-isomers were seen. The spectral patterns of Z-isomers were different from those of E-isomers and the absorption maximum wavelengths were shifted towards shorter wavelengths by 5-8 nm. An equilibrium Z/E isomer ratio was observed in 0.02-0.2% (v/v) phosphoric acid solutions. In the case of acetaldehyde- and propanal-2,4-dinitrophenylhydrazones, the equilibrium Z/E isomer ratios were 0.32 and 0.14, respectively. However, when irradiated with ultraviolet light at 364 nm, the isomer ratios were increased beyond this constant ratio and reached 0.55 and 0.33, respectively. Zero-order rates for decreases of aldehyde derivatives were observed under UV irradiation (364 nm), however the decreases of concentration were not observed in phosphoric acid solutions. The best method for the determination of aldehyde-2,4-dinitrophenylhydrazones by HPLC is to add phosphoric acid to both the sample and the standard solution, to form a 0.02-1% acid solution. 相似文献
78.
Meso and racemic isomers of 1,1′-bis(α-hydroxyalkyl)ferrocene derivatives, and trans and cis isomers of 7-oxa[3]ferrocenophanes have been isolated. The configurations of these isomers have been determined both by spectroscopy and from their reaction behavior. It has been found that the ring-closure and ring-opening interconversion reactions between 1,1′-bis(α-hydroxyalkyl)ferrocenes and 7-oxa[3]ferrocenophanes are stereospecific. PMR spectra of the diols and ethers have been examined at 100 MHz in CF3COOH, and the existence of α-[1′-(α-hydroxyalkyl)ferrocenyl]carbonium ions has been demonstrated in this acid. A mechanism for the various interconversion reactions is proposed on the basis of their stereospecific reactivity and from the PMR spectra of the carbonium ions. 相似文献
79.
Koji Kano Hirofumi Kawazumi Teiichiro Ogawa Junzo Sunamoto 《Chemical physics letters》1980,74(3):511-514
Fluorescence quenching of pyrene and pyrenedecanoic acid by various kinds of anilines has been studied in dipalmitoylphosphatidylcholine liposomes in gel phases. N,N-dimethylaniline and p-isopropyl-N,N-dimethylaniline caused anisotropic diffusional quenching, while N,N-dicetylaniline, a less mobile quencher, predominantly caused static quenching. These data suggested the location sites of both pyrenes and anilines in the membranes. 相似文献
80.
Silylcarbenes are generated by the pyrolysis of 1,1-bis(trimethylsilyl)-1-alkanols with elimination of trimethylsilanol. 相似文献