全文获取类型
收费全文 | 2180篇 |
免费 | 41篇 |
国内免费 | 3篇 |
专业分类
化学 | 1781篇 |
晶体学 | 25篇 |
力学 | 8篇 |
数学 | 104篇 |
物理学 | 306篇 |
出版年
2020年 | 17篇 |
2019年 | 18篇 |
2018年 | 14篇 |
2016年 | 22篇 |
2015年 | 24篇 |
2014年 | 32篇 |
2013年 | 85篇 |
2012年 | 71篇 |
2011年 | 96篇 |
2010年 | 41篇 |
2009年 | 63篇 |
2008年 | 105篇 |
2007年 | 111篇 |
2006年 | 132篇 |
2005年 | 111篇 |
2004年 | 118篇 |
2003年 | 116篇 |
2002年 | 103篇 |
2001年 | 37篇 |
2000年 | 35篇 |
1999年 | 21篇 |
1998年 | 29篇 |
1997年 | 20篇 |
1996年 | 18篇 |
1995年 | 18篇 |
1994年 | 36篇 |
1993年 | 18篇 |
1992年 | 28篇 |
1991年 | 22篇 |
1990年 | 20篇 |
1989年 | 14篇 |
1988年 | 30篇 |
1987年 | 20篇 |
1986年 | 24篇 |
1985年 | 33篇 |
1984年 | 30篇 |
1983年 | 16篇 |
1982年 | 40篇 |
1981年 | 44篇 |
1980年 | 36篇 |
1979年 | 46篇 |
1978年 | 25篇 |
1977年 | 39篇 |
1976年 | 30篇 |
1975年 | 38篇 |
1974年 | 29篇 |
1973年 | 33篇 |
1972年 | 13篇 |
1969年 | 12篇 |
1968年 | 25篇 |
排序方式: 共有2224条查询结果,搜索用时 187 毫秒
51.
Chin-Ping Yang Yoshiyuki Oishi Masa-Aki Kakimoto Yoshio Imai 《Journal of polymer science. Part A, Polymer chemistry》1990,28(6):1353-1359
Polyarylates containing a t-butyl pendant group were prepared from 5-t-butylisophthaloyl chloride and various bisphenols through the phase-transfer catalyzed two-phase polycondensation. The polyarylates having inherent viscosities up to 3.1 dL/g were obtained quantitatively. They were readily soluble in various solvents such as chloroform, m-cresol, and pyridine. Coloreless, transparent, and flexible films could be cast from the chloroform solutions of the polymers. The polyarylates had glass transition temperatures between 210 and 320°C, and did not lose weight below 350°C, with 10% weight loss being recorded at 395–450°C in air. 相似文献
52.
Yasuo Saegusa Sakayu Iida Shigeo Nakamura Nguyen Chau Yoshio Iwakura 《Journal of polymer science. Part A, Polymer chemistry》1984,22(5):1017-1023
Aromatic polythioamide-oxothioxoquinazolines were synthesized by the polycondensation of 2,2′-(m-phenylene)bis-1,3,4-thiadiazoline-5-thione with aromatic bis-o-amino esters. The polymerizations were carried out at 160°C in acidic media such as m-cresol, sulfolane, and polyphosphoric acid to produce polymers with reduced viscosities up to 0.5 dL/g. These polymers were soluble in polar aprotic solvents like N-methyl-2-pyrrolidone and some acidic media including m-cresol. The polythioamide-oxothioxoquinazolines showed relatively good thermal stability with 10% weight loss at 344–394°C in air. 相似文献
53.
A chiral water-soluble zinc porphyrin was optically resolved on a chiral HPLC column, and the binding of chiral amino acids and peptides to each of the enantiomers was examined spectrophotometrically in basic aqueous solution. The binding data apparently indicated that the zinc porphyrin has chiral selectivity for amino acids and dipeptides. This was reasonably explained in terms of the triple cooperation of coordination, Coulomb, and steric interactions of the chiral amino carboxylates with the porphyrin. A compensatory relationship among the thermodynamic parameters for chiral recognition was also shown. 相似文献
54.
Cycloheptatrienes were obtained by the reaction of 2-substituted allylic alcohols with alkynes in the presence of catalytic amounts of palladium complexes and p-toluenesulfonic acid. 相似文献
55.
Nakamura T Ikemoto JY Fujitsuka M Araki Y Ito O Takimiya K Aso Y Otsubo T 《The journal of physical chemistry. B》2005,109(30):14365-14374
The dramatic changes of the lifetimes of the charge-separated (CS) states were confirmed in zinc porphyrin (ZnP)-oligothiophene (nT)-fullerene (C(60)) linked triads (ZnP-nT-C(60)) with the solvent polarity. After the selective excitation of the ZnP moiety of ZnP-nT-C(60), an energy transfer took place from the (1)ZnP moiety to the C(60) moiety, generating ZnP-nT-(1)C(60). In polar solvents, the CS process also took place directly via the (1)ZnP moiety, generating ZnP(*+)-nT-C(60)(*-), as well as the energy transfer to the C(60) moiety. After this energy transfer, an indirect CS process took place from the (1)C(60) moiety. In the less polar solvent anisole, the radical cation (hole) of ZnP(*+)-nT-C(60)(*-) shifted to the nT moiety; thus, the nT moiety behaves as a cation trapper, and the rates of the hole shift were evaluated to be in the order of 10(8) s(-1); then, the final CS states ZnP-nT(*+)-C(60)(*-) were lasting for 6-7 mus. In the medium polar solvent o-dichlorobenzene (o-DCB), ZnP-nT(*+)-C(60)(*-) and ZnP(*+)-nT-C(60)(*-) were present as an equilibrium, because both states have almost the same thermodynamic stability. This equilibrium resulted in quite long lifetimes of the CS states (450-910 mus) in o-DCB. In the more polar benzonitrile, the generation of ZnP-nT(*+)-C(60)(*-) was confirmed with apparent short lifetimes (0.6-0.8 mus), which can be explained by the fast hole shift to more stable ZnP(*+)-nT-C(60)(*-) followed by the faster charge recombination. It was revealed that the relation between the energy levels of two CS states, which strongly depend on the solvent polarity, causes dramatic changes of the lifetimes of the CS states in ZnP-nT-C(60); that is, the most appropriate solvents for the long-lived CS state are intermediately polar solvents such as o-DCB. Compared with our previous data for H(2)P-nT-C(60), in which H(2)P is free-base porphyrin, the lifetimes of the CS states of ZnP-nT-C(60) are approximately 30 times longer than those in o-DCB. 相似文献
56.
The structural analysis of amylose tris(3,5-dimethylphenylcarbamate) (ADMPC) was performed by NMR spectroscopy using a sample with a lower degree of polymerization in order to understand the chiral recognition mechanism when it was used as a chiral stationary phase (CSP) in high-performance liquid chromatography (HPLC). ADMPC exhibited chiral discrimination for many enantiomers, including 1-(9-anthryl)-2,2,2-trifluoroethanol (1) and 1,1'-bi-2-naphthol (2) in both NMR and HPLC. A good agreement was observed between the HPLC and NMR results when chloroform was employed as the common solvent. The structure of ADMPC in solution was investigated by NMR using the 2D NOESY technique coupled with computer modeling, and a left-handed 4/3 helical structure was obtained as the most probable one. The binding geometry between ADMPC and the enantiomers of 1 was also investigated by (1)H NMR titration. On the basis of these results combined with molecular modeling, a rational model to explain the chiral discrimination mechanism of 1 on ADMPC was proposed. 相似文献
57.
Yoshio Iwakura Fujio Toda Kenjiro Hattori 《Journal of polymer science. Part A, Polymer chemistry》1968,6(6):1633-1642
New vinylsilanes (M2), i. e. phenylvinylsilane (I), allylmethylsilane (II), allylphenylsilane (III), and p-vinylphenylmethylsilane (IV), were prepared and copolymerized with styrene (M1). The monomer reactivity ratios were r1 = 5.7 and r2 = 0, r1 = 36 and r2 = 0, r1 = 29 and r2 = 01, and r1 = 0.91 and r2 = 1.1, respectively. From the results of infrared and NMR spectra it was indicated that the vinylsilanes participated in copolymerization in the form of a vinyl type of polymerization and not in the form of a hydrogen-transfer type of polymerization. The reaction of copolymer with alcohols and methyl methacrylate and appropriate catalysts was investigated. 相似文献
58.
Insulating tubular BN sheathing on semiconducting nanowires 总被引:1,自引:0,他引:1
Zhu YC Bando Y Xue DF Xu FF Golberg D 《Journal of the American Chemical Society》2003,125(47):14226-14227
An effective method was developed for generation of insulating tubular boron nitride (BN)-sheathed nanostructures. ZnS nanowires and multilayered Si-SiO2 nanowires were successfully sheathed with insulating tubular BN-forming nanocables. Both the semiconductor nanowire cores and the BN sheaths are crystalline with well-uniform morphologies. 相似文献
59.
Bo Jiang Hui Song Yunqing Kang Shengyao Wang Qi Wang Xin Zhou Kenya Kani Yanna Guo Jinhua Ye Hexing Li Yoshio Sakka Joel Henzie Yamauchi Yusuke 《Chemical science》2020,11(3):791
Generating high surface area mesoporous transition metal boride is interesting because the incorporation of boron atoms generates lattice distortions that lead to the formation of amorphous metal boride with unique properties in catalysis. Here we report the first synthesis of mesoporous cobalt boron amorphous alloy colloidal particles using a soft template-directed assembly approach. Dual reducing agents are used to precisely control the chemical reduction process of mesoporous cobalt boron nanospheres. The Earth-abundance of cobalt boride combined with the high surface area and mesoporous nanoarchitecture enables solar-energy efficient photothermal conversion of CO2 into CO compared to non-porous cobalt boron alloys and commercial cobalt catalysts.Generating high surface area mesoporous transition metal boride is challenging but interesting because incorporation of boron atoms can generate lattice distortion to form amorphous metal boride which has unique properties in catalysis. 相似文献
60.
(±)-1-Benzyl-3α-hydroxy-4β-methylamino-2-oxopyrrolidine (15) and its cis-isomer (16) were synthesised from 1-benzyl-4-ethoxycarbonyl-2,3-dioxopyrrolidine (2) in several steps. The former (15) was converted to 3-benzyl-6-methyl-2-oxo-3,6-diazabicyclo[3.1.0]hexane (17) with a mixture of triphenylphosphine, carbon tetrachloride and triethylamine. 相似文献