全文获取类型
收费全文 | 1142篇 |
免费 | 31篇 |
国内免费 | 1篇 |
专业分类
化学 | 691篇 |
晶体学 | 7篇 |
力学 | 43篇 |
数学 | 75篇 |
物理学 | 358篇 |
出版年
2023年 | 10篇 |
2022年 | 12篇 |
2021年 | 20篇 |
2020年 | 17篇 |
2019年 | 28篇 |
2018年 | 13篇 |
2017年 | 20篇 |
2016年 | 37篇 |
2015年 | 31篇 |
2014年 | 32篇 |
2013年 | 70篇 |
2012年 | 56篇 |
2011年 | 77篇 |
2010年 | 45篇 |
2009年 | 36篇 |
2008年 | 52篇 |
2007年 | 44篇 |
2006年 | 52篇 |
2005年 | 40篇 |
2004年 | 31篇 |
2003年 | 30篇 |
2002年 | 29篇 |
2001年 | 26篇 |
2000年 | 12篇 |
1999年 | 18篇 |
1998年 | 11篇 |
1997年 | 8篇 |
1996年 | 12篇 |
1995年 | 13篇 |
1994年 | 14篇 |
1993年 | 18篇 |
1992年 | 14篇 |
1991年 | 16篇 |
1990年 | 13篇 |
1989年 | 9篇 |
1986年 | 7篇 |
1985年 | 8篇 |
1984年 | 15篇 |
1983年 | 15篇 |
1982年 | 13篇 |
1981年 | 13篇 |
1980年 | 13篇 |
1979年 | 12篇 |
1978年 | 11篇 |
1977年 | 15篇 |
1976年 | 10篇 |
1975年 | 10篇 |
1973年 | 6篇 |
1971年 | 5篇 |
1966年 | 5篇 |
排序方式: 共有1174条查询结果,搜索用时 0 毫秒
21.
Abstract— –The high intensity laser induced photochemistry of phenanthrene is complex and appears to be non-linear with respect to laser intensity. Photochemical products primarily involve the solvent (CH2 C12 ) and phenanthrene coupling. These species exhibit strong absorption and emission which are red-shifted from that of phenanthrene. In the presence of a-methyl styrene, styrene oligomers are formed, but no dimers, indicating that there are no a-methyl styrene cation radical reactions. In all cases of laser irradiation the solutions become acidic, which is ascribed to the deprotonation of the phenanthrene cation radical. Acid formation does not occur in the presence of a-methyl styrene under CW irradiation with a conventional Xe lamp. These differences are ascribed to photoionization from the singlet state for laser irradiation while under CW conditions triplet-triplet annihilation can produce the phenanthrene cation radical. 相似文献
22.
The Born→Green→Yvon equation for molecular fluid has been deduced considering the orientational distribution functions. The
isotropic and anisotropic parts of the distribution function have been separated. The expressions deduced can be used in the
case of mixtures and for the non-central type of intermolecular potential energy. 相似文献
23.
Chatterjee S Basu S Ghosh N Chakrabarty M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(8):1887-1891
In fluorescence quenching study via electron transfer (ET), the quenching rate constant (k(q)) values generally decrease with lowering of quencher concentration, since smaller concentration of quencher always leads to a red shift in the donor-acceptor (D-A) distance in ET [M. Tachiya, S. Murata, J. Phys. Chem. 96 (1992) 8441; S. Murata, M. Tachiya, J. Phys. Chem. 100 (1996) 4064; L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A 103 (1999) 5882]. However, while doing a comparative study with different carbazole (CZ) derivatives-1,4-dicyanobenzene (DCB) systems in benzene (BZ), we observed a deviation from that normal behaviour. It was found that for all of them with lower quencher (DCB) concentration, k(q) values actually increase instead of the expected reduction. Exceptionally, for simple CZ (C12H9N) with decrease in concentration of DCB, k(q) values can even reach the order of energy transfer (10(11) s(-1)). Interestingly, it is not observed when toluene (TL) or xylene (XY) is used as solvent. To explain this unique observation, a sandwich type of molecular structure is predicted, where BZ sliding in between CZ and DCB brings them closer enough, imparting more through bond character to CZ-DCB interaction and hence a higher rate of ET (k(q)) is observed [L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A. 103 (1999) 5882]. 相似文献
24.
Pronoy K. Chatterjee Carl M. Conrad 《Journal of polymer science. Part A, Polymer chemistry》1966,4(1):233-243
The soluble cyanoethyl ether of cellulose, prepared by reaction in the presence of NaOH catalyst to high degrees of substitution (DS = 2.95), can be precipitated by various organic media and contains more nitrogen than can be accounted for by simple addition of acrylonitrile at each cellulose hydroxyl group. Infrared absorption spectra of such samples and of the reacted residues show various types of vibrational absorption bands, characteristic of amino groups. At advanced stages of the reaction the characteristic broad unresolved band of cellulose extending from 1200–950 cm.?1 largely disappears, leaving only a few weaker bands which likely overlap those due to C–N stretching. Comparison is made of the spectra of the partially cyanoethylated cellulose and the polyacrylonitrile which forms in the stock acrylonitrile, to characterize the products. It is inferred that the highly cyanoethylated cellulose, partly dissolved in the acrylonitrile, further degrades and changes under a complex mechanism to various forms of amines. The yellow to orange color of the samples is assumed to be due to these by-products. The thermogravimetric analysis reveals that these products are more heat-resistant than the cyanoethylated cellulose. 相似文献
25.
Chain transfer involving thiourea in radical polymerization of methyl methacrylate in acidic aqueous media has been studied by polymer endgroup analysis using the dye-partition technique. Thiourea has feeble reactivity in chain transfer, the transfer constant with respect to poly (methyl methacrylate) radicals being 1.21 × 10?4 at 42°. This chain transfer study led to the development of a new method for studying the tautomeric equilibrium between the thione and thiol forms of thiourea. The equilibrium is pH dependent and the equilibrium constant at 42° is 232. The ratios of the equilibrium concentrations of the thiol to thione forms of thiourea at various pH's have been calculated. The thiol form is responsible for the chain transfer reactivity; it predominates in strongly acidic media and is almost absent above pH 3.5. This new method may be used for studying the thione-thiol tautomerism of other thiourea derivates. 相似文献
26.
J. Dutta A. Chatterjee S. Basu 《Journal of Radioanalytical and Nuclear Chemistry》1994,181(2):433-439
A radiochemical solvent extraction method for the determination of iron(III) employing the chelating extractant malonic anilide (MA), synthesized in our laboratory, has been described. Effects of different parameters on the extraction of iron(III) from 2M hydrochloric acid into a mixed organic solvent (methyl isobutyl ketone (TIBK) and diethyl ether) have been studied in detail. The method was applied for the estimation of iron content in several fruits using the principle of substoiciometric isotope dilution analysis. 相似文献
27.
Preferred conformers around the central C-C and C-O bonds in n-propanol have been determined using the quantum-mechanical PCILO method and compared with those observed experimentally by microwave spectroscopy. The agreement between theory and experiment is excellent, thus minimizing time consuming searches for microwave transitions corresponding to the preferred conformers. 相似文献
28.
A theoretical model for the multiline TEA CO2 laser has been developed which takes into account the overlap of the P(20) line of (0001) (1000) regular band transition with the R(23) line of (0111) (1110) hot band transition. The model is used for the study of the influence of different parameters like laser gas temperature, gas mixture and pump rates on laser intensities of different rotational lines. This study explains the experimental results of the high power multiline TEA CO2 laser very well. 相似文献
29.
Conformational properties of 3-deazapurine nucleosides (namely, 3-deazaadenosine and 3-deazaguanosine) have been investigated by the PCILO method. Both C(2′)-endo and C(3′)-endo sugar puckers have been considered and the results indicate that the conformational preferences of these nucleoside analogs are quite different from those of their parent nucleosides adenosine and guanosine, respectively. This result has been correlated in terms of the biological inactivity of these nucleoside analogs. 相似文献
30.
The stability constants of the Ni2+ and Co2+ complexes with 1,5-diazacyclooctane-N,N′-diacetic acid (H2DACODA) have been determined potentiometrically in 0.5M KNO3 at 25°. Only M(DACODA) and M(DACODA)OH? were observed. In addition the formation and dissociation kinetics of the pentacoordinate complexes M(DACODA) has been studied in aqueous solution using a stopped-flow technique. Formation follows the rate law vf = kf [M2+] [HDACODA?]/[H+], which can be interpreted as a bimolecular process either between M2+ and DACODA2? (k) or between MOH+ and HDACODA? (k). The second order rate constants k are much higher than those expected from water exchange and can only be explained by a strong internal conjugate base effect. In the limiting case, however, this is equivalent to the second possible explanation, which assumes MOH+ and HDACODA? as reactive species. The dissociation rate is given by vd = (kML + k [H+]) · [M(DACODA)]. 相似文献