全文获取类型
收费全文 | 973篇 |
免费 | 23篇 |
国内免费 | 6篇 |
专业分类
化学 | 790篇 |
晶体学 | 9篇 |
力学 | 10篇 |
数学 | 44篇 |
物理学 | 149篇 |
出版年
2022年 | 11篇 |
2021年 | 7篇 |
2020年 | 11篇 |
2019年 | 8篇 |
2018年 | 17篇 |
2017年 | 7篇 |
2016年 | 13篇 |
2015年 | 12篇 |
2014年 | 18篇 |
2013年 | 52篇 |
2012年 | 49篇 |
2011年 | 52篇 |
2010年 | 19篇 |
2009年 | 28篇 |
2008年 | 55篇 |
2007年 | 58篇 |
2006年 | 55篇 |
2005年 | 69篇 |
2004年 | 45篇 |
2003年 | 45篇 |
2002年 | 47篇 |
2001年 | 16篇 |
2000年 | 11篇 |
1999年 | 8篇 |
1998年 | 10篇 |
1997年 | 6篇 |
1996年 | 10篇 |
1995年 | 8篇 |
1994年 | 13篇 |
1993年 | 8篇 |
1992年 | 16篇 |
1991年 | 11篇 |
1990年 | 12篇 |
1989年 | 11篇 |
1988年 | 14篇 |
1987年 | 16篇 |
1986年 | 9篇 |
1985年 | 10篇 |
1984年 | 19篇 |
1983年 | 10篇 |
1982年 | 16篇 |
1980年 | 12篇 |
1979年 | 10篇 |
1978年 | 5篇 |
1977年 | 10篇 |
1976年 | 6篇 |
1975年 | 9篇 |
1974年 | 6篇 |
1973年 | 4篇 |
1971年 | 7篇 |
排序方式: 共有1002条查询结果,搜索用时 15 毫秒
941.
Y Takemoto T Ueyama H Saito S Horio S Sanada J Shoji S Yahara O Tanaka S Shibata 《Chemical & pharmaceutical bulletin》1984,32(8):3128-3133
942.
943.
Toru Takagishi Toshihiko Ueno Nobuhiko Kuroki Shoji Shima Heiichi Sakai 《Journal of polymer science. Part A, Polymer chemistry》1984,22(6):1281-1289
The interaction of α-poly-L -lysine and ε-poly-L -lysine with methyl and ethyl orange was studied by equilibrium dialysis and spectroscopic methods. The results of the dialysis measurements indicated that the extent of binding by ε-polypeptide is substantially higher than that by α-polypeptide, despite the much greater molecular weight of the latter. This difference in binding affinity was interpreted in terms of the increased conformational adaptability of ε-polypeptide because of its highly flexible structure. Furthermore, ε-polypeptide exhibited strong cooperative binding. In addition, the effect of the successive addition of α- and ε-polypeptides on the absorption spectra of methyl and ethyl orange was investigated. The addition of α-polypeptide with a molecular weight of 400,000 produced a new absorption peak at a shorter wavelength, due to the stacked dye molecules on the polypeptide chain, whereas that of ε-polypeptide did not. From the results of spectroscopic measurements a possible mode of interaction between these two polypeptides and the small molecule is discussed. 相似文献
944.
Chiral recognition of hydroxycaboxylic acid, amino acid and 1,2-diol derivatives using diastereomeric complexation based on hydrogen bond with L(+)-N,N′-diisopropyl-tartramide (DIPTA) is described. 相似文献
945.
(E)- and (Z)-(fluoroalkenyl)boronates were prepared stereospecifically by the reaction of 2-fluoroalkylideneiodonium ylide generated from (E)- or (Z)-(2-fluoroalkenyl)iodonium salts with di(p-fluorophenoxy)alkylboranes, followed by transesterification to pinacol esters. The resulting pinacol esters of (fluoroalkenyl)boranes were used for the stereoselective synthesis of trisubstituted fluoroalkenes by cross-coupling reactions. 相似文献
946.
Li L Abe Y Kanagawa K Shoji T Mashino T Mochizuki M Tanaka M Miyata N 《Analytica chimica acta》2007,599(2):315-319
Hydroxyl radical formation by Fenton reaction in the presence of an iron-chelating agent such as EDTA was traced by two different assay methods; an electron spin resonance (ESR) spin-trapping method with 5,5-dimethyl-1-pyrroline N-oxide (DMPO), and high Performance liquid chromatography (HPLC)-fluorescence detection with terephthalic acid (TPA), a fluorescent probe for hydroxyl radicals. From the ESR spin-trapping measurement, it was observed that EDTA seemed to suppress hydroxyl radical formation with the increase of its concentration. On the other hand, hydroxyl radical formation by Fenton reaction was not affected by EDTA monitored by HPLC assay. Similar inconsistent effects of other iron-chelating agents such as nitrylotriacetic acid (NTA), diethylenetriamine penta acetic acid (DTPA), oxalate and citrate were also observed. On the addition of EDTA solution to the reaction mixture 10 min after the Fenton reaction started, when hydroxyl radical formation should have almost ceased but the ESR signal of DMPO-OH radicals could be detected, it was observed that the DMPO-OH signal disappeared rapidly. With the simultaneous addition of Fe(II) solution and EDTA after the Fenton reaction ceased, the DMPO-OH signal disappeared more rapidly. The results indicated that these chelating agents should enhance the quenching of [DMPO-OH] radicals by Fe(II), but they did not suppress Fenton reaction by forming chelates with iron ions. 相似文献
947.
The kinetics of Z-(cis)/E-(trans) isomerization of enalapril was investigated by reversed phase high-performance liquid chromatography (RP-HPLC) using a monolith ODS column under a series of different temperature and pH conditions. At a neutral pH 7, the rate (k(obs)) of Z-(cis)/E-(trans) isomerization of enalapril at 4 degrees C (9.4 x 10(-3)min(-1)) is much lower than at 23 degrees C (1.8 x 10(-1)min(-1)), while the fractional concentration of Z-(cis) isomer is always higher than that of E-(trans) isomer in the pH range 2-7. The fractional concentration of the E-(trans) isomer becomes a maximum (about 40%) in the pH range 3-6, where enalapril exists as a zwitterion. The hydrophobicity (logP(O/W)) of both isomers was estimated by high-speed counter-current chromatography (HSCCC). Normal phase HSCCC separation using a tert-butyl methyl ether-acetonitrile-20mM potassium phosphate buffer (pH 5) two-phase solvent system (2:2:3, v/v/v) at 4 degrees C was effective in partially separating the isomers, and the partition coefficient (K) of each isomer was directly calculated from the retention volume (V(R)). The logP(O/W) values of Z-(cis) and E-(trans) isomers were -0.46 and -0.65, respectively. 相似文献
948.
Yanagida A Murao H Ohnishi-Kameyama M Yamakawa Y Shoji A Tagashira M Kanda T Shindo H Shibusawa Y 《Journal of chromatography. A》2007,1143(1-2):153-161
A novel method was developed for the separation of proanthocyanidins (PAs; oligomeric flavan-3-ols) by hydrophilic interaction chromatography (HILIC) using an amide-silica column eluting with an aqueous acetonitrile mobile phase. The best separation was achieved with a linear gradient elution of acetonitrile-water at ratios of 9:1 to 5:5 (v/v) for 60 min at a flow rate of 1.0 ml/min. Under these HPLC conditions, a mixture of natural oligomeric PAs (from apple) was separated according to degree of polymerization (DP) up to decamers. The DP of each separated oligomer was confirmed by LC/electrospray ionization MS. In further HILIC separation studies of 15 different flavan-3-ol and oligomeric PA (up to pentamer) standards with an isocratic elution of acetonitrile-water (84:16), a high correlation was observed between the logarithm of retention factors (log k) and the number of hydroxyl groups in their structures. The coefficient of this correlation (r2=0.9501) was larger than the coefficient (r2=0.7949) obtained from the correlation between log k and log P(o/w) values. These data reveal that two effects, i.e. hydrogen bonding between the carbamoyl terminal on the column and the hydroxyl group of solute oligomer and hydrophilicity based on the high-order structure of oligomeric PAs, corporately contribute to the separation, but the hydrogen bonding effect is predominant in our HILIC separation mode. 相似文献
949.
Takajo Y Matsuki H Kaneshina S Aratono M Yamanaka M 《Colloids and surfaces. B, Biointerfaces》2007,59(1):52-58
The miscibility and interaction of 1-hexanol (C6OH) and 1-heptanol (C7OH) with 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) in the adsorbed films and micelles were investigated by measuring the surface tension of aqueous C6OH-DHPC and aqueous C7OH-DHPC solutions. The surface density, the mean molecular area, the composition of the adsorbed film, and the excess Gibbs energy of adsorption g(H,E), were estimated. Further, the critical micelle concentration of the mixtures was determined from the surface tension versus molality curves; the micellar composition was calculated. The miscibility of the 1-alkanols and DHPC molecules in the adsorbed film and micelles was examined using the phase diagram of adsorption (PDA) and that of micellization (PDM). The PDA and the composition dependence of g(H,E) indicated the non-ideal mixing of the 1-alkanols and DHPC molecules due to the attractive interaction between the molecules in the adsorbed film, while the PDM indicated that the 1-alkanol molecules were not incorporated in the micelles within DHPC rich region. The dependence of the mean molecular area of the mixtures on the surface composition suggested that the packing property of the adsorbed film depends on the chain length of 1-alkanol: C6OH expands the DHPC adsorbed film more than C7OH. 相似文献
950.
Osaka I Abe T Shinamura S Takimiya K 《Journal of the American Chemical Society》2011,133(17):6852-6860
Four isomeric naphthodithiophenes (NDTs) with linear and angular shapes were introduced into the polythiophene semiconductor backbones, and their field-effect transistor performances were characterized. The polymers bearing naphtho[1,2-b:5,6-b']dithiophene (NDT3), an angular-shaped NDT, exhibited the highest mobilities of ~0.8 cm(2) V(-1) s(-1) among the four NDT-based polymers, which is among the highest reported so far for semiconducting polymers. Interestingly, the trend of the mobility in the NDT-based polymers was contrary to our expectations; the polymers with angular NDTs showed higher mobilities than those with linear NDTs despite the fact that naphtho[2,3-b:6,7-b']dithiophene (NDT1), a linear-shaped NDT, has shown the highest mobility in small-molecule systems. X-ray diffraction studies revealed that angular-NDT-based polymers gave the highly ordered structures with a very close π-stacking distance of 3.6 ?, whereas linear-NDT-based polymers had a very weak or no π-stacking order, which is quite consistent with the trend of the mobility. The nature of such ordering structures can be well understood by considering their molecular shapes. In fact, a linear NDT (NDT1) provides angular backbones and an angular NDT (NDT3) provides a pseudostraight backbone, the latter of which can pack into the highly ordered structure and thus facilitate the charge carrier transport. In addition to the ordering structure, the electronic structures seem to correlate with the carrier transport property. MO calculations, supported by the measurement of ionization potentials, suggested that, while the HOMOs are relatively localized within the NDT cores in the linear-NDT-based polymers, those are apparently delocalized along the backbone in the angular-NDT-based polymers. The latter should promote the efficient HOMO overlaps between the polymer backbones that are the main paths of the charge carrier transport, which also agrees with the trend of the mobility. With these results, we conclude that angular NDTs, in particular NDT3, are promising cores for high-performance semiconducting polymers. We thus propose that both the molecular shapes and the electronic structures are important factors to be considered when designing high performance semiconducting polymers. 相似文献