全文获取类型
收费全文 | 266篇 |
免费 | 11篇 |
国内免费 | 2篇 |
专业分类
化学 | 110篇 |
晶体学 | 2篇 |
力学 | 7篇 |
数学 | 17篇 |
物理学 | 83篇 |
无线电 | 60篇 |
出版年
2024年 | 1篇 |
2023年 | 1篇 |
2022年 | 5篇 |
2021年 | 5篇 |
2020年 | 7篇 |
2019年 | 6篇 |
2018年 | 7篇 |
2017年 | 3篇 |
2016年 | 12篇 |
2015年 | 3篇 |
2014年 | 10篇 |
2013年 | 33篇 |
2012年 | 7篇 |
2011年 | 15篇 |
2010年 | 7篇 |
2009年 | 8篇 |
2008年 | 21篇 |
2007年 | 16篇 |
2006年 | 7篇 |
2005年 | 17篇 |
2004年 | 9篇 |
2003年 | 6篇 |
2002年 | 6篇 |
2001年 | 5篇 |
2000年 | 9篇 |
1999年 | 4篇 |
1998年 | 5篇 |
1997年 | 11篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1970年 | 1篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1945年 | 1篇 |
排序方式: 共有279条查询结果,搜索用时 31 毫秒
121.
Oxy anions 3 generated from 1,2-dihydrocyclobutabenzen-1-ones 1 through addition of a charged nucleophile or from 1-hydroxy-1,2-dihydrocyclobutabenzenes 2 by deprotonation with base lead to stable products through distal and/or proximal cleavage of the strained four-membered ring via benzyl carbanion 4 and/or aryl carbanion 5. A systematic study of this process reveals the relative stability of the two isomeric carbanions 4 and 5 as a key factor in determining the course of the ring-cleavage reaction. While benzyl carbanions 4 can be trapped with carbon electrophiles, attempts at trapping aryl carbanions 5 with electrophiles other than H+ failed. In protic solvents, the magnesium salt of the tertiary alcohol 2 shows an increased rate of proximal cleavage as compared to its alkali salts. From this, we conclude that, in contrast to benzyl carbanions 4 , free aryl carbanions 5 are of transient existence only. Proximal C,C-bond cleavage seems to occur either through protonation of 5 from a fast, reversible equilibrium 3 ? 5 in which 3 strongly predominates, or in protic solvents possibly even through a rate-limiting protonation of 3 at the aromatic C-atom, bypassing free anion 5 altogether. Thus, additional factors other than just the relative stability of isomeric carbanions 4 and 5 are of importance in determining the regiochemistry of the base-induced C,C-bond cleavage in ketones 1 and in alcohols 2 . 相似文献
122.
A series of 5-(arylthio)-2,4-diaminoquinazolines are known as selective inhibitors of dihydrofolate reductase (DHFR) from Candida albicans. We have performed docking and molecular dynamics simulations of these inhibitors with C. albicans and human DHFR to understand the basis for selectivity of these agents. Study was performed on a selected set of 10 compounds with variation in structure and activity. Molecular dynamics simulations were performed at 300 K for 45 ps with equilibration for 10 ps. Trajectory data was analyzed on the basis of hydrogen bond interactions, energy of binding and conformational energy difference. The results indicate that hydrogen bonds formed between the compound and the active site residues are responsible for inhibition and higher potency. The selectivity index, i.e the ratio of I50 against human DHFR to I50 against fungal DHFR, is mainly determined by the conformation adapted by the compounds within the active site of two enzymes. Since the human DHFR active site is rigid, the compound is trapped in a higher energy conformation. This energy difference between the two conformations E mainly governs the selectivity against fungal DHFR. The information generated from this analysis of potency and selectivity should be useful for further work in the area of antifungal research. 相似文献
123.
The Smoluchowski equation with a time-dependent sink term is solved exactly. In this method, knowing the probability distribution P(0, s) at the origin, allows deriving the probability distribution P(x, s) at all positions. Exact solutions of the Smoluchowski equation are also provided in different cases where the sink term has linear, constant, inverse, and exponential variation in time. 相似文献
124.
Recognizing the potential of the mixed solvent systems comprising ionic liquid as one of the constituents in real applications, the steady-state and time-resolved fluorescence behavior of C153 has been studied in neat 1-butyl-3-methylimidazolium hexafluorophosphate and its mixtures with nonpolar solvents, namely, toluene and 1,4-dioxane. No significant effect of the cosolvent on the steady-state absorption or fluorescence spectra of C153 in ionic liquid has been observed. Time-resolved fluorescence anisotropy measurements show a decrease of the rotational correlation time of C153 with gradual addition of the cosolvent. Solvation dynamics in ionic liquid-cosolvent mixtures is found to be biphasic, and a decrease of the average solvation time is observed with increasing amount of the cosolvent in solution. The time-zero spectrum of C153 is found to shift toward higher energy with gradual addition of the nonpolar solvent, suggesting that the probe molecule experiences a more nonpolar environment at the early stage of the dynamics in mixed solvents. The blue shift of the time-zero spectrum caused by the addition of the nonpolar solvent results in a larger Stokes shift of the time-dependent spectra due to solvent relaxation in mixed solvents. A comparison of the time-dependent spectral data of the ionic liquid-toluene and ionic liquid-dioxane systems shows that, while a small amount of toluene can significantly affect the dynamics, comparatively, a larger amount of dioxane is required to bring about the same effect. This is explained in terms of favorable interactions between toluene and the imidazolium ring system leading to a more effective solubilization of toluene in the cybotactic region of the probe. 相似文献
125.
Solvation dynamics in ionic liquid swollen p123 triblock copolymer micelle: a femtosecond excitation wavelength dependence study 总被引:1,自引:0,他引:1
Adhikari A Dey S Das DK Mandal U Ghosh S Bhattacharyya K 《The journal of physical chemistry. B》2008,112(20):6350-6357
Femtosecond solvation dynamics of coumarin 480 (C480) in a mixed micelle is reported. The mixed micelle consists of a triblock copolymer (PEO)20-(PPO) 70-(PEO)20 (Pluronic P123) and an ionic liquid (IL), 1-pentyl-3-methylimidazolium tetrafluoroborate ([pmim][BF4]). At a low concentration (0.3 M), the sparingly water soluble IL ([pmim][BF4]) penetrates the hydrophobic PPO core of the P123 micelles. Thus emission maximum of C480 in the core (accessed at lambdaex=375 nm) in 0.3 M IL is red-shifted by 8 nm from that in its absence and the red edge excitation shift (REES) is large (19+/-1 nm). At a high concentration (0.9 M), the ionic liquid [pmim][BF4] invades both the core and corona region and the mixed micelle exhibits very small REES (3+/-1 nm). Anisotropy decay and solvation dynamics in different regions of the mixed micelle are studied by variation of excitation wavelength (lambda ex). In P123 micelle, the average rotational time () is 2800 ps in the core (at lambdaex=375 nm) and 1350 ps in the corona region (at lambdaex=435 nm). In 0.3 M [pmim][BF4], tau rot at the core of the mixed micelle decreases to 1950 ps while that in the corona remains unaffected. In 0.9 M IL, both the core and corona (lambda ex=375 and 435 nm) exhibit similar and short approximately 600 ps. In 0.3 M IL, solvation dynamics in the core region (lambdaex=375 nm) of P123 micelle is about 2 times faster than in its absence. In 0.3 M IL, solvation dynamics in the corona region (lambdaex=435 nm) is approximately 100 times faster than that in the core. In 0.9 M IL, the solvation dynamics in the core and in the corona is, respectively, approximately 9 times and 4 times faster than that in 0.3 M IL. 相似文献
126.
Dey S Adhikari A Mandal U Ghosh S Bhattacharyya K 《The journal of physical chemistry. B》2008,112(16):5020-5026
Solvation dynamics and anisotropy decay of coumarin 480 (C480) in a supramolecular assembly containing a triblock copolymer, PEO20-PPO70-PEO20 (Pluronic P123) and a surfactant, CTAC (cetyl trimethylammonium chloride) are studied by femtosecond up-conversion. In a P123-CTAC complex, C480 displays a significant (22 nm) red edge excitation shift (REES) in the emission maximum as lambda ex increases from 335 to 445 nm. This suggests that the P123-CTAC aggregate is quite heterogeneous. The average rotational relaxation time (tau rot) of C480 in a P123-CTAC complex decreases by a factor of 2 from 2500 ps at lambda ex = 375 nm to 1200 ps at lambda ex = 435 nm. For lambda ex = 375 nm, the probe molecules in the buried core region of P123-CTAC are excited and the solvation dynamics displays three components, 2, 60, and 4000 ps. It is argued that insertion of CTAC in P123 micelle affects the polymer chain dynamics, and this leads to reduction of the 130 ps component of P123 micelle to 60 ps in P123-CTAC. For lambda ex = 435 nm, which selects the peripheral highly polar corona region, solvation dynamics in P123-CTAC and P123 are extremely fast with a major component of <0.3 ps ( approximately 80%) and a 2 ps ( approximately 20%) component. 相似文献
127.
128.
The copper complex [KGHK-Cu]+ demonstrates catalytic inactivation of human angiotensin converting enzyme at sub-saturating concentrations, under oxidative conditions, with an observed rate constant k approximately 2.9 +/- 0.5 x 10(-2) min(-1). 相似文献
129.
G. S. Gokhale M. G. K. Menon F.A.Sc. R. T. Redkar 《Proceedings Mathematical Sciences》1966,64(2):57-73
Balloons, upto two million cubic feet in volume, made out of locally extruded polyethylene film ·0011 inches thick, have been successfully flown and altitudes of upto 120,000 ft. attained. Instrumented pay-loads upto 100 kg. in weight have been floated at level ceilings around these altitudes. Various aspects, (such as balloon material, shape and design, and launching methods), which relate to the technique of flying polyethylene balloons of large volume over tropical latitudes are briefly discussed. 相似文献
130.
Ahmed N.A. Gokhale D.V. 《IEEE transactions on information theory / Professional Technical Group on Information Theory》1989,35(3):688-692
Entropy expressions for several continuous multivariate distributions are derived. Point estimation of entropy for the multinormal distribution and for the distribution of order statistics from D.G. Weinman's (Ph.D dissertation, Ariz. State Univ., Tempe, AZ, 1966) exponential distribution is considered. The asymptotic distribution of the uniformly minimum variance unbiased estimator for multinormal entropy is obtained. Simulation results on convergence of the means and variances of these estimators are provided 相似文献