全文获取类型
收费全文 | 1460篇 |
免费 | 69篇 |
国内免费 | 126篇 |
专业分类
化学 | 408篇 |
力学 | 59篇 |
综合类 | 18篇 |
数学 | 894篇 |
物理学 | 276篇 |
出版年
2023年 | 15篇 |
2022年 | 22篇 |
2021年 | 19篇 |
2020年 | 43篇 |
2019年 | 45篇 |
2018年 | 39篇 |
2017年 | 48篇 |
2016年 | 33篇 |
2015年 | 20篇 |
2014年 | 33篇 |
2013年 | 145篇 |
2012年 | 66篇 |
2011年 | 73篇 |
2010年 | 60篇 |
2009年 | 90篇 |
2008年 | 96篇 |
2007年 | 101篇 |
2006年 | 82篇 |
2005年 | 73篇 |
2004年 | 61篇 |
2003年 | 57篇 |
2002年 | 53篇 |
2001年 | 44篇 |
2000年 | 38篇 |
1999年 | 41篇 |
1998年 | 38篇 |
1997年 | 35篇 |
1996年 | 22篇 |
1995年 | 21篇 |
1994年 | 11篇 |
1993年 | 13篇 |
1992年 | 13篇 |
1991年 | 10篇 |
1990年 | 9篇 |
1989年 | 8篇 |
1988年 | 7篇 |
1987年 | 12篇 |
1986年 | 10篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 3篇 |
1972年 | 4篇 |
1971年 | 3篇 |
排序方式: 共有1655条查询结果,搜索用时 78 毫秒
31.
Partition coefficients P of the HNCS, HNCO and HN3 hydropseudohalic acids between a number of organic solvents and water were determined. It has been found that log P increases with pKa of the acid and with the basicity of the solvent, but the effect of pKa on P is the smaller the more basic is the solvent. The relationships have been explained in terms of hydrogen bond formation between undissociated acid and solvent molecules. H-bonding between the pseudohalic acids and organic solvents has been confirmed by IR spectra on the example of HN3 in benzene. Association constants for H-bonding between the three acids and water, benzene, dibutyl ether and tri-n-butyl phosphate were determined from partition data. It has been found that H-bonding increases with the strength of the acid, whereas the contribution to partition from non-specific interactions with water and organic solvents depends on the molecular surface area of the acid molecule. 相似文献
32.
Electron paramagnetic resonance study of amphiphiles partitioning behavior in desiccation-tolerant moss during dehydration 总被引:1,自引:0,他引:1
Shu Jun Xu Wei Hong Chen Ying Wen Chen Cui Fang Wang Yan Wang 《中国化学快报》2007,18(7):865-868
Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance (EPR) spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorum was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly, from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses. 相似文献
33.
Both, dielectric continuum solvation models as well as surface or group based methods using polarity and lipophilicity parameters have been proven to be useful tools for the analysis of solvation and partition questions. For the first time, COSMO-RS provides an integrated theory, which combines the aspects of continuum solvation and surface interactions, and which ends up with chemical potentials of molecules in almost arbitrary solvents and mixtures. Due to its sound theoretical basis, COSMO-RS does not only provide a new quantitative access to solvation and partition properties in well defined solvents, but it also opens a novel view and gives a better understanding of the general problem of solvation. Finally, this allows for a generalisation of COSMO-RS to sophisticatedphysiological partition problems involving as complex phases as blood, brain, or cell membranes. The use of COSMO-RS for drug discovery and design is demonstrated by applications to blood-brain partition coefficients, and water solubility. 相似文献
34.
疏水分配常数用于反相液相色谱保留值的预测 总被引:2,自引:0,他引:2
在反相液相色谱保留值基本方程log k_′=a+_cC_B的基础上,描述了采用疏水分配常数及氢键作用能来预测a、c参数的方法,并系统讨论了疏水分配常数对参数a、c的影响,借此对反相液相色谱宽浓度范围内的保留值进行了预测。 相似文献
35.
研究了丙烯腈/苯乙烯(AN/St)悬浮共聚体系中AN在水/油两相间的分配及其对AN/St共聚物组成的影响.结果表明,AN分配于水/油两相间,使油相AN的含量低于相同单体配料比的本体聚合,导致生成的AN/St共聚物组成偏离本体共聚.为了准确预测进而控制AN/St悬浮共聚物的组成,提出了在考虑AN相分配的基础上计算AN/St悬浮共聚物组成的模型.计算结果与实验值一致,计算中用到的油相实际竞聚率与本体聚合相同,但该悬浮聚合的表观竞聚率随水/油比的变化而发生较大改变. 相似文献
36.
This paper describes the chemical investigation on BuOH-soluble EtOH extract from the aerial part of Sauropus androgynus. This study led to the characterization of six bioactive ingredients including three nucleosides—adenosine (1), 5′-deoxy-5′-methylsulphinyl-adenosine ( 2 ), and uridine ( 3 ), two flavonol dioside — 3-O-β-D-glucosyl-7-O-α-L-rhamnosyl-kaempferol ( 4 ), 3-O-β-D-glucosyl-(1→6)-β-D-glucosyl-kaempferol ( 5 ), and one rare flavonol trioside — 3-O-β-D-glucosyl-(1→6)-β-D-glucosyl-7-O-α-L-rhamno-syl-kaempferol ( 6 ). Their structures were determined on the basis of spectral analysis. 相似文献
37.
W. Zielenkiewicz B. Golankiewicz G. L. Perlovich M. Koźbiał 《Journal of solution chemistry》1999,28(6):731-745
Solubilities of tricyclic analogs of acyclovir have been determined in water at 25, 35, and 45°C and in octanol, water-saturated octanol, and octanol-saturated water at 25°C. Octanol-water partition coefficients were determined at 25°C. Melting temperatures and molar enthalpies of fusion were measured. Activity coefficients in water, octanol, and in aqueous octanol solutions were determined and are discussed. The effect of hydrophilic and hydrophobic substituents in the tricyclic analogs on their thermodynamic properties are discussed. The standard Gibbs energy of transfer between the saturated phases were found to correlate with known values of the melting point of the solvents and the solubilities of the solute. For a number of the compounds examined, correlations between the minimum inhibitory concentration against the herpes simplex virus type 1 (HSV-1) and type 2 (HSV-2), varicella-zoster virus (VZV), thymidine kinase-deficient (TK–) strains of VZV and
were established. Detailed conclusions have been derived concerning the relationships between the structure and the thermodynamic parameters of the compounds examined. 相似文献
38.
Utilization of ferric chelate complex of trans-1,2-cyclohexanediaminetetraacetic acid (CDTA) for the oxidative scrubbing of H2S and CH3SH in Kraft mill streams can be beneficial from the standpoints of iron protection against precipitation and oxygen-mediated regenerative oxidation of the ferrous chelate CDTA. The physical solubility of methyl mercaptan in CDTA–Fe(III) complex cannot be measured directly because of oxidation of the sulfur-bearing gaseous species with the ferric chelate. Therefore, this investigation was carried out to determine the gas–liquid partition coefficients and Henry's law constants of methyl mercaptan in aqueous iron-free CDTA solutions and non-reacting ferrous chelate solutions (CDTA–Fe(II) complex), using the static headspace method with an estimated accuracy of about 2%. Experiments with aqueous solutions of chelate concentrations varying between 38 and 300 mol m−3 were carried out at temperatures between 298 and 333 K and atmospheric pressure. It was shown that the methyl mercaptan solubility decreases with increasing temperature for all systems but was not much influenced, in the studied conditions, by the chelate concentration especially at larger temperatures. 相似文献
39.
Y. B. Tewari D. E. Martire S. P. Wasik M. M. Miller 《Journal of solution chemistry》1982,11(6):435-445
From thermodynamics and certain assumptions it is shown that, under the usual experimental conditions, the octanol-water partition coefficient (Ko/w) of a given organic liquid should be the same whether the substance is partitioned neat or as part of a mixture. Measurements of several mixtures of n-propylbenzene (log Ko/w=3.71±0.04)+ethylbenzene (log Ko/w=3.16±0.01) clearly confirm this. It is also shown that the aqueous solubility (Sw) of a neat organic liquid can be related to its aqueous solubility (S
w
), when it is present at volume fraction in an organic liquid mixture, by S
w
=Sw, where is its activity coefficient in the organic mixture. The measured S
w
values for n-propylbenzene + ethylbenzene (1), n-hexane + nitrobenzene (>1) and di-isopropyl ether + chloroform (<1) are found to be in good agreement with the predicted values (average differences of, respectively, <2%, 8% and 6%). In general, the bounds on S
w
are expected to be 0w
w. 相似文献
40.
《Discrete Mathematics》2022,345(4):112748
It is known that all planar graphs and all projective planar graphs have an edge partition into three forests. Gonçalves proved that every planar graph has an edge partition into three forests, one having maximum degree at most four [5]. In this paper, we prove that every projective planar graph has an edge partition into three forests, one having maximum degree at most four. 相似文献