全文获取类型
收费全文 | 240篇 |
免费 | 2篇 |
国内免费 | 1篇 |
专业分类
化学 | 197篇 |
晶体学 | 8篇 |
力学 | 5篇 |
数学 | 8篇 |
物理学 | 25篇 |
出版年
2021年 | 6篇 |
2020年 | 7篇 |
2019年 | 6篇 |
2018年 | 3篇 |
2017年 | 6篇 |
2016年 | 6篇 |
2015年 | 2篇 |
2014年 | 8篇 |
2013年 | 14篇 |
2012年 | 3篇 |
2011年 | 10篇 |
2010年 | 8篇 |
2009年 | 3篇 |
2008年 | 17篇 |
2007年 | 6篇 |
2006年 | 11篇 |
2005年 | 17篇 |
2004年 | 13篇 |
2003年 | 9篇 |
2002年 | 5篇 |
2000年 | 2篇 |
1999年 | 4篇 |
1998年 | 6篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1985年 | 2篇 |
1984年 | 11篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1958年 | 1篇 |
1956年 | 1篇 |
1955年 | 2篇 |
1954年 | 1篇 |
1953年 | 1篇 |
1937年 | 2篇 |
1934年 | 2篇 |
1898年 | 1篇 |
排序方式: 共有243条查询结果,搜索用时 15 毫秒
11.
Marian Miko?ajczyk Jerzy A. Krysiak Wanda H. Midura Micha?W. Wieczorek Jaros?aw B?aszczyk 《Tetrahedron: Asymmetry》1996,7(12):3513-3520
A general and efficient synthesis of enantiomeric α-chlorovinyl p-tolyl sulfoxides 1 using (+)-(S)C(S)S-α-chloro-α-dimethoxyphosphorylmethyl p-tolyl sulfoxide as a key substrate for the Horner-Wittig reaction with carbonyl compounds is described. The ratio of geometrical isomers of 1 was determined and briefly investigated. The X-ray diffraction structures of (Z)-1-chloro-1-p-tolylsulfinyl-2-phenyl-ethene and (Z)-1-chloro-1-p-tolylsulfinyl-2-(2-thienyl)-ethene are reported. 相似文献
12.
The selenenylation of racemic and optically active α-phosphoryl sulfoxides is a key step leading efficiently to α-phosphorylvinyl sulfoxides or α-phosphorylvinyl selenides depending on the reaction conditions. Oxidation of α-phosphorylvinyl selenides and subsequent thermolysis of selenoxides afford alkynylphosphonates. Studies of the stereochemical course of nucleophilic addition to α-phosphoryl sulfoxides show high facial stereoselectivity of the reaction, however, epimerisation at the α-carbon atom leads to mixtures of diastereomers. 相似文献
13.
Summary Using the potentiometric method, the protonation constants of 1, 5- and 4, 6-benzo[h]naphthyridine (bn), as well as the stability constants of their complexes with nickel(II), cobalt(II), copper(II), or cadmium(II) were determined. 相似文献
14.
Małgorzata T. Kaczmarek Renata Jastrząb Wanda Radecka-Paryzek 《Journal of solution chemistry》2013,42(1):18-26
Formation of complexes between the lanthanide ions and N,N′-bis(salicylidene)-4-methyl-1,3-phenylenediamine ligand was studied in solution by pH potentiometry. The potentiometric titration was performed at 25.00 °C in 0.1 mol·dm?3 NaClO4 ionic strength and in DMSO:water (30:70 v:v) solvent mixture. N,N′-bis(salicylidene)-4-methyl-1,3-phenylenediamine ligand (H2L) occurs in three forms: fully or partially deprotonated and unionized. Computer analysis of potentiometric data indicated that in solution the lanthanide (Ln) complexes exist as LnL2, Ln(HL)2 and Ln(H2L)2 species. This observation appears to be in contrast to the solid-state behavior of these complexes prepared in a self-assembly process and structurally defined. Stability constants for La3+, Eu3+, Gd3+, Tb3+, Ho3+ and Lu3+ (Ln3+) complexes were determined. The order of stabilities of LnL2 species in terms of metal ions is La3+ > Eu3+ ≈ Gd3+ = Tb3+ < Ho3+ < Lu3+ with a prominent “gadolinium break”. 相似文献
15.
Mirosław Giurg Katarzyna Piekielska Magdalena Gębala Bartosz Ditkowski Marcin Wolański Wanda Peczyńska‐Czoch 《合成通讯》2013,43(11):1779-1789
The catalytic oxidative cyclocondensation of the o‐aminophenols 1a–f was investigated. The oxidants used were air/laccase, H2O2/horseradish peroxidase, H2O2/ebselen (3), and TBHP/diphenyl diselenide 4. The products obtained were 2‐amino‐3H‐phenoxazin‐3‐one—questiomycin A, its derivative 2b, and cinnabarinic acid and actinocin (2c,d). Substrates with methyl groups at 4 and 5 positions of benzene ring were converted to different dihydrophenoxazinones 2g,h. Compounds having chlorine atoms at the same positions underwent oxidation to planar phenoxa-zinones 2e,f with elimination of one hydrochloride molecule. 相似文献
16.
Janusz Malarz Anna Stojakowska Wanda Kisiel 《Applied biochemistry and biotechnology》2013,170(7):1589-1601
Foam fractionation is a promising method for separation and concentration of biochemicals. It is simple, easily scalable, inexpensive, and environment friendly. Foam fractionation thus represents an alternative to the traditional methods used for immunoglobulin enrichment. However, little, if any, literature exists documenting the utilization of foam fractionation in the enrichment of immunoglobulins. Milk were utilized as an immunoglobulin source to serve as examples of a real system in this study. The investigation examined the effects of varying five different process parameters: the initial pH value, the initial concentration of immunoglobulin, the nitrogen flow rate, the column height, and the foaming time. Experimental results demonstrated that immunoglobulin could effectively be enriched from milk by foam fractionation. The maximum enrichment ratio with pretreatment (using pH 4.6 precipitation) was 6.30 along with a more than 92 % recovery for IgG and an enrichment ratio of 5.1 with 85 % recovery for IgM. 相似文献
17.
By using calculations based on density functional theory, we investigate the physical factors determining the elemental charge transfer in Alq3, taken as a prototype of molecular systems in condensed phase. The effect of the environment on the hopping of the charge carrier is evaluated self-consistently in a model in which an Alq3 dimer is embedded in an ensemble of permanent and polarizable dipoles, including orientational disorder and the presence of impurities. The results indicate that the origin of the activation barrier is mainly extrinsic and that the local orientation of the dipole moments plays a major role. The influence of nonadiabaticity is also studied and found to be more important for a hole than for an electron. 相似文献
18.
Electrospray ionization mass spectrometry (MS) has been widely used to detect noncovalent interactions in supramolecular compounds, especially in biological systems. In our work, we present the application of the electrospray ionization MS technique to characterize the metallamacrocycles, known as metallacrowns. This project involves investigations of the aminohydroxamic acids structure and chirality influence on formation of ternary 12‐metallacrown‐4 complexes. For our experiments, we used a series of β‐aminohydroxamic acids and derivatives of histidinehydroxamic acid. A high stability of the studied supramolecular systems in the gas phase was confirmed by MS/MS experiments. We also proposed the fragmentation pathways for the studied compounds. Obtained results reveal that the ternary 12‐metallacrown‐4 formation process is not selective, and ligands of various structures and chiralities can be incorporated into these systems. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
19.
Jakub Karasiński Wanda Cegiełkowska Marcin Wojciechowski Małgorzata Wierzbicka Ewa Bulska 《Chemical Papers》2014,68(3):291-299
A specific procedure is proposed for investigating the chemical speciation of zinc (Zn) in plant tissues, viz., the extraction of Zn compounds from Plantago lanceolata L. followed by the chromatographic separation and inductively coupled plasma mass spectrometry (ICP-MS) identification of these compounds. In order to separate the Zn compounds, both size-exclusion (SEC) and ionexchange liquid chromatography (IC) were used in direct sequential and reverse sequential modes. In the direct sequential mode, the entire extract undergoes SEC separation and then the individual fractions are injected onto the ion-exchange column. The molecular size distribution is evaluated by SEC coupled on-line to the UV detector. In the reverse sequential mode, the entire extract undergoes the ion-exchange chromatographic separation and then the individual fractions are injected onto the size-exclusion column. The identification of Zn incorporated into the compounds is further performed using ICP-MS. This procedure is particularly useful in speciation studies when identification of the individual components of the element is problematic due to the lack of suitable standard substances, as is the case for Zn compounds. The proposed procedure facilitates assignment of the signals to the individual components of the fractions for both types of chromatography, thus rendering the chemical speciation of Zn possible when the lack of suitable standard substances impedes the identification of individual components. 相似文献
20.
Herein we report a study of highly efficient platinum‐catalyzed hydrosilylation of dialkenylgermanes with silsesquioxanes and spherosilicates. The use of divinyl‐ and diallylgermanes allowed the synthesis of new classes of compounds, i. e., dumbbell‐type systems, silsesquioxanes with alkenyl pendant group, and oligomeric derivatives. The results are supported by detailed data from in situ FT‐IR and NMR measurements, enabling precise monitoring of the reaction progress and determination of regioselectivity of the formed products. 相似文献