全文获取类型
收费全文 | 776篇 |
免费 | 31篇 |
国内免费 | 1篇 |
专业分类
化学 | 634篇 |
晶体学 | 4篇 |
力学 | 8篇 |
数学 | 62篇 |
物理学 | 100篇 |
出版年
2024年 | 1篇 |
2023年 | 9篇 |
2022年 | 49篇 |
2021年 | 48篇 |
2020年 | 27篇 |
2019年 | 35篇 |
2018年 | 20篇 |
2017年 | 18篇 |
2016年 | 27篇 |
2015年 | 34篇 |
2014年 | 43篇 |
2013年 | 61篇 |
2012年 | 63篇 |
2011年 | 76篇 |
2010年 | 37篇 |
2009年 | 29篇 |
2008年 | 42篇 |
2007年 | 48篇 |
2006年 | 35篇 |
2005年 | 23篇 |
2004年 | 23篇 |
2003年 | 14篇 |
2002年 | 10篇 |
2001年 | 5篇 |
2000年 | 2篇 |
1999年 | 7篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1993年 | 1篇 |
1991年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1976年 | 1篇 |
1969年 | 1篇 |
1965年 | 2篇 |
排序方式: 共有808条查询结果,搜索用时 21 毫秒
71.
The activity of enzyme I (EI), the first protein in the bacterial PEP:sugar phosphotransferase system, is regulated by a monomer–dimer equilibrium where a Mg2+-dependent autophosphorylation by PEP requires the homodimer. Using inactive EI(H189A), in which alanine is substituted for the active-site His189, substrate binding effects can be separated from those of phosphorylation. Whereas 1 mM PEP (with 2 mM Mg2+) strongly promotes dimerization of EI(H189A) at pH 7.5 and 20 °C, 5 mM pyruvate (with 2 mM Mg2+) has the opposite effect. A correlation between the coupling of N- and C-terminal domain unfolding, measured by differential scanning calorimetry, and the dimerization constant for EI, determined by sedimentation equilibrium, is observed. That is, when the coupling between N- and C-terminal domain unfolding produced by 0.2 or 1.0 mM PEP and 2 mM Mg2+ is inhibited by 5 mM pyruvate, the dimerization constant for EI(H189A) decreases from >108 to <5 × 105 or 3 × 107 M−1, respectively. With 2 mM Mg2+ at 15–25 °C and pH 7.5, PEP has been found to bind to one site/monomer of EI(H189A) with KA′106 M−1 (ΔG′=−33.7±0.2 kJ mol−1 and ΔH=+16.3 kJ mol−1 at 20 °C with ΔCp=−1.4 kJ K−1 mol−1). The binding of PEP to EI(H189A) is synergistic with that of Mg2+. Thus, physiological concentrations of PEP and Mg2+ increase, whereas pyruvate and Mg2+ decrease the amount of dimeric, active, dephospho-enzyme I. 相似文献
72.
Mariana Dennehy Oscar V. Quinzani Robert A. Burrow 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(9):m395-m397
The centrosymmetric title compound, [Ag(C7H4NO2S2)]n, consists of dinuclear units in which two thiosaccharinate anions each bridge two Ag atoms via an endocyclic N atom and an exocyclic S atom across a crystallographic centre of inversion midway between the Ag atoms. The dimeric units are connected via Ag—Sexo interactions to create two‐dimensional networks. The thiosaccharinate anions bridge in a μ3‐S:S:N manner. The Ag...Ag distance can be considered a strong argentophilic interaction. 相似文献
73.
Ayla C. do Lago Giovana de F. Lima Mariana G. Segatelli 《International journal of environmental analytical chemistry》2013,93(7):767-782
In this work a solid phase on-line uranium ion preconcentration system coupled with spectrophotometry has been developed. The method is based on uranyl ion preconcentration at pH 3.75 onto multiwall carbon nanotubes treated with HNO3. After preconcentration, the uranyl ions are eluted with 0.32?mol?L?1HCl followed by reaction with 3,6-bis[(2-arsonophenyl)-azo]-4,5-dihydroxy-2,7-naphthalendisulfonic acid 0.08%[w/v] (Arsenazo III), which had maximum monitored absorbance of 650?nm. Effects of the pertinent experimental parameters on the system were investigated by means of 26?2 fractional factorial design, while optimization was carried out using the Doehlert matrix. Under optimized conditions, detection and quantification limits were found to be 0.21 and 0.7?µg?L?1, respectively. The analytical curve ranged from 5 to 150?µg?L?1 (r?=?0.998), while the relative standard deviations (RSD) were 3.27 and 2.56% for the respective uranium concentrations of 10 and 100?µg?L?1 (n?=?10). The features obtained for the on-line preconcentration system were: preconcentration factor of 228, concentration efficiency of 57?min?1, consumption index of 0.13?mL and sample throughput of 15?h?1. In order to assess the accuracy of the proposed method, addition and recovery studies were carried out on spring water samples from different sources and synthetic seawater with satisfactory results ranging from 94.85 up to 103.65%. 相似文献
74.
Natural-based plasticizers and biopolymer films: A review 总被引:2,自引:0,他引:2
Melissa Gurgel Adeodato Vieira Mariana Altenhofen da Silva Lucielen Oliveira dos Santos Marisa Masumi Beppu 《European Polymer Journal》2011,(3):254-263
In recent years, much attention has been focused on research to replace petroleum-based commodity plastics, in a cost-effective manner, with biodegradable materials offering competitive mechanical properties. Biopolymers have been considered as the most promising materials for this purpose. However, they generally present poor mechanical properties regarding processability and end-use application, since the fragility and brittleness exhibited during thermoformation can limit their potential for application. In order to overcome this problem, plasticizers are added to provide the necessary workability to biopolymers. This class of products became more visible when biodegradable additives and plasticizers also became the focus of material scientists. The use of natural and/or biodegradable plasticizers, with low toxicity and good compatibility with several plastics, resins, rubber and elastomers in substitution of conventional plasticizers, such as phthalates and other synthetic conventional plasticizers attracted the market along with the increasing worldwide trend towards use of biopolymers. Here we discuss the main results and developments in natural plasticizer/synthetic and biopolymer-based films during the last decades. 相似文献
75.
76.
Cristina Pinedo-Rivilla Mariana Carrara Cafêu Josefina Aleu Casatejada Ângela Regina Araujo Isidro G. Collado 《Tetrahedron: Asymmetry》2009,20(23):2666-2672
A set of five fungal species, Botrytis cinerea, Trichoderma viride and Eutypa lata, and the endophytic fungi Colletotrichum crassipes and Xylaria sp., was used in screening for microbial biocatalysts to detect monooxygenase and alcohol dehydrogenase activities (for the stereoselective reduction of carbonyl compounds). 4-Ethylcyclohexanone and acetophenone were biotransformed by the fungal set. The main reaction pathways involved reduction and hydroxylations at several positions including tertiary carbons. B. cinerea was very effective in the bioreduction of both substrates leading to the chiral alcohol (S)-1-phenylethanol in up to 90% enantiomeric excess, and the cis–trans ratio for 4-ethylcyclohexanol was 0:100. trans-4-Ethyl-1-(1S-hydroxyethyl)cyclohexanol, obtained from biotransformation by means of an acyloin-type reaction, is reported here for the first time. The absolute configurations of the compounds trans-4-ethyl-1-(1S-hydroxyethyl)cyclohexanol and 4-(1S- and 4-(1R-hydroxyethyl)cyclohexanone were determined by NMR analysis of the corresponding Mosher’s esters. 相似文献
77.
Mariana Cristea Daniela Gheorghiu Ionita Maria Bruma B. C. Simionescu 《Journal of Thermal Analysis and Calorimetry》2008,93(1):63-68
Two aromatic polyimides and the corresponding poly(amic acid)s, with oxadiazole and para/meta phenoxyphenylene rings in the backbone, were synthesized and the structure — thermal properties correlation was followed
by dynamic mechanical analysis. Concerning the poly(amic acid)s, the glass transition domain was emphasized only for the compound
with meta-oriented rings because the process of imidization takes place with increasing temperature. A multiplex experiment was performed
to calculate the activation energy of the transition localized under 200°C. Consecutive heating-cooling-heating cycles were
accomplished. All phenomena are discussed by cross-examination of the storage modulus (E′), loss modulus (E″) and loss factor tanδ variation with temperature. 相似文献
78.
Torres MF Sales PS de Rossi RH Fernández MA 《Langmuir : the ACS journal of surfaces and colloids》2010,26(23):17858-17866
The mixed system of a nonionic hydrocarbon surfactant, polyoxyethylene (23) lauryl ether (Brij-35), and a perfluorinated surfactant, perfluorononanoic acid, was investigated by a combination of methods. The critical micelle concentrations (cmc's) have been determined over a wide range of sample compositions by fluorescence and UV-visible spectrophotometry using pyrene and N-(4-nitrophenyl) perfluorononanamide, respectively, as molecular probes. The values of the cmc's obtained were considerably different with the two techniques employed. Measurements of the (19)F nuclear magnetic resonance chemical shift of the same mixtures showed two breaks in the plots of Δδ(f) versus molar fraction of the perfluorinated surfactant. Conductivity and surface tension measurements also showed two breaks. The behavior is attributed to the formation of mixed micelles that change their composition when the fraction of the fluorinated compound increases and some segregation of the fluorinated compound takes place at a high total surfactant concentration. 相似文献
79.
This study investigated the organic and inorganic constituents of healthy leaves and Candidatus Liberibacter asiaticus (CLas)-inoculated leaves of citrus plants. The bacteria CLas are one of the causal agents of citrus greening (or Huanglongbing) and its effect on citrus leaves was investigated using laser-induced breakdown spectroscopy (LIBS) combined with chemometrics. The information obtained from the LIBS spectra profiles with chemometrics analysis was promising for the construction of predictive models to identify healthy and infected plants. The major, macro- and microconstituents were relevant for differentiation of the sample conditions. The models were then applied to different inoculation times (from 1 to 8 months). The models were effective in the classification of 82-97% of the diseased samples with a 95% significance level. The novelty of this method was in the fingerprinting of healthy and diseased plants based on their organic and inorganic contents. 相似文献
80.