全文获取类型
收费全文 | 4592篇 |
免费 | 204篇 |
国内免费 | 49篇 |
专业分类
化学 | 3196篇 |
晶体学 | 76篇 |
力学 | 171篇 |
综合类 | 2篇 |
数学 | 485篇 |
物理学 | 915篇 |
出版年
2024年 | 38篇 |
2023年 | 71篇 |
2022年 | 385篇 |
2021年 | 333篇 |
2020年 | 207篇 |
2019年 | 212篇 |
2018年 | 187篇 |
2017年 | 166篇 |
2016年 | 231篇 |
2015年 | 171篇 |
2014年 | 197篇 |
2013年 | 317篇 |
2012年 | 275篇 |
2011年 | 322篇 |
2010年 | 188篇 |
2009年 | 172篇 |
2008年 | 181篇 |
2007年 | 170篇 |
2006年 | 134篇 |
2005年 | 119篇 |
2004年 | 72篇 |
2003年 | 72篇 |
2002年 | 67篇 |
2001年 | 40篇 |
2000年 | 40篇 |
1999年 | 22篇 |
1998年 | 28篇 |
1997年 | 19篇 |
1996年 | 23篇 |
1995年 | 26篇 |
1994年 | 14篇 |
1993年 | 25篇 |
1992年 | 25篇 |
1991年 | 19篇 |
1990年 | 18篇 |
1989年 | 18篇 |
1988年 | 16篇 |
1987年 | 16篇 |
1986年 | 12篇 |
1985年 | 20篇 |
1984年 | 10篇 |
1983年 | 13篇 |
1982年 | 11篇 |
1981年 | 12篇 |
1980年 | 9篇 |
1979年 | 15篇 |
1978年 | 9篇 |
1977年 | 14篇 |
1976年 | 16篇 |
1974年 | 10篇 |
排序方式: 共有4845条查询结果,搜索用时 31 毫秒
21.
Bactericidal effects of photoactivated porphyrins--an alternative approach to antimicrobial drugs 总被引:7,自引:0,他引:7
Z Malik J Hanania Y Nitzan 《Journal of photochemistry and photobiology. B, Biology》1990,5(3-4):281-293
Photoactivated porphyrins display a potent cytotoxic activity towards a variety of Gram positive bacteria, mycoplasma and yeasts, but not Gram negative cells. The prerequisite for photosensitization of a microbial cell is the binding of porphyrin to the cytoplasmic membrane in a pH-dependent manner. On illumination, the membrane bound, and possibly, cytoplasmic porphyrin molecules generate singlet oxygen and radicals which sensitize biomolecules and lead to cell death. The immediate inhibition of cell growth on photodynamic treatment is accompanied by alterations in cell wall and membrane synthesis, leading to the formation of large mesosomes adjacent to the unaccomplished septa. Hemin bound to microbial cells exerts cytotoxic activity by peroxidative and oxidative reactions independent of light. Future research in the field may enhance the possibility of using porphyrin photosensitization for treatment of microbial infections. Such clinical use will be unrelated to the antibiotic resistance of the pathogen. Resistance of Gram negative bacteria to porphyrin photosensitization is the main impediment to its use as a broad spectrum antibacterial method. 相似文献
22.
A column preconcentration method has been developed for the determination of trace amounts of manganese by preconcentration on 2-nitroso-1-naphthol-4-sulfonic acid (nitroso-S)-tetradecyldimethylbenzylammonium (TDBA) naphthalene as an adsorbent using a simple funnel tipped glass tube. Manganese reacts with nitroso-S to form a water soluble brown colored chelate anion. The chelate anion forms a water insoluble Mn-Nitroso-S-TDBA ion pair on naphthalene packed in a column in the pH range 9.6-10.5 at a flow rate of 1-2 ml/min. The solid mass consisting of manganese complex and naphthalene is dissolved in 5 ml of dimethylformamide (DMF) and the metal determined by second derivative spectrophotometry. The calibration curve is linear in the concentration range 0.25-35.0 micrograms of Mn in 5 ml of the final DMF solution. Eight replicate determinations of 25 micrograms of standard manganese solution give a mean peak height of 4.0 with a correlation coefficient of 0.9995 and relative standard deviation of +/- 1.1%. The sensitivity was calculated to be 0.502(d2 A/d lambda 2)/microgram ml-1 from the slope of the calibration curve. The detection limit was 0.020 microgram ml-1 for manganese at the minimum instrumental settings (signal to noise ratio = 2). Various parameters effecting the method such as the effect of pH, volume of aqueous phase and interference of a number of metal ions on the determination of manganese have been evaluated to optimize the conditions for its determination in standard alloys and biological samples. 相似文献
23.
Marine brown alga Dictyota dichotoma (Dictyotaceae) collected from Karachi coast of Arabian Sea yielded two new (1 and 2) enones (dolastane-diterpenoids) named: dichotenone-A and -B along with an olide (loliolide, 3) as a new source. Their structures have been characterized with the aid of 2D-NMR spectroscopic techniques. 相似文献
24.
In this study, chemometric techniques such as cluster analysis (CA), discriminant analysis (DA), principal component analysis (PCA) and partial least squares (PLS) were used to analyse the wastewater dataset to identify the factors which affect the composition of sewage of domestic origin, spatial and temporal variations, similarity/dissimilarity among the wastewater characteristics of cis- and trans-drains and discriminating variables. Samples collected from 24 wastewater drains in Lucknow city and from three sites on Gomti river in the month of January/February, May, August and November during the period of 5 years (1994-1999) were characterized for 32 parameters. The multivariate techniques successfully described the similarities/dissimilarities among the sewage drains on the basis of their wastewater characteristics and sources signifying the effect of routine domestic/commercial activities in respective drainage areas. Spatial and seasonal variations in wastewater composition were also determined successfully. CA generated six groups of drains on the basis of similar wastewater characteristic. PCA provided information on seasonal influence and compositional differences in sewage generated by domestic and industrial waste dominated drains and showed that drains influenced by mixed industrial effluents have high organic pollution load. DA rendered six variables (TDS, alkalinity, F, TKN, Cd and Cr) discriminating between cis- and trans-drains. PLS-DA showed dominance of Cd, Cr, NO3, PO4 and F in cis-drains wastewater. The results suggest that biological-process based STPs could treat wastewater both from the cis- as well as trans-drains, however, prior removal of toxic metals will be required from the cis-drains sewage. Further, seasonal variations in wastewater composition and pollution load could be the guiding factor for determining the STPs design parameters. The information generated would be useful in selection of process type and in designing of the proposed sewage treatment plants (STPs) for safe disposal of wastewater. 相似文献
25.
S. Z. Haider K. M. A. Malik A. Rahman T. Wadsten 《Journal of Thermal Analysis and Calorimetry》1986,31(3):621-631
Six adducts of the tctrakis(8-hydroxyquinolinato) complex of thorium(IV) with 8-hydroxyquinoline, pyridine, urea, dimethylsulphoxide, dimethylformamide and 1,10-phenanthroline were prepared and characterized, the infrared bands for the room-temperature forms are given and their particular thermal properties are reported. The thermal analyses were performed mostly in the presence of air, but in some cases an argon atmosphere was used for comparison. The adducts were lost from the principal complex at temperatures varying between 110 and 290°. Intermediate oxygenated complexes were formed in each case at about 400°. The thermal data suggest the standardization of a procedure for the formation of Th(C9H6NO)4.
We are grateful to the Bangladesh University Grants Commission for a Fellowship Grant to AR. 相似文献
Zusammenfassung Sechs Addukte des Tetrakis(8-hydroxyquinolinato)-Komplexes von Thorium(IV) mit 8-Hydroxyquinolin, Pyridin, Harnstoff, Dimethylsulphoxid, Dimethylformamid und 1,10-Phenanthrolin wurden dargestellt und charakterisiert. Infrarotbanden und spezielle thermische Eigenschaften der Raumtemperatur-Formen sind angegeben. Die thermischen Analysen wurden meist in Luft ausgeführt, in einigen Fällen zu Vergleichszwecken aber auch in Argonatmosphäre. Die Addukte wurden vom Komplex bei Temperaturen zwischen 110 und 290 °C abgegeben. Intermediäre oxydierte Komplexe wurden in jedem Fall bei etwa 400 °C gebildet. Die thermischen Daten ermöglichen die Standardisierung eines Verfahrens zur Darstellung von Th(C9H6NO)4.
-(8- ) (IV) 8- , , , - , 1,10-. - , . , , . 110–290°. 400° . Th(C9H6NO)4.
We are grateful to the Bangladesh University Grants Commission for a Fellowship Grant to AR. 相似文献
26.
Rajapakshe A Gruhn NE Lichtenberger DL Basta R Arif AM Ernst RD 《Journal of the American Chemical Society》2004,126(43):14105-14116
Molecules of the form Cp(6,6-dmch)ZrX(2) (Cp = eta(5)-cyclopentadienyl, X = Cl, Br, I; 6,6-dmch = eta(5)-6,6-dimethylcyclohexadienyl) have been synthesized, and the molecular and electronic structures have been investigated. These molecules allow direct comparison of the bonding and properties of pentadienyl and cyclopentadienyl ligands in the same high-oxidation-state metal complexes. Unlike the well-known Cp(2)ZrX(2) analogues, these Cp(6,6-dmch)ZrX(2) molecules are intensely colored, indicating significantly different relative energies of the frontier orbitals. Also unusual, the average Zr-C distances to the 6,6-dmch pentadienyl ligand are about 0.1 A longer than the average Zr-C distances to the cyclopentadienyl ligand for these Zr(IV) complexes, opposite of what is observed for the Zr(II) complex Cp(2,6,6-tmch)Zr(PMe(3))(2) (tmch = eta(5)-2,6,6-trimethylcyclohexadienyl), reflecting a dramatic reversal in the favorability of the bonding depending on the metal oxidation state. The experimental and computational results indicate that the color of the Cp(6,6-dmch)ZrX(2) complexes is due to a 6,6-dmch ligand-to-metal charge-transfer band. Compared to the Cp(2)ZrX(2) analogues, the Cp(6,6-dmch)ZrX(2) molecules have a considerably less stable HOMO that is pentadienyl-based and an essentially unchanged metal-based LUMO. Also, the lowest unoccupied orbital of pentadienyl is stabilized relative to cyclopentadienyl and becomes a better potential delta electron acceptor, thus contributing to the differences in structure and reactivity of the low-valent and high-valent metal complexes. 相似文献
27.
Chemometric analysis of groundwater quality data of alluvial aquifer of Gangetic plain, North India 总被引:10,自引:0,他引:10
Kunwar P. Singh Amrita Malik Vinod K. Singh Dinesh Mohan Sarita Sinha 《Analytica chimica acta》2005,550(1-2):82-91
Water quality data set from the alluvial region in the Gangetic plain in northern India, which is known for high fluoride levels in soil and groundwater, has been analysed by chemometric techniques, such as principal component analysis (PCA), discriminant analysis (DA) and partial least squares (PLS) in order to investigate the compositional differences between surface and groundwater samples, spatial variations in groundwater composition and influence of natural and anthropogenic factors. Trilinear plots of major ions showed that the groundwater in this region is mainly of Na/K-bicarbonate type. PCA performed on complete data matrix yielded six significant PCs explaining 65% of the data variance. Although, PCA rendered considerable data reduction, it could not clearly group and distinguish the sample types (dug well, hand-pump and surface water). However, a visible differentiation between the water samples pertaining to two watersheds (Khar and Loni) was obtained. DA identified six discriminating variables between surface and groundwater and also between different types of samples (dug well, hand pump and surface water). Distinct grouping of the surface and groundwater samples was achieved using the PLS technique. It further showed that the groundwater samples are dominated by variables having origin both in natural and anthropogenic sources in the region, whereas, variables of industrial origin dominate the surface water samples. It also suggested that the groundwater sources are contaminated with various industrial contaminants in the region. 相似文献
28.
29.
Muhammad Adil Khan Shahid Khan Samet Erden Muhammad Samraiz 《Mathematical Methods in the Applied Sciences》2022,45(1):36-48
There are many useful applications of Jensen's inequality in several fields of science, and due to this reason, a lot of results are devoted to this inequality in the literature. The main theme of this article is to present a new method of finding estimates of the Jensen difference for differentiable functions. By applying definition of convex function, and integral Jensen's inequality for concave function in the identity pertaining the Jensen difference, we derive bounds for the Jensen difference. We present integral version of the bounds in Riemann sense as well. The sharpness of the proposed bounds through examples are discussed, and we conclude that the proposed bounds are better than some existing bounds even with weaker conditions. Also, we present some new variants of the Hermite–Hadamard and Hölder inequalities and some new inequalities for geometric, quasi-arithmetic, and power means. Finally, we give some applications in information theory. 相似文献
30.
Summary
Bis(cyclopentadienyl)titanium(IV) diisothiocyanate [(Cp)2-Ti(NCS)2] reacts with MCl2 (M = Cu, Pd or Pt), [CuCl(PPh3)3], [RuCl2(PPh3)3] and [RuCl2(DMSO)4] (DMSO = dimethylsulphoxide) giving solid compounds of stochiometry [(Cp)2Ti(-NCS)2MCl2] (M = Cu, Pd or Pt), [(Cp)2Ti(-NCS)2CuCl(PPh3)], [(Cp)2Ti(-NCS)2-RuCl(PPh3)2]Cl and [(Cp)2Ti(-NCS)2RuCl2(DMSO)2]. These products have been characterized by physicochemical and spectroscopic methods. 相似文献