全文获取类型
收费全文 | 119篇 |
免费 | 5篇 |
专业分类
化学 | 91篇 |
晶体学 | 3篇 |
力学 | 2篇 |
数学 | 4篇 |
物理学 | 24篇 |
出版年
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 4篇 |
2020年 | 9篇 |
2019年 | 3篇 |
2018年 | 2篇 |
2017年 | 3篇 |
2016年 | 6篇 |
2015年 | 4篇 |
2014年 | 6篇 |
2013年 | 9篇 |
2012年 | 6篇 |
2011年 | 9篇 |
2010年 | 8篇 |
2009年 | 6篇 |
2008年 | 7篇 |
2007年 | 3篇 |
2006年 | 5篇 |
2005年 | 2篇 |
2004年 | 4篇 |
2002年 | 5篇 |
2000年 | 2篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 6篇 |
1993年 | 3篇 |
1991年 | 1篇 |
1985年 | 1篇 |
1983年 | 2篇 |
1979年 | 1篇 |
排序方式: 共有124条查询结果,搜索用时 31 毫秒
21.
Dheer Singh Anju Chopra Ravindra Kumar M. I. S. Sastry M. B. Patel B. Basu 《Chromatographia》2014,77(1-2):165-169
EN 14103 is generally used for quantification of ester content in biodiesel free of heptadecanoate ester (C17:0) or methyl nonadecanoate (C19:0), which are employed as internal standards. It was observed that ester content obtained by EN 14103 method did not match with theoretical value of biodiesel, as the method did not take care of response factors of each component to compensate for changes in detector sensitivities. In this study, the whole range of fatty acid (C6–C24:1) methyl esters have been taken into consideration for the calculation of the ester content. Methyl nonadecanoate (C19:0) was used as an internal standard. The response factors of both the saturated and unsaturated methyl esters in the range C6–C24:1 were estimated and found in the range 0.97–1.16. The ester content was calculated after applying the response factors of each methyl ester. The results obtained by this method agreed well with the theoretical value as compared to estimated value using EN14103 method. The results obtained from this method also show good correlation (R 2 = 0.98) with 1H-NMR method. Further, this method does not depend on nature of biodiesel feed stock and is applicable to all methyl biodiesel samples obtained from different raw materials. 相似文献
22.
In this paper, the design-oriented two-stage and data-analysis one-stage multiple comparison procedures for successive comparisons of exponential location parameters under heteroscedasticity are proposed. One-sided and two-sided simultaneous confidence intervals are also given. We also extend these simultaneous confidence intervals for successive differences to a larger class of contrasts of the location parameters. Upper limits of critical values are obtained using the recent techniques given in Lam [Lam, K., 1987. Subset selection of normal populations under heteroscedasticity. In: Proceedings of the Second International Advanced Seminar/Workshop on Inference Procedures Associated with Statistical Ranking and Selection, Sydney, Australia; Lam, K., 1988. An improved two-stage selection procedure. Communications in Statistics Simulation and Computation. 17 (3), 995-1006]. These approximate critical values are shown to have better results than the approximate critical values using the Bonferroni inequality developed in this paper. Finally, the application of the proposed procedures is illustrated with an example. 相似文献
23.
The surface of a high quality soda-lime silicate glass is found to be inhomogeneous, consisting of nanometer-high ridges that extend for tens of microns. Exposure to mild and aggressive environments results in an increase in the ridge heights as they dissolve much more slowly than the rest of the glass. The ridges also exhibit enrichment of sodium, magnesium, aluminum and oxygen. The parallel nature of the ridges suggests that they originate from compositional heterogeneity during the glass processing. 相似文献
24.
Chemistry of Diruthenium and Dirhodium Analogues of Pentaborane(9): Synthesis and Characterization of Metal N,S‐Heterocyclic Carbene and B‐Agostic Complexes 下载免费PDF全文
M. Sc. Dipak Kumar Roy M. Sc. Bijan Mondal M. Sc. R. S. Anju Prof. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3640-3648
Building upon our earlier results on the synthesis of electron‐precise transition‐metal–boron complexes, we continue to investigate the reactivity of pentaborane(9) and tetraborane(10) analogues of ruthenium and rhodium towards thiazolyl and oxazolyl ligands. Thus, mild thermolysis of nido‐[(Cp*RuH)2B3H7] ( 1 ) with 2‐mercaptobenzothiazole (2‐mbtz) and 2‐mercaptobenzoxazole (2‐mboz) led to the isolation of Cp*‐based (Cp*=η5‐C5Me5) borate complexes 5 a , b [Cp*RuBH3L] ( 5 a : L=C7H4NS2; 5 b : L=C7H4NOS)) and agostic complexes 7 a , b [Cp*RuBH2(L)2], ( 7 a : L=C7H4NS2; 7 b : L=C7H4NOS). In a similar fashion, a rhodium analogue of pentaborane(9), nido‐[(Cp*Rh)2B3H7] ( 2 ) yielded rhodaboratrane [Cp*RhBH(L)2], 10 (L=C7H4NS2). Interestingly, when the reaction was performed with an excess of 2‐mbtz, it led to the formation of the first structurally characterized N,S‐heterocyclic rhodium‐carbene complex [(Cp*Rh)(L2)(1‐benzothiazol‐2‐ylidene)] ( 11 ) (L=C7H4NS2). Furthermore, to evaluate the scope of this new route, we extended this chemistry towards the diruthenium analogue of tetraborane(10), arachno‐[(Cp*RuCO)2B2H6] ( 3 ), in which the metal center possesses different ancillary ligands. 相似文献
25.
26.
A self diastereoselective, simple metal free and efficient branch domino reaction gave multiple heteroaryl substituted (±) cyclohexanols with five chiral centres in >95% yields. The reactions that occur are Claisen Schmidt condensation followed by Michael addition and Aldol reactions of heteroaryl carbaldehydes and acetyl pyridine derivatives. Mechanistic study of the reactions shows excellent self diastereoselectivity (dr > 99%) in the intermediate steps which results selectively in the formation of one set of enantiomers out of sixteen possible enantiomeric pairs. The self diastereoselectivity of reaction in all the steps dominates due to the steric hindrance induced by the bulky heteroaryl groups. The stereochemistry of the synthesized compounds is established using single crystal XRD. 相似文献
27.
Copper nanoparticles were synthesized and characterized by TEM, XRD and UV-vis techniques. The copper nanoparticles in an ionic liquid were employed as a recyclable catalyst for the synthesis of bis-(4-hydroxy-2-oxothiazolyl)methanes in excellent yields and in short reaction times. 相似文献
28.
Balakrishnan S. Anju Neeraja R. Nair Dr. Subrata Kundu 《Angewandte Chemie (International ed. in English)》2023,62(48):e202311523
Nitrite (NO2−) and nitric oxide (NO) interconversion is crucial for maintaining optimum NO flux in mammalian physiology. Herein we demonstrate that [ L 2CuII(nitrite)]+ moieties (in 2 a and 2 b ; where, L = Me2PzPy and Me2PzQu ) with distorted octahedral geometry undergo facile reduction to provide tetrahedral [ L 2CuI]+ (in 3 a and 3 b ) and NO in the presence of biologically relevant reductants, such as 4-methoxy-2,6-di-tert-butylphenol (4-MeO-2,6-DTBP, a tyrosine model) and N-benzyl-1,4-dihydronicotinamide (BNAH, a NAD(P)H model). Interestingly, the reaction of excess NO gas with [ L 2CuII(MeCN)2]2+ (in 1 a ) provides a putative {CuNO}10 species, which is effective in mediating the nitrosation of various nucleophiles, such as thiol and amine. Generation of the transient {CuNO}10 species in wet acetonitrile leads to NO2− as assessed by Griess assay and 14N/15N-FTIR analyses. A detailed study reveals that the bidirectional NOx-reactivity, namely, nitrite reductase (NIR) and NO oxidase (NOO), at a common CuII site, is governed by the geometric-preference-driven facile CuII/CuI redox process. Of broader interest, this study not only highlights potential strategies for the design of copper-based catalysts for nitrite reduction, but also strengthens the previous postulates regarding the involvement of red copper proteins in denitrification. 相似文献
29.
An environmentally friendly and rapid digestion procedure involving 10 mL of acid mixture (HNO3 : HCl : HF = 2:2:1) for 0.1 g of sample in closed vessel microwave digester following heating program : 250W for 10 min., hold time 2 min., 600 W for 17 min, and Ventilation time 10 min was developed. The operating parameters were varied and optimized by factorial design approach using "Steepest Ascent" method. The validity of the recommended digestion procedure were examined by analyzing several well characterized standard reference materials such as diabase (W2), basalt (BIR-1, JB-3, BHVO-1), granite (G2), gabbro (JGb-1), Mn-nodule (Nod-A-1, Nod-P-1), sediment (STSD-4, LKSD-2), limestone (KH-2), soil (SAu-1), ilmenite (IGS-31), rutile (IGS-32), Zircon (IGS-35) and titanium dioxide (SRM-154b) employing both inductively coupled plasma-atomic emission spectrometry (ICP-AES) and well known spectrophotometric method. An excellent agreement between the methods and the certified values of standard reference materials suggest that the digestion procedure can be used for quality control and allied purposes. 相似文献
30.
Neetu Ahlawat Ashish Agarwal Sujata Sanghi Nawal Kishore 《Solid State Ionics》2009,180(26-27):1356-1361
Glasses having compositions xLi2O∙(85 − x)Bi2O3∙15SiO2 (x = 35, 40, and 45 mol%) were prepared by normal melt quenching technique. Electrical relaxation and conductivity in these glasses were studied using impedance spectroscopy in the frequency range from 20 Hz to 1 MHz and in the temperature range from 453 to 603 K. The ac and dc conductivities, activation energy of the dc conductivity and relaxation frequency were extracted from the impedance spectra. The dc conductivity increases with increase in Li2O content providing modified glass structure and large number of mobile lithium ions. Similar values of activation energy for dc conduction and for conductivity relaxation time indicate that the ions overcome the same energy barrier while conducting and relaxing. The non-exponential character of relaxation processes increases with decrease in stretched exponential parameter ‘β’ as the composition parameter ‘x’ increases. The observed conductivity spectra follow a power law with exponent ‘s’ which increases regularly with frequency and approaches unity at higher frequencies. Nearly constant losses (NCL) characterize this linearly dependent region of the conductivity spectra. A deviation from the ‘master curve’ for various isotherms of conductivity spectra was also observed in the high-frequency region and at low temperatures, which supports the existence of different dynamic processes like NCL in addition to the ion hopping processes in the investigated glass system. 相似文献