全文获取类型
收费全文 | 1146篇 |
免费 | 73篇 |
国内免费 | 11篇 |
专业分类
化学 | 704篇 |
晶体学 | 4篇 |
力学 | 87篇 |
数学 | 179篇 |
物理学 | 256篇 |
出版年
2024年 | 2篇 |
2023年 | 4篇 |
2022年 | 29篇 |
2021年 | 51篇 |
2020年 | 64篇 |
2019年 | 65篇 |
2018年 | 65篇 |
2017年 | 66篇 |
2016年 | 94篇 |
2015年 | 67篇 |
2014年 | 85篇 |
2013年 | 111篇 |
2012年 | 109篇 |
2011年 | 115篇 |
2010年 | 62篇 |
2009年 | 52篇 |
2008年 | 42篇 |
2007年 | 33篇 |
2006年 | 23篇 |
2005年 | 21篇 |
2004年 | 17篇 |
2003年 | 7篇 |
2002年 | 11篇 |
2001年 | 7篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1996年 | 1篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 1篇 |
排序方式: 共有1230条查询结果,搜索用时 166 毫秒
1.
2.
3.
A novel sensitive and simple method for rapid and selective extraction, preconcentration and determination of iron (as its
bathophenanthroline complex) and copper (as its neocuproine complex) using octadecyl silica cartridges and dual wavelength
spectrophotometry is presented. The dual wavelength method (533 nm for the iron-bathophenanthroline and 454 nm for the copper-neocuproine
as the analytical wavelength) is used to eliminate spectral interferences. Extraction efficiency and the influence of flow
rates of sample solution and eluent, pH, amount of neocuproine, bathophenanthroline and hydroxylamine hydrochloride, type
and least amount of eluent for elution of iron and copper complexes from cartridge, break-through volume and limit of detection
are evaluated. The effects of various cationic and anionic interferences on percent recovery of iron and copper are also studied.
Extraction efficiencies >95% are obtained by elution of cartridges with minimal amount of organic solvent. Iron and copper
were determined in the range of 3–100 ng mL−1. The limits of detection are 0.98 and 1.13 ng mL−1 for iron and copper, respectively. The proposed method is applied successfully to the determination of both analytes in river,
tap and well water samples.
Author for correspondence. E-mail: yyamini@modares.ac.ir
Received September 18, 2002; accepted December 12, 2002
Published online May 5, 2003 相似文献
4.
Bis(peroxo)vanadium(V) complexes are widely investigated as anticancer agents. They exert their antitumor and cyctotoxic effects through inhibition of tyrosine phosphatases and DNA cleavage, respectively. The latter process remains poorly understood. The mechanism of DNA cleavage by NH(4)[(phen)V(O)(eta(2)-O(2))(2)] (phen = 1,10-phenanthroline) was investigated. Kinetic studies on DNA cleavage revealed that the complex is a single-strand nicking agent with no specificity. EPR experiments using 2,2,6,6-tetramethyl-4-piperidone (TMP) and 5,5'-dimethyl-1-pyrroline-N-oxide (DMPO) as spin-traps for singlet oxygen and hydroxyl radical, respectively, implicated hydroxyl radical production upon photodecomposition of bis(peroxo)vanadium(V). This was corroborated by benzoate inhibition of DNA strand scission and stoichiometric oxidation of 2-propanol to acetone upon irradiation of bis(peroxo)vanadium(V) phenanthroline. High-resolution polyacrylamide gel analysis of the vanadium cleavage reaction and [Fe(II)EDTA](2)(-)/H(2)O(2) resulted in comigration of "ladder" pattern bands, which superimposed when both reactions were run on the same lane. These findings identify hydroxyl radical produced from the photooxidation of the peroxo ligand on vanadium as the active species in DNA cleavage. 相似文献
5.
The nitridorhenium(V) complexes ReNCl(2)(PCy3)(2) (1), ReNBr(2)(PCy3)(2) (2), ReNCl(2)(PPh3)(2) (3), and ReNBr(2)(PPh3)(2) (4) produce structured emission spectra upon excitation at low temperature. The origin, E(00), occurs at 15 775, 16 375, 15 875, and 16 300 cm(-1), respectively. The vibronic peaks are regularly spaced with an average energy separation corresponding to the Re triple bond N stretching frequency. The nitridorhenium stretching frequency ranges from 1095 to 1101 cm(-1), as determined by Raman and IR spectroscopy. The excited-state distortions are calculated by fitting the emission spectra. The excited state arises primarily from a d(xy) (ReN nonbonding) to d(yz) (ReN pi antibonding) transition. The rhenium-nitrogen bond length in the excited state is 0.08 A longer than in the ground electronic state, which is consistent with the difference in bond lengths of ReN bonds of bond order 3 and bond order 2.5 as determined from molecular structures. 相似文献
6.
Mir Ali Farajzadeh Mortaza Ebrahimi Ali Ranji Elham Feyz Vali Bejani Amir Abbas Matin 《Mikrochimica acta》2006,153(1-2):73-78
High performance liquid chromatography (HPLC) and gas chromatography (GC) are introduced for analysis of polymer lubricants
(stearamide, oleamide and erucamide). In the HPLC method, a reverse phase octadecylsilane (ODS) column along with acetonitrile/methanol
(60:40) as a mobile phase were used. Detection of analytes was performed by a UV detector at 202 nm. The analysis time was
less than 8 min. In the GC method, polar capillary column and flame ionization detector (FID) were used for separations and
detection, respectively. The analysis time by GC was longer than HPLC and was about 30 min. Limits of detection, linear range
and repeatability of both methods are similar, but determination of oleamide in real samples by HPLC method is difficult due
to complexity of the initial part of HPLC chromatogram in polyethylene samples. That problem is not observed in the GC method.
Detection limits in both methods for all analytes are lower than 0.003% which are much lower than the amount of lubricants
in commercial polymers (0.05–0.2%). 相似文献
7.
The dependence of Mentha pulegium L. (pennyroyal) essential oil composition, obtained by supercritical carbon dioxide (SC-CO2), with the following parameters: pressure, temperature, extraction time (dynamic), and modifier (methanol) was studied. The results were also compared with those obtained by conventional hydrodistillation method in laboratory conditions. Regarding the percentages of menthone (30.3%) and pulegone (52.0%), the optimum SFE results were obtained at the following experimental conditions: pressure=100 atm, T=35 °C, dynamic time=10 min, and Vmodifier=0 μl. The results of hydrodistillation showed that the major components of M. pulegium L. were pulegone (37.8%), menthone (20.3%), and piperitenone (6.8%). The evaluation of the composition of each extract was performed by gas chromatography-mass spectrometry. 相似文献
8.
Holliday JD Rodgers SL Willett P Chen MY Mahfouf M Lawson K Mullier G 《Journal of chemical information and computer sciences》2004,44(3):894-902
This paper evaluates the use of the fuzzy k-means clustering method for the clustering of files of 2D chemical structures. Simulated property prediction experiments with the Starlist file of logP values demonstrate that use of the fuzzy k-means method can, in some cases, yield results that are superior to those obtained with the conventional k-means method and with Ward's clustering method. Clustering of several small sets of agrochemical compounds demonstrate the ability of the fuzzy k-means method to highlight multicluster membership and to identify outlier compounds, although the former can be difficult to interpret in some cases. 相似文献
9.
The title complexes, the Re(O)L(2)(Solv)(+) complexes (L = hoz, 2-(2'-hydroxyphenyl)-2-oxazoline(-) or thoz, 2-(2'-hydroxyphenyl)-2-thiazoline(-); Solv = H(2)O or CH(3)CN), are effective catalysts for the following fundamental oxo transfer reaction between closed shell molecules: XO + Y --> X + YO. Among suitable oxygen acceptors (Y's) are organic thioethers and phosphines, and among suitable oxo donors (XO's) are pyridine N-oxide (PyO), t-BuOOH, and inorganic oxyanions. One of the remarkable features of these catalysts is their high kinetic competency in effecting perchlorate reduction by pure atom transfer. Oxo transfer to rhenium(V) proceeds cleanly to afford the cationic dioxorhenium(VII) complex Re(O)(2)L(2)(+) in a two-step mechanism, rapid substrate (XO) coordination to give the precursor adduct cis-Re(V)(O)(OX)L(2)(+) followed by oxygen atom transfer (OAT) as the rate determining step. Electronic variations with PyO derivatives demonstrated that electron-withdrawing substituents accelerate the rate of Re(VII)(O)(2)L(2)(+) formation from the precursor adduct cis-Re(V)(O)(OX)L(2)(+). The activation parameters for OAT with picoline N-oxide and chlorate have been measured; the entropic barrier to oxo transfer is essentially zero. The potential energy surface for the reaction of Re(O)(hoz)(2)(OH(2))(+) with PyO was defined, and all pertinent intermediates and transition states along the reaction pathway were located by density functional theory (DFT) calculations (B3LYP/6-31G). In the second half of the catalytic cycle, Re(O)(2)L(2)(+) reacts with oxygen acceptors (Y's) in second-order reactions with associative transition states. The rate of OAT to substrates spans a remarkable range of 0.1-10(6) L mol(-)(1) s(-)(1), and the substrate reactivity order is Ph(3)P > dialkyl sulfides > alkyl aryl sulfides > Ph(2)S approximately DMSO, which demonstrates electrophilic oxo transfer. Competing deactivation and inhibitory pathways as well as their relevant kinetics are also reported. 相似文献
10.
Chakravarthi Simhadri Liting Bi Mathieu L. Lepage Mahdi Takaffoli Zhipeng Pei Stefania F. Musolino Abbas S. Milani Gino A. DiLabio Jeremy E. Wulff 《Chemical science》2021,12(11):4147
Motivated by a desire to develop flexible covalent adhesives that afford some of the same malleability in the adhesive layer as traditional polymer-based adhesives, we designed and synthesized two flexible, highly fluorinated bis-diazirines. Both molecules are shown to function as effective crosslinkers for polymer materials, and to act as strong adhesives when painted between two polymer objects of low surface energy, prior to thermal activation. Data obtained from lap-shear experiments suggests that greater molecular flexibility is correlated with improved mechanical compliance in the adhesive layer.Flexible, highly fluorinated covalent adhesives are synthesized, and are shown to afford comparable C–H insertion efficiency and adhesion strength relative to a rigid analogue, while providing improved mechanical compliance in the adhesion layer. 相似文献