全文获取类型
收费全文 | 533篇 |
免费 | 24篇 |
国内免费 | 7篇 |
专业分类
化学 | 425篇 |
晶体学 | 3篇 |
力学 | 8篇 |
数学 | 84篇 |
物理学 | 44篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 8篇 |
2021年 | 13篇 |
2020年 | 20篇 |
2019年 | 18篇 |
2018年 | 34篇 |
2017年 | 25篇 |
2016年 | 30篇 |
2015年 | 22篇 |
2014年 | 44篇 |
2013年 | 63篇 |
2012年 | 42篇 |
2011年 | 45篇 |
2010年 | 35篇 |
2009年 | 20篇 |
2008年 | 16篇 |
2007年 | 22篇 |
2006年 | 14篇 |
2005年 | 20篇 |
2004年 | 13篇 |
2003年 | 15篇 |
2002年 | 3篇 |
2001年 | 3篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 1篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1994年 | 5篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有564条查询结果,搜索用时 15 毫秒
1.
Leila Torkian Mostafa M. Amini Tayebeh Gorji Omid Sadeghi 《Arabian Journal of Chemistry》2019,12(7):1315-1321
In this study, multiwalled carbon nanotube (MWCNT) was modified by the pyridine group using a silane agent and characterized by infrared spectroscopy (IR), thermal analysis (TG/DTA), and elemental analysis (CHN) and scanning electron microscopy (SEM). The application of this sorbent was investigated in determination of lead ions in aqueous samples, using flame atomic absorption spectrometry (FAAS). Through this study, different parameters such as pH and sample flow rate on adsorption process and eluent concentration, volume and flow rate were optimized. The limit of detection (LOD), the relative standard deviation and the recovery of the method were 2 ng mL?1, 1.3% and 99.7%, respectively. Two standard reference materials (NIST 1571 and NIST 1572) were used to verify accuracy of this method. Finally, the sorbent was successfully applied for extraction and determination of low levels of Pb(II) ions in aqueous samples. 相似文献
2.
Latifeh Navidpour Leila Karimi Mohsen Amini Mohssen Vosooghi Abbas Shafiee 《Journal of heterocyclic chemistry》2004,41(2):201-204
Arylation of the readily available 3‐alkythio‐5‐aryl‐1,2,4‐triazoles gave 5‐alkylthio‐1,3‐diaryl‐1,2,4‐triazoles in moderate yield. The structures of the latter were confirmed by NOE and 13C‐NMR. 相似文献
3.
The principles for the determination of conditional association constants of enantiomers by capillary zone electrophoresis employing a partial filling technique (PFT) using methyl-beta-cyclodextrin as chiral selector is presented. Orciprenaline was used as a model compound. Partial filling is a separation technique, where different lengths of the chiral selector solution are introduced into the capillary to a final zone length shorter than the effective length of the capillary, prior to application of the solutes. Lengthening of the separation zone results in improving enantioresolution in addition to decreasing electrophoretic mobility of the enantiomers, because of longer interaction time between the solute and chiral selector. The degree of the reduction in electromobility depends on the affinity of the solute to the chiral selector, i.e. strength of the complex formed between the solute and cyclodextrin. The decrease in the electrophoretic mobility with increasing length of the separation zone is used for determination of the association constant. The association constants of the enantiomers of orciprenaline and the chiral selector were evaluated from the slope of the plot, observed electrophoretic mobility versus the ratio between the length of the separation zone and the effective length of the capillary. It was found that the association constants were independent of the chiral selector concentration. The mean values were 110 M(-1) and 160 M(-1) for respective enantiomer. Constants obtained by a conventional CE technique were in good agreement with those from the PFT experiments. The highest enantioselectivityy was obtained when about 50% of the solute was distributed to the selector phase. 相似文献
4.
Mostafa M. Amini Amirreza Azadmher Hamid Reza Bijanzadeh Nasser Hadipour 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(1-2):77-80
Behavior of {[(CH3)2SnCl2·H2O]2·18-crown-6}n in solution have been investigated by HMBC NMR. The results show that coordination of water to tin containing species and
its hydrogen bonding to crown ether remains intact in non-coordinating solvent in contrast to coordinating solvent. H-NMR
reveals that the chemical shift of water in complex varies by solvent of crystallization. 相似文献
5.
Ahmad Rouhollahi Mohammad Kazem Amini Mojtaba Shamsipur 《Journal of solution chemistry》1994,23(1):63-74
Proton NMR was used to study the complexation reaction between lead ion and 18-crown-6 in a number of binary acetonitrile-water mixtures. Formation constant for the resulting 11 complexes in different solvent mixtures was determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and amount of water in the mixed solvent. The dissociative kinetics of the complex was studied by proton line-shape analysis. The Arrhenius plots showed a distinct isokinetic temperature at about 25°C at which the decomplexation rate is more or less independent of the solvent composition. the complexation rate and the activation parameters E
a
, H and S, for the exchange have been determined and found to be strongly solvent dependent. There is actually a linear relationship between the mole fraction of acetonitrile in the mixed solvent and logarithm of the stability constant as well as activation parameters. 相似文献
6.
Nahid Emad 《Numerical Algorithms》1996,11(1):159-179
We make use of the Padé approximants and the Krylov sequencex, Ax,,...,A
m–1
x in the projection methods to compute a few Ritz values of a large hermitian matrixA of ordern. This process consists in approaching the poles ofR
x()=((I–A)–1
x,x), the mean value of the resolvant ofA, by those of [m–1/m]Rx(), where [m–1/m]Rx() is the Padé approximant of orderm of the functionR
x(). This is equivalent to approaching some eigenvalues ofA by the roots of the polynomial of degreem of the denominator of [m–1/m]Rx(). This projection method, called the Padé-Rayleigh-Ritz (PRR) method, provides a simple way to determine the minimum polynomial ofx in the Krylov subspace methods for the symmetrical case. The numerical stability of the PRR method can be ensured if the projection subspacem is sufficiently small. The mainly expensive portion of this method is its projection phase, which is composed of the matrix-vector multiplications and, consequently, is well suited for parallel computing. This is also true when the matrices are sparse, as recently demonstrated, especially on massively parallel machines. This paper points out a relationship between the PRR and Lanczos methods and presents a theoretical comparison between them with regard to stability and parallelism. We then try to justify the use of this method under some assumptions. 相似文献
7.
Density functional calculations were performed on bonding and structural features of [(ηn-BH4)TM(CO)4]− (n = 1, 2, 3; TM = Cr, Mo) complexes. Calculations show that the ground state is bidentate which is in good agreement with experimental results. It has been found that the bridge and terminal hydrogen atoms will interchange by two pathways: (i) twist of BH4 about one of the bridge B-H and (ii) twist of BH4 about one of the terminal B-H. The molecular orbital calculations and natural bond orbital methodologies for different isomers of these complexes have been evaluated. The final results indicate that case (i) is more preferable relative to another case. 相似文献
8.
A highly sensitive and fast responding sensor for the determination of thiosulfate, sulfite, sulfide and dithionite is described. It consists of a chemically modified carbon ceramic composite electrode (CCE) containing [Ru(bpy)(tpy)Cl]PF6 complex that was constructed by the sol-gel technique. A reversible redox couple of Ru(II)/Ru(III) was observed as a solute in acetonitrile solution and as a component of carbon based conducting composite electrode. Electrochemical behavior and stability of modified CCE were investigated by cyclic voltametry, the apparent electron transfer rate constant (kappa(S)) and transfer coefficient (a) were determined by cyclic voltametry which were about 28 s(-1) and 0.43 respectively. Electrocatalytic oxidation of S(2-), SO3(2-), S2O4(2-) and S2O3(2-) were effective at the modified electrode at significantly reduced overpotentials and in the pH range 1-11. Optimum pH values for amperometric detection of thiosulfate, dithionite, sulfide and sulfite are 7, 9, 2 and 2. Under the optimized conditions the calibration curves are linear in the concentration ranges 1-500, 3-80, 2-90 and 1-100 microM for S2O3(2-), SO3(2-), S2- and S2O4(2-) determination. The detection limit (signal to noise is 3) and sensitivity are 0.5 and 12, 2.8 and 6, 1.6 and 8, and 0.65 microM and 80 nA microM(-1) for thiosulfate, sulfite, sulfide and dithionite detection. The modified carbon ceramic electrode doped with Ru-complex shows good reproducibility, a short response time (t < 2 s), remarkable long term stability (> 6 month) and especially good surface renewability by simple mechanical polishing (RSD for eight successive polishing is 2%). The advantages of this sulfur compound amperometric detector based on ruthenium doped CCE are high sensitivity, inherent stability at a broader pH range, excellent catalytic activity, less expense and simplicity of preparation in comparison with recently published papers. This sensor can be used as a chromatographic detector for analysis of sulfur derivatives. 相似文献
9.
Mehrzad Mehran William J. Cooper Nahid Golkar Michael G. Nickelsen Eric R. Mittlefehldt Edward Guthrie Walter Jennings 《Journal of separation science》1991,14(11):745-750
The retention behavior of a heterogeneous group of solutes has been examined on seven different stationary phases under isothermal and temperature-programmed conditions. Both ΔHv (enthalpy of solute vaporization from the stationary phase) and ΔSv (entropy of solute vaporization from the stationary phase) values were determined for each solute – stationary phase combination under isothermal conditions. Both program rate and carrier gas velocity were shown to affect solute elution order. Unless these and other experimental factors discussed are controlled, column equivalency studies based on solute elution order have dubious value. 相似文献
10.
The potentiometric response properties and applications of a tetra-coordinate nickel(II) complex with relatively high selectivity toward nitrate ion are described. The nickel(II) complex of 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraene was used as a neutral carrier into plasticized poly(vinyl chloride) (PVC) membrane. The influence of several variables was investigated in order to optimize the potentiometric response and selectivity of the electrode. The resulting membrane electrode incorporating 31.0% PVC, 61.0% dioctyl phthalate (DOP) as plasticizer, 3% methyltrioctylammonium chloride (MTOAC) as a cationic additive and 5% carrier (all w/w) demonstrates a Nernstian response slope of −59.6 mV per decade over the concentration range of 5×10−6-1×10−1 M NO3−. The electrode exhibits a fast response time (≤10 s), a detection limit of 2.5×10−6 M, and can be used over a wide pH range of 4-12. The electrode shows improved selectivity in comparison to most of the previously reported nitrate-selective electrodes. It was successfully applied to the determination of nitrate ion in natural water samples. 相似文献