全文获取类型
收费全文 | 385篇 |
免费 | 9篇 |
国内免费 | 1篇 |
专业分类
化学 | 383篇 |
力学 | 2篇 |
数学 | 2篇 |
物理学 | 8篇 |
出版年
2023年 | 8篇 |
2022年 | 3篇 |
2021年 | 13篇 |
2020年 | 21篇 |
2019年 | 18篇 |
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 9篇 |
2015年 | 6篇 |
2014年 | 9篇 |
2013年 | 21篇 |
2012年 | 17篇 |
2011年 | 29篇 |
2010年 | 14篇 |
2009年 | 15篇 |
2008年 | 31篇 |
2007年 | 24篇 |
2006年 | 37篇 |
2005年 | 24篇 |
2004年 | 19篇 |
2003年 | 16篇 |
2002年 | 6篇 |
2001年 | 11篇 |
2000年 | 6篇 |
1999年 | 5篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1985年 | 2篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1977年 | 2篇 |
1975年 | 1篇 |
1937年 | 1篇 |
排序方式: 共有395条查询结果,搜索用时 15 毫秒
71.
Song L Wu W Hiberty PC Shaik S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(28):7458-7466
The recently developed (L. Song, W. Wu, Q. Zhang, S. Shaik, J. Phys. Chem. A 2004, 108, 6017) valence bond method coupled with a polarized continuum model (VBPCM) has been applied to the identity SN2 reaction of halides in the gas phase and in aqueous solution. The barriers computed at the level of the breathing orbital VB method (P. C. Hiberty, J. P. Flament, E. Noizet, Chem. Phys. Lett. 1992, 189, 259), BOVB and VBPCM//BOVB, are comparable to CCSD(T) and CCSD(T)//PCM results and to experimentally derived barriers in solution (W. J. Albery, M. M. Kreevoy, Adv. Phys. Org. Chem. 1978, 16, 85). The reactivity parameters needed to apply the valence bond state correlation diagram (VBSCD) method (S. Shaik, J. Am. Chem. Soc. 1984, 106, 1227), were also determined by VB calculations. It has been shown that the reactivity parameters along with their semiempirical derivations provide a satisfactory qualitative and quantitative account of the barriers. 相似文献
72.
Kuang D Ito S Wenger B Klein C Moser JE Humphry-Baker R Zakeeruddin SM Grätzel M 《Journal of the American Chemical Society》2006,128(12):4146-4154
Two novel heteroleptic sensitizers, Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-hexyloxystyryl)-2,2-bipyridine)(NCS)2 and Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-methoxystyryl)-2,2'-bipyridine) (NCS)2, coded as K-19 and K-73, respectively, have been synthesized and characterized by 1H NMR, FTIR, UV-vis absorption, and emission spectroscopy and excited-state lifetime and spectroelectrochemical measurements. The introduction of the alkoxystyryl group extends the conjugation of the bipyridine donor ligand increasing markedly their molar extinction coefficient and solar light harvesting capacity. The dynamics of photoinduced charge separation following electronic excitation of the K-19 dye was scrutinized by time-resolved laser spectroscopy. The electron transfer from K-19 to the conduction band of TiO2 is completed within 20 fs while charge recombination has a half-life time of 800 s. The high extinction coefficients of these sensitizers enable realization of a new generation of a thin film dye sensitized solar cell (DSC) yielding high conversion efficiency at full sunlight even with viscous electrolytes based on ionic liquids or nonvolatile solvents. An unprecedented yield of over 9% was obtained under standard reporting conditions (simulated global air mass 1.5 sunlight at 1000 W/m2 intensity) when the K-73 sensitizer was combined with a nonvolatile "robust" electrolyte. The K-19 dye gave a conversion yield of 7.1% when used in conjunction with the binary ionic liquid electrolyte. These devices exhibit excellent stability under light soaking at 60 degrees C. The effect of the mesoscopic TiO2 film thickness on photovoltaic performance has been analyzed by electrochemical impedance spectroscopy (EIS). 相似文献
73.
Cho KB Kim EJ Seo MS Shaik S Nam W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(33):10444-10453
The experimentally measured bimolecular reaction rate constant, k(2) , should in principle correlate with the theoretically calculated rate-limiting free energy barrier, ΔG(≠) , through the Eyring equation, but it fails quite often to do so due to the inability of current computational methods to account in a precise manner for all the factors contributing to ΔG(≠) . This is further aggravated by the exponential sensitivity of the Eyring equation to these factors. We have taken herein a pragmatic approach for C?H activation reactions of 1,4-cyclohexadiene with a variety of octahedral nonheme Fe(IV) O complexes. The approach consists of empirically determining two constants that would aid in predicting experimental k(2) values uniformly from theoretically calculated electronic energy (ΔE(≠) ) values. Shown in this study is the predictive power as well as insights into energy relationships in Fe(IV) O C?H activation reactions. We also find that the difference between ΔG(≠) and ΔE(≠) converges at slow reactions, in a manner suggestive of changes in the importance of the triplet spin state weight in the overall reaction. 相似文献
74.
Dr. Pierre‐Antoine Bouit Magdalena Marszalek Dr. Robin Humphry‐Baker Dr. Rafael Viruela Prof. Dr. Enrique Ortí Dr. Shaik M. Zakeeruddin Prof. Dr. Michael Grätzel Dr. Juan Luis Delgado Prof. Dr. Nazario Martín 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(37):11621-11629
Two donor–acceptor molecular tweezers incorporating the 10‐(1,3‐dithiol‐2‐ylidene)anthracene unit as donor group and two cyanoacrylic units as accepting/anchoring groups are reported as metal‐free sensitizers for dye‐sensitized solar cells. By changing the phenyl spacer with 3,4‐ethylenedioxythiophene (EDOT) units, the absorption spectrum of the sensitizer is red‐shifted with a corresponding increase in the molar absorptivity. Density functional calculations confirmed the intramolecular charge‐transfer nature of the lowest‐energy absorption bands. The new dyes are highly distorted from planarity and are bound to the TiO2 surface through the two anchoring groups in a unidentate binding form. A power‐conversion efficiency of 3.7 % was obtained with a volatile CH3CN‐based electrolyte, under air mass 1.5 global sunlight. Photovoltage decay transients and ATR‐FTIR measurements allowed us to understand the photovoltaic performance, as well as the surface binding, of these new sensitizers. 相似文献
75.
Cho KB Chen H Janardanan D de Visser SP Shaik S Nam W 《Chemical communications (Cambridge, England)》2012,48(16):2189-2191
DFT calculated barriers for C-H activation of 1,4-cyclohexadiene by nonheme iron(IV)-oxo and iron(III)-superoxo species show that the experimental trends can be explained if the spin inversion probability of the TMC iron(IV)-oxo is assumed to be poor. Also, the TMC iron(III)-superoxo reaction proceeds with an endothermic O(2)-binding energy followed by an intrinsically reactive quintet state. 相似文献
76.
77.
Finite Element-Based Characterization of Pore-Scale Geometry and Its Impact on Fluid Flow 总被引:1,自引:0,他引:1
We present a finite element (FEM) simulation method for pore geometry fluid flow. Within the pore space, we solve the single-phase
Reynold’s lubrication equation—a simplified form of the incompressible Navier–Stokes equation yielding the velocity field
in a two-step solution approach. (1) Laplace’s equation is solved with homogeneous boundary conditions and a right-hand source
term, (2) pore pressure is computed, and the velocity field obtained for no slip conditions at the grain boundaries. From
the computed velocity field, we estimate the effective permeability of porous media samples characterized by section micrographs
or micro-CT scans. This two-step process is much simpler than solving the full Navier–Stokes equation and, therefore, provides
the opportunity to study pore geometries with hundreds of thousands of pores in a computationally more cost effective manner
than solving the full Navier–Stokes’ equation. Given the realistic laminar flow field, dispersion in the medium can also be
estimated. Our numerical model is verified with an analytical solution and validated on two 2D micro-CT scans from samples,
the permeabilities, and porosities of which were pre-determined in laboratory experiments. Comparisons were also made with
published experimental, approximate, and exact permeability data. With the future aim to simulate multiphase flow within the
pore space, we also compute the radii and derive capillary pressure from the Young–Laplace’s equation. This permits the determination
of model parameters for the classical Brooks–Corey and van-Genuchten models, so that relative permeabilities can be estimated. 相似文献
78.
Condensation of 2,5‐dihydrazinyl thiadiazole with 5‐sodium sulfonate salicylaldehyde afforded dibasic tetradentate pincer N,O,O,N‐salicyldiene thiadiazole ligand (H2Sanp). The novel dipolar ligand formed para‐magnetic pincer complexes within Co (II) and Ni (II) ions (Co‐Sanp and Ni‐Sanp) under sustainable conditions. The water‐soluble ligand and its metal‐complexes were estimated by mass, IR and UV–Visible spectroscopy, EA (elemental analyses), TGA (Thermogravimetric analyses), magnetic susceptibility, and conductivity measurements. The catalytic reactivity of Co‐Sanp and Ni‐Sanp were evaluated in the Suzuki and Buchwald‐Hartwig cross coupling reaction in aqueous‐methanol binary mixtures. Both reactions of boronic acid or aryl amines with aryl halides gave high chemoselective yield of C―C or C―N product. The inhibition characteristics of H2Sanp and its Ni‐ and Co‐complexes were performed for the C‐steel corrosion in 1.0 M HCl using electrochemical measurements and surface analysis methods. These methods indicated that the synthesized compounds have served as efficient mixed‐type corrosion inhibitors and their adsorption on the steel surface obeyed isotherm model of Langmuir. Co‐Sanp inhibitor displays the best corrosion inhibition efficiency, and the capacity is up to 97.11% at of 250 mg L?1. Surface analysis confirms formation of protective layer on the C‐steel surface. 相似文献
79.
80.
Syed Farooq Adil Mohamed E. Assal Mohammed Rafi Shaik Mufsir Kuniyil Azhar Hashmi Mujeeb Khan Aslam Khan Muhammad Nawaz Tahir Abdulrahman Al-Warthan Mohammed Rafiq H. Siddiqui 《应用有机金属化学》2020,34(8):e5718
Graphene–metal nanocomposites have been found to remarkably enhance the catalytic performance of metal nanoparticle-based catalysts. In continuation of our previous report, in which highly reduced graphene oxide (HRG)-based nanocomposites were synthesized and evaluated, we present nanocomposites of graphene oxide (GRO) and ZnO nanoparticle-doped MnCO3 ([ZnO–MnCO3/(1%)GRO]) synthesized via a facile, straightforward co-precipitation technique. Interestingly, it was noticed that the incorporation of GRO in the catalytic system could noticeably improve the catalytic efficiency compared to a catalyst (ZnO–MnCO3) without GRO, for aerial oxidation of benzyl alcohol (BzOH) employing O2 as a nature-friendly oxidant under base-free conditions. The impacts of various reaction factors were thoroughly explored to optimize reaction conditions using oxidation of BzOH to benzaldehyde (BzH) as a model substrate. The catalysts were characterized using X-ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, Energy dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET), and Raman spectroscopy. The (1%)ZnO–MnCO3/(1%)GRO exhibited significant specific activity (67 mmol.g−1.hr−1) with full convversion of BzOH and >99% BzH selectivity within just 6 min. The catalytic efficiency of the (1%)ZnO–MnCO3/(1%)GRO nanocomposite was significantly better than the (1%)ZnO–MnCO3/(1%)HRG and (1%)ZnO–MnCO3 catalysts, presumably due to the existence of oxygen-possessing groups on the GRO surface and as well as a very high surface area that could have been instrumental in uniformly dispersing the active sites of the catalyst, i.e., ZnO–MnCO3. Under optimum circumstances, various kinds of alcohols were selectively transformed to respective carbonyls with full convertibility over the (1%)ZnO–MnCO3/(1%)GRO catalyst. Furthermore, the highly effective (1%)ZnO–MnCO3/(1%)GRO catalyst could be successfully reused and recycled over five consecutive runs with a marginal reduction in its performance and selectivity. 相似文献