全文获取类型
收费全文 | 208篇 |
免费 | 12篇 |
专业分类
化学 | 142篇 |
晶体学 | 1篇 |
力学 | 5篇 |
数学 | 32篇 |
物理学 | 40篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 5篇 |
2020年 | 4篇 |
2019年 | 6篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 8篇 |
2015年 | 6篇 |
2014年 | 12篇 |
2013年 | 16篇 |
2012年 | 13篇 |
2011年 | 11篇 |
2010年 | 10篇 |
2009年 | 9篇 |
2008年 | 6篇 |
2007年 | 7篇 |
2006年 | 4篇 |
2005年 | 8篇 |
2004年 | 2篇 |
2003年 | 2篇 |
2002年 | 2篇 |
2001年 | 3篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 5篇 |
1997年 | 5篇 |
1996年 | 7篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 6篇 |
1992年 | 2篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1948年 | 1篇 |
1932年 | 1篇 |
1908年 | 1篇 |
1905年 | 2篇 |
1887年 | 1篇 |
排序方式: 共有220条查询结果,搜索用时 15 毫秒
211.
We describe the total synthesis of euchrestifoline featuring an unprecedented one-pot Wacker oxidation and double aromatic C-H bond activation. 相似文献
212.
B Völker F Wölzl T Bürgi D Lingenfelser 《Langmuir : the ACS journal of surfaces and colloids》2012,28(31):11354-11363
Processing dye-sensitized solar cells gains more and more importance as interest in industrial applications grows daily. For large-scale processing and optimizing manufacturing in terms of environmental acceptability as well as time and material saving, a detailed knowledge of certain process steps is crucial. In this paper we concentrate on the sensitizing step of production, i.e., the anchoring of the dye molecules onto the TiO(2) semiconductor. A vacuum-tight attentuated total reflection infrared (ATR-IR) flow-through cell was developed, thus allowing measurements using a vacuum spectrometer to monitor infiltration of dye molecules into the porous TiO(2) film in situ at high sensitivity. In particular, the influence of the anchor and backbone of perylene dye molecules as well as the influence of solvents on the adsorption process was investigated. The experiments clearly show that an anhydride group reacts much slower than an acid group. A significantly lower amount of anhydride dye can be adsorbed on the films. Ex situ transmission experiments furthermore indicate that the availability of OH groups on the TiO(2) surface may limit dye adsorption. Also the backbone and base frame of the dye can influence the adsorption time drastically. Electrical cell characteristics correlate with the amount of adsorbed dye molecules determined by in situ ATR-IR measurements. The latter is also sensitive toward the diffusion of the dye through the porous layer. To gain a deeper understanding of the interplay between diffusion and adsorption, simulations were performed that allowed us to extract diffusion and adsorption constants. Again it was demonstrated that the anchoring group has a strong effect on the adsorption rate. The influence of the solvent was also studied, and it was found that both adsorption and desorption are affected by the solvent. Protic polar solvents are able to remove bound dye molecules, which is a possible pathway of cell degradation. Most importantly, the analysis shows the potential of this approach for the evaluation of molecules or additives concerning their characteristics important for cell processing. 相似文献
213.
In this research, a comprehensive theoretical investigation of the thermal rearrangements of 1-ethynyl-2-methylcyclopropane is carried out employing density functional theory (DFT), with the B3LYP functional, and high-level ab initio methods, such as the complete active space self-consistent field (CASSCF), multireference second-order M?ller-Plesset perturbation theory (MRMP2), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)]. In all computations Pople's polarized triple-ζ split valence basis set, 6-311G(d,p), is utilized. The potential energy surface (PES) for the relevant system is explored to provide a theoretical account of the experiments by Hopf, Ellis and Frey, Huntsman et al., and Berson. The computational results herein on the target system show that the thermal aromatization reaction does not proceed via conversion of 1,2,5-hexatriene (2) to 1,3,5-hexatriene (10a) as proposed by Hopf. Indeed, the reaction proceeds via conversion of 5 and 6 to bicyclo[3.1.0]hexene (9) as suggested by Huntsman et al. 相似文献
214.
A comprehensive theoretical investigation of thermal rearrangements of 2-vinylmethylenecyclopropane and 3-vinylcyclobutene is carried out employing density functional theory and high level ab initio methods, such as the complete active space self-consistent field, multi-reference second-order M?ller-Plesset perturbation theory, and coupled-cluster singles and doubles with perturbative triples. In all computations, Pople's polarized triple-ζ split valence basis set, 6-311G(d,p), is utilized. The potential energy surface for the relevant system is explored to provide theoretical insights for the thermal aromatizations of 2-vinylmethylenecyclopropane and 3-vinylcyclobutene. The rate constant for each isomerization reaction is computed using the transition state theory. The simultaneous first-order ordinary-differential equations are solved numerically for the considered system to obtain time-dependent concentrations, hence the product distributions at a given temperature. Our results demonstrate that at high temperatures thermal aromatizations of 2-vinylmethylenecyclopropane (at 700 °C and higher) and 3-vinylcyclobutene (at 500 °C and higher) are feasible under appropriate experimental conditions. However, at low temperatures (at 500 °C and lower), 2-vinylmethylenecyclopropane yields 3-methylenecyclopentene as a unique product, kinetically, and the formation of benzene is not favorable. Similarly, at 300 °C and lower temperatures, 3-vinylcyclobutene can only yield trans-1,3,5-hexatriene (major) and cis-1,3,5-hexatriene (minor). At 300 < T < 500 °C, 3-vinylcyclobutene almost completely yields 1,3-cyclohexadiene. Hence, our computations provide a useful insight for the synthesis of substituted aromatic compounds. Further, calculated energy values (reaction energies and activation parameters) are in satisfactory agreement with the available experimental results. 相似文献
215.
Perihan ünak F. Zümrüt Biber Müftüler ?i?dem ??hedef E. ?lker Medine Kübra ?zmen Turan ünak Ayfer Yurt Kil?ar F. Gül Gümü?er Yasemin Parlak Elvan Say?t Bilgin 《Journal of Radioanalytical and Nuclear Chemistry》2012,293(1):57-66
Diethylstilbestrol (DES) is a well known, nonsteroidal estrogen with high affinity for the estrogen receptor (ER). Today DES is used to treat breast and prostate cancers. A phosphate derivative of DES [Diethylstilbestrol diphosphate (DES-P)] which is specific to tumor cells consisting alkaline phosphatase enzyme was synthesized and labeled with 99mTc using tin chloride as reducing agent. In vivo biological activity of 99mTc labeled diethylstilbestrol phosphate compound (99mTc-DES-P) was examined by biodistribution studies on Wistar Albino rats. Statistical evaluation was performed using SPSS 13 program. The percentage (%) radiolabeling yield of 99mTc-DES-P and quality control studies were done by Thin Layer Radio Chromatography (TLRC). Results showed that, 99mTc-DES-P may be proposed as an imaging agent for ER enriched tumors such as uterus and prostate and their metastases in bones. 相似文献
216.
Lovera S Sutto L Boubeva R Scapozza L Dölker N Gervasio FL 《Journal of the American Chemical Society》2012,134(5):2496-2499
c-Src and c-Abl are two closely related protein kinases that constitute important anticancer targets. Despite their high sequence identity, they show different sensitivities to the anticancer drug imatinib, which binds specifically to a particular inactive conformation in which the Asp of the conserved DFG motif points outward (DFG-out). We have analyzed the DFG conformational transition of the two kinases using massive molecular dynamics simulations, free energy calculations, and isothermal titration calorimetry. On the basis of the reconstruction of the free energy surfaces for the DFG-in to DFG-out conformational changes of c-Src and c-Abl, we propose that the different flexibility of the two kinases results in a different stability of the DFG-out conformation and might be the main determinant of imatinib selectivity. 相似文献
217.
Using a convergent palladium-catalyzed construction of the carbazole framework as the key step we have achieved a short synthesis of the 7-oxygenated carbazole alkaloids clauszoline-K, 3-formyl-7-hydroxycarbazole, clausine C (clauszoline-L), clausine M, clausine N and the anti-HIV active siamenol. 相似文献
218.
Czerwonka R Reddy KR Baum E Knölker HJ 《Chemical communications (Cambridge, England)》2006,(7):711-713
The first enantioselective total synthesis of neocarazostatin B, the determination of its absolute configuration and transformation into carquinostatin A are described. 相似文献
219.
The kinetics of a proton transfer into dilute acid solutions containing natural zeolitic tuff was studied by following the
pH evolution of the liquid phase. Four different solutions with tuff contents of 9, 3, 1 and 0.5 (% wt) and three different
particle size fractions (≤ 2000 μm) were studied. The proton concentration of the solution was decreased by increasing the
zeolite amount and decreasing the particle size fraction. The proton transfer reaction was analyzed with chemical reactions
and diffusion model equations. Analysis shows that the adsorption and/or ion exchange are possible mechanisms and are expressed
by a second order reaction model. 相似文献
220.
For the computation of the macroscopic tangent that is required in multiscale volumetric homogenization techniques, two methods are summarized. First, a condensation approach is followed where the linearity of variational terms associated with the penalty enforcement of boundary conditions is explored in order to extract a macroscopic tangent at any stage of the Newton–Raphson iterations of a microstructural testing procedure. As an alternative approach, a second method is explored that requires only the knowledge of infinitesimally close macroscopic deformation states. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献