全文获取类型
收费全文 | 1291篇 |
免费 | 78篇 |
国内免费 | 6篇 |
专业分类
化学 | 1102篇 |
晶体学 | 5篇 |
力学 | 6篇 |
数学 | 112篇 |
物理学 | 150篇 |
出版年
2023年 | 20篇 |
2022年 | 14篇 |
2021年 | 35篇 |
2020年 | 43篇 |
2019年 | 27篇 |
2018年 | 31篇 |
2017年 | 17篇 |
2016年 | 73篇 |
2015年 | 35篇 |
2014年 | 49篇 |
2013年 | 75篇 |
2012年 | 109篇 |
2011年 | 137篇 |
2010年 | 46篇 |
2009年 | 46篇 |
2008年 | 104篇 |
2007年 | 75篇 |
2006年 | 69篇 |
2005年 | 79篇 |
2004年 | 61篇 |
2003年 | 50篇 |
2002年 | 43篇 |
2001年 | 6篇 |
2000年 | 6篇 |
1999年 | 5篇 |
1998年 | 12篇 |
1997年 | 9篇 |
1996年 | 14篇 |
1995年 | 7篇 |
1994年 | 4篇 |
1993年 | 6篇 |
1992年 | 4篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1977年 | 5篇 |
1976年 | 2篇 |
1972年 | 1篇 |
1971年 | 2篇 |
1968年 | 4篇 |
1960年 | 2篇 |
1957年 | 2篇 |
1935年 | 2篇 |
排序方式: 共有1375条查询结果,搜索用时 46 毫秒
131.
Lomaiviticins A and B are complex antitumor antibiotics that were isolated from a strain of Micromonospora. A confluence of several unusual structural features renders the lomaiviticins exceedingly challenging targets for chemical synthesis. We report an 11-step, enantioselective synthetic route to lomaiviticin aglycon. Our route proceeds by late-stage, stereoselective dimerization of two equivalent monomeric intermediates, a transformation that may share parallels with the natural products' biosyntheses. The route we describe is scalable and convergent, and it lays the foundation for determination of the mode of action of these natural products. 相似文献
132.
Loukou C Changenet-Barret P Rager MN Plaza P Martin MM Mallet JM 《Organic & biomolecular chemistry》2011,9(7):2209-2218
The design, synthesis and study of the photophysical and photochemical properties of the first biomimetic cyclodextrin (CD) model of photoactive yellow protein (PYP) are described. This model bears a deprotonated trans-p-coumaric acid chromophore, covalently linked via a cysteine moiety to a permethylated 6-monoamino β-CD. NMR and UV/Visible spectroscopy studies showed the formation of strong self-inclusion complexes in water at basic pH. Steady-state photolysis demonstrated that, unlike the free chromophore in solution, excitation of the model molecule leads to the formation of a photoproduct identified as the cis isomer by NMR spectroscopy. These observations provide evidence that the restricted CD cavity offers a promising framework for the design of biomimetic models of the PYP hydrophobic pocket. 相似文献
133.
Fischer C Kohrt C Drexler HJ Baumann W Heller D 《Dalton transactions (Cambridge, England : 2003)》2011,40(16):4162-4166
Three novel trinuclear rhodium hydride complexes of the type {[Rh(PP*)H](3)(μ(2)-H)(3)(μ(3)-H)}[BF(4)](2) containing diphosphines Tangphos, t-Bu-BisP* and Me-DuPHOS have been synthesised. The new compounds are very stable. Their structures have been characterized by X-ray analysis in the solid state and by NMR-spectroscopic investigations in solution. 相似文献
134.
Papoutsis I Nikolaou P Athanaselis S Alevizopoulos G Pistos C Paraskevopoulou C Spiliopoulou C 《Journal of separation science》2011,34(21):3037-3042
Sildenafil (SDL) is a phosphodiesterase type 5 inhibitor and it is approved for the treatment of erectile dysfunction and pulmonary hypertension. SDL is extensively metabolized to its pharmacologically active metabolite, desmethyl‐sildenafil (DSDL). A sensitive and specific GC/MS method for the determination of SDL and DSDL in whole blood was developed and validated to support therapeutic drug monitoring of SDL patients. The combination of solid‐phase extraction with derivatization using BSTFA with 1% TMCS in acetonitrile efficiently reduced matrix effect and improved sensitivity of the method. In this assay, protriptyline was used as internal standard for both analytes. The LODs were 1.50 and 5.00 ng/mL for SDL and DSDL, respectively, whereas the respective LOQs were 5.00 and 15.0 ng/mL. The calibration curves were linear up to 500.0 ng/mL (SDL: R2 0.992, DSDL: R2 0.990). Absolute recovery values for both analytes ranged from 83.1 to 93.2%. Within‐ and between‐batch accuracy was less than 11.8 and 10.2%, respectively, whereas within‐ and between‐batch precision was less than 8.1 and 10.8%, correspondingly. The developed method is suitable for the determination of SDL and DSDL concentrations in blood samples obtained from patients under Viagra® treatment, for pharmacokinetic studies or for the investigation of related forensic cases. 相似文献
135.
Smith AB Risatti CA Atasoylu O Bennett CS Liu J Cheng H TenDyke K Xu Q 《Journal of the American Chemical Society》2011,133(35):14042-14053
The design, synthesis, and biological evaluation of two diminutive forms of (+)-spongistatin 1, in conjunction with the development of a potentially general design strategy to simplify highly flexible macrocyclic molecules while maintaining biological activity, have been achieved. Examination of the solution conformations of (+)-spongistatin 1 revealed a common conformational preference along the western perimeter comprising the ABEF rings. Exploiting the hypothesis that the small-molecule recognition/binding domains are likely to comprise the conformationally less mobile portions of a ligand led to the design of analogues, incorporating tethers (blue) in place of the CD and the ABCD components of the (+)-spongistatin 1 macrolide, such that the conformation of the retained (+)-spongistatin 1 skeleton would mimic the assigned solution conformations of the natural product. The observed nanomolar cytotoxicity and microtubule destabilizing activity of the ABEF analogue provide support for both the assigned solution conformation of (+)-spongistatin 1 and the validity of the design strategy. 相似文献
136.
Wagner AM Fegley MW Warner JB Grindley CL Marotta NP Petersson EJ 《Journal of the American Chemical Society》2011,133(38):15139-15147
Methods for synthetically manipulating protein structure enable greater flexibility in the study of protein function. Previous characterization of the Escherichia coli aminoacyl tRNA transferase (AaT) has shown that it can modify the N-terminus of a protein with an amino acid from a tRNA or a synthetic oligonucleotide donor. Here, we demonstrate that AaT can efficiently use a minimal adenosine substrate, which can be synthesized in one to two steps from readily available starting materials. We have characterized the enzymatic activity of AaT with aminoacyl adenosyl donors and found that reaction products do not inhibit AaT. The use of adenosyl donors removes the substrate limitations imposed by the use of synthetases for tRNA charging and avoids the complex synthesis of an oligonucleotide donor. Thus, our AaT donors increase the potential substrate scope and reaction scale for N-terminal protein modification under conditions that maintain folding. 相似文献
137.
Conventionally, C-H oxidation reactions are used to install functional groups. The use of C-H oxidation to transform simple starting materials into highly versatile intermediates, which enable rapid access to a range of complex target structures, is a new area with tremendous potential in synthesis. Herein we report a Pd(II)/sulfoxide-catalyzed allylic C-H oxidation to form anti-1,4-dioxan-2-ones from homoallylic oxygenates. These versatile building blocks are rapidly elaborated to differentiated syn-1,2-diols, stereodefined amino-polyols, and syn-pyrans, structures ubiquitous in medicinally important complex molecules found in Nature. We also demonstrate that a C-H oxidation approach to the synthesis of these motifs is orthogonal and complementary to other state-of-the-art methods. 相似文献
138.
Photoelectron angular distributions (PADs) are obtained for a pair of 4s(1)4p(6)6p(1) (a singlet and a triplet) autoionizing states in atomic krypton. A high-order harmonic pulse is used to excite the pair of states and a time-delayed 801 nm ionization pulse probes the PADs to the final 4s(1)4p(6) continuum with femtosecond time resolution. The ejected electrons are detected with velocity map imaging to retrieve the time-resolved photoelectron spectrum and PADs. The PAD for the triplet state is inherently separable by virtue of its longer autoionization lifetime. Measuring the total signal over time allows for the PADs to be extracted for both the singlet state and the triplet state. Anisotropy parameters for the triplet state are measured to be β(2)=0.55 ± 0.17 and β(4)=-0.01 ± 0.10, while the singlet state yields β(2)=2.19 ± 0.18 and β(4)=1.84 ± 0.14. For the singlet state, the ratio of radial transition dipole matrix elements, X, of outgoing S to D partial waves and total phase shift difference between these waves, Δ, are determined to be X=0.56 ± 0.08 and Δ=2.19 ± 0.11 rad. The continuum quantum defect difference between the S and D electron partial waves is determined to be -0.15 ± 0.03 for the singlet state. Based on previous analyses, the triplet state is expected to have anisotropy parameters independent of electron kinetic energy and equal to β(2)=5∕7 and β(4)=-12∕7. Deviations from the predicted values are thought to be a result of state mixing by spin-orbit and configuration interactions in the intermediate and final states; theoretical calculations are required to quantify these effects. 相似文献
139.
The preparation of nanoengineered materials with controlled nanostructures, for example, with an anisotropic phase segregated structure or a regular periodicity rather than with a broad range of interparticle distances, has remained a synthetic challenge for intermetallics. Artificially structured materials, including multilayers, amorphous alloys, quasicrystals, metastable crystalline alloys, or granular metals, are mostly prepared using physical gas phase procedures. We report a novel, powerful solution-mediated approach for the formation of nanoparticular binary antimonides based on presynthesized antimony nanoparticles. The transition metal antimonides M-Sb (M = Co, Ni, Cu(2), Zn) were obtained with sizes ranging from 20 and 60 nm. Through careful control of the reaction conditions, single-phase nanoparticular antimonides were synthesized. The nanophases were investigated by powder X-ray diffraction and (high resolution) electron microscopy. The approach is based on activated metal nanoparticles as precursors for the synthesis of the intermetallic compounds. X-ray powder diffraction studies of reaction intermediates allowed monitoring of the reaction kinetics. The small particle size of the reactants ensures short diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. 相似文献
140.
Birkel CS Kieslich G Bessas D Claudio T Branscheid R Kolb U Panthöfer M Hermann RP Tremel W 《Inorganic chemistry》2011,50(22):11807-11812
Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder diffraction and iron-57 M?ssbauer spectroscopy showed the incipient formation of the binary phase in the temperature range of 200-250 °C. 相似文献