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1.
The electronic structure of quantum dots (QDs) including band edges and possible trap states is an important physical property for optoelectronic applications. The reliable determination of the energy levels of QDs remains a big challenge. Herein we employ cyclic voltammetry (CV) to determine the energy levels of three types of ZnO QDs with different surface ligands. Coupled with spectroscopic techniques, it is found that the onset potential of the first reductive wave is likely related to the conduction band edges while the first oxidative wave originates from the trap states. The determined specific energy levels in CV further demonstrates that the ZnO QDs without surface ligands mainly have oxygen interstitial defects whilst the ZnO QDs covered with ligands contain oxygen vacancies. The present electrochemical method offers a powerful and effective way to determine the energy levels of wide bandgap ZnO QDs, which will boost their device performance.  相似文献   
2.
在完备的度量空间中,讨论了一类新型的非线性压缩映射ρ(Tx,Ty)≤a(ρ(x,y))ρ(x,Tx)+b(ρ(x,y))ρ(y,Ty)+c(ρ(x,y))ρ(x,y)通过构造迭代序列,指出该映射的不动点的存在性和唯一性,并给出相应的误差估计式,拓展和改进了有关文献的范围.  相似文献   
3.
Peptide macrocyclization is often a slow process, plagued by epimerization and cyclodimerization. Herein, we describe a new method for peptide macrocyclization employing the AgI‐promoted transformation of peptide thioamides. The AgI has a dual function: chemoselectively activating the thioamide and tethering the N‐terminal thioamide to the C‐terminal carboxylate. Extrusion of Ag2S generates an isoimide intermediate, which undergoes acyl transfer to generate the native cyclic peptide, resulting in a rapid, traceless macrocylization process. Cyclic peptides are furnished in high yields within 1 hour, free of epimerization and cyclodimerization.  相似文献   
4.
Three mesoporous molecular sieves loaded silicotungstic acids, named HSiW/SBA-15, HSiW/MCM-41, HSiW/MCM-48, were prepared and characterised by XRD, FT-IR, TEM and SEM. The catalytic performance of the prepared materials for the Baeyer-Villiger oxidation of cyclic ketones was carried out in the presence of 30%H2O2 under mild conditions. These loading materials were proved to be efficient and reusable catalysts, they all exhibited excellent catalytic performance for the Baeyer-Villiger oxidation of cyclic ketones with 30% H2O2 as oxidant. Many cyclic ketones were efficiently converted to the corresponding lactones with up to 90% conversions and high selectivities under the optimum reaction conditions.

Cyclic ketones were efficiently oxidised by mesoporous materials sopported silicotungstic acid to the corresponding lactones with 30%H2O2 as oxidant. All of the catalysts showed promising recyclability in the reactions.  相似文献   
5.
砂土孔隙比及所受压力是其力学特性的重要影响因素. 本文基于砂土临界状态线特性分析,采用以e-(p/pa)ξ平面内的线性关系描述其等向压缩线. 通过对比分析两种不同压缩线函数 与临界状态线函数之间的关系提出更适合描述砂土在等向压缩下的参考压缩线,并给出了基于参考压缩线的等向硬化规律. 建议了适用于 描述砂土剪切特性的屈服面函数,并给出利用等向压缩和等p路径确定屈服面形状参数μ的方法. 将不同应力比对应的压缩线作为砂土状态参量参考线,以获取潜在强度Mf与特征状态应力比Mc,进而描述砂土压缩与剪切特性;基于等向压缩与等p路径建立了当前应力比与状态参量参考线之间的相关关系,从而实现了砂土状 态参量参考线由参考压缩线向临界状态线平稳过渡. 建立的砂土本构模型共11个参数,均能够通过常规土工试验或经验获取. 基于模型预测与Toyoura砂的等向压缩、三轴不排水剪切试验及排水剪切试验的对比结果,本文建立的砂土本构模型很好地描述了Toyoura 砂在不同孔隙比和不同压力下的压缩与剪切特性.   相似文献   
6.
Transition-metal-catalyzed C−H activation has shown potential in the functionalization of peptides with expanded structural diversity. Herein, the development of late-stage peptide macrocyclization methods by palladium-catalyzed site-selective C(sp2)−H olefination of tryptophan residues at the C2 and C4 positions is reported. This strategy utilizes the peptide backbone as endogenous directing groups and provides access to peptide macrocycles with unique Trp–alkene crosslinks.  相似文献   
7.
Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.  相似文献   
8.
Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710  相似文献   
9.
Here, we report a new strategy for rapid synthesis of branched peptide by side-chain hydrazide ligation at Asn. The hydrazide was converted to thioester at Asn side chain by NaNO2 and thiol reagent, and sequential ligation with an N-terminus Cys-peptide efficiently afforded the branched peptide. A branched cyclic peptide was successfully synthesized by side-chain ligation with a two-Cys-peptide and formation of a disulfide bond. This approach provides a new way for expeditious synthesis of branched peptides and facilitates the design of neopeptides as functional bio-mimics.  相似文献   
10.
为了研究酚醛层压材料的冲击力学行为并获得本构模型,利用万能试验机和整形修正的分离式霍普金森压杆(SHPB)装置,对材料试样进行了应变率范围为10-3~103 s-1的单轴压缩实验,得到了不同加载应变率下的应力应变曲线,对其在准静态、动态载荷下的压缩破坏机理进行了初步探讨。结果表明,酚醛层压材料具有较强的应变率效应,与准静态(1.67×10-3 s-1)时相比,在动态载荷(7×102 s-1)下,峰值应力增加了约10倍;破坏应变减少了约一半;在准静态和动态加载条件下试样力学性能的差异是由于纤维基体界面特性以及不同应变率下破坏模式的不同;采用朱-王-唐本构方程描述了酚醛层压材料力学行为,拟合得到了本构方程的系数,在加载过程中,理论计算值与实验结果吻合较好。  相似文献   
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