首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1212篇
  免费   446篇
  国内免费   92篇
化学   939篇
晶体学   12篇
力学   32篇
综合类   4篇
数学   290篇
物理学   473篇
  2023年   27篇
  2022年   35篇
  2021年   42篇
  2020年   63篇
  2019年   45篇
  2018年   52篇
  2017年   60篇
  2016年   47篇
  2015年   57篇
  2014年   113篇
  2013年   126篇
  2012年   136篇
  2011年   129篇
  2010年   147篇
  2009年   135篇
  2008年   95篇
  2007年   105篇
  2006年   108篇
  2005年   61篇
  2004年   47篇
  2003年   18篇
  2002年   17篇
  2001年   11篇
  2000年   8篇
  1999年   7篇
  1998年   10篇
  1997年   7篇
  1996年   8篇
  1995年   5篇
  1994年   7篇
  1993年   7篇
  1992年   4篇
  1991年   3篇
  1990年   2篇
  1989年   2篇
  1988年   1篇
  1986年   1篇
  1984年   2篇
排序方式: 共有1750条查询结果,搜索用时 31 毫秒
1.
将光活性蒽醌配体L1L2L1=N2N7-双((2,2''-联吡啶)-5-基)-9,10-蒽醌-2,7-双酰胺,L2=N2N7-双(4-((2,2''-联吡啶)-5-基)苯基)-9,10-蒽醌-2,7-双酰胺)与锌离子和亚铁离子通过配位自组装构筑得到一系列配合物1-Zn2-Zn2-Fe,单晶X射线衍射和电喷雾质谱等表征表明这一系列配合物为“2+3”的M2L3型金属-有机超分子结构。将蒽醌基金属-有机笼1-Zn2-Zn应用于甲苯光催化氧化反应中,结果表明笼状催化剂和底物分子间形成超分子主客体化合物是其能有效氧化甲苯的关键。通过对芳香醇的光氧化反应进一步探究1-Zn2-Zn的光氧化性能,实验结果表明催化产率受到取代基的电子效应和底物分子的尺寸的影响。  相似文献   
2.
3.
为了探索新型高效脲酶抑制剂,本文合成了2个新的酰腙氧钒(V)配合物,[VOL1(OCH3)(CH3OH)](1)和[VOL2(μ-OCH3)]2(2)(H2L1=N′-(5-氯-2-羟基苯亚甲基)-3-硝基苯甲酰肼;H2L2=N′-(5-氯-2-羟基苯亚甲基)-4-氯苯甲酰肼),并通过物理化学方法和单晶X-射线衍射表征了它们的结构。化合物1是一个单核配合物,而化合物2是由两个甲氧基配体桥连的具有中心对称性的双核配合物。在每个配合物中,V原子都采取八面体配位构型。本文还研究了这两个配合物的热稳定性和它们对幽门螺旋杆菌脲酶的抑制活性。在浓度为100μmol.L-1时,配合物1和2对脲酶的抑制率分别为71.4%和73.3%,其IC50值分别为63.6和37.7μmol.L-1。  相似文献   
4.
采用水热和溶剂热方法合成了4种Co(Ⅱ)配合物:[Co(btec)0.5(pz)2]n(1),[Co(btec)0.5(pz)3]n(2),[Co(phen)(Hbtc)(H3btc)(H2O)2].3H2O(3)和[Co(Imh)2(anis)2(H2O)](4)(H4btec=1,2,4,5-均苯四甲酸,pz=吡唑;H3btc=1,3,5-均苯三甲酸;phen=1,10-邻菲啰啉;Imh=咪唑;Hanis=对甲氧基苯甲酸)。通过X-射线单晶衍射、元素分析、红外光谱(IR)、紫外-可见-近红外(UV-Vis-NIR)漫反射光谱和表面光电压光谱(SPS)对配合物进行了表征。结构分析表明,配合物1是具有2D结构的Co(Ⅱ)配聚物,Co(Ⅱ)为四配位。配合物2~4中,Co(Ⅱ)均为六配位。配合物2为1D链状结构,分子间通过氢键进一步网联成2D。配合物3和4为分子型配合物,然后再分别由氢键进一步网联成3D和2D。SPS结果显示,4种配合物在300~600 nm范围内都呈现正的光伏响应(SPV),表明它们都具有一定的光-电转换能力。重点是采用SPS技术讨论了配合物结构、空间维度和中心离子配位环境对配合物光电性能的影响,并尝试采用半导体能带理论与配合物的晶体场理论相结合来分析、指认SPS各响应带。  相似文献   
5.
利用三齿席夫碱配体2-[1-(2-羟基乙亚胺基)乙基]苯酚(H2L)和二氰氨钠与氯化铁在甲醇中反应,制备了一个新的具有中心对称性的六核铁(Ⅲ)配合物[NaFe6L6(MeO)6]Cl。通过利用元素分析、红外光谱和X-射线单晶衍射表征了该配合物的结构。配合物的晶体以三斜晶系P1空间群结晶,其晶体学参数a=1.162 5(2)nm,b=1.396 4(2)nm,c=1.504 2(2)nm,α=66.154(7)°,β=68.809(7)°,γ=73.296(7)°,V=2.053 6(5)nm3,Z=1,R1=0.059 3,wR2=0.156 4。本文还研究了该配合物的热稳定性和抗菌活性。  相似文献   
6.
In recent years, the technology of using laser ultrasonic propagation imaging for damage visualization of composite structures were applied to real-world applications. Among many choices of sensor for the Ultrasonic Propagation Imager, the laser interferometry has several advantages: it is non-invasive, and portable, and with extraordinarily long-range measurement. However, the critical issue with interferometry sensing is its low signal-to-noise ratio (SNR), where the background noise can mask the damage-induced waves and making it impossible to identify the damages, especially in composite structures. In this paper, we propose a hardware-based SNR enhancement technique using multiple Laser Doppler Vibrometers (LDVs). The out-of-plane mode of ultrasonic signals are measured by multiple LDVs at a common sensing point and then averaged in real time. We showed that the SNR enhancement in experiments was consistent with the theoretical prediction, and also the test results showed a clear improvement for damage visualization of structures using Ultrasonic Wave Propagation Imaging and Ultrasonic Wavenumber Imaging algorithms.  相似文献   
7.
The effect of the primary Bjerknes force caused by a three-dimensional nonlinear standing ultrasonic wave on a population of nonlinear oscillating bubbles is studied in this paper by analyzing the results obtained from simulations performed with a numerical model at low and moderate pressure amplitudes. Small air bubbles are evenly distributed in a water filled cavity excited at resonance for which axial symmetry is assumed. Both the bubble oscillation variable and the pressure variable are unknown in the nonlinear set of coupled differential equations that describes the interaction of ultrasound and bubbles. Simulation results show that the three-dimensional primary Bjerknes force field is strongly amplitude dependent. We also analyze whether taking the term in the differential system that defines the nonlinear behavior of the pressure field into account is determinant or not on the computation of the force field. The corresponding results corroborate the one-dimensional conclusions on the fundamental importance of considering this nonlinear acoustic term to obtain an accurate approximation of the force in a cavity.  相似文献   
8.
Electronic structure properties including bond lengths, bond angles, dipole moments (μ), energies, band gaps, NMR parameters of the isotropic and anisotropic chemical shielding parameters for the sites of various atoms were calculated using the density functional theory for Si, Ge, Sn, Pb doped (6,3) Chiral single-walled carbon nanotubes (SWCNTs). The calculations indicated that average bond lengths were as: Pb3C>Sn3C>Ge3C>Si3C>C3C. The dipole moments for Si, Ge, Sn, Pb doped (6,3) Chiral single-walled carbon nanotubes structures show fairly large changes with respect to the pristine model.  相似文献   
9.
We demonstrate the coexisting four-wave mixing (FWM) signal and six-wave mixing (SWM) signal which can be enhanced both by electromagnetically induced transparency (EIT) and optical pumping effect in a common three-level and open four-level inverted-Y type systems of 85Rb. We also analyze the effect of optical pumping in different energy level systems by arranging laser beams and comparing the strength of the increased and reduced absorption caused by optical pumping.  相似文献   
10.
Micro-sized NaY(MoO4)2:Tb3+ phosphors with dendritic morphology was synthesized by a ionic liquid-assisted hydrothermal process. X-ray diffraction (XRD) indicated that the as-prepared product is pure tetragonal phase of NaY(MoO4)2. Field emission scanning electron microscopy (FE-SEM) images showed that the as-prepared NaY(MoO4)2:Tb3+ phosphors have dendritic morphology. The photoluminescent (PL) spectra displayed that the as-prepared NaY(MoO4)2:Tb3+ phosphors show a stronger green emission with main emission wavelength 545 nm corresponding to the 5D47F5 transition of Tb3+ ion, and the optimal Tb3+ doping concentration for obtaining maximum emission intensity was confirmed to be 10 mol%. Based on Van Uitert's and Dexter's models the electric dipole–dipole (D–D) interaction was confirmed to be responsible for the concentration quenching of 5D4 fluorescence of Tb3+ in the NaY(MoO4)2:Tb3+ phosphors. The intrinsic radiative transition lifetime of 5D4 level is found to be 0.703 ms.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号