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   1718篇
  免费   283篇
  国内免费   179篇
化学   1197篇
晶体学   18篇
力学   93篇
综合类   10篇
数学   148篇
物理学   714篇
  2024年   6篇
  2023年   47篇
  2022年   61篇
  2021年   65篇
  2020年   93篇
  2019年   80篇
  2018年   53篇
  2017年   51篇
  2016年   74篇
  2015年   82篇
  2014年   70篇
  2013年   100篇
  2012年   117篇
  2011年   143篇
  2010年   111篇
  2009年   118篇
  2008年   123篇
  2007年   104篇
  2006年   109篇
  2005年   92篇
  2004年   57篇
  2003年   47篇
  2002年   42篇
  2001年   50篇
  2000年   37篇
  1999年   42篇
  1998年   29篇
  1997年   25篇
  1996年   33篇
  1995年   21篇
  1994年   29篇
  1993年   16篇
  1992年   12篇
  1991年   9篇
  1990年   7篇
  1989年   9篇
  1988年   8篇
  1987年   3篇
  1986年   1篇
  1984年   3篇
  1982年   1篇
排序方式: 共有2180条查询结果,搜索用时 15 毫秒
941.
4-Methoxyphenyl glycoside of β-D-Galp-(1→6)-[α-L-Araf-(1→3)-]β-D-Galp-(1→6)-β-D-Galp-(1→6)-{β-D-Galp-(1→6)-[α-L-Araf-(1→3)-]β-D-Galp-(1→6)-β-D-Galp-(1→6)-}2β-D-Galp-(1→6)-[α-L-Araf-(1→)3)-]β-D-Galp-(1→)6)-β-D-Galp was synthesized with 2,3,4,6-tetra-O-benzoyl-α-D-galactopyranosyl trichloroacetimidate (1), 6-O-acetyl-2,3,4-tri-O-benzoyl-α-D-galactopyranosyl trichloroacetimidate (11), 4-methoxyphenyl 3-O-allyl-2,4-tri-O-benzoyl-β-D-galactopyranoside (2),isopropyl 3-O-allyl-2,4-tri-O-benzoyl--thio-β-D-galactopyranoside (12),4-methoxyphenyl 2,3,4-tri-O-benzoyl-β-D-galactopyranoside (5), and 2,3,5-tri-O-benzoyl-α-L-arabinofuranosyl trichloroacetimidate (8) as the key synthons.  相似文献   
942.
Five new copper(I)/silver(I) complexes containing 2-aminopyridine, [Cu(μ-Cl)(2-Apy)(PPh3)]2(1), [Ag(μ-Cl)(2-Apy)(PPh3)]2(2), [Ag(μ-Br)(2-Apy)PPh3)]2(3), [Ag(μ-ONO2)(2-Apy)(PPh3)]2(4), [Ag(μ-ONO2)(2-Apy)(AsPh3)]2(5) have been synthesised for the first time. Complexes 15 are obtained by the reactions of MX (MX = CuCl for 1; M = Ag for 2–5; X = Cl, Br for 23; X = NO3 for 4–5) with the monodentate ligands EPh3 (E = P for 14; E = As for 5) and 2-Apy in the molar ratio of 1:1:2 in the mixed solvent of CH2Cl2 and MeOH. Complexes 15 are characterised by IR and X-ray diffraction. In 15, chloride, bromide and nitrate ions bridge two metal atoms to form dinuclear complexes containing the parallelogram cores M2X2 (M = Cu, Ag).  相似文献   
943.
In order to avoid the shortcomings of large particle size and poor uniformity of material synthesized by the traditional solid-state method, this paper utilizes a simple improvement of calcination process (i.e., calcination–milling–recalcination) based on the traditional solid-state synthesis to successfully prepare a large number of well-distributed, micrometer-sized, spherical secondary LiNi0.5Mn1.5O4 particles. Each particle is composed of nano- and/or sub-micrometer-sized grains. Results of the electrochemical performance tests show that the material exhibits a remarkable cycle performance and rate capability compared with that obtained from traditional synthesis method; the spherical LiNi0.5Mn1.5O4 particles can deliver a large capacity of 135.8 mAh g?1 at a 1 C discharge rate with a high retention of 77 % after 741 cycles and a good capacity of 105.9 mAh g?1 at 10 C. Cyclic voltammetry measurements confirm that the significantly improved electrochemical properties are due to enhanced electronic conductivity and lithium-ion diffusion coefficient resulting from the optimized morphology and particle size. This improved method is more suitable for mass production.  相似文献   
944.
Geometries, frequencies, and energies of the 12B1, 12A2, 12B2, 22B1, 22B2, and 12A1, of the C6H5Br+ ion were calculated by using CASSCF and CASPT2 methods in conjunction with an ANO‐RCC basis. The CASPT2//CASSCF adiabatic excitation energies and CASPT2 relative energies for the six states are in good agreement with experiment. The X, A, B, C, and D electronic states of the C6H5Br+ ion were assigned to be X2B1, A2A2, B2B2, C2B1, and D2B2 based on the CASSCF and CASPT2 calculations. The assignment on the D state of the C6H5Br+ ion is different from the previously published works. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010  相似文献   
945.
将手性二茂铁双膦配体ImiFerroPhos应用到β-取代-α,β-不饱和磷酸酯的不对称氢化反应中,在温和的反应条件下,以高收率及较高对映选择性合成了一系列β-取代的手性磷酸酯,最高获得了92%的ee值.  相似文献   
946.
Unstable electrode/solid‐state electrolyte interfaces and internal lithium dendrite penetration hamper the applications of solid‐state lithium‐metal batteries (SSLMBs), and the underlying mechanisms are not well understood. Herein, in situ optical microscopy provides insights into the lithium plating/stripping processes in a gel polymer electrolyte and reveals its dynamic evolution. Spherical lithium deposits evolve into moss‐like and branch‐shaped lithium dendrites with increasing current densities. Remarkably, the on‐site‐formed solid electrolyte interphase (SEI) shell on the lithium dendrite is distinctly captured after lithium stripping. Inducing an on‐site‐formed SEI shell with an enhanced modulus to wrap the lithium precipitation densely and uniformly can regulate dendrite‐free behaviors. An in‐depth understanding of lithium dendrite evolution and its functional SEI shell will aid in the optimization of SSLMBs.  相似文献   
947.
脂性油膏药物中黄芩甙含量的高效液相色谱分析   总被引:1,自引:0,他引:1  
用0.02mol/L的三羟甲基胺基甲烷(用磷酸调pH值至7)和甲醇(含2%乙酸和0.25%庚烷磺酸钠)作流动相进行梯度洗脱,建立了脂性油膏药物中黄苓甙含量的反相高效液相色谱分析方法,本法分析速度快、重现性好,黄苓甙的平均回收率为103.7%.  相似文献   
948.
Minimizing surface defect is vital to further improve power conversion efficiency (PCE) and stability of inorganic perovskite solar cells (PSCs). Herein, we designed a passivator trifluoroacetamidine (TFA) to suppress CsPbI3−xBrx film defects. The amidine group of TFA can strongly chelate onto the perovskite surface to suppress the iodide vacancy, strengthened by additional hydrogen bonds. Moreover, three fluorine atoms allow strong intermolecular connection via intermolecular hydrogen bonds, thus constructing a robust shield against moisture. The TFA-treated PSCs exhibit remarkably suppressed recombination, yielding the record PCEs of 21.35 % and 17.21 % for 0.09 cm2 and 1.0 cm2 device areas, both of which are the highest for all-inorganic PSCs so far. The device also achieves a PCE of 39.78 % under indoor illumination, the highest for all-inorganic indoor photovoltaic devices. Furthermore, TFA greatly improves device ambient stability by preserving 93 % of the initial PCE after 960 h.  相似文献   
949.
Chiral boron/nitrogen doped multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters are promising for highly efficient and color-pure circularly polarized organic light-emitting diodes (CP-OLEDs). Herein, we report two pairs of MR-TADF materials (Czp-tBuCzB, Czp-POAB) based on planar chiral paracyclophane with photoluminescence quantum yields of up to 98 %. The enantiomers showed symmetric circularly polarized photoluminescence spectra with dissymmetry factors |gPL| of up to 1.6×10−3 in doped films. Meanwhile, the sky-blue CP-OLEDs with (R/S)-Czp-tBuCzB showed an external quantum efficiency of 32.1 % with the narrowest full-width at half-maximum of 24 nm among the reported CP-OLEDs, while the devices with (R/S)-Czp-POAB displayed the first nearly pure green CP electroluminescence with |gEL| factors at the 10−3 level. These results demonstrate the incorporation of planar chirality into MR-TADF emitter is a reliable strategy for constructing of efficient CP-OLEDs.  相似文献   
950.
Stability issues could prevent lead halide perovskite solar cells (PSCs) from commercialization despite it having a comparable power conversion efficiency (PCE) to silicon solar cells. Overcoming drawbacks affecting their long-term stability is gaining incremental importance. Excess lead iodide (PbI2) causes perovskite degradation, although it aids in crystal growth and defect passivation. Herein, we synthesized functionalized oxo-graphene nanosheets (Dec-oxoG NSs) to effectively manage the excess PbI2. Dec-oxoG NSs provide anchoring sites to bind the excess PbI2 and passivate perovskite grain boundaries, thereby reducing charge recombination loss and significantly boosting the extraction of free electrons. The inclusion of Dec-oxoG NSs leads to a PCE of 23.7 % in inverted (p-i-n) PSCs. The devices retain 93.8 % of their initial efficiency after 1,000 hours of tracking at maximum power points under continuous one-sun illumination and exhibit high stability under thermal and ambient conditions.  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