全文获取类型
收费全文 | 27999篇 |
免费 | 4599篇 |
国内免费 | 2922篇 |
专业分类
化学 | 18567篇 |
晶体学 | 274篇 |
力学 | 1945篇 |
综合类 | 224篇 |
数学 | 3445篇 |
物理学 | 11065篇 |
出版年
2024年 | 107篇 |
2023年 | 602篇 |
2022年 | 1074篇 |
2021年 | 1086篇 |
2020年 | 1120篇 |
2019年 | 1049篇 |
2018年 | 985篇 |
2017年 | 930篇 |
2016年 | 1361篇 |
2015年 | 1324篇 |
2014年 | 1546篇 |
2013年 | 2084篇 |
2012年 | 2454篇 |
2011年 | 2469篇 |
2010年 | 1643篇 |
2009年 | 1605篇 |
2008年 | 1748篇 |
2007年 | 1500篇 |
2006年 | 1377篇 |
2005年 | 1166篇 |
2004年 | 867篇 |
2003年 | 696篇 |
2002年 | 627篇 |
2001年 | 522篇 |
2000年 | 523篇 |
1999年 | 637篇 |
1998年 | 530篇 |
1997年 | 530篇 |
1996年 | 494篇 |
1995年 | 471篇 |
1994年 | 388篇 |
1993年 | 347篇 |
1992年 | 289篇 |
1991年 | 255篇 |
1990年 | 240篇 |
1989年 | 191篇 |
1988年 | 150篇 |
1987年 | 124篇 |
1986年 | 97篇 |
1985年 | 97篇 |
1984年 | 63篇 |
1983年 | 50篇 |
1982年 | 53篇 |
1981年 | 22篇 |
1980年 | 13篇 |
1979年 | 4篇 |
1976年 | 1篇 |
1959年 | 1篇 |
1957年 | 7篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
Li Wei Bin Zhang Yan Zhou Li Qiang Junyan Zhang 《Surface and interface analysis : SIA》2013,45(8):1233-1237
Fluorine‐doped hydrogenated carbon film was grown by chemical vapor deposition technique using CH4 and CF4 as feedstock, with a pulse DC‐bias power supply. The structure of as‐deposited film was characterized by transmission electron microscopy and Raman spectra. The results suggested that the film could be considered as composite thin film with curved graphitic structures embedded in amorphous carbon matrix. The mechanical properties and friction coefficient were tested by TI 950 TriboIndenter and UMT‐2 at humidity of 30%, respectively. The results showed that the film exhibited high hardness (~11.04 GPa), good elasticity recovery(~83%) and ultra‐low coefficient of friction (~0.01). Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
982.
Jing‐Tao Shi Chun‐Sheng Zhou Yong‐Liang Liu Zhi‐Guo Fang Rui‐Li Zhao Li‐Li Xu Ke‐Fen Yue 《无机化学与普通化学杂志》2013,639(1):187-192
Two coordination polymers (CPs), {[Zn2(BMB)(5‐AIPA)2] · 2H2O}n( 1 ) and [Zn(BMB)(5‐NIPA)]n( 2 ) {BMB = 1, 4‐bis[(2‐methyl‐imidazol‐1‐yl)methyl]benzene, 5‐AIPA = 5‐aminoisophthalic acid, 5‐NIPA = 5‐nitroisophthalic acid}, were synthesized under hydrothermal conditions. Compound 1 displays a 2D double‐layer structure, which is packed into a 3D supramolecule by interlayer hydrogen bonds and π–π stacking interactions. Compound 2 displays a threefold interpenetrating 3D network, which is composed of left‐handed helical chains and two types of meso‐helical chains along different directions. 相似文献
983.
Xiao‐Ying Cheng Ming‐Fang Wang Zheng‐Yin Yang Yong Li Zeng‐Chen Liu Qiao‐Xia Zhou 《无机化学与普通化学杂志》2013,639(5):832-841
The Schiff base ligand, 1‐phenyl‐3‐methyl‐5‐hydroxypyrazole‐4‐methylene‐8′‐quinolineimine, and its CuII, ZnII, and NiII complexes were synthesized and characterized. The crystal structure of the ZnII complex was determined by single‐crystal X‐ray diffraction, indicating that the metal ions and Schiff base ligand can form mononuclear six‐coordination complexes with 1:1 metal‐to‐ligand stoichiometry at the metal ions as centers. The binding mechanism and affinity of the ligand and its metal complexes to calf thymus DNA (CT DNA) were investigated by UV/Vis spectroscopy, fluorescence titration spectroscopy, EB displacement experiments, and viscosity measurements, indicating that the free ligand and its metal complexes can bind to DNA via an intercalation mode with the binding constants at the order of magnitude of 105–106 M –1, and the metal complexes can bind to DNA more strongly than the free ligand alone. In addition, antioxidant activities of the ligand and its metal complexes were investigated through scavenging effects for hydroxyl radical in vitro, indicating that the compounds show stronger antioxidant activities than some standard antioxidants, such as mannitol. The ligand and its metal complexes were subjected to cytotoxic tests, and experimental results indicated that the metal complexes show significant cytotoxic activity against lung cancer A 549 cells. 相似文献
984.
Bi‐Dong Wu Zun‐Ning Zhou Yan‐Gang Bi Li Yang Jian‐Guo Zhang Tong‐Lai Zhang 《无机化学与普通化学杂志》2013,639(5):799-803
The intriguing multi‐ligand compound [Cu(IMI)4Cl]Cl ( 1 ) with the ligand imidazole (IMI) was synthesized and characterized by elemental analysis and FT‐IR spectroscopy. The crystal structure was determined by X‐ray single crystal diffraction and the crystallographic data showed that the compound belongs to the monoclinic P21/n space group [α = 8.847(2) Å, b = 13.210(3) Å, c = 13.870(3) Å, and β = 90.164(3)°]. Furthermore, the CuII ion is five‐coordinated by four nitrogen atoms from four imidazole ligands and a chlorine atom. The thermal decomposition mechanism was determined based on differential scanning calorimetry (DSC) and thermogravimetric (TG‐DTG) analysis. The non‐isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa's method, respectively. The energy of combustion, enthalpy of formation, critical temperature of thermal explosion, entropy of activation (ΔS≠), enthalpy of activation (ΔH≠), and free energy of activation (ΔG≠) were measured and calculated. 相似文献
985.
Xiaoyu Dong Liang Cui Yunjing Shi Shilie Pan Zhongxiang Zhou Zhihua Yang Bingbing Zhang Xiangzhan Jiang Yun Yang Zhaohui Chen Zhenjun Huang 《无机化学与普通化学杂志》2013,639(6):988-993
The single crystals of Ba2Cd(B3O6)2 were grown by the spontaneous crystallization method for the first time. They crystallize in the centrosymmetric trigonal space group R$\bar{3}$ with a = 7.143(3) Å, c = 17.405(16) Å, and Z = 3. The structure is characterized by isolated B3O6 units, and the Ba2+ and Cd2+ cations connect with B3O6 rings to form three dimensional structure. The TG/DSC and XRD results reveal that Ba2Cd(B3O6)2 melts congruently. First‐principles electronic structure calculation performed with the density functional theory (DFT) method shows that the calculated bandgaps are 4.66 eV, which is in good agreement with the UV/Vis/NIR experimental value 4.59 eV. The calculation shows that the Ba2Cd(B3O6)2 crystal has a large birefringence (Δn = 0.0875–0.0569 from 270 nm to 2600 nm), which demonstrates that Ba2Cd(B3O6)2 is a potential birefringence crystal. 相似文献
986.
Yao Huang Long‐Jiang Liu Ming‐Shan Zhou Xiao‐Jun Zhou Chao Zhu Fei‐E Fu Yong‐Ming Zhang 《无机化学与普通化学杂志》2013,639(10):1884-1887
Two metal‐organic frameworks, [Zn(dmtrz)(btrc)1/3]n ( 1 ) and [Zn2(dmtrz)2(btec)(H2O)2]n ( 2 ) (dmtrz = 3, 5‐dimethyl‐1‐H‐1, 2,4‐triazole, btrc = 1, 3,5‐benzenetricarboxylate, btec = 1, 2,4, 5‐benzenetetracarboxylate), were synthesized by hydrothermal reaction. The crystal structure analysis reveals that compound 1 is a dense 3D framework with Schläfli symbols of {43}2{46 · 66 · 83}3, which is a loh1 structure. Compound 2 is a 2D network. In addition, the photoluminescence of two compounds were studied in solid state at room temperature, together with their thermal analysis. 相似文献
987.
A simple and novel flow‐injection chemiluminescence (FI‐CL) method was established for the determination of 2‐Methoxyestradiol (2‐ME) in pharmaceutical preparations and biological fluids. The method was based on the significant enhancement of the CL from the KMnO4‐Na2SO3 reaction by 2‐ME in acidic medium. Under optimized conditions, the CL intensity was correlated linearly with concentration of 2‐ME in the range of 5.0 × 10?8‐5.0 × 10?6 M (r = 0.9995). The detection limit (3σ) of 2‐ME was 7.5 × 10?9 M and the relative standard deviation was 0.8% at 5.0 × 10?7 M 2‐ME (n = 8). The proposed method was successfully applied for the flow‐injection CL determination of 2‐ME in pharmaceutical preparations and biological fluids with the recoveries from 92.4 to 106.8%. The possible CL reaction mechanism was also discussed briefly. 相似文献
988.
Dr. Guo‐Qiang Kong Zhi‐Da Han Dr. Yabing He Sha Ou Dr. Wei Zhou Prof. Dr. Taner Yildirim Prof. Dr. Rajamani Krishna Dr. Chao Zou Prof. Dr. Banglin Chen Prof. Dr. Chuan‐De Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14886-14894
Two new organic building units that contain dicarboxylate sites for their self‐assembly with paddlewheel [Cu2(CO2)4] units have been successfully developed to construct two isoreticular porous metal–organic frameworks (MOFs), ZJU‐35 and ZJU‐36, which have the same tbo topologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST‐1. Because the organic linkers in ZJU‐35 and ZJU‐36 are systematically enlarged, the pores in these two new porous MOFs vary from 10.8 Å in HKUST‐1 to 14.4 Å in ZJU‐35 and 16.5 Å in ZJU‐36, thus leading to their higher porosities with Brunauer–Emmett–Teller (BET) surface areas of 2899 and 4014 m2 g?1 for ZJU‐35 and ZJU‐36, respectively. High‐pressure gas‐sorption isotherms indicate that both ZJU‐35 and ZJU‐36 can take up large amounts of CH4 and CO2, and are among the few porous MOFs with the highest volumetric storage of CH4 under 60 bar and CO2 under 30 bar at room temperature. Their potential for high‐pressure swing adsorption (PSA) hydrogen purification was also preliminarily examined and compared with several reported MOFs, thus indicating the potential of ZJU‐35 and ZJU‐36 for this important application. Studies show that most of the highly porous MOFs that can volumetrically take up the greatest amount of CH4 under 60 bar and CO2 under 30 bar at room temperature are those self‐assembled from organic tetra‐ and hexacarboxylates that contain m‐benzenedicarboxylate units with the [Cu2(CO2)4] units, because this series of MOFs can have balanced porosities, suitable pores, and framework densities to optimize their volumetric gas storage. The realization of the two new organic building units for their construction of highly porous MOFs through their self‐assembly with [Cu2(CO2)4] units has provided great promise for the exploration of a large number of new tetra‐ and hexacarboxylate organic linkers based on these new organic building units in which different aromatic backbones can be readily incorporated into the frameworks to tune their porosities, pore structures, and framework densities, thus targeting some even better performing MOFs for very high gas storage and efficient gas separation under high pressure and at room temperature in the near future. 相似文献
989.
Wanhua Lei Dr. Guoyu Jiang Dr. Qianxiong Zhou Dr. Yuanjun Hou Prof. Baowen Zhang Prof. Xuexin Cheng Prof. Xuesong Wang 《Chemphyschem》2013,14(5):1003-1008
Nanoscaled coordination polymers based on biologically prevalent ions have potential applications in drug delivery and biomedical imaging. Herein, coordination polymer nanoparticles of anionic porphyrins, including meso‐tetra(4‐carboxyphenyl)‐porphyrin (H2TCPP4?) and meso‐tetra(4‐sulfonatophenyl)‐porphyrin (H2TPPS4?), and alkaline or alkaline earth metal cations, such as K+ and Ca2+, were constructed in aqueous solution in the presence of cucurbit[7]uril (CB7) or cucurbit[8]uril (CB8). UV/Vis absorption and fluorescence spectroscopy, dynamic light scattering (DLS), scanning electron spectroscopy (SEM), and atomic force microscopy (AFM) were applied to explore the assembly and particle formation of porphyrin anions and metal cations mediated by CBn. The particle size depends on the kinds of CBn and metal cations and their concentrations. The uptake of H2TPPS4? particles by tumor cells (A549 cells) was found to be more efficient than H2TPPS4? at 37 °C, showing the application potential of such assembled particles in biology and medicine. 相似文献
990.
A series of 5‐benzylidenerhodamine derivatives were synthesized by the cross‐aldol condensation of an aromatic aldehyde with rhodamine or rhodamine acetic acid in sodium acetate/acetic acid under microwave irradiation. The reaction was completed in 8–20 min with 63–94% yields and was environmentally benign with easy workup. 相似文献