全文获取类型
收费全文 | 1491篇 |
免费 | 132篇 |
国内免费 | 180篇 |
专业分类
化学 | 1085篇 |
晶体学 | 29篇 |
力学 | 102篇 |
综合类 | 19篇 |
数学 | 259篇 |
物理学 | 309篇 |
出版年
2024年 | 6篇 |
2023年 | 31篇 |
2022年 | 37篇 |
2021年 | 54篇 |
2020年 | 76篇 |
2019年 | 39篇 |
2018年 | 52篇 |
2017年 | 46篇 |
2016年 | 61篇 |
2015年 | 55篇 |
2014年 | 96篇 |
2013年 | 104篇 |
2012年 | 96篇 |
2011年 | 92篇 |
2010年 | 68篇 |
2009年 | 56篇 |
2008年 | 88篇 |
2007年 | 86篇 |
2006年 | 89篇 |
2005年 | 67篇 |
2004年 | 80篇 |
2003年 | 55篇 |
2002年 | 68篇 |
2001年 | 62篇 |
2000年 | 35篇 |
1999年 | 39篇 |
1998年 | 19篇 |
1997年 | 25篇 |
1996年 | 19篇 |
1995年 | 7篇 |
1994年 | 7篇 |
1993年 | 5篇 |
1992年 | 9篇 |
1991年 | 9篇 |
1990年 | 7篇 |
1989年 | 8篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1976年 | 5篇 |
1975年 | 3篇 |
1965年 | 2篇 |
1939年 | 2篇 |
1936年 | 2篇 |
排序方式: 共有1803条查询结果,搜索用时 15 毫秒
101.
102.
Hong‐Ze Gao Zhong‐Min Su Chun‐Sheng Qin Ri‐Gen Mo Yu‐He Kan 《International journal of quantum chemistry》2004,97(6):992-1001
Bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex (AlMq2OH) is used in organic light‐emitting diodes (OLEDs) as an electron transport material and emitting layer. By means of ab initio Hartree–Fock (HF) and density functional theory (DFT) B3LYP methods, the structure of AlMq2OH was optimized. The frontier molecular orbital characteristics and energy levels of AlMq2OH have been analyzed systematically to study the electronic transition mechanism in AlMq2OH. For comparison and calibration, bis(8‐quinolinolato)aluminum(III) hydroxide complex (Alq2OH) has also been examined with these methods using the same basis sets. The lowest singlet excited state (S1) of AlMq2OH has been studied by the singles configuration interaction (CIS) method and time‐dependent DFT (TD‐DFT) using a hybrid functional, B3‐LYP, and the 6‐31G* basis set. The lowest singlet electronic transition (S0 → S1) of AlMq2OH is π → π* electronic transitions and primarily localized on the different quinolate ligands. The emission of AlMq2OH is due to the electron transitions from a phenoxide donor to a pyridyl acceptor from another quinolate ligand including C → C and O → N transference. Two possible electron transfer pathways are presented, one by carbon, oxygen, and nitrogen atoms and the other via metal cation Al3+. The comparison between the CIS‐optimized excited‐state structure with the HF ground‐state structure indicates that the geometric shift is mainly confined to the one quinolate and these changes can be easily understood in terms of the nodal patterns of the highest occupied and lowest unoccupied molecular orbitals. On the basis of the CIS‐optimized structure of the excited state, TD‐B3‐LYP calculations predict an emission wavelength of 499.78 nm. An absorption wavelength at 380.79 nm on the optimized structure of B3LYP/6‐31G* was predicted. They are comparable to AlMq2OH 485 and 390 nm observed experimentally for photoluminescence and UV‐vis absorption spectra of AlMq2OH solid thin film on quartz, respectively. Lending theoretical corroboration to recent experimental observations and supposition, the reasons for the blue‐shift of AlMq2OH were revealed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004 相似文献
103.
Xin‐Yi Cao Jian Zhang Yao Kang Jian‐Kai Cheng Yuan‐Gen Yao 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(12):m654-m656
In the title compound, [Cu(C8H4O5)(C5H5N)2]n or [Cu(OH‐BDC)(py)2]n (where OH‐H2BDC is 5‐hydroxyisophthalic acid and py is pyridine), the Cu atoms are coordinated by two N atoms from the pyridine ligands and by three O atoms from hydroxyisophthalate ligands in a highly distorted triangular bipyramidal environment, with Cu—O distances in the range 1.941 (4)–2.225 (5) Å and Cu—N distances of 2.014 (6) and 2.046 (6) Å. The [Cu(OH‐BDC)]n two‐dimensional network is built up from interlocking 22‐, 15‐ and eight‐membered rings via sharing of Cu atoms and O—H⋯O hydrogen bonds. Consolidation of the packing structure is achieved by edge‐ or point‐to‐face C—H⋯π interactions and offset or slipped π–π stacking interactions. 相似文献
104.
[reaction: see text] Double phosphinylation of propargylic alcohols with diphenylphosphine oxide in the presence of a thiolate-bridged diruthenium complex as catalyst gives the corresponding 2,3-bis(diphenylphosphinyl)-1-propenes in high yields with a complete selectivity. 相似文献
105.
Biodegradable microspheres were fabricated by poly(?-caprolactone) (PCL) homopolymer and poly(?-caprolactone-b-ethylene oxide) (PCL-b-PEO) amphiphilic block copolymer. The regulation of microsphere surface morphology was successfully achieved by controlled enzymatic degradation. The morphological changes induced by biodegradation and their influences on the growth of MG-63 human osteosarcoma cells were studied. Results based on the evaluation of cytotoxicity and the morphological observation of MG-63 cells cultivated on microspheres showed better growth of cells on the surface of degraded microspheres than on the surface of those undegraded microspheres no matter they were fabricated by homopolymers or copolymers. The influences of morphological changes of microsphere surface before and after biodegradation on MG-63 cell growth were discussed. The results of this work indicated that the biodegradation-induced morphological changes of microspheres could be well controlled and were favorable for MG-63 cell attachment and proliferation. 相似文献
106.
Ming‐Shui Yao Jia‐Jia Zheng Ai‐Qian Wu Gang Xu Sanjog S. Nagarkar Gen Zhang Masahiko Tsujimoto Shigeyoshi Sakaki Satoshi Horike Kenichi Otake Susumu Kitagawa 《Angewandte Chemie (International ed. in English)》2020,59(1):172-176
Single‐ligand‐based electronically conductive porous coordination polymers/metal–organic frameworks (EC‐PCPs/MOFs) fail to meet the requirements of numerous electronic applications owing to their limited tunability in terms of both conductivity and topology. In this study, a new 2D π‐conjugated EC‐MOF containing copper units with mixed trigonal ligands was developed: Cu3(HHTP)(THQ) (HHTP=2,3,6,7,10,11‐hexahydrotriphenylene, THQ=tetrahydroxy‐1,4‐quinone). The modulated conductivity (σ≈2.53×10?5 S cm?1 with an activation energy of 0.30 eV) and high porosity (ca. 441.2 m2 g?1) of the Cu3(HHTP)(THQ) semiconductive nanowires provided an appropriate resistance baseline and highly accessible areas for the development of an excellent chemiresistive gas sensor. 相似文献
107.
SiO2/TiO2 hybrid nanofibers were prepared by electrospinning and applied for photocatalytic degradation of methylene blue (MB). The phase structure, specific surface area, and surface morphologies of the SiO2/TiO2 hybrid nanofibers were characterized through thermogravimetry (TG), X-ray diffraction (XRD) analysis, Brunauer–Emmett–Teller (BET) analysis, scanning electron microscopy (SEM), etc. XRD measurements indicated that doping of silica into TiO2 nanofibers can delay the phase transition from anatase to rutile and decrease the grain size. SEM and BET characterization proved that silica doping can remarkably enhance the porosity of the SiO2/TiO2 hybrid nanofibers. The MB adsorption capacity and photocatalytic activity of the SiO2/TiO2 hybrid nanofibers were distinguished experimentally. It was found that, although increased silica doping content could enhance the MB adsorption capacity, the intrinsic photocatalytic activity gradually dropped. The SiO2 (10 %)/TiO2 composite nanofibers exhibited the highest MB degradation rate, being superior to SiO2 (20 %)/TiO2 or pure TiO2. 相似文献
108.
Dr. Jie Wang Dr. Tian Qin Dr. Tie‐Gen Chen Dr. Laurin Wimmer Jacob T. Edwards Dr. Josep Cornella Benjamin Vokits Dr. Scott A. Shaw Prof. Phil S. Baran 《Angewandte Chemie (International ed. in English)》2016,55(33):9676-9679
A transformation analogous in simplicity and functional group tolerance to the venerable Suzuki cross‐coupling between alkyl‐carboxylic acids and boronic acids is described. This Ni‐catalyzed reaction relies upon the activation of alkyl carboxylic acids as their redox‐active ester derivatives, specifically N‐hydroxy‐tetrachlorophthalimide (TCNHPI), and proceeds in a practical and scalable fashion. The inexpensive nature of the reaction components (NiCl2?6 H2O—$9.5 mol?1, Et3N) coupled to the virtually unlimited commercial catalog of available starting materials bodes well for its rapid adoption. 相似文献
109.
Yongxing Tang Yajun Yu Xinyu Wei Jin Yang Yeting Zhu Yun-Hui Zhao Zilong Tang Zhihua Zhou Xiaofang Li Xianyong Yu 《Tetrahedron letters》2019,60(43):151187
A novel 6-endo-dig cyclization followed by oxidation/elimination of o-alkynylarylaldimines with 4-hydroxybenzylamine was developed for preparation of isoquinolines. The intermediates of this tandem reaction were monitored by mass spectroscopy (MS) to confirm the reaction pathway. This methodology was further applied to the design and synthesis of a novel ratiometric chemosensor for determination of fluoride. 相似文献
110.
Zhihua Qiao Qilong Tai Lei Song Yuan Hu Pin Lv Ganxin Jie Wei Huang Yi Fu Deqing Zhang 《先进技术聚合物》2011,22(12):2602-2608
An intumescent flame retardant system composed of ammonium polyphosphate (APP) and pentaerythritol (PER) was used for flame retarding ethylene–propylene–diene‐modified elastomer (EPDM)/polypropylene (PP) blends. Cerium phosphate (CeP) was synthesized and the effect on flame retardancy and thermal stability of EPDM/PP composites based on intumescent flame retardant (IFR) were studied by limiting oxygen index (LOI), UL‐94, and thermogravimetic analysis (TGA), respectively. Scanning electron microscopy (SEM) and Fourier transform infrared spectrometry (FTIR) were used to analyze the morphological structure and the component of the residue chars formed from the EPDM/PP composites, and the mechanical properties of the materials were also studied. The addition of CeP to the EPDM/PP/APP/PER composites gives better flame retardancy than that of EPDM/PP/APP/PER composites. TGA and RT‐FTIR studies indicated that an interaction occurs among APP, PER, and EPDM/PP. The incorporation of CeP improved the mechanical properties of the materials. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献