全文获取类型
收费全文 | 1255篇 |
免费 | 161篇 |
国内免费 | 136篇 |
专业分类
化学 | 878篇 |
晶体学 | 10篇 |
力学 | 77篇 |
综合类 | 9篇 |
数学 | 157篇 |
物理学 | 421篇 |
出版年
2024年 | 6篇 |
2023年 | 35篇 |
2022年 | 58篇 |
2021年 | 63篇 |
2020年 | 72篇 |
2019年 | 56篇 |
2018年 | 51篇 |
2017年 | 56篇 |
2016年 | 59篇 |
2015年 | 50篇 |
2014年 | 77篇 |
2013年 | 96篇 |
2012年 | 115篇 |
2011年 | 103篇 |
2010年 | 68篇 |
2009年 | 55篇 |
2008年 | 63篇 |
2007年 | 70篇 |
2006年 | 64篇 |
2005年 | 52篇 |
2004年 | 25篇 |
2003年 | 30篇 |
2002年 | 23篇 |
2001年 | 26篇 |
2000年 | 26篇 |
1999年 | 21篇 |
1998年 | 11篇 |
1997年 | 11篇 |
1996年 | 21篇 |
1995年 | 10篇 |
1994年 | 16篇 |
1993年 | 7篇 |
1992年 | 17篇 |
1991年 | 10篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1970年 | 1篇 |
1965年 | 1篇 |
1958年 | 1篇 |
排序方式: 共有1552条查询结果,搜索用时 15 毫秒
101.
Jiayi Li Liding Wang Zifeng Zhao Xiaoyue Li Xiao Yu Peihao Huo Qionghua Jin Zhiwei Liu Zuqiang Bian Chunhui Huang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(21):8287-8294
As a kind of photoluminescent material, CuI complexes have many advantages such as adjustable emission, variable structures, and low cost, attracting attention in many fields. In this work, two novel two-coordinate CuI-N-heterocyclic carbene complexes were synthesized, and they exhibit unique dual emission properties, fluorescence and phosphorescence. The crystal structure, packing mode, and photophysical properties under different conditions were systematically studied, proving the emissive mechanism to be the locally excited state of the carbazole group. Based on this mechanism, ultralong room-temperature phosphorescence (RTP) with a lifetime of 140 ms is achieved by selective deuteration of the carbazole group. These results deepen the understanding of the luminescence mechanism and design strategy for two-coordinate CuI complexes, and prove their potential in applications as ultralong RTP materials. 相似文献
102.
Dr. Subrat Kumar Barik Shou-Chih Huo Chun-Yen Wu Tzu-Hao Chiu Jian-Hong Liao Dr. Xiaoping Wang Dr. Samia Kahlal Prof. Jean-Yves Saillard Prof. C. W. Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(46):10471-10479
Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu30H18{S2P(OnPr)2}12] ( 1H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1H reveals an unprecedented central Cu12 hollow icosahedron. Six faces of this icosahedron are capped by Cu3 triangles, the whole Cu30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S6 symmetry. The locations of the 18 hydrides in 1H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ3-H, interstitial μ4-H (seesaw) and μ5-H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the 1H NMR spectrum of 1H are in line with their coordination environment in the solid state, retaining the S6 symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu30H18{Se2P(OR)2}12] ( 2H : R=iPr 3H : R=iBu) were synthesized from their sulfur relative 1H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1H – 3H . In addition, the reaction of 1H with [Pd(PPh3)2Cl2] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu14H2{S2P(OnPr)2}6(C≡CR)6] ( 4 : R=Ph; 5 : R = C6H4F). 相似文献
103.
Quan Huo Jingjing Zhao Jianshu Li Bo Wang Suyan Liu 《Research on Chemical Intermediates》2018,44(4):2347-2364
CdS-ZIF-8 photocatalyst was prepared by introducing a ZnO-rich zeolitic imidazolate framework-8 (ZIF-8) during synthesis of CdS by a facile solvothermal method, using ZnO-rich ZIF-8 and cadmium acetate [Cd(Ac)2] as support and CdS precursor, respectively. The introduction of ZnO-rich ZIF-8 and the photodegradation performance of the catalyst for methylene blue (MB) organic dye were systemically investigated. The CdS-ZIF-8 catalysts were also characterized using X-ray diffraction analysis, transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy, N2 adsorption–desorption measurements, Fourier-transform infrared (FT-IR) spectroscopy, ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy (DRS), and photoluminescence spectroscopy. The results indicated that CdS-ZIF-8 contained ZIF-8, CdS, and ZnO phases. The CdS in CdS-ZIF-8 catalysts exhibited smaller particle size compared with pure CdS. Furthermore, compared with pure CdS, CdS-ZIF-8-30 with introduction of ZnO-rich ZIF-8 exhibited higher surface area (77.3 m2/g) and pore volume (0.103 cm3/g). EDX and FT-IR results suggested that a CdS/ZnO heterostructure was formed, which effectively reduced recombination of photogenerated electron–hole pairs. Radical trapping experimental data and band edge position analysis revealed that Z-scheme behavior also played a role in the system. Relying on the combined effect of their structure, the photodegradation efficiency of all the CdS-ZIF-8 catalysts was obviously superior to that of pure CdS for degradation of MB under visible-light irradiation. Photodegradation results illustrated that CdS-ZIF-8 with introduction of 30 mg ZnO-rich ZIF-8 (denoted as CdS-ZIF-8-30) exhibited optimal photodegradation activity. 相似文献
104.
The palladium-catalyzed cyclization–allylation reaction of ortho-azido propynylbenzenes 1 and allyl methyl carbonate 2d gives the corresponding allylated quinolines in moderate to good yields. The reaction of 1-azido-2-(2-propynyl)benzene 1a proceeds smoothly with 10 mol % Pd(PPh3)4 and 5 equiv K3PO4 or NaOAc in DMF at 100 °C to afford 3,4-diallylquinoline 3a in 69% yield in the case of R2 = H and 3-allylquinoline 4 in 67% yield in the case of R2 ≠ H. 相似文献
105.
106.
The rigid amorphous phase of semicrystalline poly(phenylene sulfide) (PPS) has been studied as a function of thermal history using scanning calorimetry, dielectric relaxation, density, and small-angle x-ray scattering (SAXS). Based on the new heat of fusion of perfect crystalline PPS, which is 26.7±0.8 cal/gram, the weight fraction of rigid amorphous phase is shown to be nearly twice as large as previously reported [1]. The mass fraction of the rigid amorphous phase ranges from 0.24 to 0.42 and is dependent upon thermal treatment. We have taken the approach of assuming a three-phase model for the morphology of semicrystalline PPS consisting of crystalline lamellae, mobile amorphous, and rigid amorphous components. Using this three-phase model, we determine that the average density of the rigid amorphous fraction is 1.325 g/cc, which is slightly larger than the density of the mobile amorphous phase fraction and was insensitive to thermal history. From the SAXS long period, the layer thicknesses of the mobile amorphous phase, rigid amorphous phase, and crystal lamellae were estimated. Only the lamellar thickness shows a systematic variation with thermal history, increasing with melt or cold crystallization temperature, or with decreasing cooling rate. 相似文献
107.
108.
A series of heterometallic LnIII–SbIII edta‐containing compounds with the formulas [Sb2(edta)2Ln]NO3 · nH2O [edta = ethylenediaminetetraacetate; Ln = Eu, n = 7 ( 1 ); Gd, n = 7.5 ( 2 ) and Tb, n = 8 ( 3 )] were synthesized and characterized by elemental analyses (EA), powder X‐ray diffraction (PXDP), Fourier transform infrared spectroscopy (FT‐IR), and thermogravimetric analyses (TGA). Their fluorescence and magnetic properties were also studied. The thermal analysis demonstrates the compounds formation of the antimony, lanthanide ions, and edta4– ligands. FT‐IR spectra reveal that the antimony and lanthanide ions are connected through the carboxylate bridges. The studies of luminescence properties show that compounds 1 and 3 exhibit typical luminescence in the visible region. Furthermore, magnetic properties reveal compounds 2 and 3 have weak ferromagnetic behavior. 相似文献
109.
Adduct of magnesium tetraphenylporphyrin(MgTPP) with aniline for colorimetric detection of SO2 was investigated in CH2C12 by steady-state fluorescence and UV-vis absorption spectroscopic techniques.The UV-vis spectra showed that the increasing aniline concentrations resulted in red shift of 3 nm for MgTPP Soret absorption band.Once introduced,SO2 competes with MgTPP for aniline,which eventually leads to the release of MgTPP and changes in the solution color/absorption.The fluorescence spectra suggested that MgTPP interacted with aniline to form 1:1 molecular adducts,and showed that the binding of MgTPP with aniline with the binding constants of 1.58-1.64 is not only endothermal but entropy-driven withΔH = 1.622 kJ mol-1, AS = 9.389 J mor-1 K-1,and AG = -1.585 kJ mol-1 at T= 298.15 K. 相似文献
110.
Yun Wang Meng Huo Min Zeng Lei Liu Qi-Quan Ye Xi Chen Dan Li Liao Peng Jin-Ying Yuan 《高分子科学》2018,36(12):1321-1327
Abstract Response speed is one of the most important evaluation criteria for CO2 sensors. In this work, we report an ultrafast CO2 fluorescent sensor based on poly[oligo(ethylene glycol) methyl ether methacrylate]-b-poly[N,N-diethylaminoethyl methacrylate-r-4-(2-methylacryloyloxyethylamino)-7-nitro-2,1,3-benzoxadiazole] [POEGMA-b-P(DEAEMA-r-NBDMA)], in which DEAEMA units act as the CO2-responsive segment and 4-nitrobenzo-2-oxa-1,3-diazole (NBD) is the chromophore. The micelles composed of this copolymer could disassemble in 2 s upon CO2 bubbling, accompanying with enhanced fluorescence emission with bathochromic shift. Furthermore, the quantum yield of the NBD chromophore increases with both the CO2 aeration time and the NBD content. Thus we attribute the fluorescent enhancement to the inhibition of the photo-induced electron transfer between unprotonated tertiary amine groups and NBD fluorophores. The sensor is durable although it is based on “soft” materials. These micellar sensors could be facilely recycled by alternative CO2/Ar purging for at least 5 times, indicating good reversibility. 相似文献