全文获取类型
收费全文 | 782篇 |
免费 | 23篇 |
国内免费 | 14篇 |
专业分类
化学 | 563篇 |
晶体学 | 5篇 |
力学 | 14篇 |
数学 | 101篇 |
物理学 | 136篇 |
出版年
2023年 | 5篇 |
2022年 | 16篇 |
2021年 | 21篇 |
2020年 | 18篇 |
2019年 | 19篇 |
2018年 | 14篇 |
2017年 | 10篇 |
2016年 | 25篇 |
2015年 | 22篇 |
2014年 | 21篇 |
2013年 | 56篇 |
2012年 | 52篇 |
2011年 | 65篇 |
2010年 | 27篇 |
2009年 | 31篇 |
2008年 | 57篇 |
2007年 | 50篇 |
2006年 | 47篇 |
2005年 | 36篇 |
2004年 | 36篇 |
2003年 | 29篇 |
2002年 | 30篇 |
2001年 | 13篇 |
2000年 | 2篇 |
1999年 | 9篇 |
1998年 | 4篇 |
1997年 | 7篇 |
1996年 | 9篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 6篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 7篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 6篇 |
1982年 | 3篇 |
1981年 | 6篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1961年 | 1篇 |
排序方式: 共有819条查询结果,搜索用时 31 毫秒
21.
O.M. Lyulin V.I. Perevalov H. Tran J.-Y. Mandin V. Dana L. Rgalia-Jarlot X. Thomas D. Dcatoire 《Journal of Quantitative Spectroscopy & Radiative Transfer》2009,110(17):1815-1824
Using the Fourier transform spectra of the acetylene molecule recorded near 1.5-μm, the intensities of 111 lines belonging to seven hot bands of the main isotopologue 12C2H2 have been retrieved by means of a multispectrum fitting procedure. Considering the density of lines in the spectra, and the fact that the measured bands are the weakest observed, the accuracy of the measurements is around 10%. At first stage, an empirical treatment of these data has been performed, leading to the vibrational transition dipole moment squared and some Herman–Wallis coefficients. Then the measured line intensities of this work and collected ones from the literature have been treated simultaneously within the framework of the effective operator approach. 相似文献
22.
Cristina Bucur Romana Cerc Korošec Mihaela Badea Larisa Calu Mariana Carmen Chifiriuc Nicoleta Grecu Nicolae Stanică Dana Marinescu Rodica Olar 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1287-1295
Novel complexes of type M2LCl4·nH2O (M: Ni, n = 4; M: Cu, n = 2.5 and M: Zn, n = 1.5; L: ligand resulted from 1,3-phenylenediamine, 3,6-diazaoctane-1,8-diamine, and formaldehyde one-pot condensation) were synthesized and characterized. The ligand was also isolated and characterized. The complexes features have been assigned from microanalytical, electrospray ionization tandem mass spectrometry, IR, UV–vis, 1H NMR, and EPR spectra as well as magnetic data at room temperature. Simultaneous thermogravimetric/dynamic scanning calorimetry/evolved gas analysis measurements were performed to evidence the nature of the gaseous products formed in each step. Processes as water elimination, fragmentation, and oxidative degradation of the organic ligand as well as chloride elimination were observed during the thermal decomposition. The final product of decomposition was metal(II) oxide except for copper complex where CuCl remained also in the oxide network. The complexes exhibited an improved antibacterial activity in comparison with the ligand concerning both planktonic as well as biofilm-embedded cells. 相似文献
23.
Luminita Andronic Dana Perniu Anca Duta 《Journal of Sol-Gel Science and Technology》2013,66(3):472-480
The TiO2 powders were synthesized by versatile and low cost sol–gel process using HNO3 and titanium tetra-isopropoxide (volumetric ratio of 4:1) following by the hydrolysis reaction. The powders show the two polymorphs of TiO2: 96 % anatase and 4 % brookite, due to acidic condition (pH = 3). Thin films of titanium oxide were obtained by dip-coating, using the sol–gel of titanium oxide mixed with commercial Degussa P25 into a weight ratio 1:1 or 1:1.5, to enhance the synergistic effect of anatase/rutile ratio aiming at increasing the efficiency of the TiO2 photocatalyst in dyes degradation. The thin film surface (charge and morphology) was controlled by polymer (poly-ethylene glycol) and surfactant (Sodium dodecyl sulphate, Triton X100) addition. The titanium oxide was characterized by particle size analyzer, contact angle measurements, X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The photocatalytic properties of powders and coatings were evaluated based on the degradation efficiency of two reference dyes (methyl orange and methylene blue). The results outline that poly(ethylene glycol) and films morphologies are the most influential factors that affecting the photocatalytic activity. 相似文献
24.
Liangpo Liu Tongwei Xia Xueqin Zhang Dana Boyd Barr Ambreen Alamdar Jie Zhang Meiping Tian Qingyu Huang Heqing Shen 《Analytical and bioanalytical chemistry》2014,406(20):5049-5054
Infant exposure to endocrine disruptors (EDs) may cause adverse health effects because of their fast growth and development during this life stage. However, collecting urine from infants for exposure assessment using biological monitoring is not an easy task. For this purpose, we evaluated the feasibility of using urine expressed from disposable gel absorbent diapers (GADs) as a matrix for biomonitoring selected phenolic EDs. GADs urine was expressed with the assistance of CaCl2 and was collected using a device fabricated in our laboratory. The analytes were extracted and concentrated using a liquid-liquid method and their hydroxyl groups were modified by dansyl chloride to enhance their chromatography and detection. Finally, the analytes were measured by high-performance liquid chromatography (HPLC) coupled with electrospray ionization (ESI) tandem mass spectrometry (MS/MS). The target chemicals were bisphenol A, triclosan, 17 α-ethynylestradiol, the natural hormone estrone, and 17 β-estradiol. The ratio of the CaCl2 to the urine-wetted gel absorbent, variation of the inter-urination volume, and analyte deposition bias in the diaper were assessed. Analyte blank values in the diapers, the sample storage stabilities, and recoveries of the analytes were also evaluated. The results showed that 70–80 % of the urine could be expressed from the diaper with the assistance of CaCl2 and 70.5–124 % of the spiked analytes can be recovered in the expressed urine. The limits of detections (LODs) were 0.02–0.27 ng/mL, well within the range for detection in human populations. Our pilot data suggest that infants are widely exposed to the selected EDs. 相似文献
25.
Cristina Bucur Mihaela Badea Mariana Carmen Chifiriuc Coralia Bleotu Emilia Elena Iorgulescu Irinel Adriana Badea Maria Nicoleta Grecu Veronica Lazăr Oana-Irina Patriciu Dana Marinescu Rodica Olar 《Journal of Thermal Analysis and Calorimetry》2014,115(3):2179-2189
Novel complexes of M2LCl4·nH2O type (M:Ni, n = 4; M:Cu, n = 3 and M:Zn, n = 0; L: ligand resulted from 1,4-phenylenediamine, 3,6-diazaoctane-1,8-diamine and formaldehyde one-pot condensation) were synthesized and characterised by microanalytical, ESI–MS, IR, UV–Vis, 1H NMR and EPR spectra, magnetic data at room temperature and molar conductivities as well. The electrochemical behaviour of complexes was investigated by cyclic voltammetry. Simultaneous TG/DTA measurements were performed in order to evidence the thermal behaviour of the obtained complexes. Processes such as water elimination, fragmentation and oxidative degradation of the organic ligand as well as chloride elimination occurred during thermal decomposition. The antimicrobial assays demonstrate that the compounds exhibited good antibacterial activity, especially against S. aureus and E. coli strains, the most active being the copper(II) complex, which also exhibited the most prominent anti-biofilm effect, suggesting its potential use for the development of new antimicrobial agents. The biological activity was correlated with log P ow values. All complexes disrupt the membrane integrity of HCT 8 tumour cells. 相似文献
26.
Mihaela Badea Larisa Calu Mariana Carmen Chifiriuc Coralia Bleotu Alexandra Marin Sebastian Ion Gabriela Ioniţă Nicolae Stanică Luminiţa Măruţescu Veronica Lazăr Dana Marinescu Rodica Olar 《Journal of Thermal Analysis and Calorimetry》2014,118(2):1145-1157
A series of complexes of type [ML(CH3COO)(OH2)2] (M: Co, Ni; HL: 2-[(E)-1H-1,2,4-triazol-3-ylimino)methyl]phenol)) and [M2L2(CH3COO)2(OH2)n] (M: Cu, n = 2; M: Zn, n = 0) were synthesised by template condensation. The compounds were characterised with microanalytical, ESI–MS, IR, electronic, EPR spectra and magnetic data at room temperature. Based on the IR and ESI–MS spectra, a dinuclear structure with the acetate as bridge was proposed for Cu(II) and Zn(II) complexes. The dinuclear structure of Cu(II) complex is also consistent with both magnetic behaviour and EPR spectrum. The thermal analyses have evidenced processes as water elimination, acetate decomposition, as well as oxidative degradation of the Schiff base. The final decomposition product was the most stable metal oxide as indicated by powder X-ray diffraction. The cobalt and copper compounds exhibited a broad spectrum of antibacterial activity towards both planktonic and biofilm-embedded cells. The complexes exhibit a low cytotoxicity except for Cu(II) species that induces the early apoptosis for the HEp 2 cells. 相似文献
27.
Preparation of organic polymer monolithic columns in fused silica capillaries was aimed at fast gradient separation of proteins. For this purpose, polymerization in situ procedure was optimized, using ethylene dimetacrylate and butyl metacrylate monomers with azobisisobutyronitrile as initiator of the polymerization reaction in presence of non-aqueous porogen solvent mixtures composed of 1-propanol and 1,4-butanediol. The separation of proteins in totally monolithic capillary columns was compared with the chromatography on a new type of "hybrid interparticle monolithic" capillary columns, prepared by in situ polymerization in capillary packed with superficially porous spherical beds, 37-50 microm. The "hybrid" columns showed excellent stability and improved hydrodynamic flow properties with respect to the "totally" monolithic capillary columns. The separation selectivity is similar in the two types of columns. The nature of the superficially porous layer (bare silica or bonded C18 ligands) affects the separation selectivity less significantly than the porosity (density) of the monolithic moiety in the interparticle space, controlled by the composition of the polymerization mixture. The retention behaviour of proteins on all prepared columns is consistent with the reversed-phase gradient elution theory. 相似文献
28.
Photolysis of perfluoroazooctane with diamond powders led to chemical modification of the surface with the introduction of perfluorooctyl ester and ether functional groups, the presence of which was confirmed by means of FT-IR, XPS and 19F NMR measurements. 相似文献
29.
30.
Mihaela Badea Rodica Olar Dana Marinescu Gina Vasile 《Journal of Thermal Analysis and Calorimetry》2008,92(1):209-214
A series of new complexes with mixed ligands of the type [ML(C3H3O2)2]·nH2O (((1)
M=Mn, n=1; (2)
M=Co(II), n=2; (3)
M=Ni(II), n=4; (4)
M=Cu(II), n=1.5; (5)
M=Zn(II), n=0; L=3-amino-1,2,4-triazole and (C3H3O2)=acrylate anion) were synthesized and characterised by chemical analysis and IR data. In all complexes the 3-amino-1,2,4-triazole
acts as bridge while the acrylate acts as bidentate ligand except for complex (5) where it is found as unidentate. The thermal behaviour steps were investigated in nitrogen flow. The thermal transformations
are complex processes according to TG and DTG curves including dehydration, acrylate ion and 3-amino-1,2,4-triazole degradation
respectively. The final products of decomposition are the most stable metal oxides, except for complex (4) that leads to metallic copper. 相似文献