全文获取类型
收费全文 | 2950篇 |
免费 | 132篇 |
国内免费 | 594篇 |
专业分类
化学 | 3388篇 |
晶体学 | 21篇 |
力学 | 55篇 |
综合类 | 27篇 |
数学 | 2篇 |
物理学 | 183篇 |
出版年
2024年 | 2篇 |
2023年 | 17篇 |
2022年 | 57篇 |
2021年 | 59篇 |
2020年 | 67篇 |
2019年 | 79篇 |
2018年 | 84篇 |
2017年 | 121篇 |
2016年 | 111篇 |
2015年 | 85篇 |
2014年 | 129篇 |
2013年 | 352篇 |
2012年 | 164篇 |
2011年 | 148篇 |
2010年 | 114篇 |
2009年 | 142篇 |
2008年 | 164篇 |
2007年 | 171篇 |
2006年 | 185篇 |
2005年 | 166篇 |
2004年 | 178篇 |
2003年 | 131篇 |
2002年 | 113篇 |
2001年 | 92篇 |
2000年 | 90篇 |
1999年 | 101篇 |
1998年 | 64篇 |
1997年 | 82篇 |
1996年 | 76篇 |
1995年 | 66篇 |
1994年 | 65篇 |
1993年 | 50篇 |
1992年 | 49篇 |
1991年 | 24篇 |
1990年 | 10篇 |
1989年 | 12篇 |
1988年 | 15篇 |
1987年 | 6篇 |
1986年 | 12篇 |
1985年 | 7篇 |
1984年 | 6篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1978年 | 1篇 |
排序方式: 共有3676条查询结果,搜索用时 0 毫秒
91.
The interaction of a nonionic polymeric surfactant with an anionic surfactant at the oil–water interface has been studied
by its effects on the droplet size, stability and rheology of emulsions. Oil-in-water (o/w) emulsions were prepared using
isoparaffinic oil and mixtures of a nonionic polymeric surfactant with an anionic surfactant. The macro-molecular surfactant
was a graft copolymer with a backbone of polymethyl methacrylate and grafted polyethylene oxide (a graft copolymer with PEO
chains of MW=750). The anionic surfactant was sodium dodecyl sulfate (SDS). The stabiliza-tion of the emulsion droplets was
found to be different when using one or the other surfactant. The mechanism of stabilization of emulsion droplets by the macro-molecular
surfactant is of the steric type while the stabilization by anionic surfactant is of the electrostatic repulsion type. Emulsions
stabilized with mixtures present both types of stabilization. Other effects on the preparation and stabilization of emulsions
were found to be dependent on properties associated with the surfactant molecular weight such as the Marangoni effect and
Gibbs elasticity. The initial droplet size of the emulsions showed a synergistic effect of the surfactant combination, showing
a minimum for the mixtures compared to the pure components. Emulsion stability also shows a synergistic interaction of both
surfactants. Rheological measurements allow for the estimation of the interparticle interaction when measured as a function
of volume fraction. Most of the effects observed can be attributed to the differences in interfacial tension and droplet radius
produced by both surfactants and their mixtures. The elastic moduli are well explained on the basis of droplet deformation.
Ionic versus steric stabilization produce little difference in the observed rheology, the only important differences observed
concerned the extent of the linear viscoelasticity region.
Received: 22 November 1996 Accepted: 24 March 1997 相似文献
92.
Shixiong Chen Xiaotian Zhao Ming Jin Wanqiu Huang Guodong Ye Haiyan Pan Decheng Wan 《Journal of polymer science. Part A, Polymer chemistry》2021,59(17):1899-1911
Four 1,5-diphenyl-3-aromatic heterocyclyl-2-pyrazoline-based sulfonium salt photoacid generators (PAGs) with different aromatic heterocycles substituted on C3 atom and dimethyl sulfonium group on C5 atom were synthesized. These PAGs were highly photosensitive in the 365–425 nm light-emitting diode region, and the intramolecular charge transfer from the pyrazoline ring to sulfonium salts induced efficient photolysis and high ΦH+. The heterocycles as well as their substituted positions significantly influenced the energy of the S2 orbital, which was determined by the electrochemical and absorption properties of the PAGs. The raising of the S2 orbital energy enlarged the energy gap of S0–S2 and S1–S2, resulting in blue shift of the absorption spectra and increase in the quantum yield of photoacid generation (ΦH+), respectively. When the energy of excited electrons was higher than that of the S2 orbital, the transition from S0 to S2 (π–π*) occurred before the C-S cleavage on S1 and the PAGs showed high ΦH+ values (0.52–0.72). The transition from S0 to S1 (π–σ*) occurred when the energy of electrons is lower than that of the S2 orbital, and the PAGs showed low ΦH+ value. The photopolymerization kinetics demonstrated that these PAGs were highly efficient cationic photoinitiators. 相似文献
93.
Nikola Saka
Dean Markovi Bojan arkanj Dubravka Maduni-a
i Krunoslav Hajdek Boo Smoljan Marija Jozanovi 《Molecules (Basel, Switzerland)》2021,26(5)
A novel, simple, low-cost, and user-friendly potentiometric surfactant sensor based on the new 1,3-dihexadecyl−1H-benzo[d]imidazol−3-ium-tetraphenylborate (DHBI–TPB) ion-pair for the detection of cationic surfactants in personal care products and disinfectants is presented here. The new cationic surfactant DHBI-Br was successfully synthesized and characterized by nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectrometry, liquid chromatography–mass spectrometry (LC–MS) and elemental analysis and was further employed for DHBI–TPB ion-pair preparation. The sensor gave excellent response characteristics for CTAB, CPC and Hyamine with a Nernstian slope (57.1 to 59.1 mV/decade) whereas the lowest limit of detection (LOD) value was measured for CTAB (0.3 × 10−6 M). The sensor exhibited a fast dynamic response to dodecyl sulfate (DDS) and TPB. High sensor performances stayed intact regardless of the employment of inorganic and organic cations and in a broad pH range (2−11). Titration of cationic and etoxylated (EO)-nonionic surfactant (NSs) (in Ba2+) mixtures with TPB revealed the first inflexion point for a cationic surfactant and the second for an EO-nonionic surfactant. The increased concentration of EO-nonionic surfactants and the number of EO groups had a negative influence on titration curves and signal change. The sensor was successfully applied for the quantification of technical-grade cationic surfactants and in 12 personal care products and disinfectants. The results showed good agreement with the measurements obtained by a commercial surfactant sensor and by a two-phase titration. A good recovery for the standard addition method (98–102%) was observed. 相似文献
94.
Porphyrinic compounds are widespread in nature and play key roles in biological processes such as oxygen transport in blood, enzymatic redox reactions or photosynthesis. In addition, both naturally derived as well as synthetic porphyrinic compounds are extensively explored for biomedical and technical applications such as photodynamic therapy (PDT) or photovoltaic systems, respectively. Their unique electronic structures and photophysical properties make this class of compounds so interesting for the multiple functions encountered. It is therefore not surprising that optical methods are typically the prevalent analytical tool applied in characterization and processes involving porphyrinic compounds. However, a wealth of complementary information can be obtained from NMR spectroscopic techniques. Based on the advantage of providing structural and dynamic information with atomic resolution simultaneously, NMR spectroscopy is a powerful method for studying molecular interactions between porphyrinic compounds and macromolecules. Such interactions are of special interest in medical applications of porphyrinic photosensitizers that are mostly combined with macromolecular carrier systems. The macromolecular surrounding typically stabilizes the encapsulated drug and may also modify its physical properties. Moreover, the interaction with macromolecular physiological components needs to be explored to understand and control mechanisms of action and therapeutic efficacy. This review focuses on such non-covalent interactions of porphyrinic drugs with synthetic polymers as well as with biomolecules such as phospholipids or proteins. A brief introduction into various NMR spectroscopic techniques is given including chemical shift perturbation methods, NOE enhancement spectroscopy, relaxation time measurements and diffusion-ordered spectroscopy. How these NMR tools are used to address porphyrin–macromolecule interactions with respect to their function in biomedical applications is the central point of the current review. 相似文献
95.
Anna Hanft Dr. Krzysztof Radacki Priv.-Doz. Dr. Crispin Lichtenberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(20):6230-6239
The behavior of the redox-active aminotroponiminate (ATI) ligand in the coordination sphere of bismuth has been investigated in neutral and cationic compounds, [Bi(ATI)3] and [Bi(ATI)2Ln][A] (L=neutral ligand; n=0, 1; A=counteranion). Their coordination chemistry in solution and in the solid state has been analyzed through (variable-temperature) NMR spectroscopy, line-shape analysis, and single-crystal X-ray diffraction analyses, and their Lewis acidity has been evaluated by using the Gutmann–Beckett method (and modifications thereof). Cyclic voltammetry, in combination with DFT calculations, indicates that switching between ligand- and metal-centered redox events is possible by altering the charge of the compounds from 0 in neutral species to +1 in cationic compounds. This adds important facets to the rich redox chemistry of ATIs and to the redox chemistry of bismuth compounds, which is, so far, largely unexplored. 相似文献
96.
羧甲基纤维素系列高分子表面活性剂超声合成的研究 总被引:27,自引:2,他引:27
研究了在超声波作用下羧甲基纤维素的降解反应及CMC与具有不同亲水亲油比值的活性大单体「烷基醇(酚)聚氧乙烯醚丙烯酸酯及第三单体」的超声共聚反应。经萃取提纯的共聚产物用IR,^13C NMR和UV等方法进行表证,证实通过超声反应制得了二元和三元共聚物。 相似文献
97.
98.
Formation at low surfactant concentrations and characterization of mesoporous MCM-41 总被引:3,自引:0,他引:3
At low concentrations of cetyltrimethylammonium bromide,all silica-based mesoporous materials with hexagonal phase have been synthesized via interactions between self-assembled surfactant molecule aggregates and aniomc silicate polymers.The resulting materials are characterized by XRD,FT-IR,solid state 29Si MAS NMR,thermal analysis and N2 adsorption-desorption measurements.After soluble ions are removed,the interactors between surfactant micelles and silicate polymers are reorganized and then form mesostructures 1 he hexagonal framework is sonsistent with amorphous silica gel.The structures of materials depend on the synthesis conditions Hydrothermal process improves the interactions between molecules and increases the degree of framework silicon atom polymerization The.surface area and the mesopore volume of the material prepared at 100℃ increase by 87% and 71 %,respectively,compared with those obtained at room temperature. 相似文献
99.
100.
离子表面活性剂胶团对阿斯匹林碱水解反应的影响 总被引:3,自引:0,他引:3
离子表面活性剂胶团对阿斯匹林碱水解反应的影响史振民*刘生昆张祝莲巩育军(延安大学化学系延安716000)关键词表面活性剂,阿斯匹林,碱水解反应,胶团,抑制作用1996-05-04收稿,1996-08-12修回阿斯匹林(ASP),学名为乙酰水杨酸,有较... 相似文献