全文获取类型
收费全文 | 988篇 |
免费 | 16篇 |
国内免费 | 162篇 |
专业分类
化学 | 1044篇 |
晶体学 | 9篇 |
力学 | 48篇 |
综合类 | 1篇 |
数学 | 2篇 |
物理学 | 62篇 |
出版年
2024年 | 1篇 |
2023年 | 14篇 |
2022年 | 35篇 |
2021年 | 26篇 |
2020年 | 25篇 |
2019年 | 22篇 |
2018年 | 18篇 |
2017年 | 26篇 |
2016年 | 26篇 |
2015年 | 23篇 |
2014年 | 25篇 |
2013年 | 62篇 |
2012年 | 56篇 |
2011年 | 55篇 |
2010年 | 42篇 |
2009年 | 60篇 |
2008年 | 64篇 |
2007年 | 68篇 |
2006年 | 43篇 |
2005年 | 40篇 |
2004年 | 53篇 |
2003年 | 41篇 |
2002年 | 31篇 |
2001年 | 36篇 |
2000年 | 26篇 |
1999年 | 35篇 |
1998年 | 28篇 |
1997年 | 29篇 |
1996年 | 15篇 |
1995年 | 27篇 |
1994年 | 26篇 |
1993年 | 18篇 |
1992年 | 16篇 |
1991年 | 10篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 10篇 |
1987年 | 8篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1978年 | 1篇 |
排序方式: 共有1166条查询结果,搜索用时 0 毫秒
91.
Diana I. Martin Elena Mateescu Gabriela Craciun Daniel Ighigeanu Adelina Ighigeanu 《Radiation Physics and Chemistry》2002,64(5-6):423-428
Results obtained by accelerated electron beam, microwave and simultaneous microwave and electron beam application in the chemistry of acrylamide and acrylic acid copolymers (polymeric flocculants used for wastewater treatment) are presented. Comparative results concerning the molecular weight and Huggins’ constant for the acrylamide and acrylic acid copolymers obtained by classical heating, microwave heating, electron beam irradiation and simultaneous microwave and electron beam treatment are reported. Microwave heating produces high water solubility of the polymeric flocculants but median molecular weight values. Electron beam irradiation gives high molecular weight values but associated with a cross-linked structure (poor water solubility) while microwave energy addition to electron beam energy gives simultaneously high molecular weight values and high water solubility. 相似文献
92.
Numerous mercaptopropyl-functionalized silica spheres have been prepared by either post-synthesis grafting of MCM-41 and MCM-48 or self-assembly co-condensation of mercaptopropyltrimethoxysilane (MPTMS) or mercaptopropyltriethoxysilane (MPTES) and tetraethoxysilane (TEOS) precursors in hydroalcoholic medium in the presence of a cationic surfactant as templating agent and ammonia as catalyst. These materials of approximately the same particle size and morphology featured different functionalization levels, various degrees of structural order, and variable distribution of thiol groups in the mesopores. Their reactivity in solution has been studied using Hg(II) as model analyte. Total accessibility (on a 1:1 S:Hg stoichiometry basis) was demonstrated and quantified for well-ordered materials whereas less open and less organized structures with high degrees of functionalization were subject to less-than-complete loadings. Capacities measured at pH 2 were lower than at pH 4 because of distinct mercury-binding mechanisms. Kinetics associated to the uptake process were studied by in situ electrochemical monitoring of Hg(II) consumption from aqueous suspensions containing the various adsorbents. They indicate only little difference between materials of the MCM-41 and MCM-48 series at similar functionalization levels, fast mass transport in well-ordered mesostructures in comparison to the poorly or non-ordered ones (except at pH 2 where charge formation induced some restriction in materials characterized by long-range structural order), and even faster processes in the wormlike frameworks (characterized by shorter range structural order). Hg(II) binding to thiol-functionalized materials obtained by post-synthesis grafting was found to occur more rapidly in the early beginning of the uptake process as a result of a higher concentration of binding sites at the pore entrance in comparison to the more homogeneous distribution of these groups in the mesochannels of materials obtained by co-condensation. 相似文献
93.
Three techniques (liquid–liquid extraction, packed bed adsorption and expanded bed adsorption) have been compared for the purification of flavonoids from the leaves of Ginkgo biloba L. A crude Ginkgo extract was obtained by refluxing with ethanol for 3 h. The yield of flavonoids achieved by this crude extraction was about 19% (w/w) and the purity of flavonoids in the concentrated extract was between 1.9 and 2.3% (w/w). The crude extract was then dissolved in deionized water and centrifuged where necessary to prepare clarified feedstock for further purification. For the method using liquid–liquid extraction with ethyl acetate, the purity, concentration ratio and yield of flavonoids were 25.4–31.0%, 16–18 and >98%, respectively. For the method using packed bed adsorption, Amberlite XAD7HP was selected as the adsorbent and clarified extract was used as the feedstock. The dynamic adsorption breakthrough curves and elution profiles were measured. For a feedstock containing flavonoids at a concentration of 0.25 mg/mL, the appropriate loading volume to reach a 5% breakthrough point during the adsorption stage was estimated to be 550–600 mL for a packed bed of volume 53 mL and a flow rate of 183 cm/h. The results from the elution stage indicated that the majority of impurities were eluted by ethanol concentrations of 40% (v/v) or below and efficient separation of flavonoids from the impurities could be achieved by elution of the flavonoids with 50–80% ethanol reaching an average purity of ∼25%. The recovery yield of flavonoids using the packed bed purification method was about 60% of the flavonoids present in the clarified feedstock (corresponding to around 30% for the total flavonoids in the unclarified crude extract). For the method using expanded bed adsorption also conducted with Amberlite XAD7HP as the adsorbent, the optimal operation conditions scouted during the packed bed experiments were used but unclarified crude extract could be loaded directly into the column. For an expanded bed with a settled bed height of 30 cm, the loss of flavonoids in the column flow-through was about 30%. The two-step elution protocol again proved to be effective in separating the adsorbed impurities and flavonoids. More than 96% of the bound impurities were completely removed by 40% ethanol in the first elution stage and less than 4% remained in the final product eluted by 90% ethanol in the second elution stage. Also, ∼74% of the adsorbed flavonoids on column (corresponding to 51% of the total flavonoids in the unclarified feedstock) were recovered in the product. In addition to higher recovery yield, the average process time to obtain the same amount of product was decreased in the expanded bed adsorption (EBA) process. The results suggest that the adoption of EBA procedures can greatly simplify the process flow sheet and in addition reduce the cost and time to purify flavonoids from Ginkgo biloba. These results clearly demonstrate the potential for the use of EBA to purify pharmaceuticals from plant sources. 相似文献
94.
聚(丙烯酸-co-丙烯酰胺)/蒙脱土/腐殖酸钠复合物对Pb2+的吸附性能 总被引:3,自引:1,他引:3
用制备的聚(丙烯酸-co-丙烯酰胺)/蒙脱土/腐殖酸钠复合吸附剂,研究了溶液pH值、吸附时间和Pb2+溶液初始浓度等因素对重金属Pb2+的吸附性能,探讨了复合吸附剂对Pb2+的吸附机理。结果表明,在pH值为6.0、吸附时间2 h、Pb2+溶液初始浓度0.01 mol/L和吸附剂用量0.10 g的条件下,复合吸附剂对Pb2+的吸附量达到364.05 mg/g,平衡所需的时间为15 min。与蒙脱土相比,复合吸附剂具有更高的吸附容量和更快的吸附速率。 相似文献
95.
New types of polyurethanes (PUs) were prepared from condensation polymerization of isophorone diisocyanate (IPDI) with various combination of 9-butyl-3,6-bis(4-hydroxyphenyl)carbazole (Cz) and 2,5-bis(4-hydroxyphenyl)-1,3,4-oxadiazole (OXD), and end-capped with 4-tert-butyl phenol. The Cz-OXD PUs can also be used as host for phosphorescent dye. Red EL emission was obtained when Ir(btp)2(acac) or Ir(2-phq)2(acac) was used as the phosphorescent dyes in Cz-OXD (3:1) PU. Maximum brightness of 394 cd/m2 and EL efficiency of 1 cd/A were achieved for the Ir(2-phq)2(acac) base device. In addition, white light PLED was demonstrated when co-dopant of Ir(btp)2(acac) and Firpic were used. 相似文献
96.
97.
Gerd Vanhoenacker Alberto Dos Santos Pereira Takashi Kotsuka Deirdre Cabooter Gert Desmet Pat Sandra 《Journal of chromatography. A》2010,1217(19):3217-3222
The performance of a polymeric stationary phase with reversed-phase properties (ET-RP1) was evaluated for LC separations at elevated temperature. The most significant observation was that the reduced plate height (h) decreased from 3.4 at 25 °C (optimal flow 0.5 mL/min) to 2.4 at 150 °C (optimal flow 2.5 mL/min) which is comparable to the efficiency obtained with silica-based reversed-phase columns of 4.6 mm ID operated at 0.8 mL/min. The phase showed no deterioration after long use at 150 °C within the pH range 1–9. Catalytic activity originating from the stationary phase material, e.g. as experienced on zirconium columns operated at elevated temperature, was absent. The performance of ET-RP1 is illustrated with the analysis of some pharmaceutical samples by LC and LC–MS. Operation at elevated temperature also allows to reduce the amount of organic modifier or to replace acetonitrile and methanol by the biodegradable ethanol. 相似文献
98.
GC stationary phases composed of binary mixtures of two polymeric ionic liquids (PILs), namely, poly(1‐vinyl‐3‐hexylimidazolium) bis[(trifluoromethyl)sulfonyl]imide (poly(ViHIm‐NTf2))/poly(1‐vinyl‐3‐hexylimidazolium) chloride (poly(ViHIm‐Cl)) and poly(1‐vinyl‐3‐hexadecylimidazolium) bis[(trifluoromethyl)sulfonyl]imide (poly(ViHDIm‐NTf2))/poly(1‐vinyl‐3‐hexadecylimidazolium) chloride (poly(ViHDIm‐Cl)), were evaluated in terms of their on‐set bleed temperature and separation selectivity. A total of six neat or binary PIL stationary phases were characterized using the solvation parameter model to investigate the effects of the polymeric cation and anion and PIL composition on the system constants of the resulting stationary phases. The hydrogen bond basicity of the mixed poly(ViHIm‐NTf2)/poly(ViHIm‐Cl) stationary phases was enriched linearly with the increase in the poly(ViHIm‐Cl) content. Results revealed that tuning the composition of the stationary phase allowed for fine control of the retention factors and separation selectivity for alcohols and carboxylic acids as well as selected ketones, aldehydes, and aromatic compounds. A reversal of elution order was observed for particular classes of analytes when the weight percentage of the chloride‐based PIL was increased. 相似文献
99.
SHI Zuoqing XU Mancai LIN Xue XU Mingcheng FAN Yunge SHI Rongfu YANG Yizhong HE Binglin 《Chinese Journal of Reactive Polymers》2000,(1)
1 INTRODUCTIONPhenol and many substitUted phenols, such as nitrophenols, chlorophenols and aminophenolset al, are the common organic pollutantS existing in wane water of many chemical plants.Treatment of the wastewater containing phenols is an important project for environmentprotection and has been studied by various methods, such as dialysis ['l, microbial degradation ['1,oxidation l'l, extracting with solvents I4] and adsorption with polymeric adsorbents IS]. Theadsorption method is v… 相似文献
100.
NAK-12树脂脱除蚕蛹复合氨基酸异味及褐变物质的研究 总被引:6,自引:0,他引:6
本文研究了用NAK-12吸附树脂脱除蚕蛹复合氨基酸异味及褐变色素的条件,初步分析了蚕蛹复合氨基酸异味产生的原因,实验结果表明:当流速为3BV/h时,1ml NAK-12吸附树脂能吸附1.75g蚕蛹复合氨基酸中的异味物质;能吸附1.45g蚕蛹复合氨基酸中的褐变物质。甲醇是异味物质和褐变物质的良好洗脱剂,用pH1.0的甲醇以1BV/h流速洗脱,仅用3.5BV的洗脱剂即可完全洗脱异味物质和褐变物质,蚕蛹复合氨基酸异味产生的可能机理是:加热蚕蛹复合氨基酸液时,其苯丙氨酸,蛋氨酸,蛋氨酸,异亮氨酸,亮氨酸,苏氨酸被氧化脱氨,生成挥发性醛,而其褐变则是赖氨酸,精氨酸与还原糖发生Maillard反应生成褐变物质引起的。 相似文献