全文获取类型
收费全文 | 3869篇 |
免费 | 302篇 |
国内免费 | 669篇 |
专业分类
化学 | 4568篇 |
晶体学 | 28篇 |
力学 | 9篇 |
综合类 | 24篇 |
数学 | 1篇 |
物理学 | 210篇 |
出版年
2024年 | 11篇 |
2023年 | 29篇 |
2022年 | 87篇 |
2021年 | 113篇 |
2020年 | 192篇 |
2019年 | 146篇 |
2018年 | 114篇 |
2017年 | 137篇 |
2016年 | 142篇 |
2015年 | 165篇 |
2014年 | 207篇 |
2013年 | 366篇 |
2012年 | 254篇 |
2011年 | 207篇 |
2010年 | 187篇 |
2009年 | 217篇 |
2008年 | 215篇 |
2007年 | 197篇 |
2006年 | 196篇 |
2005年 | 179篇 |
2004年 | 190篇 |
2003年 | 185篇 |
2002年 | 117篇 |
2001年 | 92篇 |
2000年 | 90篇 |
1999年 | 89篇 |
1998年 | 93篇 |
1997年 | 57篇 |
1996年 | 82篇 |
1995年 | 64篇 |
1994年 | 62篇 |
1993年 | 73篇 |
1992年 | 55篇 |
1991年 | 39篇 |
1990年 | 30篇 |
1989年 | 26篇 |
1988年 | 25篇 |
1987年 | 18篇 |
1986年 | 20篇 |
1985年 | 10篇 |
1984年 | 16篇 |
1983年 | 7篇 |
1982年 | 10篇 |
1981年 | 7篇 |
1980年 | 6篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1972年 | 1篇 |
排序方式: 共有4840条查询结果,搜索用时 328 毫秒
171.
J. F. Fernndez-Snchez A. Segura Carretero J. M. Benítez-Snchez C. Cruces-Blanco A. Fernndez-Gutirrez 《Analytica chimica acta》2004,510(2):183-187
This paper presents an optosensor for screening of four polycyclic aromatic hydrocarbons: anthracene (ANT), benzo[a]pyrene (BaP), fluoranthene (FLT), and benzo[b]fluoranthene (Bbf) using a photomultiplier device with an artificial neural network as transducer. The optosensor is based on the on-line immobilization on a non-ionic resin (Amberlite XAD-4) solid support in a continuous flow. The determination was performed in 15 mM H2PO4−/HPO42− buffer solution at pH 7 and 25% of 1,4-dioxane. Feed forward neural networks (multiplayer perceptron) have been trained to quantify the considered Polycyclic aromatic hydrocarbons (PAHs) in mixtures under optimal conditions. The optosensor proposed was also applied satisfactorily to the determination of the considered PAHs in water samples in presence of the other 12 EPA–PAHs. 相似文献
172.
Agnieszka Bajorek Marcin Ciepluch Jerzy Pczkowski 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3481-3488
The series of 9‐acridyl derivatives of aromatic amines have been investigated as fluorescent probes for monitoring the progress of free‐radical polymerization. This study on the changes in the fluorescence intensity and spectroscopic shift of specific compounds was carried out during thermally initiated polymerization of methyl methacrylate and photoinitiated polymerization of 2‐ethyl‐2‐(hydroxymethyl)‐1,3‐propanediol triacrylate‐1‐methyl‐2‐pyrrolidonone mixture. The purpose of this investigation was to find a relationship between the changes in the shape and intensity of fluorescent probes and the degree of monomer conversion into a polymer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3481–3488, 2002 相似文献
173.
Nobuko WatanabeYasuhiro Nagashima Takahiro YamazakiMasakatsu Matsumoto 《Tetrahedron》2003,59(26):4811-4819
Tetrabutylammonium fluoride induces the decomposition of 1-tert-butyl-4,4-dimethyl-5-(3-siloxyphenyl)-2,6,7-trioxabicyclo[3.2.0]heptane (4a) in DMSO to form an oxyanion of aromatic ketone (14a) as an emitter with high singlet-chemiexcitation yield comparable with that for a chemically initiated electron exchange luminescence (CIEEL) active dioxetane producing an oxyanion of aromatic ester as an emitter. A 7-siloxynaphthalen-2-yl analog (4b) was found on similar treatment to emit light with the maximum wavelength the longest among CIEEL-active dioxetanes hitherto known. 相似文献
174.
The formation of polycyclic aromatic hydrocarbons (PAHs) during pyrolysis process of phenylalanine had been studied. Ten PAHs, including fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[k]fluoranthene, benzo[e]pyrene, and benzo[a]pyrene were analyzed by gas chromatography-mass spectrometry using selective ion monitoring mode. This technique offers the capability to analyze trace amounts of PAHs in phenylalanine pyrolyzates. The pyrolysis was carried out in a micro-furnace with quartz furnace liner. The injection was conducted with glass pelletizer syringe to avoid metal contamination. Qualitative results were obtained at 900 degrees C and quantitative analysis of 10 PAHs was done for 700 and 900 degrees C. 相似文献
175.
Zirconium(IV) chloride catalyses the nucleophilic opening of epoxide rings by amines leading to the efficient synthesis of β-amino alcohols. The reaction works well with aromatic and aliphatic amines in short times at room temperature in the absence of solvent. Exclusive trans stereoselectivity is observed for cyclic epoxides. Aromatic amines exhibit excellent regioselectivity for preferential nucleophilic attack at the sterically less hindered position during the reaction with unsymmetrical epoxides. However, in case of styrene oxide, selective formation of the benzylic amine was observed during the reactions with aromatic amines. 相似文献
176.
A simple on-column injection system for large volume of liquid samples for the GC-MS determination of traces of PAHs and PCBs has been investigated. A deactivated fused silica capillary 20 m × 0.53 mm I.D. and 2 meters of an HP5 column (0.53 mm,1 m film thickness) were used as retention gaps. Injection volumes of 80 L for PAHs and 90 L for PCBs, allow determination of 5–50 ng L–1 PAHs and 11–44 ng L–1 PCBs in hexane solution with an RSD of < 10%. The method has been used for the determination of PCBs and PAHs in soil sample. 相似文献
177.
The general synthesis and a novel intramolecular nucleophilic aromatic substitution (SNAr) reaction of 2-carboxamido-3-arylquinazolin-4-ones, a potentially useful scaffold in the field of medicinal chemistry, are described. The synthetic utility of the SNAr reaction as a tool for the synthesis of secondary aryl amines, including diaryl amines, is also demonstrated. 相似文献
178.
The most stable structure of CB2H3
–, as established computationally, is the aromatic diboracyclopropenyl (diboriranyl) anion (5), while open-chainC
2v, isomer H2BCBH (7) is only 3 kcal/mol higher in energy at the QCISD(T)/6-311 +G**//MP2/6-31+G*+ZPE (HF/6-31 +G*). The 47-kcal/mol barrier between cyclic,5, and open-chain,7, structures suggests that both of them may be observed. The aromatic stabilization energy of the diboriranyl anion (18 kcal/mol) is half the value in the isoelectronic cyclopropenium ion, C3H3
+. The computed, by IGLO method (5a), and experimental (6a) chemical shifts,(13C) and(11B), agree within 4 ppm range. The theoretical vibrational frequencies of the most stable isomers,5 and7, are presented for experimental verification of these species. 相似文献
179.
链酚胺型配体锌(Ⅱ)配合物模拟碳酸酐酶研究 总被引:1,自引:2,他引:1
合成了酚胺型链状配体,N,N'-二(2-羟基苄基)丙二胺(H~2L)及其Zn(Ⅱ)配合物(ZnL),通过元素分析、IR和^1HNRM等手段进行了表征。采用pH电位滴定法,在25℃±0.1℃,I=0.1mol·dm^-^3(KNO~3)条件下,测定了配体的质子化常数以及配体与金属离子Zn(Ⅱ)配位反应平衡常数。讨论了配体与金属离子Zn(Ⅱ)的配位情况,得到了配位酚羟基的解离常数。运用分光光度法,在25℃±0.1℃,I=0.1mol·dm^-^3(KNO~3)条件下,在pH=5.5~9.0(50mmol·dm^-^3缓冲溶液)范围内,研究了配合物作为碳酸酐酶模拟物催化对-硝基苯酚乙酸酯(NA)水解动力学,得到了NA酯水解的配合物催化速率常数k~N~P。实验结果表明,ZnHL^+的配位酚羟基的解离常数pK~a为6.83;催化速率常数k~N~P与pH之间不存在Sigmoidal型曲线关系,而是在pH值中性附近有最大值,ZnHL^+对NA酯水解有很好的催化效果,并且采取双重催化机理,是碳酸酐酶很好的模拟物。 相似文献
180.
An HPLC post column chemical derivatization procedure based on the interaction between an acridinium triflate and amines to form highly colored derivatives on-line is described for the determination of aromatic amines. Benzocaine and butesin, local anesthetic agents that contain the aromatic amine group, were used as model compounds. Reversed-phase HPLC conditions were developed for both the separation of analytes and the reaction between analytes and the acridinium triflate in the system. Three-dimensional knitted teflon shape coils and the internal diameter and length of the coils were important parameters in reducing band broadening and background noise.N-Methyl-9-chloroacridinium triflate was shown to be applicable to the determination of primary aromatic amines, selected secondary aromatic amines, hydrazides, and hydrazines. Application of the on-line chemical derivatization procedure to the analysis of pharmaceutical dosage forms containing procainamide (primary aromatic amine), isoniazid (hydrazide), and hydralazine (hydrazine) is also described. 相似文献