全文获取类型
收费全文 | 1168篇 |
免费 | 40篇 |
国内免费 | 23篇 |
专业分类
化学 | 651篇 |
晶体学 | 1篇 |
力学 | 23篇 |
数学 | 231篇 |
物理学 | 168篇 |
无线电 | 157篇 |
出版年
2023年 | 6篇 |
2022年 | 14篇 |
2021年 | 12篇 |
2020年 | 18篇 |
2019年 | 27篇 |
2018年 | 27篇 |
2017年 | 18篇 |
2016年 | 46篇 |
2015年 | 30篇 |
2014年 | 37篇 |
2013年 | 77篇 |
2012年 | 65篇 |
2011年 | 71篇 |
2010年 | 44篇 |
2009年 | 45篇 |
2008年 | 86篇 |
2007年 | 72篇 |
2006年 | 86篇 |
2005年 | 64篇 |
2004年 | 57篇 |
2003年 | 42篇 |
2002年 | 42篇 |
2001年 | 21篇 |
2000年 | 7篇 |
1999年 | 18篇 |
1998年 | 6篇 |
1997年 | 17篇 |
1996年 | 15篇 |
1995年 | 16篇 |
1994年 | 9篇 |
1993年 | 12篇 |
1992年 | 17篇 |
1991年 | 9篇 |
1990年 | 5篇 |
1989年 | 12篇 |
1988年 | 9篇 |
1987年 | 7篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1970年 | 2篇 |
1959年 | 2篇 |
排序方式: 共有1231条查询结果,搜索用时 15 毫秒
111.
Lucas D Minami T Iannuzzi G Cao L Wittenberg JB Anzenbacher P Isaacs L 《Journal of the American Chemical Society》2011,133(44):17966-17976
We report that the p-xylylenediammonium ion (11) acts as a template in the cucurbit[n]uril forming reaction that biases the reaction toward the production of methylene bridged glycoluril hexamer (6C) and bis-nor-seco-CB[10]. Hexamer 6C is readily available on the gram scale by a one step synthetic procedure that avoids chromatography. Hexamer 6C undergoes macrocylization with (substituted) phthalaldehydes 12, 14, 15, and 18-in 9 M H(2)SO(4) or concd HCl at room temperature to deliver monofunctionalized CB[6] derivatives 13, 16, 17, and 19-that are poised for further functionalization reactions. The kinetics of the macrocyclization reaction between hexamer and formaldehyde or phthalaldehyde depends on the presence and identity of ammonium ions as templates. p-Xylylenediammonium ion (11) which barely fits inside CB[6] sized cavities acts as a negative template which slows down transformation of 6C and paraformaldehyde into CB[6]. In contrast, 11 and hexanediammonium ion (20) act as a positive template that promotes the macrocyclization reaction between 6C and 12 to deliver (±)-21 as a key intermediate along the mechanistic pathway to CB[6] derivatives. Naphthalene-CB[6] derivative 19 which contains both fluorophore and ureidyl C═O metal-ion (e.g., Eu(3+)) binding sites forms the basis for a fluorescence turn-on assay for suitable ammonium ions (e.g., hexanediammonium ion and histamine). 相似文献
112.
Alya Al-EtaibiElizabeth John Maher R. IbrahimNouria A. Al-Awadi Yehia A. Ibrahim 《Tetrahedron》2011,67(34):6259-6274
Intramolecular base catalyzed C-C bond formation led to exclusive stereoselective syntheses of trans-6,7-dihydro-5H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazines, trans-7,8-dihydro-6H-[1,2,4]triazino[3,4-b][1,3,4]thiadiazin-4-ones, and trans-3,4-dihydro-2H-[1,3,4]thiadiazino[2,3-b]quinazolin-10-one. trans-6,7-Dihydro-5H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazines isomerize slowly in CDCl3 and more rapidly in DMSO-d6 into the corresponding cis-stereoisomers. The other trans-6,7-dihydro-[1,3,4]thiadiazines isomerize also in DMSO-d6 into the corresponding cis-stereoisomers. Pyrolytic conversion of these heterocyclic condensed dihydrothiadiazines into their corresponding pyrazolo[5,1-b][1,2,4]triazoles, pyrazolo[5,1-c][1,2,4]triazin-4-ones and pyrazolo[4,3-b]quinazolin-9-ones via desulfurization ring contraction is described. 相似文献
113.
114.
Chemorheology investigation of a glassy epoxy thermoset on tensile plastic flow and fracture morphology 下载免费PDF全文
Stephen F. Foster Emily A. Hoff Greg W. Curtzwiler Eric B. Williams Kevin B. Davis Derek L. Patton James W. Rawlins 《Journal of Polymer Science.Polymer Physics》2015,53(19):1333-1344
Reproducible and uncharacteristic tensile stress–strain behavior of cured glassy epoxy‐amine networks produces distinctive fracture surfaces. Test specimens exhibiting plastic flow result in mirror‐like fracture surfaces, whereas samples that fail during yield or strain softening regions possess nominal mirror‐mist‐hackle topography. Atomic force microscopy and scanning electron microscopy reveal branched nodule morphologies in the 50‐nm size scale that may be responsible for the unusual tensile properties. Current hypothesis is that plastic flow of the glassy thermoset occurs through the existence and deformation of these nodular nanostructures. The thermal cure profile of the epoxy‐amine thermoset affects the size and formation of the nodular nanostructure. Eliminating vitrification during thermoset polymerization forms a more continuous phase, reduction in size of the nodules, and eliminates the capacity of the material to yield in plastic flow. This maximizes nanostructure connectivity of the glassy epoxy‐amine thermoset and reduces strain to failure significantly. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1333–1344. 相似文献
115.
The Direct Synthesis of Hydrogen Peroxide Using Platinum‐Promoted Gold–Palladium Catalysts 下载免费PDF全文
Dr. Jennifer K. Edwards James Pritchard Li Lu Marco Piccinini Greg Shaw Dr. Albert F. Carley David J. Morgan Prof. Christopher J. Kiely Prof. Graham J. Hutchings 《Angewandte Chemie (International ed. in English)》2014,53(9):2381-2384
The direct synthesis of hydrogen peroxide offers a potentially green route to the production of this important commodity chemical. Early studies showed that Pd is a suitable catalyst, but recent work indicated that the addition of Au enhances the activity and selectivity significantly. The addition of a third metal using impregnation as a facile preparation method was thus investigated. The addition of a small amount of Pt to a CeO2‐supported AuPd (weight ratio of 1:1) catalyst significantly enhanced the activity in the direct synthesis of H2O2 and decreased the non‐desired over‐hydrogenation and decomposition reactions. The addition of Pt to the AuPd nanoparticles influenced the surface composition, thus leading to the marked effects that were observed on the catalytic formation of hydrogen peroxide. In addition, an experimental approach that can help to identify the optimal nominal ternary alloy compositions for this reaction is demonstrated. 相似文献
116.
117.
The ability to separate nitroaromatic and nitramine explosives in seawater sample matrices is demonstrated using both MEKC and CEC. While several capillary-based separations exist for explosives, none address direct sampling from seawater, a sample matrix of particular interest in the detection of undersea mines. Direct comparisons are made between MEKC and CEC in terms of sensitivity and separation efficiency for the analysis of 14 explosives and explosive degradation products in seawater and diluted seawater. The use of high-salt stacking with MEKC results, on average, in a three-fold increase in the number of theoretical plates, and nearly double resolution for samples prepared in 25% seawater. By taking advantage of long injection times in conjunction with stacking, detection limits down to sub mg/L levels are attainable; however, resolution is sacrificed. CEC of explosive mixtures using sol-gels prepared from methyltrimethoxysilane does not perform as well as MEKC in terms of resolving power, but does permit extended injection times for concentrating analyte onto the head of the separation column with little or no subsequent loss in resolution. Electrokinetic injections of 8 min at high voltage allow for detection limits of explosives below 100 microg/L. 相似文献
118.
Greg Hughes Paul O'Shea Julie Goll Danny Gauvreau Jennifer Steele 《Tetrahedron》2009,65(16):3189-5650
Effective protocols for the introduction of chiral α-trifluoromethyl benzyl moieties by nucleophilic displacement of enantiomerically enriched α-trifluoromethyl benzylic triflates are presented. The effects of substrate electronics, solvent polarity, temperature, and base are studied by measuring the diastereomeric or enantiomeric excesses of the displacement products formed by coupling a variety of α-trifluoromethyl benzylic triflates with a range of nucleophiles including amines, carboxylates, thiols, and malonates. Preliminary investigations to elucidate the mechanism(s) involved in the loss of stereochemical integrity at the benzylic center in the nucleophilic displacement reactions are also reported. 相似文献
119.
Promising voltammetric sensors based on the modification of Pt and poly(3-methylthiophene) (PMT) electrodes with Pd nanoparticles were achieved for the determination of catecholamine neurotransmitters, ascorbic acid and acetaminophen. Electrochemistry of the indicated compounds was studied at these electrodes and interesting electrocatalytic effects were found. Furthermore, simple, easily prepared one electrochemical step Pd-modified Pt electrode (Pt/Pd) is reported for the first time. Cyclic voltammetry (CV) and chronocoulometry (CC) were used for the determination of the apparent diffusion coefficients in different electrolytes at these electrodes and the values are in the range from 10−4 to 10−5 cm2 s−1. Furthermore, it was found that the method of polymer formation had a substantial effect on the synergism between the polymer film and the loaded metal particles towards the oxidation of dopamine (DA) in different supporting electrolytes. This was confirmed by the CV, CC and EIS (electrochemical impedance spectroscopy) as well as SEM (Scanning Electron Microscopy) results. Pt and PMT electrodes modified with Pd nanoparticles showed excellent results for the simultaneous determination of tertiary and quaternary mixtures of the studied compounds. 相似文献
120.
Schabas G Wang CW Oskooei A Yusuf H Moffitt MG Sinton D 《Langmuir : the ACS journal of surfaces and colloids》2008,24(19):10596-10603
The controlled self-assembly of polymer-stabilized quantum dots (QDs) into mesoscale aqueous spherical assemblies termed quantum dot compound micelles (QDCMs) using a two-phase gas-segmented microfluidic reactor is described. Self-assembly is initiated by the fast mixing of water (approximately 1 s) with a blend solution of polystyrene-coated QDs and amphiphilic polystyrene-block-poly(acrylic acid) stabilizing chains via chaotic advection within liquid plugs moving through a sinusoidal channel. Subsequent recirculating flow within a post-formation channel subjects the dynamic QDCMs to shear-induced processing, controlled via the flow rate and channel length, before a final quench into pure water. During processing, larger QDCMs within the initial population undergo breakup into smaller particles, resulting in smaller mean particle sizes, smaller relative standard deviations, and more skewed distribution shapes, as the overall shear exposure is increased. For these cases, shear-induced size reduction is sufficient to dominate surface tension-driven growth. 相似文献