全文获取类型
收费全文 | 163篇 |
免费 | 5篇 |
国内免费 | 1篇 |
专业分类
化学 | 116篇 |
晶体学 | 3篇 |
数学 | 2篇 |
物理学 | 48篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 3篇 |
2020年 | 1篇 |
2016年 | 4篇 |
2015年 | 1篇 |
2014年 | 3篇 |
2013年 | 5篇 |
2012年 | 8篇 |
2011年 | 10篇 |
2010年 | 8篇 |
2009年 | 4篇 |
2008年 | 10篇 |
2007年 | 10篇 |
2006年 | 4篇 |
2005年 | 14篇 |
2004年 | 9篇 |
2003年 | 7篇 |
2002年 | 11篇 |
2001年 | 4篇 |
2000年 | 6篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1976年 | 3篇 |
1975年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有169条查询结果,搜索用时 453 毫秒
71.
Morton H. Litt Wha-Tzong Whang Kung-Ti Yen Xue-Jun Qian 《Journal of polymer science. Part A, Polymer chemistry》1993,31(1):183-191
Difunctional acrylates and methacrylate monomers have been made which are high order smectic liquid crystal (or crystalline) at room temperature. This report discusses materials with the following structure: F–S–M–S–F, where F is a functional group, acrylate or methacrylate (A or M); S is a spacer (CH2)n(n), and M is a mesogen—in this case 4,4′-dioxybiphenyl (B). They are codified as BnA or BnM where n is the number of methylenes in the spacer. High conversion with high Tg can be obtained when polymerizing in the smectic state because the reactive end groups are concentrated in a small volume and can react well with little or no diffusion. B2A, B3A, B6A, B11A, and B3M were polymerized in the smectic state and compared to polymers made at temperatures where the monomers were isotropic. High conversion was obtained below final Tg—even then, probably because the polymers were ordered. All the polymers were studied by WAXD and dynamic mechanical spectroscopy. Solid-state NMR on B3A showed that there was very high conversion of the double bonds at all temperatures. B3A photopolymerized in the smectic state (60–76°C) produced a crystalline polymer with Tg = 185°C (1 Hz). When photopolymerized at 85°C, above the isotropization temperature (Ti), a poorly organized polymer was obtained with a Tg of 155°C (1 Hz). Monomers with an odd number of methylene groups as spacers were crystalline after polymerization. With an even number of methylene groups, they lost most of their crystallinity on polymerization below Ti, but retained a low order smectic structure. Similar structures were obtained with all the monomers when they were polymerized above Ti. There was little effect of polymerization temperature on Tg when the spacers had an even number of methylene groups. © 1993 John Wiley & Sons, Inc. 相似文献
72.
A new analytical method for baclofen (4-amino-3-p-chlorophenylbutyric acid) based on capillary electrophoretic separation and laser-induced fluorescence detection has been developed. Naphthalene-2,3-dicarboxaldehyde was used for precolumn derivatization of the non-fluorescent drug. Optimal separation and detection were obtained with an electrophoretic buffer of 50 mM sodium borate (pH 9.5) and a He-Cd laser (excitation at 442 nm, emission at 500 nm). Linearity (r > or = 0.99) over three orders of magnitude was generally obtained and the concentration limit of detection was in the nanomolar level. Coupled with a simple cleanup procedure, the method was successfully applied to the analysis of baclofen in human plasma. Recovery of spiked baclofen in plasma was 98%. The relative standard deviation values on peak size and migration time were 7.9% and 0.4%, respectively. The limit of detection of baclofen in plasma was 10 ng/ml. 相似文献
73.
Lanthanide(III) Cryptate (2.2.1) chlorides (Ln(2.2.1)Cl(3); Ln = La (1a), Ce(1b), and Eu(1c); (2.2.1) = 4,7,13,16,21-pentaoxa-1,10-diazabicyclo[8.8.5]tricosane) are effective for the catalytic hydrolysis of bis(4-nitrophenyl) phosphate. Kinetic studies reveal that the europium(III) complex (1c) catalyzes the hydrolysis to produce 6 equiv of 4-nitrophenol with a significant rate (k(1) = 1.5 x 10(-)(4) s(-)(1) at 0.40 mM) at pH 8.5 and 50 degrees C. The catalytic activity of the complexes is increased with decreasing the ionic size, i.e, La < Ce < Eu. While the use of hydrogen peroxide further increase the activity of 1b (k(1) = 1.6 x 10(-)(3) s(-)(1) at 0.40 mM), the presence of molecular oxygen does not affect the activity at all. Crystal of 1a.CH(3)OH([La(2.2.1)(Cl)(2)](Cl)(CH(3)OH)) belongs to the space group Pnma with a = 17.072(3) ?, b = 19.037(3) ?, c = 14.725(2) ?, V = 4786(1) ?(3), Z = 8, D(x)() = 1.691 g cm(-)(3), &mgr; = 21.7 cm(-)(1). The encryptated metal ion is nine-coordinated, and all the heteroatoms of the cryptate (2.2.1) ligand coordinate the metal center to form a bowl-shaped structure. Two coordinating chloride anions are located on the open face with a cis geometry. The existence of coordinated water to the europium(III) complex 1c in the aqueous solution was confirmed by time-resolved Eu(III) luminescence spectroscopy. From the decay constants in H(2)O and D(2)O, the numbers of coordinated water molecules (q) are found to be 3.02 at pH of 5.0. The above kinetic and spectroscopic observation are supportive of mechanisms in which the metal complexes act as a center for binding and activation as well as a source of nucleophilic metal hydroxides. 相似文献
74.
Highly Enhanced Fluorescence of Supramolecular Polymers Based on a Cyanostilbene Derivative and Cucurbit[8]uril in Aqueous Solution 下载免费PDF全文
Hyeong‐Ju Kim Dr. Dong Ryeol Whang Dr. Johannes Gierschner Prof. Soo Young Park 《Angewandte Chemie (International ed. in English)》2016,55(51):15915-15919
Supramolecular polymers (SPs) have received great attention because of their potential for various practical applications. As part of our search for SPs that are highly fluorescent in aqueous media, we designed a system based on a cucurbit[8]uril (CB[8]) host and a newly designed cyanostilbene guest. Fluorescence quantum yields of ≈0 % in the disassembled monomer state and 91 % in the CB[8]‐induced SP state were obtained. The intriguing photophysical properties of the SP are elucidated through detailed experimental and computational analysis, paving the way towards a fascinating class of water‐soluble fluorescent SPs. 相似文献
75.
Release characteristics of the non-toxic insect repellant 2-undecanone from its crystalline inclusion compound with α-cyclodextrin 总被引:1,自引:0,他引:1
Hyun Suk Whang Alan Tonelli 《Journal of inclusion phenomena and macrocyclic chemistry》2008,62(1-2):127-134
2-Undecanone (methyl nonyl ketone), a natural non-toxic insect repellant compound, was recently isolated from the trichomes of wild tomatoes, and is currently being introduced as a replacement for insect repellants containing N,N-diethyl-meta-toluamide or DEET, which are permitted for use on children older than 2 months. In an effort to improve the delivery of the somewhat volatile 2-undecanone, we have successfully formed the crystalline inclusion compound (IC) between 2-undecanone and α-cyclodextrin (α-CD), using a coprecipitation method. Employing WAXD, DSC, FT-IR, and NMR observations, we have confirmed that 2-undecanone is included as a guest inside the host α-CD cavities, and forms a channel-type crystalline IC. The release characteristics of 2-undecanone insect repellant from its α-CD-IC were studied using TGA either at a heating rate of 20 °C/min in nitrogen, and air atmospheres or at constant temperatures of 25, and 40 °C over a period of 24 h. The release/loss of 2-undecanone insect repellant from its α-CD-IC was ~60% after 24 h at 40 °C. By comparison, ~97% of pure 2-undecanone was volatilized, and lost over 24 h at 40 °C. In addition, insecticidal activity of 2-undecaonone from its α-CD complex against German cockroaches was evaluated. The results show an excellent repellency that 100% of the cockroaches were repelled for the first 2 days after application. These results suggest that the gradual, long-term delivery of the insect repellant 2-undecanone can be significantly improved through employment of its crystalline α-CD-IC. 相似文献
76.
The influences of various parameters in a single-step electrodeposition of CuInSe2 from aqueous solution containing CuCl2, InCl3, and SeO2, with sodium citrate as the complexing agent, are investigated. Co-deposition of CuInSe2 from a room temperature, aqueous bath of these electrolytes is accomplished by the aid of sodium citrate. In this work the optimum potential for deposition of CuInSe2 is found to be −0.5 V vs. Ag/AgCl, the deposition time is 800 s, the concentration ratio of CuCl2, InCl3, and SeO2 is 9 mM:22 mM:22 mM in aqueous solution, and the annealing temperature is 225 °C. Under the optimum conditions, crystalline layers of CuInSe2 having the chalcopyrite structure can be successfully synthesized. Cyclic voltammetry (CV), scanning electron microscope (SEM), X-ray diffractometer (XRD), and energy dispersive X-ray spectrometer (EDX) were used to examine the electrochemistry, morphologies, structures, and compositions of CuInSe2 thin films deposited on ITO glass. 相似文献
77.
Kinetic studies on the reactions of O‐methyl ( 2 ) and O‐ethyl ( 3 ) phenyl phosphonochloridothioates with X‐pyridines have been carried out in acetonitrile at 35.0°C. The pyridinolysis rates of 2 are slightly faster than those of 3 . The substituent effects of X on the pyridinolysis rates of 2 and 3 are similar. The Hammett and Brönsted plots with X in the nucleophiles are biphasic concave upward with a break point at X = 3‐Ph for both substrates. The stepwise mechanism with rate‐limiting leaving group departure from the intermediate is proposed based on the βX values and biphasic concave upward free energy relationship for both substrates. The biphasic concave upward free energy relationships are rationalized by a frontside nucleophilic attack TSf with more basic pyridines and backside attack TSb with less basic pyridines for both substrates. 相似文献
78.
Pt-polyaniline nanocomposite on boron-doped diamond electrode for amperometic biosensor with low detection limit 总被引:1,自引:0,他引:1
Min-Jung Song Jong Hoon Kim Seung Koo Lee Jae-Hyun Lee Dae Soon Lim Sung Woo Hwang Dongmok Whang 《Mikrochimica acta》2010,171(3-4):249-255
Boron-doped diamond electrodes covered with a nanostructured Pt nanoparticle-polyaniline composite have been fabricated and employed as sensitive amperometric sensors with low detection limit. A highly conductive boron-doped diamond thin film (BDD) was prepared by chemical vapor deposition, and its morphology was characterized by scanning electron microscopy and transmission electron microscopy. The nanostructured composite layer was grown on the BDD electrode by electrochemical deposition of polyaniline and Pt nanoparticles. Glucose oxidase (GOx) was then adsorptively immobilized on the modified BDD electrode. The biosensor displays a large surface area, high catalytic activity of the Pt nanoparticles, efficient electron mediation through the conducting polymer, and low background current of the electrode. The biosensor exhibits an excellent response to glucose, with a broad linear range from 5.9 μM to 0.51 mM, a sensitivity of 5.5 μA·mM?1, a correlation coefficient (R) of 0.9947, and a detection limit of 0.10 μM. The apparent Michaelis-Menten constant (K M app ) and the maximum current density of the electrode are 4.1 mM and 0.021 mA, respectively. This suggests that the immobilized GOx possesses a higher affinity for glucose at the lower K M app , and that the enzymatic reaction rate constitutes the rate-limiting step of the response. 相似文献
79.
A simple, rapid and sensitive CE-fluorescence (FL) detection method for the analysis of alendronate (ALEN), a bisphosphonate drug, has been developed. Using a buffer solution of 20 mM sodium phosphate (pH 10.0) and a voltage of 24 kV, separation of ALEN in a 55-cm length (35-cm effective length) capillary was achieved in 5 min. FL detection of ALEN was performed via pre-column derivatization with 2,3-naphthalene dicarbox-yaldehyde (NDA). Linear correlation (r=0.9981, n=6) between FL intensity and analyte concentration was obtained in the range of 7-200 ng/mL ALEN. The developed CE-FL method was applied to the analysis of ALEN in human urine and plasma samples. In order to eliminate the interfering matrix components, SPE using magnetic Fe(3) O(4) @Al(2) O(3) nanoparticles as solid sorbents was employed to clean the biological fluids before CE-FL analysis. The linear ranges of ALEN in urine and plasma were 5-100 ng/mL (r = 0.9982, n = 7) and 5-70 ng/mL (r = 0.9954, n = 7), respectively. The LOD and LOQ in both urine and plasma samples were 1.5 and 5 ng/mL ALEN, respectively. Total analysis time including sample pre-treatment and CE separation was less than 1.5 h. 相似文献
80.
Headspace solid-phase microextraction (HS-SPME) and gas chromatography with flame photometric detection (GC-FPD) have been
investigated for determination of butyltin and octyltin stabilizers in poly(vinyl chloride) (PVC) products. The organotin
stabilizers were first released from the plastic matrix by dissolving the PVC sample in tetrahydrofuran (THF). The stabilizers
were then hydrolyzed to the chloride forms, by treatment with 6 mol L−1 HCl, then derivatized with sodium tetraethylborate (NaBEt4) in 0.2 mol L−1 sodium acetate buffer (pH 4.5) at 50 °C. HS-SPME was performed with a fused-silica fiber coated with a 100-μm film of polydimethylsiloxane
(PDMS). The collected organotin compounds were then desorbed in the GC injector at 280 °C and analyzed by GC-FPD. Linearity
(r≥0.994) over a concentration of approximately two orders of magnitude was usually obtained. Limits of quantitation (LOQ) of
the four organotin compounds studied, viz., monobutyltin (MBT), dibutyltin (DBT), monooctyltin (MOT), and dioctyltin (DOT),
were in the range 0.3–1.0 ng Sn mL−1. Recovery was >90% for butyltins and >80% for octyltins. The method was validated by analyzing two reference standard PVC
sheets with known organotin content. The applicability of the method to analysis of organotin stabilizers in commercial PVC
products was also demonstrated. 相似文献