全文获取类型
收费全文 | 276篇 |
免费 | 12篇 |
专业分类
化学 | 226篇 |
晶体学 | 2篇 |
力学 | 8篇 |
数学 | 3篇 |
物理学 | 49篇 |
出版年
2020年 | 4篇 |
2019年 | 3篇 |
2018年 | 3篇 |
2017年 | 2篇 |
2016年 | 6篇 |
2015年 | 7篇 |
2014年 | 9篇 |
2013年 | 20篇 |
2012年 | 19篇 |
2011年 | 16篇 |
2010年 | 9篇 |
2009年 | 17篇 |
2008年 | 15篇 |
2007年 | 16篇 |
2006年 | 21篇 |
2005年 | 11篇 |
2004年 | 11篇 |
2003年 | 9篇 |
2002年 | 8篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1997年 | 2篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 8篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1965年 | 2篇 |
1961年 | 1篇 |
1956年 | 1篇 |
1909年 | 1篇 |
1908年 | 2篇 |
1905年 | 2篇 |
排序方式: 共有288条查询结果,搜索用时 22 毫秒
21.
Synthesis of well-defined polystyrene with multi-functional end groups utilizing cyclotriphosphazene
Kenzo Inoue Sadao Negayama Tomoyuki Itaya Minoru Sugiyama 《Macromolecular rapid communications》1997,18(3):225-231
Telechelic polystyrenes with five benzyl chloride moieties at the polymer end (PSt-E) were prepared by coupling reaction of polystyryllithium with hexakis(4-chloromethyl-phenoxy)cyclotriphosphazene ( 4 ). The coupling reaction occurs almost quantitatively and unfavorable side reactions were not operative. When a mole ratio [ 4 ]/[sec-BuLi] = 9.3 was used, polystyrenes with cyclophosphazene carrying five benzyl chloride moieties at the polymer end (PSt-E) were obtained in more than 90% yield, which have narrow and predictable molecular weights (M w/M n = 1.05). A star shaped polystyrene with phosphazene core could also be prepared by using excess polystyryl anions. 相似文献
22.
Gabriela Petroselli Mridul Kanti Mandal Lee Chuin Chen Gustavo T. Ruiz Ezequiel Wolcan Kenzo Hiraoka Hiroshi Nonami Rosa Erra‐Balsells 《Journal of mass spectrometry : JMS》2012,47(3):313-321
A group of rhenium (I) complexes including in their structure ligands such as CF3SO3‐, CH3CO2‐, CO, 2,2′‐bipyridine, dipyridil[3,2‐a:2′3′‐c]phenazine, naphthalene‐2‐carboxylate, anthracene‐9‐carboxylate, pyrene‐1‐carboxylate and 1,10‐phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF‐ESI‐CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M]+. and to produce their reduction yielding the gas species [M]–.. It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV–visible region, particularly at 355 nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix‐assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor‐harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M]–. species. Results obtained with 2‐[(2E)‐3‐(4‐tert‐buthylphenyl)‐2‐methylprop‐2‐enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
23.
24.
Zhan Yu Lee Chuin Chen Rosa Erra‐Balsells Hiroshi Nonami Kenzo Hiraoka 《Rapid communications in mass spectrometry : RCM》2010,24(11):1507-1513
Probe electrospray ionization (PESI) is a modified version of the electrospray ionization (ESI), where the capillary for sampling and spraying is replaced by a solid needle. High tolerance to salts and direct ambient sampling are major advantages of PESI compared with conventional ESI. In this study, PESI‐MS was used to monitor some biological and chemical reactions in real‐time, such as acid‐induced protein denaturation, hydrogen/deuterium exchange (HDX) of peptides, and Schiff base formation. By using PESI‐MS, time‐resolved mass spectra and ion chromatograms can be obtained reproducibly. Real‐time PESI‐MS monitoring can give direct and detailed information on each chemical species taking part in reactions, and this is valuable for a better understanding of the whole reaction process and for the optimization of reaction parameters. PESI‐MS can be considered as a potential tool for real‐time reaction monitoring due to its simplicity in instrumental setup, direct sampling with minimum sample preparation and low sample consumption. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
25.
Atsushi Takamizawa Kayoko Mishina Kenzo Hiraoka 《Journal of mass spectrometry : JMS》2012,47(2):221-225
Covalent bonds are often created by a reaction between chemicals and protein before causing various adverse effects in a cell. Dimethylaminoethyl methacrylate (DMAEMA), which has moderate toxicity, causes skin inflammation and throat irritation. For this study, we investigated a reaction mechanism between myoglobin and (DMAEMA) using a new analytical tool developed at our laboratory: laser spray mass spectrometry technique. It was found that initially DMAEMA was added to the amino group of protein by the Michael addition mechanism; the added DMAEMA was hydrolyzed to methacrylic acid using an autocatalytic system. The results of this study indicate the feasibility of the laser spray technique in analyses of reaction dynamics. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
26.
Pressure, temperature, and composition phase equilibrium diagrams of new solid solution systems of the Cd1?xMxS (M = Mg, Ca, Sr) type were investigated using the quenching method. The stable region for the rock-salt-type phase is widely extended toward the high-temperature/low-pressure region by substituting 10–20 mole% of Cd with Ca or Sr. Temperature and composition phase diagrams for each solid solution system were obtained at 2 GPa. The rock-salt-type phase stability is discussed in view of these phase relations. 相似文献
27.
Joichi Koga Keisuke Taguchi Nobuhiko Kuroki Kenzo Konishi 《Colloid and polymer science》1967,215(1):45-47
Summary Some organic acids, alcohol and amine which have an asymmetric carbon atom were used for an investigation of asymmetric absorption
on wool. Racemic mixture of hydratropic acid, mandelic acid andα-phenethylamine have shown the selective absorption on wool from their aqueous and alcoholic aqueous solutions and S-form
of their diastereoisomers preferentially absorbed on wool. According to the results we obtained so far, it is concluded that
the preferential absorption strongly depends on the configuration of the substance of which wool is composed. 相似文献
28.
Hiraoka K Asakawa Y Kawashima Y Okazaki S Nakamura M Yamamoto Y Takamizawa A 《Rapid communications in mass spectrometry : RCM》2004,18(20):2437-2442
The effect of the presence of foreign salts (NaCl, aerosol OT, tetra-n-hexylammonium bromide, and CH3COONH4) on the formation of gaseous ions for electrospray (ES) and laser spray (LS) was studied in the positive and negative modes of operations. The ion signals for amino acids show sudden decrease with the concentration of foreign salts greater than 10(-5) M for both ES and LS. When the surface-active counter ions were added, the signal intensities showed a marked decrease for both ES and LS. This may be due to the enrichment of the surface-active counter ions on the surface of the charged droplets. When CH3COONH4 was added to an aqueous solution of 10(-6) M lysozyme chloride, an increase of the signal intensities for (lysozyme+nH)n+ and a decrease in the values of n were observed. The decrease in n may be due to the salt formation of (lysozyme+nH)n+ with the negative acetate ion leading to the reduction of positive charges. 相似文献
29.
Rapid detection of trace level anabolic steroids in urine is highly desirable to monitor the consumption of performance enhancing anabolic steroids by athletes. The present article describes a novel strategy for identifying the trace anabolic steroids in urine using Leidenfrost phenomenon assisted thermal desorption (LPTD) coupled to dielectric barrier discharge (DBD) ionization mass spectrometry. Using this method the steroid molecules are enriched within a liquid droplet during the thermal desorption process and desorbed all-together at the last moment of droplet evaporation in a short time domain. The desorbed molecules were ionized using a dielectric barrier discharge ion-source in front of the mass spectrometer inlet at open atmosphere. This process facilitates the sensitivity enhancement with several orders of magnitude compared to the thermal desorption at a lower temperature. The limits of detection (LODs) of various steroid molecules were found to be in the range of 0.05–0.1 ng mL−1 for standard solutions and around two orders of magnitude higher for synthetic urine samples. The detection limits of urinary anabolic steroids could be lowered by using a simple and rapid dichloromethane extraction technique. The analytical figures of merit of this technique were evaluated at open atmosphere using suitable internal standards. The technique is simple and rapid for high sensitivity and high throughput screening of anabolic steroids in urine. 相似文献
30.