全文获取类型
收费全文 | 492篇 |
免费 | 9篇 |
国内免费 | 1篇 |
专业分类
化学 | 329篇 |
晶体学 | 2篇 |
力学 | 1篇 |
数学 | 21篇 |
物理学 | 149篇 |
出版年
2023年 | 2篇 |
2022年 | 2篇 |
2021年 | 5篇 |
2020年 | 3篇 |
2019年 | 8篇 |
2018年 | 3篇 |
2017年 | 6篇 |
2016年 | 8篇 |
2015年 | 9篇 |
2014年 | 20篇 |
2013年 | 21篇 |
2012年 | 17篇 |
2011年 | 32篇 |
2010年 | 17篇 |
2009年 | 25篇 |
2008年 | 23篇 |
2007年 | 22篇 |
2006年 | 25篇 |
2005年 | 29篇 |
2004年 | 27篇 |
2003年 | 25篇 |
2002年 | 19篇 |
2001年 | 10篇 |
2000年 | 17篇 |
1999年 | 6篇 |
1998年 | 7篇 |
1997年 | 6篇 |
1996年 | 8篇 |
1994年 | 2篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1991年 | 6篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 8篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 6篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 7篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1975年 | 7篇 |
1974年 | 4篇 |
1973年 | 5篇 |
1970年 | 2篇 |
排序方式: 共有502条查询结果,搜索用时 15 毫秒
51.
Takeshi Taniguchi Takashi Kawakami Youhei Nishimura Mistutaka Okumura Kizashi Yamaguchi 《Chemical physics letters》2006,420(4-6):397-400
The one-dimensional intermolecular ferromagnetic interaction of a charge-transfer (CT) complex, (BDTA)[Ni(mnt)2] (BDTA: 1,3,2-benzodithiazolyl, mnt: maleonitriledithiolate), is studied by the Kohn–Sham hybrid density functional method, in order to understand the mechanism of the magnetism. All possible effective exchange integrals, J, between the spin pairs of the system indicate that a ferromagnetic interaction (J = 172 cm−1) exists along the b-axis. Magnetic susceptibility, simulated with the ab initio determined J values by the quantum Monte Carlo (QMC) method, is qualitatively consistent with that measured experimentally. 相似文献
52.
The ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynes developed by Dixneuf and co-workers was applied to the synthesis of 2-alkyl- or 2-aryl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-bis(trimethylsilyl)-1,3-butadienes by use of alkynylboronates instead of alkynes. Di- and tetrasubstituted 1,3-butadienes were prepared from a 2-boryl-1,4-disilyl-1,3-butadiene, using the Suzuki-Miyaura coupling reaction, iodolysis of the alkenylsilane moieties with N-iodosuccinimide and hydrolysis of the carbon-silicon bonds with trifluoroacetic acid. The same compound was converted also to a bicyclic compound, a trisubstituted 1,3-butadiene and a dienone through the Diels-Alder reaction, oxidation of the alkenylboronate moiety and the Mukaiyama aldol reaction. 相似文献
53.
The analytical method of determining enzyme activity by liquid chromatography-mass spectrometry (LC/MS) was developed and
applied for investigation of the effect of polycyclic aromatic hydrocarbons (PAHs) on the enzyme activity of chitinase. The
measurement of chitinase activity by LC/MS is useful in order to use the nonderivatized substrate, which can show in vivo
chitinase activity. Substrate consumption and product formation were monitored in order to determine chitinase activity. It
was shown that, for the first time, in vitro addition of PAHs inhibited the activity of chitinase in a noncompetitive manner.
The IC50 value of benzo[a]pyrene was 1.4 μM, and PAHs containing four or more aromatic rings showed the same or higher inhibitory effect, whereas PAHs
with a lower number of aromatic rings showed lower inhibition of the chitinase activity than benzo[a]pyrene. 相似文献
54.
Contamination of the exterior surface of vials of cytostatic drugs by the drugs themselves is a potential hazard to human health. This study developed a validated method using liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) for the determination of contamination of the exteriors of vials of cisplatin and carboplatin. Large Alpha® sampling swabs were employed to wipe the vial exterior. Cisplatin or carboplatin and gold(III) as an internal standard were derivatized by N,N-diethyldithiocarbamate (DDTC). Pt(DDTC)3+ and Au(DDTC)2+ were monitored by the respective transitions of m/z 639.3-490.9 and 493.0-345.0, respectively. Each separation was completed within 9 min using a 3 μm particle ODS-column. Calibration curves for cisplatin and carboplatin were linear over concentration ranges of 30-10,000 and 30-30,000 pg vial−1, respectively. The accuracies and precisions were 96.1-102.5% and within 8.2% for intra-assay and 99.6-103.3% and within 7.6% for inter-assay, respectively. Their lower limit of quantification was 30 pg vial−1. Amounts of 0.17-17.0 ng vial−1 as cisplatin and 0.48-794 ng vial−1 as carboplatin were detected from the exterior surface of the vials. This validated method using LC-ESI-MS/MS for the determination of platinum anticancer drugs is helpful for monitoring contamination of the exterior surface of drug vials. 相似文献
55.
The wavelet transform has been shown to be a useful tool for multivariate calibration. However, the choice of wavelet transform settings (wavelet family, length and number of decomposition levels) for a given application is still an open problem. The present paper proposes an alternative approach, which consists of generating an ensemble model by combining individual models obtained with different wavelet transform settings. The advantages of the proposed method are demonstrated in two analytical problems, namely the determination of moisture and protein in wheat by near infrared spectroscopy and the determination of specific mass and three distillation temperatures (T10, T50, T90) in gasoline by middle infrared spectroscopy. In these problems, the results varied considerably among individual models, which underlines the risk associated to an inadequate choice of wavelet transform settings. In contrast, the ensemble model always provided adequate results in terms of prediction error and noise sensitivity. The proposed method can be seen as an advantageous alternative for multivariate calibration in the wavelet domain, as it frees the analyst from the need to choose a particular configuration for the wavelet transform. 相似文献
56.
N-(omega-Bromoalkyl)-amino acid derivatives, readily prepared from natural alpha-amino acids, gave cyclic amino acids with a quaternary stereocenter by treatment with potassium hexamethyldisilazaide in DMF. The chirality of parent amino acids was almost completely preserved during an enolate-formation and cyclization process, giving aza-cyclic amino acids in up to 98% ee in retention of configuration. This method is applicable to the asymmetric synthesis of azetidine, pyrrolidine, piperidine, and azepane derivatives. The asymmetric cyclization seems to proceed via an axially chiral enolate intermediate and not through a concerted SEi process. 相似文献
57.
Vuthichai Ervithayasuporn Junichi Abe Toshinori Matsushima Yusuke Kawakami 《Tetrahedron》2010,66(48):9348-9355
Two new classes of mono- and oligo(p-phenylene ethynylene)s grafted with polyhedral oligomeric silsesquioxanes (POSS) were synthesized via ‘click’ chemistry and palladium-catalyzed Sonogashira cross-coupling. These materials with cubic silsesquioxanes are very robust with excellent thermal stability in air (T5%loss>330 °C) and exhibited Tg>80 °C. All the compounds showed high photoluminescence with a range of blue emission and quantum yield up to 80% in the solution. Extended π conjugation molecules of oligo-pPEs POSS maintain relatively high PL quantum efficiencies in the solid state, compared to mono-pPEs POSS. A preliminary report is made of some of the materials as multilayer OLED components with active dopants PVK and PBD. 相似文献
58.
59.
One of the key differences of a semiconductor optical amplifier (SOA) with internal lasing oscillation (ILO) from a SOA with external light injection (ELI) lies in a carrier-sharing mechanism. Since the internal lasing mode shares the same pool of carriers with the signals, the carriers (or photons) withdrawn from the circulating laser mode speed up the gain recovery. On the other hand, the external light injected into the SOA shortens the carrier recovery time through optical pumping without any carrier sharing involved. To find out a better scheme, we have made a comparative investigation on the effects of the ILO and ELI on the SOA performance. It turns out by way of simulation that the ELI scheme provides faster gain recovery, shorter carrier lifetime, and higher saturation power when the external injection power is higher than the internal lasing power. The performance enhancement is not so pronounced with the carrier-sharing mechanism, as the internal lasing mode itself gives rise to severe longitudinal spatial hole burning (LSHB). Nevertheless, the ILO scheme is preferable for linear-amplification applications. We also examine the use of the ELI for low-crosstalk optical amplifiers. It is found that the ELI scheme does not bring in a very strong resonance peak in the crosstalk, which appears in a SOA with ILO due to relaxation oscillations of the lasing mode. In comparison to the ILO in SOAs, the ELI into SOAs is likely to leave more optical gain for multi-channel amplification without any sacrifice on the crosstalk. 相似文献
60.
Hyperfine Interactions - First off-line tests at the ion trap facility SHIPTRAP took place. The facility is being set up to deliver very clean and cooled beams of singly-charged recoil ions (Rare... 相似文献