全文获取类型
收费全文 | 2600篇 |
免费 | 425篇 |
国内免费 | 258篇 |
专业分类
化学 | 1632篇 |
晶体学 | 8篇 |
力学 | 66篇 |
综合类 | 14篇 |
数学 | 53篇 |
物理学 | 1510篇 |
出版年
2024年 | 6篇 |
2023年 | 101篇 |
2022年 | 123篇 |
2021年 | 281篇 |
2020年 | 262篇 |
2019年 | 86篇 |
2018年 | 150篇 |
2017年 | 167篇 |
2016年 | 155篇 |
2015年 | 115篇 |
2014年 | 218篇 |
2013年 | 144篇 |
2012年 | 161篇 |
2011年 | 152篇 |
2010年 | 111篇 |
2009年 | 117篇 |
2008年 | 113篇 |
2007年 | 115篇 |
2006年 | 116篇 |
2005年 | 94篇 |
2004年 | 83篇 |
2003年 | 71篇 |
2002年 | 41篇 |
2001年 | 38篇 |
2000年 | 37篇 |
1999年 | 43篇 |
1998年 | 33篇 |
1997年 | 33篇 |
1996年 | 25篇 |
1995年 | 22篇 |
1994年 | 7篇 |
1993年 | 12篇 |
1992年 | 7篇 |
1991年 | 9篇 |
1990年 | 12篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有3283条查询结果,搜索用时 31 毫秒
41.
Synthesis of porphyrin nitrogen mustards with potential anti-tumor activities in chemotheraphy and photodynamic therapy 总被引:3,自引:0,他引:3
2,7,12,18-Tetramethyl-13,17-di[3'-N,N'-di(2"-chloroethyl)aminopropyl]porphin and it's 3,8-di(1'-alkyloxyethyl)-analogous or porphyrin-nitrogen mustards were synthesized for the first time Their structures were determined by spectroscopics and elemental analyses.Most of the compounds possess both the chemotherapeutic and photodynamic effects on tumor and deserve further investigation. 相似文献
42.
Roland A. Obermüller Christoph Etzlstorfer Heinz Falk 《Monatshefte für Chemie / Chemical Monthly》2002,133(1):89-96
Summary. A hypericin derivative was synthesized in which instead of the methyl groups two benzene rings were condensed to the chromophoric
system in order to extend its conjugation. This derivative showed lowered fluorescence and concomitantly enhanced sensitized
production of active oxygen species as compared to hypericin. However, in contrast to intuition its long wavelength band remained
unshifted in comparison to its parent compound hypericin. Geometry and absorption properties were also investigated by means
of semiempirical calculations.
Received July 27, 2001. Accepted August 9, 2001 相似文献
43.
Bernd?Lackner Yulita?Popova Christoph?Etzlstorfer Andrija A.?Smelcerovic Christian W.?Klampfl Heinz?FalkEmail author 《Monatshefte für Chemie / Chemical Monthly》2005,136(5):777-793
Summary. The syntheses of the two heterocyclically substituted title hypericin derivatives were achieved starting either from 6-benzothiazolyl-tri-O-methyl-6-demethylemodin or 6-benzoxazolyl-tri-O-methyl-6-demethylemodin. The use of microwave assisted synthesis for the preparation of these anthraquinone synthons and the chemical as well as photochemical properties of the corresponding unique hypericin derivatives, which might constitute new photodynamic therapy agents, are reported. The tautomeric and stereochemical aspects of these hypericin derivatives were investigated by means of semiempirical calculations (AM1). 相似文献
44.
Rory?H.?Uibel Emily?C.?Heider Jennifer?L.?Gasser Joel?M.?HarrisEmail author Edward?M.?Eyring Sergio?Petrucci 《Journal of solution chemistry》2005,34(5):499-514
Advances have been made recently in broadening the accessible ultrasonic absorption frequency range and improving the detectability of minor species present in solution using Raman spectroscopy. Development of chemometric techniques in these areas needs to keep pace with the improvement of these experimental methods. Refinements in the analysis of ultrasonic and Raman data based on multivariable least squares and factor analysis, respectively, are examined to investigate the kinetics of zinc thiocyanate complex formation in water. Analysis of ultrasonic absorption relaxation spectra verified that the observed process in aqueous Zn(SCN)2 involves substitution of water from the first coordination shell of Zn2+. Use of a multivariable least-squares error surface is described that enhances the reliability of assigned frequencies of ultrasonic absorption maxima. Factor analysis of Raman scattering data provided direct evidence that at least four complex species, such as Zn(SCN)+ and Zn(SCN)2, are simultaneously present in the aqueous zinc thiocyanate solutions. 相似文献
45.
D. A. Rudakov V. L. Shirokii V. I. Potkin E. A. Dikusar V. I. Bragin P. V. Petrovskii I. B. Sivaev V. I. Bregadze A. V. Kisin 《Russian Journal of Electrochemistry》2006,42(3):280-284
By electrochemical iodination of potassium 7-methyl-7,8-dicarba-nido-undecaborate and potassium 7,8-dimethyl-7,8-dicarba-nido-undecaborate, their monoiodine derivatives (extracted as tetramethylammonium salts) are synthesized. Their structure is confirmed by NMR and IR spectra and also by elemental analysis data. 相似文献
46.
Mariana Antunes Vieira Bernhard Welz Adilson Jos Curtius 《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(12):251-2067
A simple and reliable method for the determination of arsenic in sediment and in coal without sample digestion, based on hydride generation from slurry samples is proposed. After grinding the samples to a particle size of 50 μm, the sample powder was mixed with aqua regia and hydrofluoric acid in an ultrasonic bath for 30 min. After diluting the mixture with hydrochloric acid, the slurry was allowed to stand for 48 h, and an aliquot was used for hydride generation with sodium borohydride. More than 80% of the arsenic was leached to the aqueous phase under these conditions, except for one sediment sample with very high silica content. The generated arsine was collected in a graphite tube, treated with 0.5 mg of iridium as a permanent modifier, and the arsenic determination was carried out by electrothermal atomic absorption spectrometry. The same tube could be used for at least 160 cycles without any re-treatment. The greatest advantage of the method was that only a minimum of reagents and sample handling were required, reducing the risks of contamination and/or analyte loss. However, the addition calibration technique had to be used in order to obtain results within the 95% confidence level for 11 certified reference materials, 5 sediments, 5 coals and one coal fly ash. One certified sediment slurry was spiked with the analyte and the resulting addition calibration curve was used for the analysis of the certified sediments. Similarly, one certified coal was used to obtain the addition calibration curve for the coal and coal fly ash samples. The recoveries of the certified values, except for one sediment, were between 91 and 115%. The limits of detection in the samples were 0.54 and 0.7 μg g−1 for the coal and sediment samples, respectively, obtained for 1 ml of slurry containing 1 mg of sample. 相似文献
47.
Detlef Gabel Claudia Bauer Mohamed E. El-Zaria Afaf R. Genady Udo Drfler 《Journal of organometallic chemistry》2003,680(1-2):23-26
The preparation and properties of the R1R2NH---B8H11NHR cluster are described. The cluster is stable to aqueous solutions and can be made water-soluble by the introduction of a few hydrophilic groups. This makes the cluster a good candidate as the boron moiety in compounds for boron neutron capture therapy. The chemistry of the cluster preparation, the stability of the cluster, and conditions for reactions of the organic moieties are reviewed. Pyridine derivatives of the cluster show electronic interaction between the cluster and the pyridine. 相似文献
48.
The paper presents a comparative analysis of the possibilities and characteristic features of the application of various polyhedral boron compounds, viz., the closo-decaborate anion [B10H10]2–, the closo-dodecaborate anion [B12H12]2–, the carba-closo-dodecaborate anion [CB11H12]–, carboranes C2B10H12, and the bis(dicarbollide) complexes [M(C2B9H11)2]– (M = Fe, Co, or Ni), in boron neutron capture therapy (BNCT) for cancer. The requirements on compounds used in BNCT are formulated and the advantages of the application of the closo-dodecaborate anion are considered. The data on the synthesis of various derivatives of the closo-dodecaborate anion, which either already found use in BNCT or are most promising in this field, are summarized. The possibilities of the application of agents derived from the closo-dodecaborate anion in medical diagnostics are discussed. 相似文献
49.
Singlet oxygen generation ability of squarylium cyanine dyes 总被引:1,自引:0,他引:1
P. F. Santos L. V. Reis P. Almeida A. S. Oliveira L. F. Vieira Ferreira 《Journal of photochemistry and photobiology. A, Chemistry》2003,160(3):159-161
The quantum yields for singlet oxygen generation of several squarylium cyanine dyes derived from benzothiazole, benzoselenazole and quinoline, displaying absorption within the so-called “phototherapeutic window” (600–1000 nm), were determined, envisioning their potential usefulness for photodynamic therapy (PDT). The determination was performed by a direct method measuring the luminescence decay of the dyes in the near infrared. Considering the absorption and the quantum yields displayed by some of the dyes, these seemed to be potential candidates as sensitizers for PDT. 相似文献
50.
Dmitri S. Kilin Kiril Tsemekhman Oleg V. Prezhdo Eduard I. Zenkevich Christian von Borczyskowski 《Journal of photochemistry and photobiology. A, Chemistry》2007,190(2-3):342-351
The observed resonance energy transfer in nanoassemblies of CdSe/ZnS quantum dots and pyridyl-substituted free-base porphyrin molecules [Zenkevich et al., J. Phys. Chem. B 109 (2005) 8679] is studied computationally by ab initio electronic structure and quantum dynamics approaches. The system harvests light in a broad energy range and can transfer the excitation from the dot through the porphyrin to oxygen, generating singlet oxygen for medical applications. The geometric structure, electronic energies, and transition dipole moments are derived by density functional theory and are utilized for calculating the Förster coupling between the excitons residing on the quantum dot and the porphyrin. The direction and rate of the irreversible exciton transfer is determined by the initial photoexcitation of the dot, the dot–porphyrin coupling and the interaction to the electronic subsystem with the vibrational environment. The simulated electronic structure and dynamics are in good agreement with the experimental data and provide real-time atomistic details of the energy transfer mechanism. 相似文献