全文获取类型
收费全文 | 674篇 |
免费 | 16篇 |
国内免费 | 3篇 |
专业分类
化学 | 445篇 |
晶体学 | 7篇 |
力学 | 19篇 |
数学 | 76篇 |
物理学 | 146篇 |
出版年
2024年 | 1篇 |
2023年 | 3篇 |
2022年 | 14篇 |
2021年 | 24篇 |
2020年 | 19篇 |
2019年 | 17篇 |
2018年 | 15篇 |
2017年 | 31篇 |
2016年 | 33篇 |
2015年 | 14篇 |
2014年 | 31篇 |
2013年 | 70篇 |
2012年 | 42篇 |
2011年 | 76篇 |
2010年 | 37篇 |
2009年 | 24篇 |
2008年 | 44篇 |
2007年 | 38篇 |
2006年 | 28篇 |
2005年 | 24篇 |
2004年 | 17篇 |
2003年 | 20篇 |
2002年 | 11篇 |
2001年 | 5篇 |
2000年 | 5篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 7篇 |
1996年 | 8篇 |
1995年 | 5篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1988年 | 2篇 |
1987年 | 6篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1973年 | 1篇 |
1972年 | 2篇 |
排序方式: 共有693条查询结果,搜索用时 15 毫秒
141.
Asker E Masnovi J 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2009,71(5):1973-1978
1,n-Di(9-ethylcarbazol-3-yl)alkanes, where n=1-5, as the dichromophoric model compounds of poly-3-vinylcarbazoles were synthesized to examine their complexation behaviors with the electron acceptors tetracyanoethylene (TCNE) and tetranitromethane (TNM). 9,9'-Diethyl-3,3'-dicarbazolyl, di(3-ethylcarbazol-9-yl)methane, and three monomeric analogues were also included for comparison. In dichloromethane solution, the dicarbazoles formed stable 1:1 electron donor-acceptor complexes with TCNE having formation enthalpies around -3.5kcal/mol. With TNM they formed more weakly bound complexes that showed little dependence on concentration and almost zero dependence on temperature changes having nearly 0kcal/mol enthalpies of formation. The smaller gap between the two carbazole groups in 1,n-di(9-ethylcarbazol-3-yl)alkanes with nor=3. 相似文献
142.
Ulku Dilek Uysal Zeineb Aturki Maria Augusta Raggi Salvatore Fanali 《Journal of separation science》2009,32(7):1002-1010
In this paper, the simultaneous separation of several polyphenols such as (+)‐catechin, (–)‐epicatechin, (–)‐epigallocatechin, theophylline, caffeine in green and black teas by capillary electrochromatography (CEC) was developed. Several experimental parameters such as stationary phase type, mobile phase composition, buffer and pH, inner diameter of the columns, sample injection, were evaluated to obtain the complete separation of the analysed compounds. Baseline resolution of the studied polyphenols was achieved within 30 min by using a capillary column (id 100 μm) packed with bidentate C18 particles for 24.5 cm and a mobile phase composed of 5 mM ammonium acetate buffer pH 4 with H2O/ACN (80:20, v/v). The applied voltage and the temperature were set at 30 kV and 20°C. Precision, detection and quantification limits, linearity, and accuracy were investigated. A good linearity (R2 > 0.9992) was achieved over a concentration working range of 2–100 μg/mL for all the analytes. LOD and LOQ were 1 and 2 μg/mL, respectively, for all studied compounds. The CEC method was applied to the analysis of those polyphenols in green and black tea samples after an extraction procedure. Good recovery data from accuracy studies ranged between 90% and 112% for all analytes. 相似文献
143.
Schiff base oligomer of 2-[(4-fluorophenyl) imino methylene] phenol (FPIMP) was synthesized via oxidative polycondensation reaction in an alkaline medium. Oligomer-metal complex compounds were synthesized from the reactions of oligo-2-[(4-fluorophenyl) imino methylene] phenol (OFPIMP) with Co+2, Ni+2 and Cu+2 ions. The synthesis was achieved by oxidative coupling based on air oxygen as an oxidant. While synthesized Schiff base oligomer was soluble in most common organic solvents, its metal complexes were only soluble in dimethylsulfoxide. Electrochemical HOMO and LUMO band gap (Eg) of monomer, oligomer and its metal complexes were calculated from oxidation and reduction onset values. According to cyclic voltammetry (CV) and UV-vis measurements, electrochemical energy gaps and optical band gap (Eg) values of monomer and oligomer were found to be 3.26 and 3.10; 3.15 and 2.96 eV, respectively. Conductivity measurements of doped and undoped Schiff base oligomer and its metal complexes were carried out by electrometer at a room temperature and atmospheric pressure and were calculated from four-point probe technique. When iodine was used as doping agent, conductivity of this oligomer and its metal complexes were observed to be increased. 相似文献
144.
Kirgöz UA Odaci D Timur S Merkoçi A Alegret S Beşün N Telefoncu A 《Analytica chimica acta》2006,570(2):165-169
A gelatin membrane with carboxyl esterase and alcohol oxidase was subsequently integrated onto the surface of a graphite epoxy composite electrode (GECE). The developed biosensors showed linearity in the range of 2.5–400 μM for aspartame and 2.5–25 μM for ethanol with response times of 170 and 70 s for each analyte, respectively. The resulting bienzyme biosensor was used for aspartame detection in diet coke samples and ethanol detection in beer and wine samples. From the obtained results, it can be concluded that the developed biosensor is a selective, practical and economic tool for aspartame and ethanol detection in real samples. 相似文献
145.
M. S. Murib Y. O. Yılmaz A. Demir Ş. Işçi T. Bilici A. Kurt P. Wagner A. Serpengüzel 《The European physical journal. Special topics》2014,223(10):1995-2002
Elastic light scattering is performed in the original band of optical fiber communication at 1300 nm for a 500 μm sapphire microsphere placed on a silica optical fiber half coupler. The morphology dependent resonances (MDRs) are observed in the transverse magnetically (TM) polarized and transverse electrically (TE) polarized 0° transmission and 90° elastic scattering obtained from the sapphire microsphere. The TE and TM MDRs can be detected selectively with the use of a Glan polarizer. The TE and TM polarization selectivity provides the ability to select relative MDR to BG levels. The TM polarization provides higher MDR signal to background ratio (SBR) and is suitable for optical monitoring, biological sensing or any other optoelectronic application that requires a high resolution optical filter. The polar angular mode spacing of 0.36 nm of the resonances correlates well with the optical size of the sapphire microsphere. The autocorrelation of the 90° elastic scattering spectra also shows peaks at 0.36 nm. The spectral linewidths of the resonances are on the order of 0.1 nm, which corresponds to quality factors on the order of 104. A sapphire sphere with a radius of 500 μm and relative refractive index of 1.31, resonances will red-shift by 1.01 nm (0.077%). This shift is on the order of 10 linewidths, making sapphire biophotonic sensors an interesting alternative to silica biophotonic sensors. 相似文献
146.
Güleç Özcan Türkeş Cüneyt Arslan Mustafa Demir Yeliz Yeni Yeşim Hacımüftüoğlu Ahmet Ereminsoy Ergün Küfrevioğlu Ömer İrfan Beydemir Şükrü 《Molecular diversity》2022,26(5):2825-2845
Molecular Diversity - The acetylcholinesterase and carbonic anhydrase inhibitors (AChEIs and hCAIs) remain key therapeutic agents for many bioactivities such as anti-Alzheimer and antiobesity... 相似文献
147.
148.
We examine theoretically the effects of the bonding geometries at the gold-thiol interfaces on the inelastic tunneling spectra of propanedithiolate (PDT) molecules bridging gold electrodes and show that inelastic tunneling spectroscopy combined with theory can be used to determine these bonding geometries experimentally. With the help of density functional theory, we calculate the relaxed geometries and vibrational modes of extended molecules each consisting of one or two PDT molecules connecting two gold nanoclusters. We formulate a perturbative theory of inelastic tunneling through molecules bridging metal contacts in terms of elastic transmission amplitudes, and use this theory to calculate the inelastic tunneling spectra of the gold-PDT-gold extended molecules. We consider PDT molecules with both trans and gauche conformations bound to the gold clusters at top, bridge, and hollow bonding sites. Comparing our results with the experimental data of Hihath et al. [Nano Lett. 8, 1673 (2008)], we identify the most frequently realized conformation in the experiment as that of trans molecules top-site bonded to both electrodes. We find the switching from the 42 meV vibrational mode to the 46 meV mode observed in the experiment to be due to the transition of trans molecules from mixed top-bridge to pure top-site bonding geometries. Our results also indicate that gauche molecular conformations and hollow site bonding did not contribute significantly to the experimental inelastic tunneling spectra. For pairs of PDT molecules connecting the gold electrodes in parallel we find total elastic conductances close to twice those of single molecules bridging the contacts with similar bonding conformations and small splittings of the vibrational mode energies for the modes that are the most sensitive to the molecule-electrode bonding geometries. 相似文献
149.
From readily available starting materials, six 1,3‐dialkyl‐imidazolinium bromides ( 2a–f ) have been prepared and characterized by conventional spectroscopic methods and elemental analyses. The incorporation of saturated N‐heterocyclic carbenes into palladium precatalysts gives high catalyst activity in the Suzuki coupling of deactivated aryl chloride substrates in aqueous media. The complexes were generated in the presence of Pd(OAc)2 by in situ deprotonation of 2a–f . © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:557–561, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20140 相似文献
150.
In this study, the metastable zone width of potassium tetraborate tetrahydrate was determined for four different temperatures and cooling rates. The induction period of potassium tetraborate tetrahydrate in aqueous solution was examined according to polythermal method by using visual observation. The induction period, which changes inversely proportional to the nucleation rate has been used to determine the interfacial tension between the potassium tetraborate tetrahydrate and aqueous solution. By using interfacial tension, the nucleation parameters such as Gibbs free energy change for the formation of critical nucleus, ΔG*, free energy of formation, ΔG, radius of critical nucleus, r and number of molecules in the critical nucleus, i* has been calculated. The effect of Li+ and Ca2+ impurities on metastable zone width has been studied. The metastable zone width of aqueous solution of potassium tetraborate tetrahydrate decreases with increasing impurity concentrations. The equilibrium saturation concentration change is high in the presence of Ca2+ ions while it is low in the presence of Li+ ions. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献