全文获取类型
收费全文 | 183篇 |
免费 | 8篇 |
专业分类
化学 | 141篇 |
晶体学 | 3篇 |
力学 | 2篇 |
数学 | 4篇 |
物理学 | 41篇 |
出版年
2023年 | 1篇 |
2022年 | 3篇 |
2021年 | 4篇 |
2020年 | 6篇 |
2019年 | 2篇 |
2018年 | 3篇 |
2017年 | 2篇 |
2016年 | 5篇 |
2015年 | 10篇 |
2014年 | 11篇 |
2013年 | 21篇 |
2012年 | 15篇 |
2011年 | 14篇 |
2010年 | 4篇 |
2009年 | 11篇 |
2008年 | 13篇 |
2007年 | 12篇 |
2006年 | 17篇 |
2005年 | 7篇 |
2004年 | 6篇 |
2003年 | 6篇 |
2002年 | 7篇 |
2001年 | 1篇 |
2000年 | 3篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1982年 | 2篇 |
排序方式: 共有191条查询结果,搜索用时 31 毫秒
71.
72.
Matthiesen JE Jose D Sorensen CM Klabunde KJ 《Journal of the American Chemical Society》2012,134(22):9376-9379
Gold-acetone-dodecanethiol and gold-acetone-phenylethanethiol colloids were prepared by the solvated metal atom dispersion method. Hydrogen evolution occurred at fairly low temperature, when the melting acetone-gold solvate encountered the thiol molecules, due to S-H bond scission. The gas inside the reactor was analyzed by gas chromatography, and the moles of H(2) was determined by calibration curves obtained from a series of known concentration samples. The gold-to-thiolate ratio was calculated using thermal gravimetric analysis. The average particle diameter was also calculated using the gold-to-thiolate ratio. 相似文献
73.
The singlet potential‐energy surface (PES) of the system involving the atoms H, X, and E (the (H, X, E) system) in which X=N–Bi and E=C–Pb has been explored at the CCSD(T)/TZVPP and BP86/TZ2P+ levels of theory. The nature of the X? E bonding has been analyzed with charge‐ and energy‐partitioning methods. The calculations show that the linear isomers of the nitrogen systems lin ‐HEN and lin ‐HNE are minima on the singlet PES. The carbon compound lin ‐HCN (HCN=hydrogen cyanide) is 14.9 kcal mol?1 lower in energy than lin ‐HNC but the heavier group 14 homologues lin ‐HEN (E=Si–Pb) are between 64.8 and 71.5 kcal mol?1 less stable than the lin ‐HNE isomers. The phosphorous system (H, P, E) exhibits significant differences concerning the geometry and stability of the equilibrium structures compared with the nitrogen system. The linear form lin ‐HEP of the former system is much more stable than lin ‐HPE . The molecule lin ‐HCP is the only minimum on the singlet PES. It is 78.5 kcal mol?1 lower in energy than lin ‐HPC , which is a second‐order saddle point. The heavier homologues lin ‐HPE , in which E=Si–Pb, are also second‐order saddle points, whereas the bent ‐HPE structures are the global minima on the PES. They are between 10.3 (E=Si) and 36.5 kcal mol?1 (E=Pb) lower in energy than lin ‐HEP . The bent ‐HPE structures possess rather acute bending angles H‐P‐E between 60.1 (E=Si) and 79.7° (E=Pb). The energy differences between the heavier group 15 isomers lin ‐HEX (X=P–Bi) and the bent structures bent ‐HXE become continuously smaller. The silicon species lin ‐HSiBi is even 3.1 kcal mol?1 lower in energy than bent ‐HBiSi . The bending angle H‐X‐E becomes more acute when X becomes heavier. The drastic energy differences between the isomers of the system (H, X, E) are explained with three factors that determine the relative stabilities of the energy minima: 1) The different bond strength between the hydrogen bonds H? X and H? E. 2) The electronic excitation energy of the fragment HE from the X 2Π ground state to the 4Σ? excited state, which is required to establish a E≡X triple bond in the molecules lin ‐HEX . 3) The strength of the intrinsic X? E interactions in the molecules. The trends of the geometries and relative energies of the linear, bent, and cyclic isomers are explained with an energy‐decomposition analysis that provides deep insight into the nature of the bonding situation. 相似文献
74.
K.S. Sibi A.N. Radhakrishnan M. Deepa P. Prabhakar Rao Peter Koshy 《Solid State Ionics》2009,180(20-22):1164-1172
CaREZrNbO7 (RE = La, Nd, Sm, Gd and Y) system changed from fluorite (F)-type to pyrochlore (P)-type structure when the ionic radius ratios, r(Ca2+–RE3+)av/r(Zr4+–Nb5+)av were larger than 1.34. Thus, the La, Nd, and Sm compounds have a cubic P-type structure and the Gd and Y ones have a defect F-type structure. The electrical conductivity was measured using complex-plane impedance analysis over a wide temperature (300–750 °C) and frequency (1 Hz–1 MHz) ranges. The conductivity relaxation phenomenon was observed in these compounds and the relaxation frequencies were found to show Arrhenius-type behavior and activation energies were in good agreement with those obtained from high temperature conductivity plots. These results support the idea that the relaxation process and the conductivity have the same origin. The ionic conductivity of CaREZrNbO7 (RE = La, Nd, Sm, Gd and Y) system showed the maximum at the phase boundary between the F-type and P-type phases. On the other hand, the activation energy for the conduction decreased in the F-type phase and increased in the P-type phase with increasing ionic radius ratio. Among the prepared compounds, CaGdZrNbO7 showed the highest ionic conductivity of 9.47 × 10− 3 S/cm at 750 °C which was about twice as high as that observed in Gd2Zr2O7 (4.2 × 10− 3 S/cm at 800 °C). The grain morphology observation by scanning electron microscope (SEM) showed well-sintered grains. AC impedance measurements in various atmospheres further indicated that they are predominantly oxide ion conductors at elevated temperatures (> 700 °C). 相似文献
75.
A.N. Radhakrishnan P. Prabhakar Rao K.S. Sibi M. Deepa Peter Koshy 《Journal of solid state chemistry》2009,182(8):2312-2318
Order–disorder transformations in a quaternary pyrochlore oxide system, Ca–Y–Zr–Ta–O, were studied by powder X-ray diffraction (XRD) method, transmission electron microscope (TEM) and FT-NIR Raman spectroscopic techniques. The solid solutions in different ratios, 4:1, 2:1, 1:1, 1:2, 1:4, 1:6, of CaTaO3.5 and YZrO3.5 were prepared by the conventional high temperature ceramic route. The XRD results and Rietveld analysis revealed that the crystal structure changed from an ordered pyrochlore structure to a disordered defect fluorite structure as the ratios of the solid solutions of CaTaO3.5 and YZrO3.5 were changed from 4:1 to 1:4. This structural transformation in the present system is attributed to the lowering of the average cation radius ratio, rA/rB as a result of progressive and simultaneous substitution of larger cation Ca2+ for Y3+ at A sites and smaller cation Ta5+ for Zr4+ at B sites. Raman spectroscopy and TEM analysis corroborated the XRD results. 相似文献
76.
Dr. Sasi Divya Satya Narayan Prof. Sri Rama Koti Ainavarapu Prof. Deepa Khushalani 《Chemphyschem》2019,20(7):984-990
High quantum yield, photoluminescence tunability, and sensitivity to the environment are a few distinct trademarks that make carbon nanodots (CDs) interesting for fundamental research, with potential to replace the prevalent inorganic semiconductor quantum dots. Currently, application and fundamental understanding of CDs are constrained because it is difficult to make a quantitative comparison among different types of CDs simply because their photoluminescence properties are directly linked to their size distribution, the surface functionalization, the carbon core structures (graphitic or amorphous) and the number of defects. Herein, we report a facile one-step synthesis of mono-dispersed and highly fluorescent nanometre size CDs from a ‘family’ of glucose-based sugars. These CDs are stable in aqueous solutions with photoluminescence in the visible range. Our results show several common features in the family of CDs synthesized in that the fluorescence, in the visible region, is due to a weak absorption in the 300–400 nm from a heterogeneous population of fluorophores. Fluorescence quenching experiments suggest the existence of not only surface-exposed fluorophores but more importantly solvent inaccessible fluorophores present within the core of CDs. Interestingly, time-resolved fluorescence anisotropy experiments directly suggest that a fast exchange of excitation energy occurs that results in a homo-FRET based depolarization within 150 ps of excitation. 相似文献
77.
Minju Kim Kandhasamy Sowndhararajan Ponnuvel Deepa Songmun Kim 《Molecules (Basel, Switzerland)》2022,27(21)
The genus Thymus (Lamiaceae) contains numerous medicinally important species. Among them, Thymus quinquecostatus Celak. has been extensively utilized as a traditional medicine and a food flavoring agent in the Korean peninsula, owing to its unique aroma. In particular, T. quinquecostatus has been used for the treatment of gastroenteritis, inflammation, stomach problems, liver disease, arthritis, arteriosclerosis, and menstrual problems. This study aimed to investigate the chemical diversity of essential oils among 103 Korean native populations of T. quinquecostatus. For this purpose, seedlings of T. quinquecostatus populations were purchased from different regions in the Korean Peninsula, and seedlings were grown in the experimental field under the same environmental conditions. The chemical compositions of steam-distilled essential oils were determined using GC-MS. In total, 212 components were identified from 103 populations of T. quinquecostatus. Furthermore, principal component analysis (PCA) was performed in order to understand variations in the essential oil compositions among 103 Korean native populations of T. quinquecostatus. According to the essential oil compositions, 30 components were selected for PCA. Based on the most abundant essential oil components, four chemotypes were identified in T. quinquecostatus populations. PCA and cluster analyses revealed that 103 individuals of T. quinquecostatus could be classified into four clusters, such as thymol, geraniol, geranyl acetate, and linalool. Furthermore, dendrogram construction demonstrated that geraniol and geranyl acetate, as well as linalool and thymol groups, were closely related. This study suggested the significant chemical polymorphism of essential oils in local populations of T. quinquecostatus in Korea. It could be concluded that the intraspecific variations in the essential oil compositions may be associated with genetic diversity among the individuals. 相似文献
78.
79.
A reversible ‘turn-on’ sensor has been designed for ‘naked-eye’ detection of oxalate at nanomolar concentration (~12.5?nM) at pH 7.4. The sensory system shows a highly specific response towards oxalate among a wide range of antinutrients and biologically relevant anionic species. Mechanistic investigations indicate that oxalate can turn the pink-colored solution colorless by dissociating the preformed metal complex. Additionally, high specificity and good accuracy with recovery values ranging from 93.3 to 105.0% were obtained during oxalate estimation in spiked water and human urine samples, confirming the suitability of the present method in estimating trace-level of oxalate in complex matrices. With these results, quantitative estimations of endogenous oxalate were achieved in more than twenty-five different agricultural crops. Finally, low-cost, portable paper strips were developed for on-site detection of oxalate. 相似文献
80.
Isonicotinic acid hydrazide or isonicotinylhydrazide, commonly known as isoniazid, is an antibacterial agent that has been
used to treat tuberculosis. It interacts with microbial cell walls. Schiff’s bases or anils are the compounds having >C=N−N<
linkages, which have immense applications as catalysts, stabilizers, pigments, dyes, and drugs. They have good ability to
form chelates with many metal ions. Isoniazid can form Schiff’s bases with diketones such as acetoacetanilide. Acetoacetanilide
isonicotinylhydrazone and its metal chelates exhibit anticancer activity. Our studies on N-methyl-acetoacetanilide isonicotinylhydrazone and its metal chelates revealed that they are active against pathogenic fungal
strains. Hence, it is worthwhile to synthesize new complexes of ligands having different substituents on the acetoacetanilide
moiety. We synthesized five new metal chelates of ω-bromoacetoacetanilide isonicotinylhydrazone. The ligand behaved as a tridentate
monoanion or as a tridentate dianion in the complexes. These compounds were characterized mainly by elemental analysis; conductivity
measurements; and electronic, infrared, and nuclear magnetic resonance spectral studies. We also carried out antifungal studies
of these compounds against four selected pathogenic fungal strains using a cup-plate technique. Both the ligand and its metal
chelates were active against all fungal strains investigated. However, the chelates were found to be more active than the
ligand. 相似文献