全文获取类型
收费全文 | 595篇 |
免费 | 61篇 |
国内免费 | 195篇 |
专业分类
化学 | 743篇 |
晶体学 | 2篇 |
力学 | 6篇 |
综合类 | 2篇 |
数学 | 1篇 |
物理学 | 97篇 |
出版年
2023年 | 5篇 |
2022年 | 6篇 |
2021年 | 14篇 |
2020年 | 25篇 |
2019年 | 12篇 |
2018年 | 14篇 |
2017年 | 19篇 |
2016年 | 25篇 |
2015年 | 32篇 |
2014年 | 44篇 |
2013年 | 51篇 |
2012年 | 27篇 |
2011年 | 38篇 |
2010年 | 46篇 |
2009年 | 43篇 |
2008年 | 39篇 |
2007年 | 47篇 |
2006年 | 45篇 |
2005年 | 44篇 |
2004年 | 36篇 |
2003年 | 33篇 |
2002年 | 34篇 |
2001年 | 22篇 |
2000年 | 27篇 |
1999年 | 12篇 |
1998年 | 26篇 |
1997年 | 12篇 |
1996年 | 15篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 6篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1968年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有851条查询结果,搜索用时 15 毫秒
41.
Li‐Jun Yang Kun Jiang Jun‐Jie Tan Shi‐Jin Qu Hong‐Feng Luo Chang‐Heng Tan Da‐Yuan Zhu 《Helvetica chimica acta》2013,96(1):119-123
Chemical investigation on the stem and root of Melicope pteleifolia afforded three new prenylated benzene metabolites as racemic mixtures, named pteleifolins A–C ( 1 – 3 , resp.). Their gross structures were elucidated on the basis of spectroscopic analysis, especially 2D‐NMR experiments. An enantiomer resolution of (±)‐ 1 using chiral HPLC was performed, and the absolute configuration of the enantiomers were determined to be (+)‐(S)‐ 1 and (?)‐(R)‐ 1 by means of circular‐dichroism analysis. 相似文献
42.
Acid catalysed epoxy ring opening of several lupane type triterpenoids leads to unusual allylic hydroxylation. The reaction involves the formation of epoxide by m‐chloroperbenzoic acid followed by the treatment of mineral acid. The simple methodology finds utility to introduce a hydroxyl function at the allylic position in these triterpenoids, which is otherwise quite difficult. 相似文献
43.
A novel and convenient synthetic route for preparing aza-phthalimidine hydroxylactams (5a–j) by N-bromosuccinimide (NBS) was developed. This method involved the substitution reactions of substrates (3a–j) with NBS via unstable intermediate bromides (4a–j) rapidly hydrolyzed into hydroxyl products in the course of the workup process. 相似文献
44.
Pavel F. Vlad Alexandru G. Ciocarlan Mihai N. Coltsa Alexandr V. Baranovsky Natalya B. Khripach 《合成通讯》2013,43(22):3960-3972
This article describes a new efficient synthesis of drim-7,9(11)-diene and its hydroxylated derivates from drim-8-en-7-one. Reduction of this ketone with NaBO4 in the presence of CeCl3 · 7H2O afforded regio- and stereoselectively drim-8-en-7β-ol in a high yield. Its dehydration with H2SO4 under mild conditions led to drim-7,9(11)-diene. Noncatalytic oxidation of drim-7,9(11)-diene with OsO4 and the catalytic oxidation with the pair OsO4–NMO gave, in a high yield, depending on conditions, driman-7β,8β,9α,11-tetraol or its mixture with drim-7-en-9α,11-diol and drim-9(11)-en-7α,8α-diol. Under optimal conditions the total yield of these diols reached 89%. The separate, noncatalytic oxidation of drim-7-en-9α,11-diol and of drim-9(11)-en-7α,8α-diol with OsO4 afforded driman-7α,8α,9α,11-tetraol. 相似文献
45.
A compact measurement system based on a novel combination of cantilever enhanced photoacoustic spectroscopy (CEPAS) and optical parametric oscillator (OPO) was applied to the gas phase measurement of benzene, toluene, and o-, m- and p-xylene (BTX) traces. The OPO had a band width (FWHM) of 1.3 nm, was tuned from 3237 to 3296 nm in steps of 0.1 nm and so spectra of BTX at different concentrations were recorded. The power emitted by the OPO increased from 88 mW at 3237 nm to 103 mW at 3296 nm. The univariate detection limits (3σ, 0.951 s) for benzene, toluene, p-, m- and o-xylene at 3288 nm were 12.0, 9.8, 13.2, 10.1 and 16.0 ppb, respectively. Multivariate data analysis using science-based calibration was used to resolve the interference of the analytes. The multivariate detection limits (3σ, 3237–3296 nm, 591 spectral points each 0.951 s) for benzene, toluene, p-, m- and o-xylene in the multi-compound sample, where all other analytes and water interfere were 4.3, 7.4, 11.0, 12.5 and 6.2 ppb, respectively. Without interferents, the multivariate detection limits varied between 0.5 and 0.6 ppb. The sum of the cross-selectivities (3237–3296 nm, 591 spectral points, each 0.951 s) per analyte were below 0.05 ppb/ppb, with an average of 0.038 ppb/ppb. The cross-selectivity of water to the analytes was on average 1.22 × 10−4 ppb/ppb. The OPO is small in size (L × W × H 125 × 70 × 45 mm), commercially available, and easy to operate and integrate to setups. The combination with sensitive CEPAS enables compact measurement systems for industrial as well as environmental trace gas monitoring. 相似文献
46.
Dr. Yan‐Fen Fang Prof. Wan‐Hong Ma Prof. Ying‐Ping Huang Prof. Gen‐Wei Cheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(9):3224-3229
The band structure of multicomponent semiconductor photocatalysts, as well as their reactivity distinction under different wavelengths of light, is still unclear. BiOBr, which is a typical multicomponent semiconductor, may have two possible valence‐band structures, that is, two discrete valence bands constructed respectively from O 2p and Br 4p orbitals, or one valence band derived from the hybridization of these orbitals. In this work, aqueous photocatalytic hydroxylation is applied as the probe reaction to investigate the nature and reactions of photogenerated holes in BiOBr. Three organic compounds (microcystin‐LR, aniline, and benzoic acid) with different oxidation potentials were selected as substrates. Isotope labeling (H218O as the solvent) was used to determine the source of the O atom in the hydroxyl group of the products, which distinguishes the contribution of different hydroxylation pathways. Furthermore, a spin‐trapping ESR method was used to quantify the reactive oxygen species (.OH and .OOH) formed in the reaction system. The different isotope abundances of the hydroxyl O atom of the products formed, as well as the reverse trend of the .OH/.OOH ratio with the oxidative resistance of the substrate under UV and visible irradiation, reveal that BiOBr has two separate valence bands, which have different oxidation ability and respond to UV and visible light, respectively. This study shows that the band structure of semiconductor photocatalysts can be reliably analyzed with an isotope labeling method. 相似文献
47.
Minami Odagi Kota Furukori Tatsuya Watanabe Prof. Dr. Kazuo Nagasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16740-16745
Highly enantioselective catalytic oxidation of 1‐tetralone‐derived β‐keto esters was achieved by using a guanidine–urea bifunctional organocatalyst in the presence of cumene hydroperoxide (CHP), a safe, commercially available oxidant. The α‐hydroxylation products were obtained in 99 % yield with up to 95 % enantiomeric excess (ee). The present oxidation was successfully applied to synthesize a key intermediate of the anti‐cancer agent daunorubicin ( 2 ). 相似文献
48.
Transition-metal free direct C–H arylation of benzene with aryl halides was achieved by meso-aryl-substituted [14]triphyrins(2.1.1) catalysts in an air atmosphere. Various aryl halides underwent successful direct C–H arylation of benzene to give moderate to high yields of biaryls. A radical mechanism is proposed for this triphyrin catalyzed C–H arylation reaction. 相似文献
49.
Non-thermal plasma (NTP) and combined plasma-MnO2 catalytic (CPMC) air cleaners were tested for removal of low-concentration benzene in air. Both air cleaners were made of stainless steel needle matrix plate and used DC corona discharger. The effects of discharge power and relative humidity (RH) on benzene removal efficiency were investigated in a closed chamber. The intermediate products produced in purification processes were analyzed using gas chromatography-mass spectrometer (GC-MS). The concentrations of discharge byproducts and CO2 selectivity produced in both processes were also compared. It was found that the benzene removal efficiency increased with discharge power in both systems; With the increase of RH in air, benzene removal efficiency firstly increased and then decreased in NTP while it gradually decreased in CPMC. For a fixed discharge power of 9 W and RH of 20% in CPMC, the conversion of benzene increased from 82.9% to 89.6%, the CO2 selectivity increased from 38% to 80%, the concentration of O3 decreased from 25.3 ppm to 1.3 ppm, and NO2 formation decreased from 234 ppm to 25.7 ppm, compared with NTP. 相似文献
50.
Highly Efficient CH Hydroxylation of Carbonyl Compounds with Oxygen under Mild Conditions 下载免费PDF全文
A transition‐metal‐free Cs2CO3‐catalyzed α‐hydroxylation of carbonyl compounds with O2 as the oxygen source is described. This reaction provides an efficient approach to tertiary α‐hydroxycarbonyl compounds, which are highly valued chemicals and widely used in the chemical and pharmaceutical industry. The simple conditions and the use of molecular oxygen as both the oxidant and the oxygen source make this protocol very environmentally friendly and practical. This transformation is highly efficient and highly selective for tertiary C(sp3)? H bond cleavage. 相似文献