全文获取类型
收费全文 | 121篇 |
免费 | 7篇 |
国内免费 | 1篇 |
专业分类
化学 | 101篇 |
力学 | 1篇 |
数学 | 19篇 |
物理学 | 8篇 |
出版年
2023年 | 3篇 |
2022年 | 3篇 |
2021年 | 1篇 |
2020年 | 3篇 |
2019年 | 1篇 |
2018年 | 3篇 |
2017年 | 2篇 |
2016年 | 4篇 |
2015年 | 6篇 |
2014年 | 3篇 |
2013年 | 9篇 |
2012年 | 8篇 |
2011年 | 12篇 |
2010年 | 4篇 |
2009年 | 9篇 |
2008年 | 7篇 |
2007年 | 7篇 |
2006年 | 7篇 |
2005年 | 7篇 |
2004年 | 6篇 |
2003年 | 2篇 |
2002年 | 7篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1993年 | 1篇 |
1991年 | 2篇 |
1985年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有129条查询结果,搜索用时 296 毫秒
21.
Antonella Fontana Paolo Lo Meo Stefano Morganti Egon Rizzato Romina Zappacosta 《Tetrahedron》2008,64(4):733-740
Rate constants, kA,R, for the rearrangement of the (Z)-phenylhydrazones (1a-e) of a series of 5-alkyl-3-benzoyl-1,2,4-oxadiazoles substituted at C(5) with linear alkyl chains of different length (from C4 up to C12) into the relevant 4-acylamino-2,5-diphenyl-1,2,3-triazoles (2a-e) have been measured in dioxan/water in the base-catalyzed region (pS+ 10.5-12.6). For each substrate log kA,R are linearly related to pS+. The significant decrease of the slopes of these straight lines (from 0.96 down to 0.78) upon increasing the length of the linear alkyl chain at C(5) and that of the reactivity (down to 14-26%) upon increasing the substrate concentration suggest a decrease of the polarity of the ‘actual’ reaction medium and provide indirect evidence of the tendency of the substrates (Z)-1a-e to self-assemble. To confirm the above outcome direct evidence of the formation of self-assemblies in solution were obtained from 1H NMR and spectrofluorimetry measurements while ESI-MS experiments point out the presence of aggregated substrates also in the gas phase. 相似文献
22.
Petroselli G Dántola ML Cabrerizo FM Capparelli AL Lorente C Oliveros E Thomas AH 《Journal of the American Chemical Society》2008,130(10):3001-3011
UV-A radiation (320-400 nm) induces damage to the DNA molecule and its components through different photosensitized reactions. Among these processes, photosensitized oxidations may occur through electron transfer or hydrogen abstraction (type I) and/or the production of singlet molecular oxygen ((1)O2) (type II). Pterins, heterocyclic compounds widespread in biological systems, participate in relevant biological processes and are able to act as photosensitizers. We have investigated the photosensitized oxidation of 2'-deoxyguanosine 5'-monophosphate (dGMP) by pterin (PT) in aqueous solution under UV-A irrradiation. Kinetic analysis was employed to evaluate the participation of both types of mechanism under different pH conditions. The rate constant of (1)O2 total quenching (k(t)) by dGMP was determined by steady-state analysis of the (1)O2 NIR luminescence, whereas the rate constant of the chemical reaction between (1)O2 and dGMP (k(r)) was evaluated from kinetic analysis of concentration profiles obtained by HPLC. The results show that the oxidation of dGMP photosensitized by PT occurs through two competing mechanisms that contribute in different proportions depending on the pH. The dominant mechanism in alkaline media involves the reaction of dGMP with (1)O2 produced by energy transfer from the PT triplet state to molecular oxygen (type II). In contrast, under acidic pH conditions, where PT and the guanine moiety of dGMP are not ionized, the main pathway for dGMP oxidation involves an initial electron transfer between dGMP and the PT triplet state (type I mechanism). The biological implications of the results obtained are also discussed. 相似文献
23.
Petroselli G Erra-Balsells R Cabrerizo FM Lorente C Capparelli AL Braun AM Oliveros E Thomas AH 《Organic & biomolecular chemistry》2007,5(17):2792-2799
UV-A radiation (320-400 nm) induces damages to the DNA molecule and its components through photosensitized reactions. Pterins, heterocyclic compounds widespread in biological systems, participate in relevant biological processes and are able to act as photosensitizers. We have investigated the photosensitization of 2'-deoxyadenosine-5'-monophosphate (dAMP) by pterin (PT) in aqueous solution under UV-A radiation. The effect of pH was evaluated, the participation of oxygen was investigated and the products analyzed. Kinetic studies revealed that the reactivity of dAMP towards singlet oxygen (1O2) is very low and that this reactive oxygen species does not participate in the mechanism of photosensitization, although it is produced by PT upon UV-A excitation. In contrast, analysis of irradiated solutions by means of electrospray ionization mass spectrometry strongly suggested that 8-oxo-7,8-dihydro-2'-deoxyadenosine-5'-monophosphate (8-oxo-dAMP) was produced, indicating that the photosensitized oxidation takes place via a type I mechanism (electron transfer). 相似文献
24.
Cabrerizo FM Dántola ML Petroselli G Capparelli AL Thomas AH Braun AM Lorente C Oliveros E 《Photochemistry and photobiology》2007,83(3):526-534
Pterins (PTs) belong to a class of heterocyclic compounds present in a wide range of living systems. They participate in relevant biological functions and are involved in different photobiological processes. We have investigated the reactivity of conjugated PTs (folic acid [FA], 10-methylfolic acid [MFA], pteroic acid [PA]) and unconjugated PTs (PT, 6-hydroxymethylpterin [HPT], 6-methylpterin [MPT], 6,7-dimethylpterin [DPT], rhamnopterin [RPT]) with singlet oxygen (1O2) in aqueous solutions, and compared the efficiencies of chemical reaction and physical quenching. The chemical reactions between 1O2, produced by photosensitization, and PT derivatives were followed by UV-visible spectrophotometry and high-performance liquid chromatography, and corresponding rate constants (k(r)) were evaluated. Whenever possible, products were identified and quantified. Rate constants of 1O2 total quenching by the PT derivatives investigated were obtained from steady-state 1O2 luminescence measurements. Results show that the behavior of conjugated PTs differs considerably from that of unconjugated derivatives, and the mechanisms of 1O2 physical quenching by these compounds and of their chemical reaction with 1O2 are discussed in relation to their structural features. 相似文献
25.
AndrsH. Thomas Gustavo Surez FrancoM. Cabrerizo AlbertoL. Capparelli 《Helvetica chimica acta》2001,84(12):3849-3860
6‐formylpterin solutions at pH 11 were photolyzed at 350 nm at room temperature. The photochemical reactions were followed by UV/VIS spectrophotometry, thin layer chromatography (TLC), and high‐performance liquid chromatography (HPLC). In the presence of oxygen, 6‐carboxypterin is the only photoproduct detected by the analytical techniques mentioned. In the absence of oxygen, a new compound showing an absorbance maximum at 480 nm is observed. The latter compound is thermally oxidized very fast in the presence of oxygen to 6‐carboxypterin. The quantum yields of substrate disappearance and of photoproduct formation are reported 相似文献
26.
27.
Pulsed electrochemical detection (PED) following reversed-phase liquid chromatography (LC) has been applied recently to the detection of ethyl glucuronide (EtG) in the urine of live and deceased individuals. In this paper, several key improvements to the method are made to enhance sensitivity, reproducibility, and accuracy. These improvements include (i) further optimization of the sample preparation procedure that has increased the recovery from ca. 50% to 84 ± 3% in synthetic urine matrix; (ii) changing the internal standard from methyl glucuronide (MetG) to propyl glucuronide (ProG), which does not elute within the interference of the matrix; and (iii) altering the mobile phase of the separation from acetonitrile to t-butanol to virtually eliminate signal suppression in PED. As a consequence, detection limits have been reduced to 0.01 μg mL−1, reproducibility has been improved by a factor of two, and sample size has been reduced five-fold. Blind studies in synthetic urine showed no significant difference between the amount recovered and the true value determined at the 95% confidence level for all samples. Importantly, PED requires no derivatization, and it can detect virtually all glucuronides. 相似文献
28.
Florian D. Jochum F. Romina Forst Patrick Theato 《Macromolecular rapid communications》2010,31(16):1456-1461
A series of thermo‐responsive PNIPAM copolymers containing different amounts of fulgimide moieties has been synthesized via a polymer analogous reaction of poly(pentafluorophenyl acrylate). All copolymers were designed to exhibit a lower critical solution temperature (LCST) in water, which was only weakly dependent on the amount of incorporated chromophoric fulgimide groups. The copolymers showed a photocyclization of the fulgimide side groups upon irradiation with UV‐light accompanied with a color change. The closed form of the chromophore had a halftime of 136 min for the visible reisomerization and did not affect the LCST of the polymer. This led to the realization of a logic “NOT A” for the fulgimide containing PNIPAM, while a corresponding azobenzene containing PNIPAM resulted in a different logic “A implies B”.
29.
A thermodynamic model for multicomponent mixtures is derived introducing the Carnahan and Starling expression for the free volume in the van der Waals partition function. The derivation of the model is equivalent to the one for the Prigogine-Flory-Patterson (PFP) model, and our results are compared with those of the PFP model.Expressions for the equation of state, excess properties, thermal expansion and thermal pressure coefficients are given. The values of the characteristic parameters for some molecules are calculated, and the results of predicted excess properties are compared with those already known for the PFP model. The discussion of binary mixtures is centred on the families of systems formed by benzene or cyclohexane and an alkane. 相似文献
30.