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31.
Extraordinary Changes in the Electronic Structure and Properties of CdS and ZnS by Anionic Substitution: Cosubstitution of P and Cl in Place of S 下载免费PDF全文
Summayya Kouser S. R. Lingampalli Dr. P. Chithaiah Anand Roy Sujoy Saha Prof. Umesh V. Waghmare Prof. C. N. R. Rao 《Angewandte Chemie (International ed. in English)》2015,54(28):8149-8153
Unlike cation substitution, anion substitution in inorganic materials such as metal oxides and sulfides would be expected to bring about major changes in the electronic structure and properties. In order to explore this important aspect, we have carried out first‐principles DFT calculations to determine the effects of substitution of P and Cl on the properties of CdS and ZnS in hexagonal and cubic structures and show that a sub‐band of the trivalent phosphorus with strong bonding with the cation appears in the gap just above the valence band, causing a reduction in the gap and enhancement of dielectric properties. Experimentally, it has been possible to substitute P and Cl in hexagonal CdS and ZnS. The doping reduces the band gap significantly as predicted by theory. A similar decrease in the band gap is observed in N and F co‐substituted in cubic ZnS. Such anionic substitution helps to improve hydrogen evolution from CdS semiconductor structures and may give rise to other applications as well. 相似文献
32.
Dong Cao Huogao Huang Ming Hu Lin Cui Fanglan Geng Ziyu Rao Hongyun Niu Yaqi Cai Yuehui Kang 《Analytica chimica acta》2015
Natural organic matter (NOM) is a complex and non-uniform mixture of organic compounds which plays an important role in environmental processes. Due to the complexity, it is challenging to obtain fully detailed structural information about NOM. Although Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) has been demonstrated to be a powerful tool for providing molecular information about NOM, multiple ionization methods are needed for comprehensive characterization of NOM at the molecular level considering the ionizing selectivity of different ionization methods. This paper reports the first use of matrix assisted laser desorption/ionization (MALDI) method coupled with FT-ICR-MS for molecular characterization of NOM within a mass range of 200–800 Da. The mass spectral data obtained by MALDI were systematically compared with data generated by electrospray ionization (ESI). It showed that complementary molecular information about NOM which could not be detected by ESI, were provided by MALDI. More unsaturated and aromatic constituents of NOM with lower O/C ratio (O/C ratio < 0.5) were preferentially ionized in MALDI negative mode, whereas more polar constituents of NOM with higher O/C ratio were preferentially ionized in ESI negative mode. Molecular anions of NOM appearing at even m/z in MALDI negative ion mode were detected. The results show that NOM molecules with aromatic structures, moderate O/C ratio (0.7 > O/C ratio > 0.25) and lower H/C ratio were liable to form molecular anions at even m/z, whereas those with higher H/C ratio are more likely to form deprotonated ions at odd m/z. It is speculated that almost half of the NOM molecules identified by MALDI may be aromatic or condensed aromatic compounds with special groups which are liable to absorb electron from other molecules to generate free radical anions during MALDI ionization. 相似文献
33.
Sivaiah Areti Jayshree K. Khedkar Sateesh Bandaru Rohit Teotia Jayesh Bellare Chebrolu Pulla Rao 《Analytica chimica acta》2015
A coumarine–imino–C2-glucosyl conjugate (L) was synthesized and characterized. The conjugate L is found to recognize Cu2+ in aqueous HEPES buffer by exhibiting a 95% fluorescence quenching in pH range 7–10 even in the presence of several biologically and ecologically relevant metal ions. Fluorescence on–off behavior has been clearly demonstrated on the basis of the binding variability of Cu2+ to L. The binding has been elicited through the changes observed in fluorescence, absorption, ESI-MS and 1H NMR titrations. All the other thirteen metal ions studied did not show any change in the fluorescence emission. These ions do not interfere with the recognition of Cu2+ by L. The structural features of [CuL]2 complex in both the isomeric forms were established by DFT computational calculations. The utility of L has been demonstrated by showing its sensitivity toward Cu2+ on a thin layer of silica gel. The L gives sensitive fluorescence signals for Cu2+ even in blood serum and exhibits appropriate fluorescence responses in living cells. 相似文献
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35.
First Stereoselective Synthesis of the Cytotoxic Polyketide (4R)‐1‐(3,5‐Dihydroxyphenyl)‐4‐hydroxypentan‐2‐one 下载免费PDF全文
Kothakonda Rajendra Prasad Sudina Purushotham Reddy Katragadda Suresh Babu Janaswamy Madhusudana Rao 《Helvetica chimica acta》2015,98(1):143-147
The first stereoselective synthesis of the cytotoxic polyketide (4R)‐1‐(3,5‐dihydroxyphenyl)‐4‐hydroxypentan‐2‐one ( 1 ) was achieved from readily available propylene oxide and 3,5‐dimethoxybenzyl alcohol. The synthesis involves Jacobsen's hydrolytic kinetic resolution (HKR) and Grignard reaction as key steps. 相似文献
36.
Alkyne‐Mediated Approach to the Synthesis of (4R,5R)‐5‐Hydroxy‐4‐decanolide and (−)‐Muricatacin 下载免费PDF全文
The asymmetric synthesis of two naturally occurring 5‐hydroxy‐γ‐butyrolactones, (4R,5R)‐5‐hydroxy‐4‐decanolide ( 1a ) and (?)‐muricatacin ( 2 ), is described using a general alkyne‐mediated strategy. The key steps involved are Sonogashira coupling for the desired carbon‐chain extension followed by Sharpless asymmetric dihydroxylation to construct the hydroxy‐lactone framework. 相似文献
37.
An Efficient,Multicomponent Synthesis of Pyrazolyl Triazolo Thiadiazinyl Chromen ‐ 2 ‐ Ones 下载免费PDF全文
One‐pot synthesis of 3‐(3‐(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)‐7H‐[1,2,4]triazolo[3,4‐b][1,3,4]thiadiazin‐6‐yl)‐2H‐chromen‐2‐ones was achieved via the multicomponent reaction of purpald, acetyl acetone, and different derivatives of 3‐(2‐bromo‐acetyl)‐2H‐chromen‐2‐one in absolute ethanol. All the synthesized compounds were characterized by analytical and spectral data. 相似文献
38.
An Efficient Synthesis of 3‐(3‐benzyl‐2‐(phenylimino)‐2,3‐dihydrothiazol‐4‐yl)‐6‐methyl‐4‐(2‐oxo‐2‐phenylethoxy)‐3,4‐dihydro‐2H‐pyran‐2‐one Derivatives via Multi‐Component Approach 下载免费PDF全文
An easy, highly efficient and a new convenient one‐pot, two‐step approach to the synthesis of 3‐(3‐benzyl‐2‐(phenylimino)‐2,3‐dihydrothiazol‐4‐yl)‐6‐methyl‐4‐(2‐oxo‐2‐phenylethoxy)‐3,4‐dihydro‐2H‐pyran‐2‐one is described. These compounds were synthesized from 3‐(3‐benzyl‐2‐(phenylimino)‐2,3‐dihydrothiazol‐4‐yl)‐4‐hydroxy‐6‐methyl‐3,4‐dihydro‐2H‐pyran‐2‐one and α‐bromoketones in good yields. The compounds 4 were synthesized by a multi‐component reaction between 1 , 2 , and 3 and the prominent features of this protocol are mild reaction conditions, operation simplicity, and good to high yields of products. 相似文献
39.
40.
Screening of drugs of abuse and toxic compounds in human whole blood using online solid‐phase extraction and high‐performance liquid chromatography with time‐of‐flight mass spectrometry 下载免费PDF全文
Xiaomei Teng Chen Liang Rong Wang Tao Sun Yulan Rao Chunfang Ni Libo Zeng Lingjuan Xiong Yuan Li Yurong Zhang 《Journal of separation science》2015,38(1):50-59
A novel method for the screening of 151 drugs of abuse and toxic compounds in human whole blood has been developed and validated by online solid‐phase extraction with liquid chromatography coupled to time‐of‐flight mass spectrometry. Analytes were extracted and separated by using a fully automated online solid‐phase extraction liquid chromatography system with total chromatographic run time of 26 min. Time‐of‐flight mass spectrometry screening of 151 drugs of abuse and toxic compounds was performed in a full‐scan (m/z 50–800) mode using an MSE acquisition of molecular ions and fragment ions data at two collision energies (one was 6 eV and another one was in the range of 5–45 eV). The compounds were identified based on retention times and exact mass of molecular ions and fragment ions. The limit of detection ranged from 1 to 100 ng/mL and the recovery of the method ranged from 6.3 to 163.5%. This method is proved to be a valuable screening method allowing fast and specific identification of drugs in human whole blood. 相似文献