Conformational analysis of the electron-transfer kinetics across oligoproline peptides using N,N-dimethyl-1,4-benzenediamine donors and pyrene-1-sulfonyl acceptors

Photoinduced intramolecular charge separation across proline-bridged donor-acceptor complexes of the type Pyr-(Pro)n-DMPD (where Pyr=pyrene-1-sulfonyl and DMPD=N,N-dimethyl-1,4-phenylenediamine) was studied. The steady-state emission spectrum for n=0, 1, 2, 3 showed an increase in emission intensity with the number of proline residues. Time-dependent emission measured by streak camera showed increasing emission signal amplitude with increasing n, along with a decrease in decay rate. In all these studies, Pyr-Pro was used as a control complex for the decay of the excited pyrene acceptor moiety without the donor DMPD. Detailed photon counting experiments carried out in DMF/water, DMF, and toluene showed single-exponential kinetics for n=0, 1 and multiexponential kinetics for n=2, 3. Rate constants observed in DMF are for n=0, k=approximately 5x10(10) s(-1); n=1, k=9.70x10(8) s(-1); n=2, k=35.9x10(8) s(-1) (70%) and 5.58x10(8) s(-1) (30%); and n=3, k=16.6x10(8) s(-1) (55%) and 3.87x10(8) s(-1) (45%). These results show that a significant percentage of the n=2 and n=3 molecules undergo faster electron transfer than for the n=1 case. Conformational analysis for Pyr-(Pro)n-DMPD molecules in water showed that whereas only one conformation is possible for n=1, eight are possible for n=2, and 32 are possible for n=3. Calculation of the free energy and electronic coupling for these conformers in water showed that only a few of these conformations have the appropriate energy and electronic coupling to be observed in the experimental time window from 20 ps to 20 ns. Assignment of the conformers undergoing electron transfer in Pyr-(Pro)n-DMPD for n=2 and 3 was based on the values for the n=1 case, for which the measured rate constant is approximately 10(9) s(-1) and the calculated electronic coupling matrix element Hda is 297 cm(-1). The similarity in ground state energy between the cis and trans conformers for n=2 and 3, their use in aqueous-organic and organic solvents, and the nature of the Pyr and DMPD acceptor and donor groups could be contributing causes for the multiexponential kinetics, which was not observed for the metal ion derivatives of proline peptides studied earlier in aqueous solution.     

Supramolecular structures and stereochemical versatility of azoquinoline containing novel rare earth metal complexes

Rare earth complexes of 5-(phenylazo)-8-hydroxyquinoline (HL) of composition [M(L)(2)X.H(2)O] [where M=La, Ce, Pr, Nd and X=NO(3)(-) or NCS(-)] have been prepared and characterized on the basis of their chemical analyses, (1)H NMR, magnetic measurements, conductance, and visible and IR spectral data. Composition, conductance and IR spectral data of the complexes show that the HL acts as a bidentate monobasic ligand. The visible spectra of Pr(3+) and Nd(3+) show characteristic f-f transitions, and the nephelauxetic effect (1-beta) of these transitions has been evaluated. These data indicate the weak involvement of the 4f orbitals in complex formation.     

Phytochemistry,Food Application,and Therapeutic Potential of the Medicinal Plant (Withania coagulans): A Review

Herbal plants have been utilized to treat and cure various health-related problems since ancient times. The use of Ayurvedic medicine is very significant because of its least reported side effects and host of advantages. Withania coagulans (Family; Solanaceae), a valuable medicinal plant, has been used to cure abnormal cell growth, wasting disorders, neural as well as physical problems, diabetes mellitus, insomnia, acute and chronic hepatic ailments. This review provides critical insight regarding the phytochemistry, biological activities, and pharmacognostic properties of W. coagulans. It has been known to possess diuretic, anti-inflammatory, anti-bacterial, anti-fungal, cardio-protective, hepato-protective, hypoglycemic, anti-oxidative, and anti-mutagenic properties owing to the existence of withanolides, an active compound present in it. Apart from withanolides, W. coagulans also contains many phytochemicals such as flavonoids, tannins, and β-sterols. Several studies indicate that various parts of W. coagulans and their active constituents have numerous pharmacological and therapeutic properties and thus can be considered as a new drug therapy against multiple diseases.     

Quantification of Caffeine and Chlorogenic Acid in Green and Roasted Coffee Samples Using HPLC-DAD and Evaluation of the Effect of Degree of Roasting on Their Levels

Chlorogenic acid and caffeine are among the important components in coffee beans, determining the taste and aroma. In addition, phenols and antioxidants content possess vital health values. The main aim of this study is to determine the levels of caffeine and chlorogenic acid in several coffee samples of different origins and degrees of roasting. The coffee samples were extracted using hot water. The levels of caffeine and chlorogenic acid were quantified using high-performance liquid chromatography (HPLC) equipped with a diode array detector, a reverse phase system, and an ODS column (C18). Total phenol and antioxidant contents were previously determined for the same samples. The results showed that the highest content of caffeine was found in the medium roasted coffee (203.63 mg/L), and the highest content of chlorogenic acid content was found in the green coffee (543.23 mg/L). The results demonstrated a negative correlation between the chlorogenic acid levels with the degree of roasting, while it showed a positive correlation between the caffeine levels with the degree of roasting till a certain point where the levels dropped in the dark roasted coffee. The origin of coffee samples did not show any effect on any of the measured variables. Antioxidant effects of coffee samples were largely determined by chlorogenic acid content.     

Efficient and green synthesis of tetrasubstituted pyrroles promoted by task-specific basic ionic liquids as catalyst in aqueous media

Synthesis of tetrasubstituted pyrroles by the three-component condensation reaction of acid chlorides, dialkyl acetylenedicarboxylates, and amino acids in the presence of various room-temperature ionic liquids (RTILs) as catalysts in water is reported. Among the ionic liquids used, the basic functionalized ionic liquid, butyl methyl imidazolium hydroxide [bmim]OH, was the most effective catalyst. The influence of reaction temperature, reaction time, and amount of ionic liquid on the reaction was investigated. The [bmim]OH/H₂O catalyst system could be reused for at least five recycles without appreciable loss of efficiency.     

N-Methylimidazole-promoted efficient synthesis of 1,3-oxazine-4-thiones under solvent-free conditions

Abstract  A novel method for oxazine ring formation is established using the reaction of ammonium thiocyanate and acid chlorides with napthols in the presence of N-methylimidazole to afford [1,3]oxazine-4-thione derivatives in excellent yields. Graphical abstract        

A synthesis of diethyl alkylsulfanylmethylmalonates catalyzed by KOH in an ionic liquid

Abstract  1-Ethyl-3-methylimidazolium bromide was used as a green recyclable alternative to volatile organic solvents for KOH catalyzed three-component synthesis of diethyl alkylsulfanylmethylmalonates from aldehydes, diethyl malonate, and alkylthiols. Graphical Abstract  A synthesis of diethyl alkylsulfanylmethylmalonates catalyzed by KOH in an ionic liquid      

The reaction of (N‐isocyanimino) triphenylphosphorane with (E)‐3‐aryl‐2‐ propenoic acid derivatives: One‐pot synthesis of 2‐[(E)‐2‐aryl‐1‐ethenyl]‐1,3,4‐oxadiazoles via intramolecular aza‐Wittig reaction

The reaction of (E)‐3‐aryl‐2‐propenoic acid derivatives with (N‐isocyanimino) triphenylphosphorane proceeds smoothly at room temperature to afford the corresponding 2‐[(E)‐2‐aryl‐1‐ethenyl]‐1,3,4‐oxadiazole via an intramolecular aza‐Wittig reaction in good yields under neutral conditions. The structures of the products were deduced from their IR, ¹H NMR, and ¹³C NMR spectra and mass spectrometry. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:612–616, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20701