Flavonol Glycosides and Iridoids from Asperula lilaciflora

A new flavonol glycoside, quercetin 3‐O‐[6′′′‐O‐3,5‐dihydroxycinnamoyl‐β‐glucopyranosyl‐(1→2)]‐β‐galactopyranoside (named lilacifloroside; 1 ) and a new iridoid 2 (named asperulogenin), were isolated from the aerial parts of Asperula lilaciflora in addition to eight known secondary metabolites, i.e., quercetin, kaempferol, quercetin 3‐O‐β‐glucopyranosyl‐(1→2)‐β‐galactopyranoside, quercetin 3‐O‐β‐glucopyranosyl‐(1→2)‐arabinopyranoside, asperuloside, deacetylasperulosidic acid, asperulosidic acid methyl ester, and chlorogenic acid. The structures were elucidated on the basis of extensive 1D‐ and 2D‐NMR experiments as well as MS data. Compound 1 contains the rare 3,5‐dihydroxycinnamoyl moiety in its structure. This work constitutes the first phytochemical study of the title plant.     

Recognition-directed orthogonal self-assembly of polymers and nanoparticles on patterned surfaces

We demonstrate the patterning of silica substrates with thymine (Thy-PS) and positively charged N-methylpyridinium (PVMP) polymers using photolithography and the subsequent orthogonal modification of these surfaces using diaminopyridine-functionalized polystyrene (DAP-PS) and carboxylate-derivatized CdSe/ZnS core-shell nanoparticles (COO-NP) through diamidopyridine-thymine three-point hydrogen bonding and pyridinium-carboxylate electrostatic interactions, respectively. This two-component orthogonal surface modification was accomplished in a self-sorting, single-step fashion, providing a versatile tool for the rapid and efficient creation of complex materials.     

Direct DNA Hybridization on the Single‐Walled Carbon Nanotubes Modified Sensors Detected by Voltammetry and Electrochemical Impedance Spectroscopy

Carboxylic acid functionalized single‐walled carbon nanotubes modified graphite sensors (SWCNT‐PGEs) were developed for electrochemical monitoring of direct DNA hybridization related to specific sequence of Hepatitis B virus, which substantially enhance the electrochemical transduction resulting from guanine oxidation signal comparison to bare PGEs. The performance characteristics of DNA hybridization on disposable CNT‐PGE were explored measuring the guanine signal in terms of optimum analytical conditions; probe and target concentration, hybridization time, and selectivity. The voltammetric results were also complemented with electrochemical impedance spectroscopy (EIS), that was used to characterize the successful construction of carbon nanotubes modification onto the surface of PGEs.     

1H magnetic resonance spectroscopy of the normal testis: preliminary findings

PURPOSE: The purpose of this study was to determine the pre- and postpubertal 1H magnetic resonance spectroscopic characteristics of the normal testis to establish baseline values for further clinical studies. MATERIALS AND METHODS: The subjects consisted of male volunteers, of whom 19 were prepubertal with ages between 7 and 13 years and 24 were postpubertal with ages between 19 and 39 years. Their testes were evaluated at 1.5 T with magnetic resonance spectroscopy; in addition, testis volumes were measured. Major metabolite peaks were identified and their ratios were calculated. Metabolite differences of testis between pre- and postpubertal age were analyzed. RESULTS: Major constituents of spectra were 3.21 ppm choline and 0.9-1.3 ppm lipid peaks. At the echo time (TE) spectrum of 31 ms, choline/lipid ratios ranged from 0.35 to 8.30 (mean=1.87) in postpubertal males and from 0.06 to 5.45 (mean=0.88) in prepubertal males (P<.013). At the TE spectrum of 136 ms, choline/lipid ratios ranged from 0.66 to 15.42 (mean=4.09) in postpubertal males and from 0.05 to 4.91 (mean=0.9) in prepubertal males (P<.016). CONCLUSIONS: Choline/lipid ratio was higher in the postpubertal period. The existence of higher choline peak in that age group should be due to the initiation of spermatogenesis. The decrease in the lipid peak may represent the effect of testosterone on testicular tissue or may be due to histochemical changes initiated by puberty. The significant decrease in choline/lipid ratio noted after puberty could represent the presence of spermatogenesis. This hypothesis should be evaluated by further studies on postpubertal subjects with impaired spermatogenesis.     

Orthogonal Nanoparticle Catalysis with Organogermanes

Although nanoparticles are widely used as catalysts, little is known about their potential ability to trigger privileged transformations as compared to homogeneous molecular or bulk heterogeneous catalysts. We herein demonstrate (and rationalize) that nanoparticles display orthogonal reactivity to molecular catalysts in the cross‐coupling of aryl halides with aryl germanes. While the aryl germanes are unreactive in L_nPd⁰/L_nPd^II catalysis and allow selective functionalization of established coupling partners in their presence, they display superior reactivity under Pd nanoparticle conditions, outcompeting established coupling partners (such as ArBPin and ArBMIDA) and allowing air‐tolerant, base‐free, and orthogonal access to valuable and challenging biaryl motifs. As opposed to the notoriously unstable polyfluoroaryl‐ and 2‐pyridylboronic acids, the corresponding germanes are highly stable and readily coupled. Our mechanistic and computational studies provide unambiguous support of nanoparticle catalysis and suggest that owing to the electron richness of aryl germanes, they preferentially react by electrophilic aromatic substitution, and in turn are preferentially activated by the more electrophilic nanoparticles.     

Electrochemical Behavior and Ultrasensitive,Simple and Effective Voltammetric Determination of Acetaminophen Using Modified Glassy Carbon Electrode Based on 4-Hydroxyquinoline-3-carboxylic Acid

An electrochemical oxidation of acetaminophen (ACOP) has been successfully performed by using glassy carbon electrode covered with 4-hydroxyquinoline-3-carboxylic acid (4HQ3CA) to reinforce electrode's feature. To characterize the modified electrode (4HQ3CA/GC), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and Fourier transform infrared spectroscopy (FT-IR) techniques were used. The finding optimum conditions (supporting electrolyte, pH) and the electrochemical determination studies were performed with differential pulse voltammetry (DPV). It was decided that the supporting electrolyte medium suitable for ACOP determination was Britton-Robinson (BR) buffer and the effect of pH change on the oxidation peak of ACOP in this media was investigated. The effect of changing scan rate on the oxidation peak of ACOP was examined and this study showed that the oxidation process of ACOP on the 4HQ3CA/GC modified electrode surface was diffusion and adsorption controlled process. A wide concentration range from 0.0025 μM to 141 μM with a limit of detection (LOD) of 5.98×10⁻¹⁰ M (3 s/m) was obtained. This prepared sensor was carried out for the determination of ACOP in pharmaceutical sample.     

Interaction of pentafluoroguanidine with fluoronitro-containing alcohols

Russian Chemical Bulletin -     

Dissipative photonic lattice solitons

We show that discrete dissipative optical lattice solitons are possible in waveguide array configurations that involve periodically patterned semiconductor optical amplifiers and saturable absorbers. The characteristics of these low-power soliton states are investigated, and their propagation constant eigenvalues are mapped on Floquet-Bloch band diagrams. The prospect of observing such low-power dissipative lattice solitons is discussed in detail.