Speciation of aqueous chromium(VI) solutions with the aid of Q-mode factor analysis followed by oblique projection

The identities of the species of chromium(VI) that are present in aqueous solution, their spectra and their equilibria, continue to be a subject of discussion in the literature. In this paper, the composition of the Cr(VI) equilibria was estimated from the UV-vis spectra of dilute potassium dichromate solutions, without any prior knowledge of the quantities of pure components, with the aid of Imbrie Q-mode factor analysis (Q-mode FA) followed by Varimax rotation and Imbrie oblique projection. Combining these results with the k-matrix method, it was possible to obtain the spectra of the individual Cr(VI) species. Sets of 3.3x10(-4) and 3.3x10(-5) mol l(-1) Cr(VI) solutions were studied. In the pH range from 1 to 12, two factors were identified, which were related to the two species, chromate ion (CrO(4)(2-)) and bichromate ion (HCrO(4)(-)). When the analysis was extended to concentrated acid media, another factor appeared, which was related to chromic acid (H(2)CrO(4)). No evidence for the dichromate ion (Cr(2)O(7)(2-)) was seen at the Cr(VI) concentrations used. The spectra of the pure components were obtained and pK values for the first and second chromic acid dissociations were estimated as -0.54 and 5.8, respectively.     

Ring-hydrogen participation in the keto--enol isomerization of the acetophenone radical cation

Molecular ions obtained from acetophenone have been observed to undergo proton transfer reactions in competition with unimolecular blackbody dissociation in a Fourier transform ion cyclotron resonance spectrometer provided with an in situ high temperature blackbody source. The ionizing energy dependence of these two processes and generation of the enol molecular ion by fragmentation of butyrophenone reveal that the keto ion undergoes blackbody dissociation exclusively while the enol ion promotes fast proton transfer reactions and undergoes very slow blackbody induced dissociation. Experiments with labeled acetophenone either on the methyl group or on the ring reveal that the enol ions can transfer both H+ and D+ suggesting that the mechanism responsible for the tautomerization process of these radical cations may involve scrambling of the methyl and ring hydrogens, or more than one mechanism. Theoretical calculations at the B3LYP level predict that the most favorable pathway for unimolecular isomerization of the keto ion involves initial migration of an ortho hydrogen to the carbonyl. The subsequent rearrangement to the enol form is calculated to require enough internal energy that would allow hydrogen walk around the benzene ring in agreement with the experimental results. The possibility that isomerization may also occur by a direct 1,3-hydrogen migration is also explored in terms of possible excited electronic states of the ion.     

Simultaneous determination of potassium nitrate and sodium monofluorophosphate in dentifrices by single column ion chromatography

The simultaneous determination of potassium nitrate and sodium monofluorophosphate in dentifrices by single column ion chromatography is described. Nitrate and monofluorophosphate are extracted from the dentifrice with deionized water and separated by a low capacity anion separator column with 0.2% sodium benzoate (adjusted to pH 5.8 +/- 0.1 with formic acid) as the mobile phase. A conductivity meter is used for concentration measurements. The method has been applied to commercial dentifrices containing both potassium nitrate and sodium monofluorophosphate. The mean recoveries for potassium nitrate and monofluorophosphate from spiked samples were 99.0% and 99.2%, respectively, with corresponding standard deviations of 1.73% and 2.55%. The minimum detectable concentration is 5 micrograms/ml for both nitrate and monofluorophosphate.     

Crystal structures and melting thermodynamics of N-acetylsarcosinamide and N-acetyl-L-isoleucinamide

Crystal structures together with enthalpies and temperatures of fusion of two substituted amino acids, N-acetylsarcosinamide (NASarA) and N-acetyl-L-isoleucinamide (NAIA), were determined by single crystal X-ray analysis and differential scanning calorimetry, respectively. The results were compared with those of some analogous amino acid derivatives previously studied. The detailed knowledge of crystallographic parameters is undoubtedly useful for discussing the thermodynamic results and rationalizing the fusion behaviour, owing to the rather poor knowledge of the molecular interactions occurring in the melt.Associated to the National Institute for the Chemistry of Biological Systems-CNRThe authors thank prof. Guido Barone for useful discussions.     

Low-intensity pulsed ultrasound (LIPUS) and cell-to-cell communication in bone marrow stromal cells

Low-intensity pulsed ultrasound (LIPUS) is an established therapy for fracture repair and has been used widely in the clinics, but its underlying mechanism of action remains unclear. The aim of the current research was to determine the effect of LIPUS on gap junctional cell-to-cell intercellular communication in rat bone marrow stromal cells (BMSC) in vitro and to determine whether the ability of BMSCs to communicate by gap junctions would affect their response to LIPUS. Single or daily-multiple LIPUS treatment at 1.5 MHz, 30 mW/cm², for 20 min was applied to BMSC. We demonstrated that BMSC form functional gap junctions and single LIPUS treatment significantly increased the intracellular dye transfer between BMSC. In addition, activated phosphorylation of ERK1/2 and p38 by LIPUS stimulation was diminished when cells were treated with a gap junction inhibitor 18β-glycyrrhetinic acid (18β). We further demonstrated that 18β diminished the significant increase in alkaline phosphatase activity following LIPUS stimulation. These results suggest a potential role of gap junctional cell-to-cell intercellular communication on the effects of LIPUS in BMSC.     

Direct determination of trans-resveratrol in human plasma by spectrofluorimetry and second-order standard addition

Trans-resveratrol (RVT) is an antioxidant found in red grapes and their derivatives, which has been related to the reduction of cardiovascular diseases and cancer incidence.This work developed a new spectrofluorimetric-chemometric method for the direct determination of RVT in human plasma. For each measurement, excitation-emission matrices were obtained from 280 to 360 nm (excitation) and from 380 to 550 nm (emission). The strategy adopted in this work combined data treatment with parallel factor analysis (PARAFAC), for extracting the pure analyte signal, using the standard addition method, which permits determinations in the presence of a strong matrix effect caused by plasma analyte-protein binding. Plasma samples were diluted 10 times and, for each, four standard additions of RVT were performed, in triplicate. A specific PARAFAC model was built for the three replicates of each sample, from three-way arrays formed by five measurements (initial sample plus four additions), 17 excitation wavelengths and 86 emission wavelengths. The best models were selected with four factors and accounted for more than 99.90% of the data variance. The loadings obtained were related to RVT and three interferences. The scores related to the analyte were used for linear regressions and all standard addition curves presented correlation coefficients equal or greater than 0.99. Good results were obtained in the concentration range from 0.10 to 5.00 μg mL⁻¹, with recoveries between 94.0 and 110.0%. The proposed method was also validated through the estimates of several figures of merit: sensitivity, analytical sensitivity, selectivity, precision, and limits of detection and quantitation.     

Industrial cutting waste granite dust reinforced cardanol benzoxazine/epoxy resin hybrid composites for high-voltage electrical insulation applications

An attempt has been made to develop hybrid composites from benzoxazine monomer (C-ddm) hybridized with DGEBA epoxy resin (EP) and reinforced with varying weight percentages (20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt%) of glycidoxypropyltrimethoxy- silane (GPTMS) functionalized granite dust (GD) obtained from industrial granite cutting and polishing process in order to utilize them for electrical insulation applications. The thermal stability of granite dust reinforced poly(EP-co-C-ddm) composites was studied by TGA analysis. Among the composites samples studied, 100 wt% GD reinforced poly(EP-co-C-ddm) composites possess better thermal stability than that of other neat matrices and composites. Among the composites prepared using varying weight percentages of functionalized GD reinforcement, it was observed that 80 wt% GD reinforced poly(EP-co-C-ddm) composites possesses better hydrophobic character than that of other neat matrices and composites. The value of LOI calculated for neat matrix (poly[EP-co-C-ddm]) and 20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt% GD reinforced composites was found to be 22, 28, 34, 40, 43 and 45 respectively. The 80 wt% GD reinforced poly(EP-co-C-ddm) composites possess the higher values of tensile strength and flexural strength of 47 MPa and 140 MPa, respectively than those of their samples. The values of electrical surface resistivity and electrical volume resistivity of all the neat matrices and GD reinforced polybenzoxazine composites were found to be in the order of 10¹² and 10¹³ respectively. The values of dielectric strength obtained from break down voltage (BDV) for neat matrix [poly(EP-co-C-ddm)] and 20 wt%, 40 wt%, 60 wt%, 80 wt% and 100 wt% of GD reinforced poly(EP-co-C-ddm) composites are 15.0, 15.5, 16.5, 17.0, 17.0 and 17.0 kV/mm, respectively. Data obtained from thermal stability, hydrophobic behavior and dielectric studies it was inferred that the hybrid polymer composites developed in the present work can be conveniently used in the form insulators, sealants, adhesives and matrices where application demands at high-performance industrial and engineering applications.