Electroreductive polymerization of trans-[RuCl 2(vpy) 4] on Nd-Fe-B magnets: electrochemical impedance spectroscopy interpretation, Raman spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy analysis

The electropolymerization of trans-[RuCl₂(vpy)₄] (vpy=4-vinylpyridine) monomer on Nd-Fe-B magnets was studied by electrochemical impedance spectroscopy (EIS). Impedance diagrams obtained during the polymerization process were used to monitor film formation. The EIS results gave insight into the electrochemical phenomena occurring at the magnet surface as the polymerization process progressed. The film structure and morphology were also studied by X-ray photoelectron spectroscopy, scanning electron microscopy and Raman spectroscopy. The Raman spectroscopy results showed that the polymerization takes place at the vinyl groups of the monomer and also that the redox polymer structure is very similar to that of the monomer. The ratio of the intensity of the XPS peaks for fluorine (from the electrolyte PF₆ ^–) and ruthenium present in the film showed that the polymer on Nd-Fe-B contained an equal proportion of Ru²⁺ and Ru³⁺, indicating that part of the film is positively charged, i.e. {[RuCl₂(vpy)₄]⁺} _n .     

Mixed biopolymer systems based on starch

A binary mixture of starch-starch or starch with other biopolymers such as protein and non-starch polysaccharides could provide a new approach in producing starch-based food products. In the context of food processing, a specific adjustment in the rheological properties plays an important role in regulating production processing and optimizing the applicability, stability, and sensory of the final food products. This review examines various biopolymer mixtures based on starch and the influence of their interaction on physicochemical and rheological properties of the starch-based foods. It is evident that the physicochemical and rheological characteristics of the biopolymers mixture are highly dependent on the type of starch and other biopolymers that make them up mixing ratios, mixing procedure and presence of other food ingredients in the mixture. Understanding these properties will lead to improve the formulation of starch-based foods and minimize the need to resort to chemically modified starch.     

All Non-Carbon B3NO2 Exotic Heterocycles: Synthesis,Dynamics, and Catalysis

The B₃NO₂ six-membered heterocycle (1,3-dioxa-5-aza-2,4,6-triborinane=DATB), comprising three different non-carbon period 2 elements, has been recently demonstrated to be a powerful catalyst for dehydrative condensation of carboxylic acids and amines. The tedious synthesis of DATB, however, has significantly diminished its utility as a catalyst, and thus the inherent chemical properties of the ring system have remained virtually unexplored. Here, a general and facile synthetic strategy that harnesses a pyrimidine-containing scaffold for the reliable installation of boron atoms is disclosed, giving rise to a series of Pym-DATBs from inexpensive materials in a modular fashion. The identification of a soluble Pym-DATB derivative allowed for the investigation of the dynamic nature of the B₃NO₂ ring system, revealing differential ring-closing and -opening behaviors depending on the medium. Readily accessible Pym-DATBs proved their utility as efficient catalysts for dehydrative amidation with broad substrate scope and functional-group tolerance, offering a general and practical catalytic alternative to reagent-driven amidation.     

Absorption of diltiazem in beagle dog from pulsatile release tablet.

An orally applicable pulsatile drug delivery system in dry-coated tablet form was prepared using diltiazem hydrochloride as the model drug, and a polyvinyl chloride-hydrogenated castor oil-polyethyleneglycol mixture as the outer shell of the tablet. In vitro drug release from the prepared tablet exhibited a typical pulsatile pattern with a 7 h lag phase (non-drug release period). This dosage form was orally administered to three beagle dogs under non-fasting and fasting conditions, and the plasma concentration level of diltiazem was determined according to time after administration. The result of the in vivo study in non-fasting dogs suggested that the drug could be released in the gastrointestinal tract as in the in vitro test. However, under the fasting condition, a large difference in the plasma concentration profile was found, suggesting that the disintegration time of the tablet tended to be influenced by the feeding condition of subject.     

Proposal of sampling process for collecting human sweat and determination of caffeine concentration in it by using GC/MS

Caffeine concentration in human sweat was estimated by measuring separately the amounts of water and caffeine. After washing a finger with tap water for 15 s and waiting 2 min for drying, 70 microL aqueous ethanol solution in a small vial (0.6 mL) was used to sample for several minutes. Then 3 microL of the aliquot was used for GC/MS analysis of caffeine. As a first-order relationship between the sweat amount secreted on the left and right hands was obtained (correlation factor 0.848), the amount of sweat secretion during sampling on one hand was estimated by the value obtained on the other hand. This new indirect evaluation was used for the estimation of the amount of sweat secreted during sampling. Typical variations of caffeine concentration in sweat were demonstrated. Thirty minutes after the intake of caffeine, it was secreted in sweat, and the secretion had continued for more than 4 h.     

Continuous process for ATRP: Synthesis of homo and block copolymers

Continuous ATRP of MMA was carried out in a flow tubular reactor with varying flow rate, temperature, and [monomer]/[initiator] ratios. Changing the flow rate directly relates to the reaction time. This process produces polymer continuously with the conversion increasing with decreasing flow rate. The molecular weight (relating to the flow rate) increases linearly with conversion which is also observed when the [monomer]/[initiator] ratio was changed. The effect of altering the reaction temperature was studied and the apparent activation energy of the propagation reaction of MMA in this system was calculated to be ∼56.9 kJ mol⁻¹, close to the values reported previously. Preparation of diblock copolymers is also reported with varying comonomers and the conversion, and SEC results suggested that this continuous system is an excellent and facile way to have a continuous ATRP process.     

Some novel layered-silicate nanocomposites based on a biodegradable hydroxybutyrate copolymer

This paper describes the preparation, characterization, mechanical properties and thermal stability of layered silicate nanocomposites based on poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHB-co-PHH, known as Nodax^TM). The dispersed phases were organically modified montmorillonites (clay 20A and clay 25A), mica, and talc, and they were introduced by solution mixing. Wide-angle X-ray scattering results and transmission electron microscopy (TEM) images confirmed that these two clays were intercalated and finely distributed in the Nodax^TM matrix. This type of layered filler led to remarkable improvements in mechanical properties even at very low loadings. Minimizing aggregation was more of a problem in the case of the mica and the talc, at least in this particular matrix. In some cases, these layered fillers slightly decreased the thermal stability of the Nodax^TM.     

Direct Estimation of the Surface Location of Immobilized Functional Groups for Concerted Catalysis Using a Probe Molecule

The location of active sites during concerted catalysis by a metal complex and tertiary amine on a SiO₂ surface is discussed based on the interaction between the functionalized SiO₂ surface and a probe molecule, p‐formyl phenylboronic acid. The interactions of the probe molecule with the surface functionalities, diamine ligand, and tertiary amine, were analyzed by FT‐IR and solid‐state ¹³C and ¹¹B MAS NMR. For the catalyst exhibiting high 1,4‐addition activity, the diamine ligand and tertiary amine base exist in closer proximity than in the catalyst with low activity.     

Orientation control of perovskite thin films on glass substrates by the application of a seed layer prepared from oxide nanosheets

Orientation control of perovskite compounds was investigated by the application of a seed layer prepared from oxide nanosheets. An aqueous suspension of oxide nanosheets was prepared by the exfoliation of a layered compound of KCa₂Nb₃O₁₀ oxide grains. A seed layer composed of (TBA)Ca₂Nb₃O₁₀ nanosheets (TBA = tetrabutylammonium) was formed on a glass substrate by simply dip coating it in the suspension. Two kinds of perovskite compounds, LaNiO₃ (LNO) and Pb(Zr,Ti)O₃ (PZT) with a preferred orientation of (00l) were successfully grown on this seeded glass substrate. In this study, the relation between lattice mismatch and electrical properties is investigated. A large, oriented PZT film with a size of 5 ×4 cm shows an improved P-E hysteresis behavior by use of this orientation control.