High pressure DSC of phenolformaldehyde moulding compounds

The influence of pressure on the polycondensation reaction between novolac resin (N) present in commercially available moulding compounds and hexamethylenetetramine (HMTA) was studied up to 80 bars under air and in an inert atmosphere. For a low HMTA content (N/HMTA=98/2 mass ratio) high pressure enables the detection of two successive curing reactions. With increasing HMTA content the peak due to the first curing reaction becomes less pronounced at high pressure, while the enthalpy of the second increases. In an inert atmosphere both curing reactions are well observable even at ambient pressure and for lower HMTA content take place at lower temperatures, as expected. For the sample with N/HMTA=98/2 the curing reaction was followed using TG-MS.     

Bismuth film electrode for anodic stripping voltammetric determination of tin

The bismuth film electrode (BiFE), in combination with anodic stripping voltammetry, offers convenient measurement of low concentrations of tin. The procedure involves simultaneous in situ formation of the bismuth film electrode on a glassy carbon substrate electrode, together with electrochemical deposition of tin, in a non-deaerated model solution containing bismuth ions, catechol as complexing agent and the metal analyte, followed by an anodic stripping scan. The BiFE is characterized by an attractive electroanalytical performance, with two distinct voltammetric stripping signals corresponding to tin, accompanied with low background contributions. Several experimental parameters were optimized, such as concentration of bismuth ions and catechol, deposition potential, deposition time and pH of the model solution. In addition, a critical comparison is given with bare glassy carbon and mercury film electrodes, revealing the superior characteristics of BiFE for measurement of tin. BiFE exhibited highly linear behavior in the examined concentration range from 1 to 100 μg L⁻¹ of tin (R² = 0.997), an LoD of 0.26 μg L⁻¹ tin, and good reproducibility with a calculated R.S.D. of 7.3% for 10 μg L⁻¹ tin (n = 10). As an example, the practical applicability of BiFE was tested with the measurement of tin in a real sample of seawater.     

Programmed Self‐Assembly of a Quadruplex DNA Nanowire

The ability to produce, reproducibly and systematically, well‐defined quadruplex DNA nanowires through controlled rational design is poorly understood despite potential utility in structural nanotechnology. The programmed hierarchical self‐assembly of a long four‐stranded DNA nanowire through cohesive self‐assembly of GpC and CpG “sticky” ends is reported. The encoding of bases within the quadruplex stem allows for an uninterrupted π‐stacking system with rectilinear propagation for hundreds of nanometers in length. The wire is mechanically stable and features superior nuclease resistance to double‐stranded DNA. The study indicates the feasibility for programmed assembly of uninterrupted quadruplex DNA nanowires. This is fundamental to the systematic investigation of well‐defined DNA nanostructures for uses in optoelectronic and electronic devices as well as other structural nanotechnology applications.     

Rheological Analysis of Biopolymer Produced by Aureobasidium Pullulans in Different Sources of Nitrogen

Summary: In this study, the rheological behaviors of media fermented by two Aureobasidium pullulans strains (IOC 3467 and IOC 3011) were evaluated in different nutritional conditions. The media consisted of crystal sugar (sucrose), as the main carbon source, and different nitrogen sources (ammonium sulfate, sodium nitrate, ammonium nitrate, urea or residual brewery yeast - RBY). Viscosity measurements were performed on cell-free supernatants, from 48-hour fermentation assays, at 25 ^°C. Shear rates ranged between 0.1000 and 500 s⁻¹. All samples showed pseudoplastic behavior. Nevertheless, the viscosimetric profile of each one varied according to the nitrogen source, its concentration and the strain used. The maximum viscosity of 0.06 Pa.s. was achieved at 15.6 s⁻¹ for IOC 3011 strain grown on RBY as nitrogen source.     

Rationally designed pincer-type heck catalysts bearing aminophosphine substituents: Pd IV intermediates and palladium nanoparticles

The aminophosphine-based pincer complexes [C6H3-2,6-(XP(piperidinyl)2)2Pd(Cl)] (X=NH 1; X=O 2) are readily prepared from cheap starting materials by sequential addition of 1,1',1'-phosphinetriyltripiperidine and 1,3-diaminobenzene or resorcinol to solutions of [Pd(cod)(Cl)2] (cod=cyclooctadiene) in toluene under N2 in "one pot". Compounds 1 and 2 proved to be excellent Heck catalysts and allow the quantitative coupling of several electronically deactivated and sterically hindered aryl bromides with various olefins as coupling partners at 140 degrees C within very short reaction times and low catalyst loadings. Increased reaction temperatures also enable the efficient coupling of olefins with electronically deactivated and sterically hindered aryl chlorides in the presence of only 0.01 mol % of catalyst. The mechanistic studies performed rule out that homogeneous Pd 0 complexes are the catalytically active forms of 1 and 2. On the other hand, the involvement of palladium nanoparticles in the catalytic cycle received strong experimental support. Even though pincer-type Pd IV intermediates derived from 1 (and 2) are not involved in the catalytic cycle of the Heck reaction, their general existence as reactive intermediates (for example, in other reactions) cannot be excluded. On the contrary, they were shown to be thermally accessible. Compounds 1 and 2 show a smooth halide exchange with bromobenzene to yield their bromo derivatives in DMF at 100 degrees C. Experimental observations revealed that the halide exchange most probably proceeded via pincer-type Pd IV intermediates. DFT calculations support this hypothesis and indicated that aminophosphine-based pincer-type Pd IV intermediates are generally to be considered as reactive intermediates in reactions with aryl halides performed at elevated temperatures.     

Tuning Single‐Molecule Dynamics in Functionalized Mesoporous Silica

Diffusion of single molecules of a substituted terrylene diimide dye in functionalized mesoporous silica films was monitored by single‐molecule fluorescence microscopy. By varying the chemical nature and density of the functional groups, the diffusion dynamics of the dye molecules can be controlled precisely. The picture shows a sketch of a dye molecule in a pore, diffusion data for different phenyl functionalization densities, and the trajectory of one molecule in a cyanopropyl‐functionalized film.

     

Hydrophosphination of boron–boron multiple bonds

Five compounds containing boron–boron multiple bonds are shown to undergo hydrophosphination reactions with diphenylphosphine in the absence of a catalyst. With diborenes, the products obtained are highly dependent on the substitution pattern at the boron atoms, with both 1,1- and 1,2-hydrophosphinations observed. With a symmetrical diboryne, 1,2-hydrophosphination yields a hydro(phosphino)diborene. The different mechanistic pathways for the hydrophosphination of diborenes are rationalised with the aid of density functional theory calculations.

Compounds containing boron–boron double and triple bonds are shown to undergo uncatalysed hydrophosphination reactions with diphenylphosphine.     

Influence of Cotton Pre-Treatment on Dyeing with Onion and Pomegranate Peel Extracts

In this paper the possibility of applying natural dyes on cellulose fibres were researched with respect to the impact of cotton material pre-treatment (scouring, chemical bleaching, mercerization and mordanting), using renewable sources of natural dyes (waste as a source). As mordants, metal salts of copper, aluminium and ferrum were used, and the influence on colour change as well as on fastness properties were analysed. The natural dyes were extracted from onion peel (Allium cepa L.) and pomegranate peel (Punica granatum L.). In spectrophotometric analysis performed of the plant extracts, the onion extract has peaks at 400 and 500 nm, resulting in red-orange colourations and the pomegranate extract shows a maximum at 400 nm, i.e., in the yellow region, which is characteristic of punicalin. Results show significant influence of cotton pre-treatments on colour appearance and fastness properties, caused by pre-treatments affecting the properties and structure of the cotton itself. The positive effect of mercerization on dye absorption and bonding is confirmed. For wash and light fastness properties, more satisfactory results have been obtained for yarns dyed with pomegranate peel natural dye, and the key importance of mordants for fastness properties has been confirmed.     

The Superacid HBr/AlBr3: Protonation of Benzene and Ordered Crystal Structure of [C6H7]+[Al2Br7]−

Crystalline and properly ordered protonated benzene as the [C₆H₇]⁺[Al₂Br₇]^??(C₆H₆) salt 1 are obtained by the combination of solid AlBr₃, benzene, and HBr gas. Compound 1 was characterized and verified by NMR, Raman and X‐Ray spectroscopy. This unexpected simple and straight forward access shows that HBr/AlBr₃ is an underestimated superacid that should be used more frequently.