The influence of nucleus density on optical properties in nucleated isotactic polypropylene

The effect and efficiency of three nucleating agents, a sorbitol based clarifier, a traditional heterogeneous nucleating agent and poly(vinylcyclohexane) (PVCH) was studied in polypropylene (iPP) homopolymer. The nucleating agents were added to iPP in different amounts; PVCH in 0–200 ppm, while the other two in 0–2000 ppm. Optical and mechanical properties were determined on injection molded plates or bars, respectively. Nucleation efficiency was studied by thermal analysis, while structure was characterized by polarized light (PLM), scanning electron (SEM) and atomic force microscopy (AFM). Nucleus density was calculated using the method of Lamberti, which is based on the kinetic theory of the crystallization developed by Lauritzen and Hoffmann. The results proved that the nucleating agents modify properties in different ways and extent. PVCH is very efficient already at small concentrations and increases the stiffness of iPP considerably more than the other two compounds. On the other hand, the clarifier and the traditional nucleating agent induce better optical properties even at smaller efficiency. The structure developing in the presence of the three nucleating agents is also different. The clarifier forms a network in iPP and induces the formation of a microcrystalline structure according to the former literature data. Microspherulitic structure develops in the presence of the heterogeneous nucleating agent studied, while relatively large supermolecular units form in iPP nucleated by PVCH even under the conditions of injection molding. The calculation of nucleus density by existing models and the comparison of the results to optical properties proved that haze is determined by the size of the supermolecular units of the polymer and this latter depends on nucleus density.     

Chiral discrimination of β‐3‐homo‐amino acids using the kinetic method

Chiral discrimination of seven enantiomeric pairs of β‐3‐homo‐amino acids was studied by using the kinetic method and trimeric metal‐bound complexes, with natural and unnatural α‐amino acids as chiral reference compounds and divalent metal ions (Cu²⁺ and Ni²⁺) as the center ions. The β‐3‐homo‐amino acids were selected for this study because, first of all, chiral discrimination of β‐amino acids has not been extensively studied by mass spectrometry. Moreover, these β‐3‐homo‐amino acids studied have different aromatic side chains. Thus, the emphasis was to study the effect of the side chain (electron density of the phenyl ring, as well as the difference between phenyl and benzyl side chains) for the chiral discrimination. The results showed that by the proper choice of a metal ion and a chiral reference compound, all seven enantiomeric pairs of β‐3‐homo‐amino acids could be differentiated. Moreover, it was noted that the β‐3‐homo‐amino acids with benzyl side chains provided higher enantioselectivity than the corresponding phenyl ones. However, increasing or decreasing the electron density of the aromatic ring by different substituents in both the phenyl and benzyl side chains had practically no role for chiral discrimination of β‐3‐homo‐amino acids studied. When copper was used as the central metal, the phenyl side chain containing reference molecules (S)‐2‐amino‐2‐phenylacetic acid (L ‐Phg) and (S)‐2‐amino‐2‐(4‐hydroxyphenyl)‐acetic acid (L ‐4′‐OHPhg) gave rise to an additional copper‐reduced dimeric fragment ion, [Cu^I(ref)(A)]⁺. The inclusion of this ion improved noticeably the enantioselectivity values obtained. Copyright © 2010 John Wiley & Sons, Ltd.     

Enzymatic hydrolysis of native cellulose nanofibrils and other cellulose model films: effect of surface structure

Model films of native cellulose nanofibrils, which contain both crystalline cellulose I and amorphous domains, were used to investigate the dynamics and activities of cellulase enzymes. The enzyme binding and degradation of nanofibril films were compared with those for other films of cellulose, namely, Langmuir-Schaefer and spin-coated regenerated cellulose, as well as cellulose nanocrystal cast films. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the changes in frequency and energy dissipation during incubation at varying enzyme concentrations and experimental temperatures. Structural and morphological changes of the cellulose films upon incubation with enzymes were evaluated by using atomic force microscopy. The QCM-D results revealed that the rate of enzymatic degradation of the nanofibril films was much faster compared to the other types of cellulosic films. Higher enzyme loads did not dramatically increase the already fast degradation rate. Real-time measurements of the coupled contributions of enzyme binding and hydrolytic reactions were fitted to an empirical model that closely described the cellulase activities. The hydrolytic potential of the cellulase mixture was found to be considerably affected by the nature of the substrates, especially their crystallinity and morphology. The implications of these observations are discussed in this report.     

UV Sensitivity of Vegetative and Reproductive Tissues of Two Antarctic Brown Algae is Related to Differential Allocation of Phenolic Substances

UV sensitivity of the vegetative and reproductive tissues of two Antarctic brown macroalgae was compared. Photosynthesis as well as the content and localization of phenolic substances were determined. Responses to UV radiation were quantified as chlorophyll fluorescence (F_v/F_m). Ascoseira mirabilis showed high UV tolerance, while in Cystosphaera jacquinotii F_v/F_m decreased by 15–21%, the receptacles being more tolerant than the vegetative blades. The phlorotannin contents showed an opposite pattern: the soluble fraction dominated in C. jacquinotii while in A. mirabilis the insoluble fraction was more abundant. Soluble phlorotannins were higher in the reproductive than in vegetative tissues in both species. Images of tissue cross‐sections under violet‐blue light excitation confirmed a high allocation of phenolic compounds (as blue autofluorescence) in C. jacquinotii, both in reproductive and vegetative blades. The allocation and proportions of the soluble and insoluble phlorotannins could be related with the observed UV tolerance of the vegetative and reproductive tissues.     

Ammonium ion mediated resorcarene capsules: ESI-FTICRMS study on gas-phase structure and ammonium ion affinity of tetraethyl resorcarene and its per-methylated derivative

The ammonium ion binding affinities of tetraethyl resorcarene (1) and its per-methylated derivative (2) were studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. Ten different ammonium ions were tested as guests for the resorcarenes. A strong tendency for complex formation was observed with all ammonium ions of size and charge distribution suitable for noncovalent interactions with the cavities of the resorcarene hosts 1 and 2. Although differences in ammonium ion affinities were observed between 1 and 2 due to the dissimilar conformations, the overall tendency was that increase in the degree of substitution and the length of carbon chain of the ammonium cation facilitated the complex formation until the sterical hindrance impeded the complexation. Dimeric as well as monomeric ammonium ion complexes were formed with resorcarene 1, but resorcarene 2 was unable to form the dimeric capsules because of the lack of H-bond donor possibilities. The nature of binding of the guest was further investigated with ion-molecule reactions and by determination of the single crystal X-ray structure of host 1 complexed with tetramethyl ammonium bromide.     

Electrospray ionization mass spectrometric studies of nucleophilic carbenes derived from pyrazolium and indazolium carboxylates

Pyrazolium-3-carboxylate and indazolium-3-carboxylate, which belong to the class of pseudo-cross-conjugated mesomeric betaines and which represent the electronically relevant partial structures of the betaine alkaloid Nigellicin, were examined by electrospray ionization mass spectrometry. These compounds decarboxylate to pyrazol-3-ylidene and indazol-3-ylidene. The formation of adducts of these new nucleophilic carbenes under the measurement conditions was examined.     

Monitoring of fluid motion in a micromixer by dynamic NMR microscopy

The velocity distribution of liquid flowing in a commercial micromixer has been determined directly by using pulsed-field gradient NMR. Velocity maps with a spatial resolution of 29 microm x 43 microm were obtained by combining standard imaging gradient units with a homebuilt rectangular surface coil matching the mixer geometry. The technique provides access to mixers and reactors of arbitrary shape regardless of optical transparency. Local heterogeneities in the signal intensity and the velocity pattern were found and serve to investigate the quality and functionality of a micromixer, revealing clogging and inhomogeneous flow distributions.     

Parameter study of electrospinning of polyamide-6

Importance of different solution and process parameters were evaluated in multi-nozzle electrospinning of polyamide-6. We were interested in how those parameters affect firstly on fibre diameters and fibre diameter distribution and secondly on production rate and disturbances of the process. The trial series was planned using orthogonal experimental design. Altogether eight parameters having three or two levels each were chosen for this study. The chosen solution parameters were polymer grade, viscosity of solution, salt content and solvent grade and process parameters, voltage, distance, nozzle size and feeding pressure of solution. This study was performed using continuous electrospinning equipment consisting of multiple nozzles and horizontal electric field. Literature findings about the influences of certain variables are often contradictory. These contradictions and their possible causes were discussed.     

Gas-phase oxidation and reduction of some 1-(2-benzothiazolyl)-3,5-diphenyl formazans. Complex formation with transition metals under laser desorption ionization

Five differently substituted 1-(2-benzothiazolyl)-3,5-diphenyl formazans were studied by laser desorption ionization (LDI) and matrix assisted laser desorption/ionization (MALDI) mass spectrometry. The best explanation of the results is that the formazan molecules are photoionized to molecular radical ions, which then further react by ion-molecule reactions. Supporting this proposal was the abundant formation of [M − H]⁺ ions under LDI. These ions are not observed at all under either electron or chemical ionization. Under MALDI, the extent of the oxidation process is clearly dependent on the ability of the matrix to act as a reducing agent. With transition metals the formazans formed singly charged 1:2 metal:formazan complexes. The most stable electronic configuration of the complex determined the oxidation state of the metal regardless of its initial oxidation state. In some cases, this process also demanded a gas-phase reduction of the formazan. The ionization efficiency and affinity for complex formation depended on the substituent at the 3-phenyl group; both were increased by an electron donating substituent. The formazans were also tested as potential matrices for MALDI. Reasonable results were observed for several groups of compounds; however, only the piperazine ligands produced higher quality spectra with formazans than with common commercial matrices.     

A mass spectrometric study of metal binding to osteocalcin

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry was used to investigate Ca(2+), Mg(2+), and La(3+) binding to bovine bone osteocalcin (OCN). OCN was shown to bind 3 mol Ca(2+) per mol protein. There was also evidence for the presence of four additional metal binding sites. Ca(2+) increased the formation of the OCN dimer. Mg(2+) bound to OCN to the same extent as Ca(2+) but did not induce the dimerization of OCN. La(3+) bound to a lesser extent than either Ca(2+) or Mg(2+) to OCN and, like Mg(2+), did not influence dimerization. Each Gla residue of OCN participates in Ca(2+) binding, whereas Mg(2+) binding may occur preferentially at sites other than Gla residues. This implies that the different natures of Ca(2+)- and Mg(2+)-containing OCN complexes influence the tendency of OCN to form a dimer.