Flow-induced crystallization in polymer melts: how Winter’s gelation concept fits into the picture

Nobody could expect that gelation times of many hours, which were observed in quiescent polymer melts below the melting temperature of the spherulites, would play a role in flow-induced crystallization. However, this role became obvious for an iPP, when special polarization optics were employed in the well-known arrangement of the Linkam CSS450 apparatus (parallel glass plate rheometer). With the aid of a λ-plate, the interference color red of first order was created in white polarized light. This sensitive interference color changes quickly into blue, when a small phase difference is added (with subtraction a yellow color is obtained). With the aid of the great number of blue halos, which came up at 145 °C after the cessation of flow, an oriented gelation was identified. It spreads faster over the sample than the spherulites. The unwieldy gelation times, which have been found in quiescent melts, seem to be the consequence of a shortage of nuclei.     

Determining pesticide contamination in honey by LC-ESI-MS/MS – Comparison of pesticide recoveries of two liquid–liquid extraction based approaches

Honey, a valuable food product, may be contaminated by xenobiotics during its production and/or harvest. The determination of trace levels of contaminants in a complex matrix like honey still presents a challenge to analytical chemists. The aim of this work was to assess and compare the extraction efficiencies of 30 pesticide residues (acaricides, insecticides, herbicides, fungicides), belonging to over 15 different chemical classes. Two common extraction approaches were applied – the increasingly popular QuEChERS method and extraction on a diatomaceous earth support. Both are used for pesticide determinations in fruits and vegetables, and with some adjustments they can be used for honey samples. In order to assess whether the differences in recoveries between the two investigated methods were statistically significant, the F-Snedecor and T-test were employed. The recoveries ranged from 34 to 96%, and in the case of 4 pesticides the differences in the values were statistically significant. Both methods showed good linearity (R² > 0.991), and the extraction efficiencies enabled method quantification limits well below EU-recommended Maximum Residue Levels to be achieved for the investigated pesticides.     

Electric properties of monophase polycrystalline sinters SiC, B4C, TiC and their composites as non-inductive volume resistors

Monophase polycrystalline SiC, B₄C, TiC and their SiC-TiC, SiC-B₄C composite sinters with a theoretical density of 97% are characterized by good mechanical and thermal durability as well as a wide range of electrical conductivity values. SiC, which has semiconductor conductivity and negative TCR, was combined with TiC, which has metallic conductivity and positive TCR. Produced in this way resistive elements, within a temperature range from 293 K to 348 K, exhibit a TCR close to zero, and an impedance independent of frequency within a range from 100 Hz to 1 MHz. The combination SiC with 40 wt% of B₄C has been produced resistive elements, which are resistive to oxidation. This combination has also completly resistive character, within a range of 100 Hz to 1 MHz. Most of the investigated materials are suitable for high temperature, noninductive volume resistors.     

Synthesis of polylactide/clay composites using structurally different kaolinites and kaolinite nanotubes

Polymer/clay nanocomposites receive much attention due to their interesting mechanical and thermal properties. Currently, the vast majority of plastics are made from petroleum-based synthetic polymers that do not degrade in a natural environment and their disposal poses a serious problem. An environmentally-conscious alternative is to design polymer nanocomposites that are biodegradable.In the present work the synthesis and properties of novel polymer/clay nanocomposites based on biodegradable polymer-polylactide (PLA) were investigated. Kaolinite nanotubes obtained by an intercalation/deintercalation method as well as platey kaolinites of different structural orders were used as fillers. Mechanical properties of composites (tensile strength (S_U) and Young's modulus (E)) were measured. The surface of the formed polymer derivatives was examined by AFM (Atomic Force Microscopy). The structural characterization was carried out using infrared spectroscopy (IR). Composites surface wettability was studied by measuring the water contact angle.The mechanical tests revealed that both S_U and E values increased significantly after addition of the nano-filler in comparison to the pure PLA. Regardless of the filler content the increase of S_U and E values was higher in the case of the nanotubular kaolinite. In particular, a threefold increase of the E value was noticed. For the most homogeneous kaolinite nanotubes/PLA nanocomposite S_U increased from ~ 29 MPa (pure PLA) to ~ 43 MPa, while E increased from ~ 0.7 GPa (pure PLA) to ~ 2.3 GPa. These mechanical parameters were comparable with the ones measured for polypropylene (S_U = 40 MPa; E = 1.5–2.0 GPa) and polystyrene (S_U = 40 MPa; E = 3.0–3.5 GPa). Differential IR spectra of the nanocomposites indicated an interaction of kaolinites inner surface hydroxyls with PLA which was confirmed by an intensity decrease of a band at ~ 3690 cm^? 1. The presence of highly dispersed nanotubular kaolinite particles in the polymer matrix which contributed to the improvement of PLA mechanical properties was observed using AFM. The contact angle measurements showed that the addition of kaolinites led to changes of wettability, yet the synthesized materials still possessed hydrophilic surfaces.     

The AT2 Domain of KirCI Loads Malonyl Extender Units to the ACPs of the Kirromycin PKS

The antibiotic kirromycin is assembled by a hybrid modular polyketide synthases (PKSs)/nonribosomal peptide synthetases (NRPSs). Five of six PKSs of this complex assembly line do not have acyltransferase (AT) and have to recruit this activity from discrete AT enzymes. Here, we show that KirCI is a discrete AT which is involved in kirromycin production and displays a rarely found three‐domain architecture (AT₁‐AT₂‐ER). We demonstrate that the second AT domain, KirCI‐AT₂, but not KirCI‐AT₁, is the malonyl‐CoA‐specific AT which utilizes this precursor for loading the acyl carrier proteins (ACPs) of the trans‐AT PKS in vitro. In the kirromycin biosynthetic pathway, ACP5 is exclusively loaded with ethylmalonate by the enzyme KirCII and is not recognized as a substrate by KirCI. Interestingly, the excised KirCI‐AT₂ can also transfer malonate to ACP5 and thus has a relaxed ACP‐specificity compared to the entire KirCI protein. The ability of KirCI‐AT₂ to load different ACPs provides opportunities for AT engineering as a potential strategy for polyketide diversification.     

Comparison of anti-angiogenic properties of pristine carbon nanoparticles

Angiogenesis is vital for tumour formation, development and metastasis. Recent reports show that carbon nanomaterials inhibit various angiogenic signalling pathways and, therefore, can be potentially used in anti-angiogenic therapy. In the present study, we compared the effect of different carbon nanomaterials on blood vessel development. Diamond nanoparticles, graphite nanoparticles, graphene nanosheets, multi-wall nanotubes and C60 fullerenes were evaluated for their angiogenic activities using the in ovo chick embryo chorioallantoic membrane model. Diamond nanoparticles and multi-wall nanotubes showed the greatest anti-angiogenic properties. Interestingly, fullerene exhibited the opposite effect, increasing blood vessel development, while graphite nanoparticles and graphene had no effect. Subsequently, protein levels of pro-angiogenic growth factor receptors were analysed, showing that diamond nanoparticles decreased the expression of vascular endothelial growth factor receptor. These results provide new insights into the biological activity of carbon nanomaterials and emphasise the potential use of multi-wall nanotubes and diamond nanoparticles in anti-angiogenic tumour therapy.     

Diffusion layers produced on carbon steel surface by means of vacuum chromizing process

This work investigated diffusion layers produced on carbon (C) steel surfaces in the vacuum chromizing process. Studies of layer, thickness, morphology, and chromium (Cr), C, and iron (Fe) concentration depth profiles in the diffusion zone of chromized layers were carried out. The effect of process parameters such as time and temperature on the kinetics of layer growth on steel surface was investigated. The tribocorrosion resistance of chromized layers was determined.     

Calculations of chemical equilibria in the Mo-B-N system

Calculations of chemical equilibria for the Mo-B-N system using the VCS algorithm were carried out for the 30–1727°C temperature range and the 1·3 × 10⁻³−1 × 10⁷ Pa pressure range. Two BN: Mo molar ratios were selected: 1 : 1 and 2 : 1. It follows from these studies that Mo can react with BN in a very wide range of temperatures and pressures, giving new phases, namely Mo₂B, MoB, MoB₂, Mo₂B₅ and MoB₄. The formation of these phases is strongly influenced by pressure-temperature parameters. In order to verify theoretical calculations by experiment equimolar and 2 : 1 BN : Mo batches were prepared and heated at 1427°C in vacuum and in argon atmosphere. Phase identification carried out by X-ray diffraction fully corroborated the computational results.