Effects of the catalyst system on the crystallization of polypropylene*

In search of a better understanding of catalyst effects on final product qualities of polypropylene, an attempt was made to establish a correlation between catalyst type, polymer chain structure of homopolymers, crystallization behavior, as well as final morphology and mechanical properties. Conventional Ziegler–Natta catalyst systems as well as novel metallocene catalysts were investigated, and influences of molar mass distribution and chain regularity were investigated as separate factors. Metallocene-based isotactic polypropylene shows some special effects regarding the nucleation density and the correlation between stereoregularity and mechanics that do not fit into the general picture for Ziegler–Natta catalyst based products. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2507–2515, 1999     

The Obscure Effect of Tribulus terrestris Saponins Plus Inulin on Liver Morphology,Liver Fatty Acids,Plasma Glucose,and Lipid Profile in SD Rats with and without Induced Type 2 Diabetes Mellitus

Diabetes is a predictor of nonalcoholic fatty liver disease (NAFLD). There are data suggesting that Tribulus terrestris (TT) saponins act as antidiabetic agents and protect against NAFLD. The effect of saponins may be increased by fermentable fibers such as inulin. The aim of the present study was to investigate the influence of TT saponins and TT saponins plus inulin on the plasma lipid profile and liver fatty acids of rats with induced diabetes mellitus type 2 (T2DM). The study was performed on 36 male Sprague–Dawley rats divided into two main groups: control and diabetic. Animals of the diabetic (DM) group were fed a high-fat diet and injected with streptozotocin (low doses). Animals of the control group (nDM) were on a regular diet and were injected with buffer. After the injections, the animals were split into subgroups: three non-diabetic (nDM): (i) control (c-C); (ii) saponin-treated rats (C-Sap); (iii) rats treated with saponins + inulin (C-Sap + IN), and three diabetic subgroups (DM): (iv) control (c-DM); (v) saponin-treated rats (DM-Sap); (vi) rats treated with saponins + inulin (DM-Sap + IN). Liver fatty acids were extracted and analyzed by gas chromatography, and plasma glucose and lipids were measured. The study showed significant changes in liver morphology, liver fatty acids, plasma lipid profile, and plasma glucose. In summary, supplementation with TT saponins or saponins with inulin for one month decreased the level of steatosis in rats with induced type 2 diabetes. Moreover, there were favorable effects on the plasma lipid profile in the rats. However, additional supplementation with inulin had a negative effect on liver morphology (with a microvesicular type of steatosis) in the non-diabetes group. Moreover, supplementation with inulin had a negative effect on plasma glucose in both diabetic and non-diabetic rats. These data show that a diet enriched with fermentable fibers reveals different effects in different organisms, and not all sources and forms of fiber are beneficial to health.     

A New Mechanism of the Selective Photodegradation of Antibiotics in the Catalytic System Containing TiO2 and the Inorganic Cations

The mechanism of sulfisoxazole (SFF) selective removal by photocatalysis in the presence of titanium (IV) oxide (TiO₂) and iron (III) chloride (FeCl₃) was explained and the kinetics and degradation pathways of SFF and other antibiotics were compared. The effects of selected inorganic ions, oxygen conditions, pH, sorption processes and formation of coordination compounds on the photocatalytic process in the presence of TiO₂ were also determined. The Fe³⁺ compounds added to the irradiated sulfonamide (SN) solution underwent surface sorption on TiO₂ particles and act as acceptors of excited electrons. Most likely, the SFF degradation is also intensified by organic radicals or cation organic radicals. These radicals can be initially generated by reaction with electron holes, hydroxyl radicals and as a result of electron transfer mediated by iron ions and then participate in propagation processes. The high sensitivity of SFF to decomposition caused by organic radicals is associated with the steric effect and the high bond polarity of the amide substituent.     

Identification of weak and strong organic acids in atmospheric aerosols by capillary electrophoresis/mass spectrometry and ultra-high-resolution fourier transform ion cyclotron resonance mass spectrometry

A novel approach using a combination of capillary electrophoresis/mass spectrometry (CE/MS) and off-line Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) revealed the structural details of acidic constituents of atmospheric organic aerosol. Both techniques utilized electrospray ionization (ESI), a soft ionization method, to facilitate the analysis of complex mixtures of organic compounds. CE/ESI-MS using an UltraTrol LN-precoated capillary and acidic background electrolytes at different pH values (2.5 and 4.7) was used to differentiate between weak (carboxylic) and strong (sulfonic) organic acids. On the basis of the electrophoretic mobility, m/z constraints from CE/ESI(-)-MS, and elemental composition information retrieved from off-line FTICR-MS, a variety of aliphatic and aromatic carboxylic acids (CHO-bearing molecules), nitrogen-containing carboxylic acids (CHON-bearing molecules), organosulfates (CHOS-bearing molecules), and (nitrooxy)organosulfates (CHONS-bearing molecules) were tentatively identified in the Oasis-HLB-extracted urban PM(2.5) (particulate matter with an aerodynamic diameter of <2.5 μm). The chemical known/unknown structures of detected compounds were confirmed by the semiempirical Offord model (effective mobility linearly correlated to Z/M(2/3)). The majorities of the identified compounds are products of atmospheric reactions and are known contributors to secondary organic aerosols.     

Dithizone modified gold nanoparticles films for potentiometric sensing

For the first time, application of a membrane composed of gold nanoparticles decorated with complexing ligand for potentiometric sensing is shown. Gold nanoparticles drop cast from a solution form a porous structure on a substrate electrode surface. Sample cations can penetrate the gold nanoparticles layer and interact with ligand acting as a charged ionophore, resulting in Nernstian potentiometric responses. Anchoring of complexing ligand on the gold surface abolishes the necessity of ionophore application. Moreover, it opens the possibility of preparation of potentiometric sensors using chelators of significantly different selectivity patterns further enhanced by the absence of polymeric membrane matrix. This was clearly seen, for example, for gold nanoparticles stabilizing the applied ligand-dithizone-thiol conformation leading to a high potentiometric selectivity toward copper ions, much higher than that of ionophores typically used to induce selectivity for polymeric ion-selective membranes.     

Synthesis and photocatalytic performance of TiO<Subscript>2</Subscript> nanospheres–graphene nanocomposite under visible and UV light irradiation

In this article, we present a fast and simple method to produce TiO₂ nanospheres–graphene nanocomposite with high photocatalytic activity under visible and UV light irradiation. TiO₂ nanospheres were adsorbed on graphene in sol–gel process. First, titanium (IV) butoxide underwent hydrolysis in graphene oxide (GO) ethanol solution resulting in TiO₂ nanospheres deposition on GO. Next, the material was calcinated to generate the phase transition of TiO₂ into anatase and reduce GO to graphene. The detailed characterization of the material was performed via transmission electron microscopy, energy dispersive X-rays spectrometer, Fourier-transformed infrared spectroscopy, X-ray diffraction, and Raman spectroscopy. Interestingly, the band-gap energy of the prepared photocatalyst was drastically decreased in comparison with the commercial photocatalyst P25 from 3.05 to 2.36 eV. This influenced in the activation of the material under visible light and resulted in high photocatalytic activity in the process of phenol decomposition in visible and UV irradiation.     

Poly(etherimide)s and poly(esterimide)s containing azobenzene units: Characterization and study of photoinduced optical anisotropy

In this paper novel processable, photoresponsible aromatic polymers with imide rings and covalently boned azobenzene units are presented. Prepolymerization strategy based on polycondensation of two diamines with azobenzene group, that is, 2,4-diamino-4′-cyanoazobenzne and 2,4-diamino-4′-nitroazobenzene and two dianhydrides, was utilized for preparation of the new photochromic polyimides. The obtained polymers differ in the chemical structure of polymer backbone and the kind of substituents on azobenzene moieties. Polymers were characterized and evaluated by FT-IR, ¹H NMR, X-ray, UV-vis, DSC, and TGA methods. The synthesized azopolymers exhibited glass transition temperatures in the range of 140-170 °C, thermal stability with initial decomposition temperatures (T_d) in the range of 266-290 °C, and excellent solubilities in common organic solvents, providing optical-quality films. The light-induced optical anisotropy was studied in obtained polymers by photoinduced birefringence measurements. The birefringence was generated by the femtosecond pulses at 400 nm via a linear absorption of the trans-azobenzene. A large light-induced birefringence (Δn = 0.02) was achieved in poly(esterimide)s contrary to poly(etherimide)s. The birefringence exhibited a very stable behavior after switching off the writing light indicating a permanent storage capacity.     

Pesticide Residue Determination by Gas Chromatography-Tandem Mass Spectrometry as Applied to Food Safety Assessment on the Example of Some Fruiting Vegetables

A multiresidue method for the analysis of over 140 multiclass pesticides in fruiting vegetables, based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation procedure followed by gas chromatography-tandem mass spectrometry (GC-MS/MS), was established. In the validation study, the overall recoveries from spiked samples were 102?±?7, 95?±?7, and 95?±?7 % with RSD values of 7?±?3, 7?±?4, and 7?±?3 % at the spiking levels of 0.01, 0.05, and 0.5 mg kg^?1, respectively, demonstrating fitness for purpose of the method. The limit of quantification (LOQ) was 0.01 mg kg^?1 for more than 90 % of the target compounds. The analysis of over 300 samples of tomatoes, sweet peppers, and cucumbers was carried out in 2006–2014. Of these samples, 52 % contained pesticide residues but the results of the assessment of dietary exposure supported the conclusion that the presence of pesticide residues was unlikely to have a negative effect on the health of consumers. Although some of the pesticides detected in years 2006–2009 are no longer approved in the European Union member countries (namely endosulfan, oxadixyl, procymidone, propargite, and tolylfluanid), the consumer dietary exposure was low and did not exceed 12 % of the acceptable daily intake (ADI) considering both adults’ and children’s diet. Regarding short-term exposure (acute), in only one case of procymidone in sweet pepper, the acute reference dose (ARfD) for children was exceeded by 139.6 % of the ARfD.