Investigation of thermal and catalytic degradation of polystyrene waste into styrene monomer over natural volcanic tuff and Florisil catalysts

Thermal and catalytic degradation of polystyrene waste over two different samples of natural volcanic tuff catalyst comparative with Florisil catalyst has been carried out in order to establish the conversion degree into styrene monomer. The polystyrene waste (PS) was subjected to a thermal degradation process in the range of 380–500°C in presence of studied catalysts in a ratio of 1/10 in mass, catalyst/PS. The catalysts were characterized by N₂ adsorption-desorption isotherms (BET), Scanning Electron Microscopy (SEM) and Fourier-transform infrared spectrometry (FTIR). Influences of temperature and type of catalysts on the yields and on the distribution of end-products obtained by thermal and catalytic degradation of polystyrene waste have been studied. The maximum yields of liquid products were obtained at 460°C degradation temperature and were calculated between 83.45% and 90.11%. The liquid products were characterized by gas chromatography mass spectrometry (GC-MS) and FTIR analytical techniques. The GC-MS results showed that the liquid products contained styrene monomer up to 55.62%. The FTIR spectra of liquid products indicated the specific vibration bands of the functional groups of compounds of liquid products. The amounts of styrene monomer obtained were influenced by structural and textural properties of studied catalyst and the contribution on product distribution is discussed.      

SORPTION OF OXYANIONS BY SURFACTANT-MODIFIED ZEOLITE

Zeolite has high internal and external surface areas and high internal and external cation exchange capacities suitable for surface modification by cationic surfactants. When the initial surfactant concentration is less than the critical micelle concentration, the sorted surfactant molecules primarily form a monolayer. Limited chromate sorption indicates that patchy bilayer may also form. When the initial surfactant concentration is greater than the critical micelle concentration and enough surfactant exists in the system, the sorbed surfactant molecules form bilayers, producing maximum chromate sorption. On a meq/kg basis, planar nitrate sorbs more on surfactant-modified zeolite surfaces than tetrahedral chromate. In the presence of sulfate or nitrate, chromate sorption is hindered due to competition for sorption sites. Quantitative sorption of nitrate and chromate and desorption of bromide indicate that the sorption of oxyanions is primarily due to surface anion exchange.     

Poly(N-isopropylacrylamide-co-N-t-butylacrylamide)-block-poly(ethylene glycol)-block-poly(N-isopropylacrylamide-co-N-t-butylacrylamide) triblock copolymers: synthesis and thermogelation properties of aqueous solutions

Novel triblock copolymers with PEG middle blocks of 1–10 kDa and poly(N-isopropylacrylamide-co-t-butylacrylamide) statistical copolymer side arms with DP_n?≈?88 and different compositions, were synthesized by SET-LRP. The thermogelation properties of their aqueous solutions depended on both hydrophobic monomer content of the side blocks and molecular weight (MW) of the poly(ethylene glycol) (PEG) middle block, as proven by dynamic rheometry, DSC, and tube inversion method measurements. At constant PEG chain length, increasing TBAM proportions led to a gelation process occurring at progressively lower temperatures, as well as to a lower stability of the forming hydrogels in the case of shorter-PEG-chain block copolymers. By employing longer PEG blocks (M_PEG ≥6,000 Da), stable hydrogels with the gelation temperature below 37 °C could be obtained. For a constant composition of the copolyacrylamide blocks, the dependence of the phase transition temperature (T_ph) on M_PEG displayed a different shape at different polymer solution concentrations, because of the stronger variation of T_ph with polymer concentration as M_PEG increased. Also, the viscoelastic properties of the hydrogels resulting from 20 wt.% polymer aqueous solutions at 37 °C were stronger affected by the MW of the PEG middle block than by the hydrophobic character of the thermosensitive side blocks.     

Chemoenzymatic synthesis of (R)- and (S)-1-heteroarylethanols

A chemoenzymatic methodology for the synthesis of highly enantiomerically enriched (S)- and (R)-1-heteroarylethanols by enantioselective bioreduction with baker’s yeast of the corresponding 1-heteroarylethanones followed by three racemization free chemical steps including a Mitsunobu reaction was developed.     

Conformational Isomers of Calcineurin Follow Distinct Dissociation Pathways

In the gas-phase, ions of protein complexes typically follow an asymmetric dissociation pathway upon collisional activation, whereby an expelled small monomer takes a disproportionately large amount of the charges from the precursor ion. This phenomenon has been rationalized by assuming that upon activation, a single monomer becomes unfolded, thereby attracting charges to its newly exposed basic residues. Here, we report on the atypical gas-phase dissociation of the therapeutically important, heterodimeric calcium/calmodulin-dependent serine/threonine phosphatase calcineurin, using a combination of tandem mass spectrometry, ion mobility mass spectrometry, and computational modeling. Therefore, a hetero-dimeric calcineurin construct (62?kDa), composed of CNa (44?kDa, a truncation mutant missing the calmodulin binding and auto-inhibitory domains), and CNb (18?kDa), was used. Upon collisional activation, this hetero-dimer follows the commonly observed dissociation behavior, whereby the smaller CNb becomes highly charged and is expelled. Surprisingly, in addition, a second atypical dissociation pathway, whereby the charge partitioning over the two entities is more symmetric is observed. The presence of two gas-phase conformational isomers of calcineurin as revealed by ion mobility mass spectrometry (IM-MS) may explain the co-occurrence of these two dissociation pathways. We reveal the direct relationship between the conformation of the calcineurin precursor ion and its concomitant dissociation pathway and provide insights into the mechanisms underlying this co-occurrence of the typical and atypical fragmentation mechanisms.     

Enhanced electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry of long-chain polysaccharides

A novel strategy was developed to extend the application of electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry (MS) to the analysis of long-chain polysaccharides. High molecular weight polydisperse maltodextrins (poly-alpha(1-4) glucose) and dextrans (poly-alpha(1-6) glucose) were chosen as model compounds in the present study. Increased ionization efficiency of these mixtures in the positive ion mode was achieved upon modification of their reducing end with nitrogen-containing groups. The derivatization method is based on the formation of a new C--N bond between 1,6-hexamethylenediamine (HMD) and the reducing end of the polysaccharide, which exists in solution as an equilibrium between the hemiacetal and the open-ring aldehyde form. To achieve the chemical modification of the reducing end, two synthetic pathways were developed: (i) coupling of HMD by reductive amination and (ii) oxidation of the hemiacetal to lactone, followed by ring opening by HMD to yield the maltodextrin lactonamide of 1,6-hexanediamine (HMMD). Amino-functionalized polysaccharides were analyzed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR-MS) in the positive ion mode by direct flow injection. The hexamethylenediamine (HMD) and maltodextrin lactonamide of 1,6-hexanediamine (HMMD) moieties provide increased proton affinities which dramatically improve the detection of the long-chain polysaccharides by FTICR-MS. The present approach allowed for identification of single components in mixtures with prominent heterogeneity in the degree of polymerization (DP), without the need for chromatographic separation prior to MS. The high mass accuracy was essential for the unambiguous characterization of the species observed in the analyzed mixtures. Furthermore, molecular components containing up to 42 glucose residues were detected, representing the largest polysaccharide chains analyzed so far by ESI FTICR-MS.     

Giant hemangioma of the liver: MR imaging characteristics in 24 patients

We retrospectively reviewed the magnetic resonance imaging (MRI) of giant hemangiomas in 24 patients. MRI studies comprised T1-weighted, T2-weighted and serial gadolinium-enhanced spoiled gradient echo (SGE) images. Morphologic features, signal characteristics and enhancement patterns were assessed. Histopathologic evaluation was obtained in nine patients. On T2-weighted images all lesions (size 5.7-24 cm) were hyperintense relative to the spleen and two dominant patterns of heterogeneity were demonstrated: a central heterogeneous area of either bright, dark, or mixed signal intensity, and a network of multiple fibrous septa of low signal intensity. Histopathologic evaluation of two lesions with a central bright area demonstrated the presence of hypocellular myxoid tissue. Central enhancement (9 lesions) and an irregular flame-shaped peripheral pattern of enhancement (12 lesions) were present in lesions with a mean diameter greater than 10 cm. Although giant hemangiomas show greater variability in their MR imaging appearance, an accurate diagnosis can be made through still characteristic features of high signal intensity on T2-weighted images and discontinuous peripheral enhancement.     

Total assignment and structure in solution of tetrandrine by NMR spectroscopy and molecular modelling

High-resolution 1- and 2D NMR spectra of tetrandrine and molecular modelling were employed to characterise its structure in solution. Complete and unambiguous assignment of all proton and carbon resonance signals is reported. Scalar couplings were determined from dihedral angles with the Karplus equation. Inter-proton distances were evaluated from NOE correlation peaks. Comparison of simulated and X-ray conformations of tetrandrine reveals only small differences.     

The Effects of Capsaicin on Gastrointestinal Cancers

Gastrointestinal (GI) cancers are a group of diseases with very high positions in the ranking of cancer incidence and mortality. While they show common features regarding the molecular mechanisms involved in cancer development, organ-specific pathophysiological processes may trigger distinct signaling pathways and intricate interactions with inflammatory cells from the tumoral milieu and mediators involved in tumorigenesis. The treatment of GI cancers is a topic of increasing interest due to the severity of these diseases, their impact on the patients’ survivability and quality of life, and the burden they set on the healthcare system. As the efficiency of existing drugs is hindered by chemoresistance and adverse reactions when administered in high doses, new therapies are sought, and emerging drugs, formulations, and substance synergies are the focus of a growing number of studies. A class of chemicals with great potential through anti-inflammatory, anti-oxidant, and anti-tumoral effects is phytochemicals, and capsaicin in particular is the subject of intensive research looking to validate its position in complementing cancer treatment. Our paper thoroughly reviews the available scientific evidence concerning the effects of capsaicin on major GI cancers and its interactions with the molecular pathways involved in the course of these diseases.     

Assessing the Functional Properties of TiZr Nanotubular Structures for Biomedical Applications,through Nano-Scratch Tests and Adhesion Force Maps

In this work we present the results of a functional properties assessment via Atomic Force Microscopy (AFM)-based surface morphology, surface roughness, nano-scratch tests and adhesion force maps of TiZr-based nanotubular structures. The nanostructures have been electrochemically prepared in a glycerin + 15 vol.% H₂O + 0.2 M NH4F electrolyte. The AFM topography images confirmed the successful preparation of the nanotubular coatings. The Root Mean Square (RMS) and average (Ra) roughness parameters increased after anodizing, while the mean adhesion force value decreased. The prepared nanocoatings exhibited a smaller mean scratch hardness value compared to the un-coated TiZr. However, the mean hardness (H) values of the coatings highlight their potential in having reliable mechanical resistances, which along with the significant increase of the surface roughness parameters, which could help in improving the osseointegration, and also with the important decrease of the mean adhesion force, which could lead to a reduction in bacterial adhesion, are providing the nanostructures with a great potential to be used as a better alternative for Ti implants in dentistry.