Stereoregular poly‐O‐methyl [m,n]‐polyurethanes derived from D‐mannitol

Novel linear carbohydrate‐derived [m,n]‐polyurethanes are successfully prepared using D ‐mannitol as renewable and low cost starting material. The key comonomer, 1,6‐di‐O‐phenylcarbonyl‐2,3,4,5‐tetra‐O‐methyl‐D ‐mannitol is polymerized with a diamine synthesized from D ‐mannitol or with alkylenediamines. These polymerization reactions afford, respectively, a [6,6]‐polyurethane entirely based on a carbohydrate derivative or [m,n]‐polyurethanes constituted by a poly‐O‐methyl substituted unit alternating with a polymethylene chain. All these polymers are stereoregular, as result of the C₂ axis of symmetry of mannitol. The optically active polyurethanes are characterized by standard methods (FTIR, RMN, GPC, TGA, and DSC). Thus, GPC analysis reveals weight‐average molecular weights between 18,000 and 25,000 Da. Thermal studies (DSC) indicate that the polymers obtained are amorphous materials with T_g values dependent on the structure and chain length of the diamine constituent. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Combined cysteine and homocysteine quantitation in plasma by trap and release membrane introduction mass spectrometry

Recently, a new and efficient method for total homocysteine (tHcy) quantitation in plasma using trap and release membrane introduction mass spectrometry (T&R-MIMS) with a versatile removable direct introduction membrane probe (DIMP) was described [R. Haddad, M. A. Mendes, N. F. Hoehr and M. N. Eberlin, Analyst, 2001, 126, 1212]. Herein we report on the use of the DIMP-T&R-MIMS technique for total cysteine (tCys) quantitation; hence combined tCys and tHcy quantitation in plasma or serum can be achieved. The method employs Cys and Hcy derivatization with ethyl chloroformate (after disulfide bond reduction with dithiothreitol and protein precipitation with trichloroacetic acid), preconcentration in a capillary silicone membrane, and their thermal desorption to the gas phase inside the ion source region of a mass spectrometer, at a point exactly between the two ionization filaments. Thermal desorption uses the uniform heat radiation provided by the two ionization filaments. The analytes are then ionized by electron ionization and both Cys and Hcy are quantitated by mass spectrometry using selected ion monitoring. For tCys quantitation, good linearity and reproducibility was observed for concentrations ranging from 5 to 350 microM, recovery was near 95%, and the limit of detection (LOD) was of 2 microM. This LOD is well below the mean Cys concentration in plasma, and serum samples from a large group of healthy people showed a mean tCys concentration of 132 +/- 45 microM.     

Amplified Chirality Transfer to Aromatic Molecules through Non-specific Inclusion by Amorphous,Hyperbranched Poly(fluorenevinylene) Derivatives

Optically active, hyperbranched, poly(fluorene-2,4,7-triylethene-1,2-diyl) [poly(fluorenevinylene)] derivatives bearing a neomenthyl group and a pentyl group at the 9-position of the fluorene backbone at various ratios acted as a chirality donor (host polymers) efficiently included naphthalene, anthracene, pyrene, 9-phenylanthracene, and 9,10-diphenyanthracene as a chirality acceptor (guest molecules) in their interior space in film as well as in solution, with the guest molecules exhibiting intense circular dichroism through chirality transfer with chirality amplification. The efficiency of the chirality transfer was much higher with higher-molar-mass polymers than lower-molar-mass ones as well as with hyperbranched polymers compared to the analogous linear ones. The hyperbranched polymers include the small molecules in their complex structure without any specific interactions at various stoichiometries. The included molecules may have ordered intermolecular arrangement that may be somewhat similar to those of liquid crystals. Naphthalene, anthracene, and pyrene included in the polymer exhibited efficient circularly polarized luminescence, where the chirality was remarkably amplified in excited states, and anthracene exhibited especially high anisotropies in the emission on the order of 10⁻².     

Analysis of DNA methylation markers for tissue identification in individuals with different clinical phenotypes

Deoxyribonucleic acid (DNA) methylation patterns can be used to identify the type of tissue or body fluid found at a crime scene. However, tissue-related methylation levels have not been analyzed in individuals with different illnesses and medical conditions in forensic-specific studies. The primary goal of this study was to investigate if certain clinical phenotypes can alter the methylation levels of CpG sites in genes involved in tissue typing. Four studies with focus on DNA methylation analysis on individuals with different clinical conditions were selected from the Gene Expression Omnibus database. Then, a list of 137 CpG sites was compiled for further investigation. Statistical tests were performed to compare the beta-values results obtained for the control groups and the individuals affected by medical conditions. For each study, CpG sites that presented significant statistical differences between patients and control group were identified and it was possible to notice that DNA methylation levels can be affected in sites with potential forensic use. Although the observed DNA methylation variation (less than 10% difference) in this study would likely not cause any issues in body fluid identification, the results are important to show that this type of analysis should be taken into consideration when investigating and further validating body fluid markers. The CpG sites identified in this study should be further investigated by future studies on body fluids identification, and due to the significant difference in methylation levels in samples from affected individuals, caution must be taken before including these sites in tissue identification investigations.     

High‐density polyethylene/expanded graphite nanocomposites produced by polymerization‐filling technique using an industrial heterogeneous catalyst

High‐density polyethylene nanocomposites with different expanded graphite (EG) contents (0.34–1.80 wt %) were prepared by polymerization‐filling technique using an industrial heterogeneous catalyst ( cat K ), and characterized using a range techniques: melting flow index (MFI), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM). The MFI data showed that EG acts as a plasticizer decreasing melt viscosity in comparison to neat HDPE produced exclusively by cat K . DSC results showed that EG nucleated the HDPE crystallization as established by the increased crystallization temperature, and the degree of crystallinity. HDPE/EG nanocomposites displayed a significant improvement in the flexural (increased from 1458 to 1831 MPa), and storage modulus (increased from 122 to 1627 MPa) at only 1.80 wt % EG content. TEM images confirmed a homogeneous distribution of EG into the polymer matrix with the presence of dispersed, intercalated and aggregated EG nanofillers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 55, 1260–1267     

Compatibility study of tobramycin and pharmaceutical excipients using differential scanning calorimetry,FTIR, DRX,and HPLC

Differential scanning calorimetry (DSC), isothermal stress testing–Fourier transform infrared spectroscopy (IST–FTIR), isothermal stress testing–high-performance liquid chromatography, and powder X-ray diffraction (PDRX) were used as screening techniques for assessing the compatibility of tobramycin with some currently employed ophthalmic excipients. In the first phase of the study, DSC was used as a tool to detect any interaction. The absolute value of the difference between the enthalpy of the pure tobramycin melting peak and that of its melting peak in the different analyzed mixtures was chosen as a parameter of the drug–excipient interaction degree. DSC results demonstrated that benzalkonium chloride, monobasic sodium phosphate, boric acid, edetate disodium, sodium metabisulfite, thimerosal, and potassium sorbate interact with tobramycin. Taking into account these results, it could be suggested that some of the changes observed in the IST–FTIR spectra of binary blends of tobramycin and some of the excipients would account for a possible interaction between the mixture component. In this study, PDRX did not provide much information, since only tobramycin–thimerosal interactions could be detected. DSC and IST–FTIR are suitable and simple methods for the detection of potential incompatibilities between active pharmaceutical ingredient (API) and excipients.

     

Thermogravimetric characterization of styrene–divinylbenzene copolymers containing alpha-isopropylaminophosphonic acid groups

A commercial styrene–divinylbenzene copolymer was functionalized by multistep reactions with alpha-isopropylaminophosphonic acid groups. Three different functionalized copolymers were obtained in which the phosphonic groups are in meta (1E), para (2E), and ortho (3E) positions. The thermal behavior was studied using the TG/IR hyphenated technique and kinetic analysis of thermo-oxidation under nonisothermal conditions. The evolved gas analysis confirms the partial thermo-oxidative degradation of polymeric materials, with significant preservation of the aromatic ring. The kinetic analysis was performed by three methods: Friedman, Flynn–Wall–Ozawa, and nonparametric kinetic.     

New Features in the Lipid A Structure of <Emphasis Type="Italic">Brucella suis</Emphasis> and <Emphasis Type="Italic">Brucella abortus</Emphasis> Lipopolysaccharide

Brucellaceae are Gram-negative bacteria that cause brucellosis, one of the most distributed worldwide zoonosis, transmitted to humans by contact with either infected animals or their products. The lipopolysaccharide exposed on the cell surface has been intensively studied and is considered a major virulence factor of Brucella. In the last years, structural studies allowed the determination of new structures in the core oligosaccharide and the O-antigen of this lipopolysaccharide. In this work, we have reinvestigated the lipid A structure isolated from B. suis and B. abortus lipopolysaccharides. A detailed study by MALDI-TOF mass spectrometry in the positive and negative ion modes of the lipid A moieties purified from both species was performed. Interestingly, a new feature was detected: the presence of a pyrophosphorylethanolamine residue substituting the backbone. LID-MS/MS analysis of some of the detected ions allowed assurance that the Lipid A structure composed by the diGlcN3N disaccharide, mainly hexa-acylated and penta-acylated, bearing one phosphate and one pyrophosphorylethanolamine residue.

Open image in new window

Graphical abstract ?

     

Thermal analysis of heat-treated silver fir wood and larval frass

Glasses having composition 5Li₂O–5ZnO– xBi₂O₃ –(90 ? x) P₂O₅ (x = 5, 10, 15, 20 and 25 mol%) were prepared by the normal melt quenching technique. Nanocomposite glass containing bismuth phosphate BiPO₄ nanocrystals was obtained, which can be attributed to homogeneous nucleation process. The formation of BiPO₄ nanocrystals was confirmed and characterized by X-ray diffraction patterns (XRD), transmission electron microscopy (TEM), differential scanning calorimetry, optical absorption (UV–Vis) and micro-hardness studies. The morphological analysis by XRD and TEM microscopy showed the formation of hexagonal BiPO₄ nanocrystals, and its estimated nanocrystalline sizes were found to be varying from 5.35 to 11.53 nm depending on the Bi₂O₃ concentrations. The density (ρ) and molar volume (V _m) were also determined and found to be in compositional dependence. Glass transition temperature (T _g) and glass crystallization temperature (T _c) were obtained and found to be increased (from 240.0 to 337.2 °C) with increasing Bi₂O₃ up to 20 mol% and then decreased (from 337.2 to 331.8 °C) due to the structural changes in the glass network. Effect of BiPO₄ content on the optical properties had been investigated. From the UV–Vis spectra, it was observed that the fundamental absorption edge shifts toward lower wavelengths, i.e., blueshifts with increasing Bi₂O₃ mol% up to 20 mol%, and then shifts toward higher wavelengths, i.e., redshifts beyond 20 mol%. It was also observed that the obtained E _opt (for indirect and direct transitions) increases with gradual increase in Bi₂O₃ content up to 20 mol% and then decreases beyond 20 mol%. This may be due to the introduction of Bi cations into the glass network as a network former up to 20 mol% causing a decrease in ΔE values, beyond 20 mol%, the introduction of Bi ions into the glass network interstitially leads to increase the values of ΔE. The optical properties of the present nanocrystallized glasses showed a quantum size dependence, in which the optical band gap energy (E _opt) was changed as a function of BiPO₄ nanocrystalline sizes.     

Minimising movements for the motion of discrete screw dislocations along glide directions

In Alicandro et al. (J Mech Phys Solids 92:87–104, 2016) a simple discrete scheme for the motion of screw dislocations toward low energy configurations has been proposed. There, a formal limit of such a scheme, as the lattice spacing and the time step tend to zero, has been described. The limiting dynamics agrees with the maximal dissipation criterion introduced in Cermelli and Gurtin (Arch Ration Mech Anal 148, 1999) and predicts motion along the glide directions of the crystal. In this paper, we provide rigorous proofs of the results in [3], and in particular of the passage from the discrete to the continuous dynamics. The proofs are based on \(\Gamma \)-convergence techniques.