(2‐Hydroxy isobutyric) acid containing poly(glycolic acid): Structure–properties relationship

Poly(glycolic acid) (PGA) and a series of novel random copolymers of PGA containing 2‐hydroxyisobutyrric acid (PGAPHIB) (HIB unit content from 1.5 to 7.4 mol %) were synthesized and characterized in terms of chemical structure and molecular weight. Afterward, the polyesters were examined by thermogravimetric analysis, differential scanning calorimetry, and X‐ray diffraction techniques. The copolymers, which displayed a better thermal stability than PGA, at room temperature appeared as semicrystalline materials: the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of the melting temperature with respect to homopolymer PGA. Baur's equation described well the T_m‐composition data. X‐ray diffraction measurements allowed the identification of the PGA crystalline structure in all cases. After melt quenching, semicrystalline samples were obtained with the exception of PGAPHIB7.4 copolymer. The introduction of HIB units decreased the crystallization rate compared with pure PGA. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1901–1910, 2010     

Protein analysis of laser capture micro-dissected tissues revealed cell-type specific biological functions in developing barley grains

Both the nucellar projection (NP) and endosperm transfer cells (ETC) of the developing barley grain (harvested 8 days after flowering) were isolated by laser capture micro-dissection combined with pressure catapulting. Protein extracts were analyzed by nanoUPLC separation combined with ESI-Q-TOF mass spectrometry. The majority of the ～160 proteins identified were involved in translation, protein synthesis, or protein destination. The NP proteome was enriched for stress defense molecules, while proteins involved in assimilate transport and the mobilization of nutrients were common to both the NP and the ETC. The combined qualitative and quantitative protein profiling allowed for the identification of several proteins showing tissue specificity in their expression, which underlines the distinct biological functions of these two tissues within the developing barley grain.     

Development and validation of a liquid chromatography–tandem mass spectrometry method for the simultaneous analysis of androgens,estrogens, glucocorticoids and progestagens in human serum

We present a liquid chromatography tandem mass spectrometry method for the simultaneous analysis of 16 endogenous steroids (androgens, estrogens, glucocorticoids and progestogens) in human serum. Samples (250 μl of matrix) were extracted with t-butylmethyl ether prior to LC–MS/MS analysis. The chromatographic separation was achieved on a reversed-phase column using a methanol–water gradient. The HPLC was coupled to a triple quadrupole mass spectrometer equipped with an electrospray ionization source with acquisition in multiple reaction monitoring mode. The method was validated using surrogate matrices and human serum samples. The specificity of the method was confirmed for all of the considered steroids; linearity was also assessed (R² > 0.99, lack-of-fit test) in the ranges of concentrations investigated. The lower limits of quantification were in the range 10–400 pg/ml depending on the target steroid. Accuracy was in the range 85–115% for all target steroids except for the lower limit of quantitation levels where it was 80–120%. The extraction recovery was always >65%. No significant matrix effects were observed. To test the reliability of the method, the analysis of serum samples collected from 10 healthy subjects (5 M/5F) was performed. The present method can be used to identify the trajectories of deviation from the concentration normality ranges applied to disorders of the gonadal and adrenal axes.     

Zn(NCN)单轴的负热膨胀性及机理研究

负热膨胀(NTE)是一种反常的物理现象, 已在合金和框架结构化合物等材料中被观察到, 但NTE材料的种类仍然有限. 本文合成了一种单轴NTE材料Zn(NCN), 该材料在c轴方向及在100~475 K下的热膨胀系数为-3.35×10^?6 K^?1, 而a轴和b轴方向则呈低热膨胀性, 体积具有低的热膨胀系数[6.13×10^?6 K^?1(100~475 K)]. 通过同步辐射X射线衍射、 扩展X射线吸收精细结构和拉曼光谱等方法, 研究了Zn(NCN)的NTE机理. 结果表明, Zn—N键具有明显的横向振动, 一些低频振动模Grüneisen参数为负值. 直接的实验证据表明, N=C=N的横向振动以及准刚性ZnN₄四面体的耦合旋转和扭摆导致了c轴方向的NTE.     

Fibril Structure Demonstrates the Role of Iodine Labelling on a Pentapeptide Self-Assembly

Iodination has long been employed as a successful labelling strategy to gain structural insights into proteins and other biomolecules via several techniques, including Small Angle X-ray Scattering, Inductively Coupled Plasma Mass Spectrometer (ICP-MS), and single-crystal crystallography. However, when dealing with smaller biomolecular systems, interactions driven by iodine may significantly alter their self-assembly behaviour. The engineering of amyloidogenic peptides for the development of ordered nanomaterials has greatly benefitted from this possibility. Still, to date, iodination has exclusively been applied to aromatic residues. In this work, an aliphatic bis-iodinated amino acid was synthesized and included into a custom pentapeptide, which showed enhanced fibrillogenic behaviour. Peptide single crystal X-ray structure and powder X-ray diffraction on its dried water solution demonstrated the key role of iodine atoms in promoting intermolecular interactions that drive the peptide self-assembly into amyloid fibrils. These findings enlarge the library of halogenated moieties available for directing and engineering the self-assembly of amyloidogenic peptides.     

Chiral Fibers Formation Upon Assembly of Tetraphenylalanine Peptide Conjugated to a PNA Dimer

Self-assembly of biomolecules such as peptides, nucleic acids or their analogues affords supramolecular objects, exhibiting structures and physical properties dependent on the amino-acid or nucleobase composition. Conjugation of the peptide diphenylalanine (FF) to peptide nucleic acids triggers formation of self-assembled structures, mainly stabilized by interactions between FF. In this work we report formation of homogeneous chiral fibers upon self-assembly of the hybrid composed of the tetraphenylalanine peptide (4F) conjugated to the PNA dimer adenine-thymine (at). In this case nucleobases seem to play a key role in determining the morphology and chirality of the fibers. When the PNA “at” is replaced by guanine-cytosine dimer “gc”, disordered structures are observed. Spectroscopic characterization of the self-assembled hybrids, along with AFM and SEM studies is reported. Finally, a structural model consistent with the experimental evidence has also been obtained, showing how the building blocks of 4Fat arrange to give helical fibers.     

Multifunctional polyurethane foams with thermal energy storage/release capability

Journal of Thermal Analysis and Calorimetry - In this work, polyurethane (PU) insulating panels containing different amounts of a microencapsulated paraffin with a nominal melting temperature of...     

Fingerprinting pre-historical symbolic artefacts by a non-destructive methodological approach

Journal of Radioanalytical and Nuclear Chemistry - A contribution to the discussion about Vila Nova de São Pedro (VNSP) as a production centre of symbolic lithic artefacts, the origin of raw...