Dynamic interplay between phase separation and crystallization in a poly(?-caprolactone)/poly(ethylene glycol) oligomer blend

We have investigated the crystallization effect on the phase separation of a poly(?-caprolactone) and poly(ethylene glycol) oligomer (PCL/PEGo) blending system using simultaneous small-angle light scattering and differential scanning calorimetry (SALS/DSC) as well as simultaneous small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and DSC (SAXS/WAXS/DSC). When the PCL/PEGo system, of a weight ratio of 7/3, is quenched from a melt state (160 °C) to temperatures below the spinodal point and the melting temperature of PCL (63 °C), the structural evolution observed exhibits characteristics of (I) early stage of spinodal decomposition (SD), (II) transient pinning, (III) crystallization-induced depinning, and (IV) diffusion-limited crystallization. The time-dependent scattering data of SALS, SAXS and WAXS, covering a wide range of length scale, clearly show that the crystallization of PCL intervenes significantly in the ongoing viscoelastic phase separation of the system, only after the early stage of SD. The effect of preordering before crystallization revives the structural evolution pinned by the viscoelastic phase separation. The growth of SAXS intensity during the preordering period conforms to the Cahn-Hilliard theory. In the later stage of the phase separation, the PCL-rich matrix, of spherulite crystalline domains developed due to the faster crystallization kinetics, traps the isolated PEGo-rich domains of a slower viscoelastic separation.     

The correlation between protein stability and dipole moment: a critical test

Improving the stability of proteins is a major aim in basic and applied protein science. Querol and coworkers calculated changes in the quasi-electric dipole moment of a protein and used it as a simple criterion to predict stabilizing charge mutations. They employed this method to propose for the bacterial cold shock protein Bc-Csp a number of charge mutations that should have a strong influence on stability. We produced eight variants of Bc-Csp with such mutations and measured their stabilities experimentally. However, we could not find a correlation between the stability and the quasi dipole moment of these variants. Possibly, the quasi dipole moment reflects only a secondary aspect of the changes that are caused by charge mutations in a protein.     

Dynamic mechanical measurements: Comparison between bending and torsion methods on a graphite-reinforced and a rubber-modified epoxy

Dynamic mechanical measurements in the cantilever bending and torsion rectangular modes were compared on two epoxy samples: one unidirectionally reinforced by 42 vol.% graphite fibers, the other modified by 15 wt.% carboxy terminated acrylonitrile butadiene rubber. Two forced oscillation instruments were used: cantilever bending on a Polymer Labs DMTA and torsion with a Rheometrics System Four. In the cantilever mode, the storage modulus on both samples was measured at about two to three times too low because of compliance of the instrument. The two instruments agreed and appeared to measure accurately tan δ on the graphite-reinforced samples. Agreement was only fair on tan δ for the rubber-modified sample. Multiple frequency data were used to separate the glass-transition temperature of the rubber from the epoxy β transition. Activation energies of these transitions are within the range reported. This study demonstrates the value of forced oscillation methods and the importance of selecting sample dimensions to fit instrument limits.     

Correlation between stability of a protein and its dipeptide composition: a novel approach for predicting in vivo stability of a protein from its primary sequence

Statistical analysis of 12 unstable and 32 stable proteins revealedthat there are certain dipeptides, the occurrence of which issignificantly different in the unstable proteins compared withthose in the stable ones. Based on the impact of these dipeptideson the unstable proteins over the stable ones, a weight valueof instability is assigned to each of the dipeptides. For agiven protein the summation of these weight values normalizedto the length of its sequence helps to distinguish between unstableand stable proteins. Results suggest that the in vivo instabilityof proteins is possibly determined by the order of certain aminoacids in its sequence. An attempt is made to correlate metabolicstability of proteins with features of their primary sequencewhere weight values of instability for a protein of known sequencecould thus be used as an index for predicting its stabilitycharacteristics.     

H2S在颗粒脱硫剂上反应的动力学性能

以自制含３０％Ｋ２ＣＯ３的固体脱硫剂在２０℃常压下分离Ｎ２－Ｈ２Ｓ气体混合物,Ｈ２Ｓ与柱形颗粒固体中的Ｋ２ＣＯ３反应的动力学性能。在灰层扩散控制区,由核收缩模型得到的方程：Ｋｔ＝（１－ｘ）ｌｎ（１－ｘ）＋ｘ能很好地描述实验数据,并由此得到了Ｈ２Ｓ的颗粒灰层内的有效扩散系数。发现在低浓度条件下,Ｈ２Ｓ在灰层内的有效扩散系数与其浓度无关。     

Grain growth and segregation in Fe-doped SrTiO3: Experimental evidence for solute drag

In functional ceramics, the impact of dopants on bulk crystals is generally well understood. Their impact on grain boundaries is less well known. The present study investigates the impact of acceptor dopants on grain growth in strontium titanate. Scanning electron microscopy and analytical (scanning) transmission electron microscopy have been used to gain knowledge on Fe segregation behavior, grain sizes, and grain size distributions of SrTiO₃. While undoped microstructures show normal grain growth at low temperatures (<1350 °C), doped microstructures evolve bimodally. With increasing acceptor dopant concentration, an increasing population of small grains develops. It is shown that Fe segregates to the grain boundaries due to its negative charge and a positive boundary potential. Thus, the experimental findings seem to be well explained by the theory of solute drag: The diffusion of segregated defects (‘solutes’) at grain boundaries can retard grain boundary migration.     

H2O2/nitrite-induced post-translational modifications of human hemoglobin determined by mass spectrometry: redox regulation of tyrosine nitration and 3-nitrotyrosine reduction by antioxidants

Covalent modifications of proteins by endogenous reactive nitrogen oxide species lead to cytotoxic effects that are implicated in diseases associated with chronic infections and inflammation. Tyrosine nitration is a major post-translational modification of proteins by reactive nitrogen oxide species. Recent studies suggest that nitrotyrosine is not a permanent protein modification. We previously demonstrated that lipoyl dehydrogenase is capable of converting 3-nitrotyrosine into 3-aminotyrosine in the presence of certain reducing agents. In this study, we compared the abilities of various hemoproteins, hemin, and the cobalt-containing cofactor cyanocobalamin to mediate H(2)O(2)/nitrite-dependent tyrosine nitration and found that these hemoproteins and metal-containing cofactors also catalyzed the reduction of 3-nitrotyrosine to various extents in the presence of thiol reducing agents or ascorbate. The H(2)O(2)/nitrite-induced post-translational modifications of human hemoglobin identified by nanoLC/nanospray ionization tandem mass spectrometric analysis of the tryptic digest include nitration of tyrosine and tryptophan, as well as oxidation of methionine and cysteine residues. Nitration of human hemoglobin by H(2)O(2)/nitrite was detected on Tyr24 and Tyr42 (alpha-chain) and on Tyr130 and Trp15 (beta-chain) in the alphabeta-dimer. Oxidation of methionine and cysteine residues was also observed. Furthermore, hemoglobin also catalyzed nitro reduction of 3-nitrotyrosine to form 3-aminotyrosine, at Tyr24 in the alpha-chain peptide of human Hb in the presence of ascorbate. The enhanced peroxidase activity of nitrated hemoglobin can be reversed by the antioxidant ascorbate. These results suggest a possible in vivo pathway for hemoglobin contributing to denitration of nitrated proteins through redox regulation.     

Melamine-(H2SO4)3/melamine-(HNO3)3 instead of H2SO4/HNO3: a safe system for the fast oxidation of thiols and sulfides under solvent-free conditions

Melamine reacted with neat sulfuric acid and fuming nitric acid readily to form two new organic solid acids, namely melamine-(H₂SO₄)₃ and melamine-(HNO₃)₃. Mixture of them acts as a unique powerful system instead of a hazardous H₂SO₄/HNO₃ system for the direct oxidation of thiols. Also, this system can oxidize the sulfides in the presence of a catalytic amount of KBr and few drops of water. This procedure offers advantages such as very low reaction time, simple work-up, excellent yield and matching with some green chemistry protocols.     

On the nature and importance of the transition between molecules and nanocrystals: towards a chemistry of "nanoscale perfection"

This paper discusses the importance of the transition between molecular compounds and nanocrystals. The boundary between molecular and nanocrystals/nanoclusters can be defined by the emergence of the bulk phase; atoms in the core of the nanoclusters that are not bound to ligands. This transition in dimensions and structural organization is important because it overlaps with the boundary between atomically defined moieties (molecules can be isolated with increasing purity) and mixtures (nanocrystals have a distribution of sizes, shapes, and defects; they cannot be easily separated into batches of structurally identical species). Passing through this boundary, as the size of a structure increases beyond a few nanometres, the information about the position of each atom gradually disappears. This loss of structural information about a chemical structure fundamentally compromises our ability to use it as a part of a complex chemical system. If we are to engineer complex functions encoded in a chemical language, we will need pure batches of atomically defined (truly monodisperse) nanoscale compounds, and we will need to understand how to make them and preserve them over a broad range of length scales, compositions, and timeframes. In this review we survey most classes of monodisperse nanomaterials (mostly nanoclusters) and highlight the recent breakthroughs in this area which might be spearheading the development of a chemistry of "nanoscale perfection".     

Enhancement of up-conversion emission and emerging cool white light emission in co-doped Yb3+/ Er3+: Li2O-LiF-B2O3-ZnO glasses for photonic applications

A series of co-doped (Yb³⁺/Er³⁺): Li₂O-LiF-B₂O₃-ZnO glasses were prepared by standard melt quenching technique. Structural and morphological studies were carried out by XRD and FESEM. Phonon energy dynamics have been clearly elucidated by Laser Raman analysis. The pertinent absorption bands were observed in optical absorption spectra of singly doped and co-doped Yb³⁺/Er³⁺: LBZ glasses. We have been observed a strong up-conversion red emission pertaining to Er³⁺ ions at 1.0 mol% under the excitation of 980 nm. However, the up-conversion and down conversion (1.53 µm) emission intensities were remarkably enhanced with the addition of Yb³⁺ ions to Er³⁺: LBZ glasses due to energy transfer from Yb³⁺ to Er³⁺. Up-conversion emission spectra of co-doped (Yb³⁺/Er³⁺): LBZ glasses exhibits three strong emissions at 480 nm, 541 nm and 610 nm which are assigned with corresponding electronic transitions of ²H_9/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 respectively. Consequently, the green to red ratio values (G/R) also supports the strong up-conversion emission. The Commission International de E′clairage coordinates and correlated color temperatures (CCT) were calculated from their up-conversion emission spectra of co-doped (Yb³⁺/Er³⁺): LBZ glasses. The obtained chromaticity coordinates for optimized glass (0.332, 0.337) with CCT value at 5520 K are very close to the standard white colorimetric point in cool white region. These results could be suggested that the obtained co-doped (Yb³⁺/Er³⁺): LBZ glasses are promising candidates for w-LEDs applications.     

Towards Dynamic Drug Design: Identification and Optimization of β‐Galactosidase Inhibitors from a Dynamic Hemithioacetal System

A discovery strategy relying on the identification of fragments through resolution of a constitutional dynamic system, coupled to subsequent static ligand design and optimization, is demonstrated. The strategic design and synthesis of the best molecular fragments identified from a dynamic hemithioacetal system into static ligand structures yielded a range of β‐galactosidase inhibitors. Two series of structures mimicking the hemithioacetal motif were envisaged: thioglycosides and C‐glycosides. Inhibition studies provided important structural information for the two groups, and 1‐thiobenzyl‐β‐D ‐galactopyranoside demonstrated the best inhibitory effects.     

Interaction between CD3OH and a H-mordenite studied by 1H NMR, broad-line at 4 K and MAS at 300 K

The simulation of 4 K ¹H broad-line NMR spectra of CD₃OH interacting with the acidic OH groups of H-mordenite zeolite shows no CD₃OH₂ ⁺ ions but hydrogen-bonded complexes. For high CD₃OH concentrations, clusters of hydrogen-bonded methanol molecules are formed, also hydrogen-bonded to Brønsted acid sites of the zeolite. The 300 K ¹H MAS spectra prove that the desorbed H-mordenite sample contains also silanol groups in electrostatic interaction with the framework; these silanols do not interact with methanol under our experimental conditions.     

Physicochemical factors for discriminating between soluble and membrane proteins: hydrophobicity of helical segments and protein length

The average hydrophobicity of a polypeptide segment is consideredto be the most important factor in the formation of transmembranehelices, and the partitioning of the most hydrophobic (MH) segmentinto the alternative nonpolar environment, a membrane or hydrophobiccore of a globular protein may determine the type of proteinproduced. In order to elucidate the importance of the MH segmentin determining which of the two types of protein results froma given amino acid sequence, we statistically studied the characteristicsof MH helices, longer than 19 residues in length, in 97 membraneproteins whose three-dimensional structure or topology is known,as well as 397 soluble proteins selected from the Protein DataBank. The average hydrophobicity of MH helices in membrane proteinshad a characteristic relationship with the length of the protein.All MH helices in membrane proteins that were longer than 500residues had a hydrophobicity greater than 1.75 (Kyte and Doolittlescale), while the MH helices in membrane proteins smaller than100 residues could be as hydrophilic as 0.1. The possibilityof developing a method to discriminate membrane proteins fromsoluble ones, based on the effect of size on the type of proteinproduced, is discussed.     

Sequence differences between glycosylated and non-glycosylated Asn-X-Thr/Ser acceptor sites: implications for protein engineering

In N-glycosylated glycoproteins, carbohydrate is attached toAsn in the sequence Asn-X-Ser/Thr, where X denotes any aminoacid. However, the presence of this consensus peptide does notalways lead to glycosylation. We have compiled an extensivecollection of glycosylated and non-glycosylated Asn-X-Thr/Sersites and present a statistical study based on this data set.Our results indicate that non-glycosylated sites tend to befound more frequently towards the C termini of glycoproteins,and that proline residues in positions X and Y in the consensusAsn-X-Thr/Ser-Y strongly reduce the likelihood of N-linked glycosylation.Beyond this, there are no obvious local sequence features thatseem to correlate with the absence or presence of N-linked glycosylation.These findings are discussed in terms of the prediction andengineering of glycosylation sites in secretory proteins.     

MolCom: a method to compare protein molecules based on 3-D structural and chemical similarity

This paper describes an improved method for conducting globalfeature comparisons of protein molecules in three dimensionsand for producing a new form of multiple structure alignment.Our automated MolCom method incorporates an octtree strategyto partition and examine molecular properties in three-dimensionalspace at multiple levels of analysis. The MolCom method’smultiple alignment is in the form of an octtree which locatesregions in three-dimensional space where correspondence betweenmolecules is identified based on a dynamic set of molecularfeatures. MolCom offers a practical solution to the inherentcompromise between computational complexity and analytical detail.MolCom is currently the only method that can analyze and comparea series of defined physicochemical properties using multiple,simultaneous levels of resolution. It is also the only methodthat provides a consensus structure outlining precisely wherethe similarity exists in three-dimensional space. Using a modest-sizedcollection of structural properties, separate experiments wereconducted to calibrate MolCom and to verify that the spatialanalyses and resulting structure alignments accurately identifiedboth similar and dissimilar structures. The accuracy of MolComwas found to be over 99% and the similarity scores correlatedstrongly with the z-scores of the Alignment by Incremental CombinatorialExtension of the Optimal Path method.     

Aromatization of propane over Ga/H-ZSM-5: An explanation of the synergy observed between Ga3+ and H+

The aromatization of propane is investigated for Ga₂O₃, H-ZSM-5 and Ga₂O₃/H-ZSM-5 catalysts, and the results are discussed for a series of ZSM-5 catalysts containing varying SiO₂/Al₂O₃ ratios. It is apparent that on addition of a gallium phase to H-ZSM-5, the yield of methane is significantly decreased. These results are discussed with respect to the mechanism of formation of the initial reaction product from propane. It is proposed that the synergy observed between the gallium compound and the zeolite can be explained in terms of a mechanism in which the role of the gallium phase is to induce C-H bond polarization in the propane, which leads to attack via the Bronsted acid sites of the zeolite, which leads to initial C-H bond cleavage occurring.     

Fe3O4@MCM-41@NH-SO3H: an Efficient Magnetically Reusable Nano-Catalyst for the Formylation of Amines and Alcohols

Silicon - In this article the preparation of Fe3O4@MCM-41@NH-SO3H, a new sulfonated magnetic mesoporous nanocomposite, is reported. The introduced catalyst is structurally based on MCM-41 as the...