Electronic structure and magnetic properties of Al‐doped Ca2Fe2O5 brownmillerite compounds

Polycrystalline Ca₂Fe_2?xAl_xO₅ (x = 0‐1.4) samples were prepared by conventional solid‐state reactions. Their crystalline/electronic structures and magnetic properties were characterized in detail. Powder X‐ray diffraction analyses revealed that the samples crystallized in orthorhombic brownmillerite‐type structures with the occurrence of the Pcmn‐Ibm2 phase separation in the region between x = 0.4 and 0.6. The results obtained from analyzing Raman scattering and X‐ray‐absorption fine‐structure spectra also indicated this phase separation. Although x in Ca₂Fe_2?xAl_xO₅ varies in a wide range from 0 to 1.4, the +3 oxidation state of Fe remained almost unchanged. Magnetization measurements revealed that all Ca₂Fe_2?xAl_xO₅ samples have weak ferromagnetic order, and both the saturation magnetization and coercive force are dependent on the temperature, x, and structure phases.     

Late-Stage Hydrocarbon Conjugation and Cyclisation in Synthetic Peptides and Proteins

The conventional S-alkylation of cysteine relies upon using activated electrophiles. Here we demonstrate high-yielding and selective S-alkylation and S-lipidation of cysteines in unprotected synthetic peptides and proteins by using weak electrophiles and a Zn²⁺ promoter. Linear or branched iodoalkanes can S-alkylate cysteine in an unprotected 38-residue Myc peptide fragment and in a 91-residue miniprotein Omomyc, thus highlighting selective late-stage synthetic modifications. Metal-assisted cysteine alkylation is also effective for incorporating dehydroalanine into unprotected peptides and for peptide cyclisation via aliphatic thioether crosslinks, including customising macrocycles to stabilise helical peptides for enhanced uptake and delivery to proteins inside cells. Chemoselective and efficient late-stage Zn²⁺-promoted cysteine alkylation in unprotected peptides and proteins promises many useful applications.     

Phase evolution,crystal structure,and microwave dielectric properties of gillespite-type ceramics

A gillespite-structured MCuSi₄O₁₀ (M = Ba_1-xSr_x, Sr_1-xCa_x) ceramics with tetrahedral structure (P4/ncc) were prepared by solid-state reaction method. X-ray diffraction and thermogravimetry with differential scanning calorimetry (TG-DSC) were employed to study the phase synthesis process of BaCuSi₄O₁₀. Pure BaCuSi₄O₁₀ phase was obtained at 1075°C and decomposed into BaSiO₃, BaCuSi₂O₆, and SiO₂ when calcined at 1200°C. The relationships between the crystal structure and microwave dielectric properties of MCuSi₄O₁₀ ceramics were revealed based on the Rietveld refinement and P-V-L complex chemical bond theory. The dielectric constant (ε_r) decreased linearly with decreasing total bond susceptibility and ionic polarizability. Quality factor (Q × f) was closely dependent on bond strength and lattice energy. The temperature coefficient of resonant frequency (τ_f) was controlled by the stability of [CuO₄]⁶⁻ plane in MCuSi₄O₁₀. Optimum microwave dielectric properties were obtained for SrCuSi₄O₁₀ when sintered at 1100°C for 3 hours with a ε_r of 5.59, a Q × f value of 82 252 GHz, and a τ_f of −41.34 ppm/°C. Thus, SrCuSi₄O₁₀ is a good candidate for millimeter-wave devices.     

Near infrared light-induced disassembly of polymeric micelles based on methylene blue conjugated polyethylene glycol

Light-sensitive drug delivery systems are considered ideal for applications in the biomedical fields for their ability to release the payload in an on-demand spatiotemporal controlled manner through the manipulation of the light source. Among the broad radiation spectrum, near infrared (NIR) light is considered advantageous compared to UV and visible light, due to its inherently lower photodamage to normal tissues and deeper penetration to lesion areas. In this study, we report a successful synthesis of a polymer capable of undergoing partial degradation upon irradiation with NIR light by conjugating 10-N-carbamoyl linkage methylene blue (MB) moiety, a NIR photocleavable ligand, with polyethylene glycol (PEG). Through effective coupling of MB, a hydrophobic moiety, to the hydrophilic PEG molecule, an amphiphilic polymer was synthesized, as demonstrated by a lowered surface tension (55 mN/m at 0.1% wt/vol). Subsequently, photo-induced reversal of surface activity associated with self-assembled structure disruption, was displayed by surface tension measurements, size distribution analysis, and burst release profile of paclitaxel (PTX) from polymeric micelles upon the exposure to NIR irradiation.     

Kinetics of reversible addition–fragmentation transfer (RAFT) miniemulsion polymerization of styrene using dibenzyl trithiocarbonate as RAFT reagent and costabilizer

The roles of dibenzyl trithiocarbonate (DBTTC) as both costabilizer and reversible addition–fragmentation transfer (RAFT) reagent in RAFT miniemulsion polymerizations of styrene were investigated. The effectiveness of DBTTC costabilizer in retarding Ostwald ripening involved in the storage stability of miniemulsion is comparable to that of conventional low‐molecular‐weight costabilizers such as cetyl alcohol, but inferior to that of hexadecane. The major variables chosen for studying kinetics of RAFT miniemulsion polymerizations include the type of initiators and levels of DBTTC and surfactant. At a constant level of DBTTC, the rate of polymerization for benzoyl peroxide (BPO)‐initiated polymerization is slower than that for sodium persulfate (SPS)‐initiated polymerization. Furthermore, the polymerization rate decreases with increasing level of DBTTC for polymerizations initiated by BPO (or SPS). It is the monomer droplet nucleation that governs BPO‐initiated polymerizations. In contrast, for SPS‐initiated polymerizations, the probability for homogeneous nucleation to take place is greatly increased, especially for polymerizations with lower levels of DBTTC and higher levels of surfactant. © 2015 Society of Chemical Industry     

Comparative study of methods for producing gum arabic powder and the impact of DIC treatment (instant controlled pressure drop) on the properties of the product

In this study, gum arabic powder was produced according to four methods by inserting a restructuring stage by DIC treatment (instant controlled pressure drop) in the classic process of grinding and spray drying. Properties of the final product were compared, and the results show that DIC treatment enables to control and improve the properties of the powder. The DIC treatment can cause a controlled increase in the tapped bulk density, filling rate, compressibility, porosity; and a reduction in interstitial air volume and the loose bulk density. It also facilitated the subsequent grinding and intensified the drying kinetics. The impacts of pressure and DIC treatment time were examined. Pressure was the strongest factor influencing the properties of the gum arabic powder. Selecting an optimal pressure and treatment time plays a decisive role in controlling the properties of powders.     

Oscillator strengths of allowed transitions for O III

The electric dipole oscillator strengths for lines in O III between some singlet and triplet levels have been calculated using the weakest bound electron potential model theory and the quantum defect orbital theory. In the calculations, both multiplet and fine-structure transitions are studied. The calculated oscillator strengths have been compared with available theoretical and experimental results. Good agreement with results in the literature has been obtained.