Tube-like natural halloysite/fluoroelastomer nanocomposites with simultaneous enhanced mechanical, dynamic mechanical and thermal properties

A novel kind of fluoroelastomer nanocomposites based on tube-like halloysite clay mineral were successfully prepared using a bis-phenol curing system, which resulted in prominent improvements in mechanical and dynamic mechanical properties and in the elevation as high as 30 K of the thermal decomposition temperature. Wide-angle X-ray scattering and transmission electron microscopy techniques were employed to assess the morphology developed in the nanocomposites, while stress strain diagrams were used to evaluate the mechanical properties. These nanocomposites were further characterized by moving die rheometer, dynamic mechanical properties and thermo-gravimetric analysis. Structure-properties relationship and the improvement of the mechanical, dynamic mechanical and thermal properties of fluoroelastomers are reported in the present study. Increasing amount of the filler reduced the curing efficiency of the bis-phenol curing system, which was evident from the rheometric and physical properties of the resulting composites. A sort of filler–filler interaction was perceived during the strain sweep analysis of the composites. The polymer–filler interaction was reflected in the improved mechanical and thermal properties which were the consequence of proper dispersion of the nanotubes in the polymer matrix; whereas the intercalation of macromolecular chains into the nanotubes was not reflected in the X-ray diffraction analysis.     

Allylation of N‐Benzoylhydrazones (=N′‐Alkylidene‐Substituted Benzohydrazides) by Treatment with Allyl Bromide in the Presence of Zinc in Aqueous Ammonium Chloride Solution

N‐Benzoylhydrazones (=N′‐alkylidene‐substituted benzohydrazides) 1 are allylated efficiently by reaction with allyl bromide ( 2 ) in the presence of Zn in aqueous NH₄Cl solution. The products 3 are formed in excellent yields (85–94%) within 35–50 min (Scheme, Table).     

Synthesis and chromatographic evaluation of molecularly imprinted polymers prepared by the substructure approach for the class-selective recognition of glucuronides

Two series of molecularly imprinted polymers (MIPs) for the class-selective recognition of glucuronides have been prepared by using lipophilic substructures of the target analyte as template molecule and potent host monomers against oxyanions, that are expected to establish a strong stoichiometric interaction with the single carboxylic group of the template. The polymers were tested as stationary phases in liquid chromatography for specific recognition. A preliminary investigation of the imprinting properties of eleven MIPs was carried out, by comparing the retention time of the template and of structurally related compounds on the MIP column with that on the corresponding non-imprinted polymer (NIP). The two polymers showing the best performance were selected to further test cotinine, mycophenolic acid, testosterone and their respective glucuronides as model compounds. The high specificity obtained against glucuronides and the different chemical structure of the parent drug make the two MIPs class-selective imprinted receptors, also suitable for SPE application.     

Total synthesis of (+)-mupirocin H from D-glucose

Enantioselective total synthesis of mupirocin H is accomplished starting from D-glucose featuring strategic application of D-glucose derived chirality, diastereoselective Still-Barrish hydroboration, and further elaboration of carbon chain to furnish a phenyltetrazolyl sulfone intermediate, which on coupling with (2S,3S)-2-methyl-3-(triisopropylsilyloxy)butanal under Julia-Kocienski olefination conditions gave an advanced E-olefinic intermediate selectively. The E-olefin was transformed to the 4-hydroxynitrile, a prefinal substrate, which on acid-catalyzed oxidative lactonization furnished the target molecule mupirocin H in 19 steps from known compound 6 (longest linear sequence) with an overall yield of 4.96%.     

Synthesis of pyridin-2(1H)-one derivatives via enamine cyclization

The nucleophilic vinylic substitution reaction of the aliphatic enaminone 3-dimethylamino-2-formyl acrylonitrile 1 with the nucleophiles malononitrile and ethyl cyanoacetate produced the two unusual reaction adducts 3a and 3b in good to moderate yield under milder reaction conditions. Upon reaction with aromatic amines, these adducts yielded enamines 4 and 5, which eventually cyclized in the presence of base to produce the novel pyridin-2(1H)-one derivatives 8 and 9.     

Synthesis and characterization of NiCoMnCuFe1.96O4 for circulator application

Modern accelerator design practice includes the use of high-quality ferrites for circulator applications with ever-increasing requirements on power handling ability. Modeling studies of new designs are of increasing economic importance, but are frequently hindered by lack of measured values of the ceramic loss factors. We have developed a nanocrystalline ferrite material with composition Ni_0.94Co_0.03Mn_0.04Cu_0.03Fe_1.96O₄. Nanocrystalline NiCoMnCu ferrite powders were synthesized using a microwave-hydrothermal method at 160 °C for 40 min. The ferrite formation conditions, such as pH, temperature and time, were optimized. The phase of the samples was identified by X-ray diffraction and was characterized by Fourier transformation infrared spectroscopy. The size of the nanocrystalline ferrite of as-synthesized powders was 10 nm. The powder was densified at different temperatures using a microwave sintering method. The complex permittivity and permeability of the sintered samples were measured over a frequency range from 10 kHz to 1.8 GHz at room temperature. The applicability of the samples for circulators was tested via the measurement of the ferromagnetic resonance linewidth and the results are presented.     

Efficient Access to Enantiopure γ4‐Amino Acids with Proteinogenic Side‐Chains and Structural Investigation of γ4‐Asn and γ4‐Ser in Hybrid Peptide Helices

Hybrid peptides composed of α‐ and β‐amino acids have recently emerged as new class of peptide foldamers. Comparatively, γ‐ and hybrid γ‐peptides composed of γ⁴‐amino acids are less studied than their β‐counterparts. However, recent investigations reveal that γ⁴‐amino acids have a higher propensity to fold into ordered helical structures. As amino acid side‐chain functional groups play a crucial role in the biological context, the objective of this study was to investigate efficient synthesis of γ⁴‐residues with functional proteinogenic side‐chains and their structural analysis in hybrid‐peptide sequences. Here, the efficient and enantiopure synthesis of various N‐ and C‐terminal free‐γ⁴‐residues, starting from the benzyl esters (COOBzl) of N‐Cbz‐protected (E)‐α,β‐unsaturated γ‐amino acids through multiple hydrogenolysis and double‐bond reduction in a single‐pot catalytic hydrogenation is reported. The crystal conformations of eight unprotected γ⁴‐amino acids (γ⁴‐Val, γ⁴‐Leu, γ⁴‐Ile, γ⁴‐Thr(OtBu), γ⁴‐Tyr, γ⁴‐Asp(OtBu), γ⁴‐Glu(OtBu), and γ‐Aib) reveals that these amino acids adopted a helix favoring gauche conformations along the central C^γ? C^β bond. To study the behavior of γ⁴‐residues with functional side chains in peptide sequences, two short hybrid γ‐peptides P1 (Ac‐Aib‐γ⁴‐Asn‐Aib‐γ⁴‐Leu‐Aib‐γ⁴‐Leu‐CONH₂) and P2 (Ac‐Aib‐γ⁴‐Ser‐Aib‐γ⁴‐Val‐Aib‐γ⁴‐Val‐CONH₂) were designed, synthesized on solid phase, and their 12‐helical conformation in single crystals were studied. Remarkably, the γ⁴‐Asn residue in P1 facilitates the tetrameric helical aggregations through interhelical H bonding between the side‐chain amide groups. Furthermore, the hydroxyl side‐chain of γ⁴‐Ser in P2 is involved in the interhelical H bonding with the backbone amide group. In addition, the analysis of 87 γ⁴‐residues in peptide single‐crystals reveal that the γ⁴‐residues in 12‐helices are more ordered as compared with the 10/12‐ and 12/14‐helices.     

An efficient and greener protocol towards synthesis of unsymmetrical N,N′-biphenyl urea

A simple and efficient route for the synthesis of Unsymmetrical N,N′-diphenyl urea have been developed in aqueous medium under base and catalyst free condition from corresponding substituted isocyanate and amines. The remarkable key feature of the reaction includes the use of water as an inexpensive and environmentally benign reaction medium, absence of base and any additional catalyst, and easy isolation of the product.     

Europium-Activated Orthophosphate Phosphors For Energy-Efficient Solid-State Lighting: A Review

As a new class of inorganic phosphor, orthophosphate phosphors materials have received great interest because of their potential applications in solid-state lightings and displays. In this article, we focus on current developments in the synthesis, crystal structure and luminescence properties of orthophosphate phosphors for solid-state lightings. We discuss the synthesis of a family of orthophosphate phosphor doped with europium (Eu²⁺ and Eu³⁺) by traditional and novel methods. In the fluorescent lamp, phosphor materials convert UV radiation into visible radiation. Lamp phosphors are mostly white in color and they should not absorb the visible radiation. New phosphors that can absorb excitation energy from blue or near ultraviolet (n-UV) LEDs and generate visible emissions efficiently are desired. The criteria of choosing the best phosphors, for blue (450–480 nm) and n-UV (380–400 nm) LEDs, strongly depends on the absorption and emission of the phosphors. Here, we will review the status of phosphors for solid-state lightings and prospect the future development. The impacts of doping of europium and photoluminescence properties on orthophosphate phosphors were investigated and we propose a feasible interpretation.     

Utilization of pneumatic carrier facility of Dhruva reactor for trace element determination by neutron activation analysis

The pneumatic carrier facility (PCF) of Dhruva reactor is being extensively used for neutron activation analysis (NAA) studies pertaining to research work as well as routine sample analysis. It is useful for the determination of trace elements using short and medium half-lives radioisotopes produced in neutron activation with available higher neutron flux (~5 × 10¹³ cm^?1 s^?1). Solid samples placed in high density polypropylene capsule, are irradiated for 1 min duration and radioactive assay is carried out by high resolution gamma ray spectrometry. Design aspects of PCF and various applications to samples of diverse matrices using NAA are presented.