Click‐ligation of coumarin to polyether polyols for polyurethane foams

A simple strategy for the synthesis and functionalization of polyurethanes is described. Anionic ring‐opening polymerization was combined with ‘click’ chemistry to synthesize polyols with fluorescent properties. This route allows the incorporation of a wide range of functionalities in the polyols with an easy, clean and highly selective process compatible with several types of functional groups. The proposed strategy opens the way to the production, in a cost‐effective way, of ‘smart’ polyurethanes with non‐conventional properties like fire retardancy, antimite properties, antibacterial properties, etc. Alkynyl groups were introduced into the polyol chains by the controlled addition of glycidyl propargyl ether as co‐monomer during a conventional anionic ring‐opening copolymerization with propylene oxide. Subsequently 4‐azidomethyl‐7‐methoxycoumarin molecules were introduced onto the alkynyl‐polyether polyols by copper‐catalysed cycloaddition reactions to produce end‐functionalized polyols. The chemical structure of the novel polyols was characterized using infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography with triple detection and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy. These characterization techniques confirmed the presence of a considerable amount of functional groups in the structure of the polyols. Finally, various fluorescent rigid foams, based on the functionalized polyols, were synthesized. Copyright © 2012 Society of Chemical Industry     

Photocatalytic degradation of 4-nitroaniline using solar and artificial UV radiation

The photocatalytic degradation (PCD) of 4-nitroaniline was studied in the presence of TiO₂ suspensions in a batch and continuous annular reactor. Artificial and solar radiation was employed as sources of UV radiation. The effect of catalyst loading, pH, presence of anions and initial concentration on the rate of photocatalytic degradation was investigated. p-Aminophenol, p-benzoquinone and hydroquinone were identified as the intermediates during the degradation process. A kinetic expression for PCD of 4-NA is provided.     

Fabrication and morphological control of three-dimensional cage type mesoporous titanosilicate with extremely high Ti content

TiSBA-1 materials with extremely high Ti content, up to silicon to titanium ratio (n_Si/n_Ti) of 2.4, have been successfully prepared through direct synthesis method by controlling the molar ratio of hydrochloric acid to silicon (n_HCl/n_Si). It has been found that the amount of Ti content and the structure of the TiSBA-1 can easily be controlled by the simple adjustment of n_HCl/n_Si ratio. X-ray diffraction pattern (XRD) of the obtained materials revealed that the materials are highly ordered and possess cubic three-dimensional cage type structure with open windows. N₂ adsorption–desorption measurement confirmed the narrow pore size distribution, high specific surface area (1317–1491 m² g⁻¹), and large specific pore volume (0.68–0.75 cm³ g⁻¹) for all the samples. UV–vis DR spectra of the prepared materials confirmed that Ti atoms are exclusively incorporated within silica framework and occupy the tetrahedral position while the presence of isolated bulk titania could be negligible. Morphologies of the TiSBA-1 materials have been also controlled by simply adjusting the n_Si/n_Ti ratio. With the appropriate Ti content, TiSBA-1 materials can be obtained as regular fine spheres. Moreover, the detailed mechanism on the morphological and phase transition control, and the incorporation of high amount of Ti in the framework of TiSBA-1 materials has been also discussed in detail.     

IN-SITU REDUCTION OF A METHANOL SYNTHESIS CATALYST IN A THREE-PHASE SLURRY REACTOR

ABSTRACT

A new method for the reduction of metal oxide catalysts has been developed, for the reduction of the CuO - ZnO - A1203 catalyst for liquid phase methanol synthesis. The reducing agent is a 5% hydrogen in nitrogen mixture and the operation is carried out at 446.09 KPa. This method makes it possible to reduce finely crushed catalyst (-100 + 120 mesh) in a three phase slurry reactor. This method offers several advantages over methods in which the catalyst is reduced in a gas-solid contact mode and then slurried for use. The catalyst has been shown to be very effectively reduced and reaches its full production capacity after reduction.     

Synthesis of submicron size hollow carbon spheres by a chemical reduction — solvothermal method using carbon tetrachloride as carbon source

A simple, rapid and energy efficient approach based on copper mediated chemical reduction — solvothermal method was employed to prepare submicron size hollow carbon spheres (SHCS) using carbon tetrachloride as carbon source. The obtained SHCS were characterized by means of various physico-chemical techniques like nitrogen adsorption-desorption measurements at 77 K, XRD, SEM, TEM, EDX and FT-Raman techniques. Thus characterized samples displayed macroporous nature of carbon with carbon and chloride contents of about 73% and 12% on atomic basis respectively. The presence of chloride content may open new avenues for surface modifications of SHCS in the area of catalysis and separation science.     

A survey of foodborne pathogens in bulk tank milk and raw milk consumption among farm families in pennsylvania

A 2-part study was conducted to determine the risk of exposure to human pathogens from raw milk. The first part of the study focused on determining raw milk consumption habits of dairy producers. A total of 248 dairy producers from 16 counties in Pennsylvania were surveyed. Overall, 105 (42.3%) of the 248 dairy producers consumed raw milk and 170 (68.5%) of the 248 dairy producers were aware of foodborne pathogens in raw milk. Dairy producers who were not aware of foodborne pathogens in raw milk were 2-fold more likely to consume raw milk compared with dairy producers who were aware of foodborne pathogens. The majority of dairy producers who consumed raw milk indicated that taste (72%) and convenience (60%) were the primary factors for consuming raw milk. Dairy producers who resided on the dairy farm were nearly 3-fold more likely to consume raw milk compared with those who lived elsewhere. In the second part of the study, bulk tank milk from the 248 participating dairy herds was examined for foodborne pathogens. Campylobacter jejuni (2%), Shiga toxin-producing Escherichia coli (2.4%), Listeria monocytogenes (2.8%), Salmonella (6%), and Yersinia enterocolitica (1.2%) were detected in the milk samples. Salmonella isolates were identified as S. enterica serotype Typhimurium (n = 10) and S. enterica serotype Newport (n = 5). Of the 248 bulk tank milk samples, 32 (13%) contained ≥1 species of bacterial pathogens. The findings of the study could assist in developing farm community-based educational programs on the risks of consuming raw milk.     

Identification of microglial signal transduction pathways mediating a neurotoxic response to amyloidogenic fragments of beta-amyloid and prion proteins

Microglial interaction with amyloid fibrils in the brains of Alzheimer's and prion disease patients results in the inflammatory activation of these cells. We observed that primary microglial cultures and the THP-1 monocytic cell line are stimulated by fibrillar beta-amyloid and prion peptides to activate identical tyrosine kinase-dependent inflammatory signal transduction cascades. The tyrosine kinases Lyn and Syk are activated by the fibrillar peptides and initiate a signaling cascade resulting in a transient release of intracellular calcium that results in the activation of classical PKC and the recently described calcium-sensitive tyrosine kinase PYK2. Activation of the MAP kinases ERK1 and ERK2 follows as a subsequent downstream signaling event. We demonstrate that PYK2 is positioned downstream of Lyn, Syk, and PKC. PKC is a necessary intermediate required for ERK activation. Importantly, the signaling response elicited by beta-amyloid and prion fibrils leads to the production of neurotoxic products. We have demonstrated in a tissue culture model that conditioned media from beta-amyloid- and prion-stimulated microglia or from THP-1 monocytes are neurotoxic to mouse cortical neurons. This toxicity can be ameliorated by treating THP-1 cells with specific enzyme inhibitors that target various components of the signal transduction pathway linked to the inflammatory responses.     

Diabetic ketoacidosis and rhabdomyolysis following excessive intake of a weight reducing diet

We describe two unusual cases in sheep of subclinical mastitis caused by Streptococcus parasanguinis. This bacterium has been associated with the development of experimental endocarditis; its presence at relatively high concentrations in apparently healthy sheep milk may pose a health risk in persons with predisposing heart lesions.     

The Australian brushtail possum (Trichosurus vulpecula) gonadotrophin alpha-subunit: analysis of cDNA sequence and pattern of expression

Substantial evidence has accumulated to suggest that in the near future implementation of the veto-cell-suppressor concept in the treatment of kidney allograft recipients might lead to the establishment of life-long specific allograft tolerance in the absence of further immunosuppressive therapy. Veto suppression prevents the generation of antigen-specific T-helper and cytotoxic T lymphocytes in vitro provided that the T-lymphocyte precursors specifically recognize antigenic peptides associated with the major histocompatibility complex molecules class II and class I, respectively, expressed on the surface of the veto-active cell. Data from a large number of experimental and clinical studies strongly indicate that veto-active cells function in vivo and are capable of preventing allograft rejection. Thus, donor-cell-mediated veto activity is the most likely explanation for the well-known graft tolerizing effect of pretransplant donor blood transfusions in kidney graft recipients. A prerequisite for a veto-active environment in vivo is the establishment of lymphoid microchimerism, in which veto-active donor and recipient cells mutually downregulate potential alloaggression.