Influence of β‐nucleation on polymorphism and properties in random copolymers and terpolymers of propylene

The competition between α, β, and γ polymorphs has been studied in several random copolymers and terpolymers of propylene, by performing X‐ray diffraction and differential scanning calorimetry experiments. Formation of β‐crystals, achieved by the addition of a β‐nucleating agent, was found to be highly dependent on comonomer type and crystallization conditions. Additionally, the mechanical properties have been evaluated from stress‐strain, microhardness and dynamic‐mechanical thermal analyses. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Characterisation of the Dynamic Interactions between Complex N-Glycans and Human CD22

CD22 (Siglec-2) is a B-cell surface inhibitory protein capable of selectively recognising sialylated glycans, thus dampening autoimmune responses against self-antigens. Here we have characterised the dynamic recognition of complex-type N-glycans by human CD22 by means of orthogonal approaches including NMR spectroscopy, computational methods and biophysical assays. We provide new molecular insights into the binding mode of sialoglycans in complex with h-CD22, highlighting the role of the sialic acid galactose moieties in the recognition process, elucidating the conformational behaviour of complex-type N-glycans bound to Siglec-2 and dissecting the formation of CD22 homo-oligomers on the B-cell surface. Our results could enable the development of additional therapeutics capable of modulating the activity of h-CD22 in autoimmune diseases and malignancies derived from B-cells.     

Synthesis,characterization and rheological properties of multiblock associative copolymers by RAFT technique

Polymer Bulletin - Preparation of associating multiblock copolymer electrolytes mediated by radical addition–fragmentation chain transfer (RAFT) technique has been evaluated and reported in...     

Selective homogeneous and heterogeneous catalytic conversion of methanol/dimethyl ether to triptane

The demand for specific fuels and chemical feed-stocks fluctuates, and as a result, logistical mismatches can occur in the supply of their precursor raw materials such as coal, biomass, crude oil, and methane. To overcome these challenges, industry requires a versatile and robust suite of conversion technologies, many of which are mediated by synthesis gas (CO + H(2)) or methanol/dimethyl ether (DME) intermediates. One such transformation, the conversion of methanol/DME to triptane (2,2,3-trimethylbutane) has spurred particular research interest. Practically, triptane is a high-octane, high-value fuel component, but this transformation also raises fundamental questions: how can such a complex molecule be generated from such a simple precursor with high selectivity? In this Account, we present studies of this reaction carried out in two modes: homogeneously with soluble metal halide catalysts and heterogeneously over solid microporous acid catalysts. Despite their very different compositions, reaction conditions, provenance, and historical scientific context, both processes lead to remarkably similar products and mechanistic interpretations. In both cases, hydrocarbon chains grow by successive methylation in a carbocation-based mechanism. The relative rates of competitive processes-chain growth by methylation, chain termination by hydrogen transfer, isomerization, and cracking-systematically depend upon the structure of the various hydrocarbons produced, strongly favoring the formation of the maximally branched C(7) alkane, triptane. The two catalysts also show parallels in their dependence on acid strength. Stronger acids exhibit higher methanol/DME conversion but also tend to favor chain termination, isomerization, and cracking relative to chain growth, decreasing the preference for triptane. Hence, in both modes, there will be an optimal range: if the acid strength is too low, activity will be poor, but if it is too high, selectivity will be poor. A related reaction, the methylative homologation of alkanes, offers the possibility of upgrading low-value refinery byproducts such as isobutane and isopentane to more valuable gasoline components. With the addition of adamantane, a hydride transfer catalyst that promotes activation of alkanes, both systems effectively catalyze the reaction of methanol/DME with lighter alkanes to produce heavier ones. This transformation has the further advantage of providing stoichiometric balance, whereas the stoichiometry for conversion of methanol/DME to alkanes is deficient in hydrogen and requires rejection of excess carbon in the form of carbon-rich arenes, which lowers the overall yield of desired products. Alternatively, other molecules can serve as sacrificial sources of hydrogen atoms: H(2) on heterogeneous catalysts modified by cations that activate it, and H(3)PO(2) or H(3)PO(3) on homogeneous catalysts. We have interpreted most of the features of these potentially useful reactions at a highly detailed level of mechanistic understanding, and we show that this interpretation applies equally to these two widely disparate types of catalysts. Such approaches can play a key role in developing and optimizing the catalysts that are needed to solve our energy problems.     

Molecular Epidemiology of Enteroaggregative Escherichia coli (EAEC) Isolates of Hospitalized Children from Bolivia Reveal High Heterogeneity and Multidrug-Resistance

Enteroaggregative Escherichia coli (EAEC) is an emerging pathogen frequently associated with acute diarrhea in children and travelers to endemic regions. EAEC was found the most prevalent bacterial diarrheal pathogen from hospitalized Bolivian children less than five years of age with acute diarrhea from 2007 to 2010. Here, we further characterized the epidemiology of EAEC infection, virulence genes, and antimicrobial susceptibility of EAEC isolated from 414 diarrheal and 74 non-diarrheal cases. EAEC isolates were collected and subjected to a PCR-based virulence gene screening of seven virulence genes and a phenotypic resistance test to nine different antimicrobials. Our results showed that atypical EAEC (a-EAEC, AggR-negative) was significantly associated with diarrhea (OR, 1.62, 95% CI, 1.25 to 2.09, p < 0.001) in contrast to typical EAEC (t-EAEC, AggR-positive). EAEC infection was most prevalent among children between 7–12 months of age. The number of cases exhibited a biannual cycle with a major peak during the transition from warm to cold (April–June). Both typical and a-EAEC infections were graded as equally severe; however, t-EAEC harbored more virulence genes. aap, irp2 and pic were the most prevalent genes. Surprisingly, we detected 60% and 52.6% of multidrug resistance (MDR) EAEC among diarrheal and non-diarrheal cases. Resistance to ampicillin, sulfonamides, and tetracyclines was most common, being the corresponding antibiotics, the ones that are frequently used in Bolivia. Our work is the first study that provides comprehensive information on the high heterogenicity of virulence genes in t-EAEC and a- EAEC and the large prevalence of MDR EAEC in Bolivia.     

The method of moments used in polymerization reaction engineering for 70 years: An overview,tutorial, and minilibrary

In the last seven decades, the method of moments (MoM) has become an invaluable tool in the field of polymerization reaction engineering, due to the simplicity of translating a complex set of population balance equations (PBE) into a system with a limited number of equations. In this work, we offer an overview of the MoM, describing the derivation of the moment equations in a basic kinetic mechanism. Some tools and strategies for the derivation of the moment equations are reviewed and explained in detail, such as the binomial theorem, the method of series expansion and pattern identification (SEPI), extensively used by the community, and a graphical approach of summation inversion. The treatment for multivariate distributions is also exposed, taking advantage of the complete and partial moment techniques. The derivation of the MoM contribution by kinetic mechanisms beyond the basic ones or involving special difficulties, such as depropagation, long chain branching (LCB), random chain scission, LCB and β-scission, short chain branching (SCB) and scission, internal double bond (IDB) (polymerization), termination by combination, reversible deactivation radical polymerization (RDRP), and intermolecular transesterification reactions (ITRs), are explained in a tutorial way. Additionally, the fundamentals of the MoM in copolymerization and the application of the pseudo-homopolymerization approach are briefly described. An introduction of the MoM to emulsion polymerization is also presented. Finally, some advanced applications of MoM in recent works are exposed: MoM models with chain-length dependent or diffusion-controlled termination, and the extension of the MoM for the prediction of the molecular weight distribution (MWD ) .     

A Facile and Green Microwave-Assisted Strategy to Induce Surface Properties on Complex-Shape Polymeric 3D Printed Structures

Light- induced polymeric 3D printing is becoming a well-established fabrication method, showing manifold advantages such as control of the local chemistry of the manufactured devices. It can be considered a green technology, since the parts are produced when needed and with minimum amount of materials. In this work 3D printing is combined with another green technology, microwave-assisted reaction, to fabricate objects of complex geometry with controllable surface properties, exploiting the presence of remaining functional groups on the surface of 3D printed specimens. In this context, surface functionalization with different amines is studied, optimizing formulations, reaction times, and avoiding surface deterioration. Then, two different applications are investigated. MW-functionalized filter-type structures have been tested against Staphylococcus aureus bacteria, showing high bactericidal activity on the surface along all areas of the complex-shaped structure. Second, a fluidic chip composed of three separated channels is 3D printed, filled with different amine-reactive dyes (dansyl and eosine derivatives), and made to react simultaneously. Complete and independent functionalization of the surface of the three channels is achieved only after 2 min of irradiation. This study demonstrates that light induced 3D printing and microwave-induced chemistry can be used together effectively, and used to produce functional devices.     

Characterization of nickel-bearing ferrites obtained as by-products of hydrochemical wastewater purification processes

The efficiency of the ‘ferrite process’ for the purification of wastewater heavily contaminated with nickel is evaluated, and the solid residues formed are characterised. The efficiency of the purification process is always above 99.9% for Fe²⁺/Ni²⁺ ratios greater than 3. The tested Fe²⁺/Ni²⁺ molar ratios (15/1, 7/1 and 3/1) yielded three different nickel ferrites. Inductively-coupled plasma atomic emission spectroscopy (ICP-AES), potentiometric titration, X-ray fluorescence (XRF), X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) yielded Ni_xFe_1−x^IIFe₂^IIIO₄ (x=0.18, 0.40 and 0.65, respectively) as the most probable stoichiometry, and inverse spinel as the most probable structure. Heating at 600 °C causes the transformation of the solids into a mixture of NiFe₂O₄, α-Fe₂O₃ and NiO. Electrochemical analysis of the solid nickel ferrites was performed using carbon paste electrodes (CPEs) in HClO₄ and HCl media. In each case, the first cyclic voltammogram showed the participation of solid species in the electrochemical transformation process, since the shape of the redox peaks could be related to the structure and stoichiometry of the ferrites. In second and successive scans, the voltammograms indicated the redox couples Fe_ads³⁺+1e⁻⇔Fe_ads²⁺ (0.525 V vs. Ag/AgCl) and Ni_ads²⁺+2e⁻⇔Ni(s) (−0.470 V) in HClO₄, and FeCl_2,ads⁺+1e⁻⇔FeCl_ads⁺+Cl⁻ (0.475 V) and NiCl_x,ads^(x−2)−+2e⁻⇔Ni(s)+xCl⁻ (−0.550 V) in HCl.