Glycol-modified silanes: novel possibilities for the synthesis of hierarchically organized (hybrid) porous materials

The preparation of porous hierarchical architectures that have structural features spanning from the nanometer to micrometer and even larger dimensions and that exhibit certain functionalities is one of the new challenging frontiers in materials chemistry. The sol-gel process is one of the most promising synthesis routes toward such materials because it not only offers the possibility to incorporate organic functions into the porous host but also offers the possibility to deliberately tailor the pore structure. In this Account, the opportunities given by the application of novel diol-modified silanes are discussed for the synthesis of hierarchically organized inorganic and also inorganic-organic porous monoliths.     

Cell-Free DNA Fragments as Biomarkers of Islet β-Cell Death in Obesity and Type 2 Diabetes

Type 2 diabetes (T2D) typically occurs in the setting of obesity and insulin resistance, where hyperglycemia is associated with decreased pancreatic β-cell mass and function. Loss of β-cell mass has variably been attributed to β-cell dedifferentiation and/or death. In recent years, it has been proposed that circulating epigenetically modified DNA fragments arising from β cells might be able to report on the potential occurrence of β-cell death in diabetes. Here, we review published literature of DNA-based β-cell death biomarkers that have been evaluated in human cohorts of islet transplantation, type 1 diabetes, and obesity and type 2 diabetes. In addition, we provide new data on the applicability of one of these biomarkers (cell free unmethylated INS DNA) in adult cohorts across a spectrum from obesity to T2D, in which no significant differences were observed, and compare these findings to those previously published in youth cohorts where differences were observed. Our analysis of the literature and our own data suggest that β-cell death may occur in subsets of individuals with obesity and T2D, however a more sensitive method or refined study designs are needed to provide better alignment of sampling with disease progression events.     

Moving ion fronts in mixed ionic‐electronic conducting polymer films

The aim of this paper is to analyze moving front dynamics of ions and holes in a planar, mixed ionic‐electronic conducting polymer film. As cations invade the film, holes evacuate; thus, an ionic current is converted to an electronic signal. Recent experiments show that the location of the advancing ion front increases as the square‐root of time, a scaling typically associated with diffusive transport, which is surprising given the large driving voltages utilized. Ionic and electronic transport is modeled via the drift‐diffusion equations. A similarity transformation reduces the governing partial differential equations to ordinary differential equations that are solved numerically. The similarity transformation elucidates the origin of the square‐root‐of‐time front scaling. The similarity solution is then compared to the numerical solution of the full drift‐diffusion equations, finding excellent agreement. When compared with experimental data, our model captures the front location; however, qualitative differences between the ion profiles are observed. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1447–1454, 2015     

Structural and Biochemical Studies of Actin in Complex with Synthetic Macrolide Tail Analogues

The actin filament‐binding and filament‐severing activities of the aplyronine, kabiramide, and reidispongiolide families of marine macrolides are located within the hydrophobic tail region of the molecule. Two synthetic tail analogues of aplyronine C (SF‐01 and GC‐04) are shown to bind to G‐actin with dissociation constants of (285±33) and (132±13) nM , respectively. The crystal structures of actin complexes with GC‐04, SF‐01, and kabiramide C reveal a conserved mode of tail binding within the cleft that forms between subdomains (SD) 1 and 3. Our studies support the view that filament severing is brought about by specific binding of the tail region to the SD1/SD3 cleft on the upper protomer, which displaces loop‐D from the lower protomer on the same half‐filament. With previous studies showing that the GC‐04 analogue can sever actin filaments, it is argued that the shorter complex lifetime of tail analogues with F‐actin would make them more effective at severing filaments compared with plasma gelsolin. Structure‐based analyses are used to suggest more reactive or targetable forms of GC‐04 and SF‐01, which may serve to boost the capacity of the serum actin scavenging system, to generate antibody conjugates against tumor cell antigens, and to decrease sputum viscosity in children with cystic fibrosis.     

Continuously extruded micro‐textured polypropylene films

The continuous extrusion of micro‐textured isotactic polypropylene (i‐PP) film and its tribological properties are reported. As analyzed by scanning electron microscopy, a rectangular‐semicircular micro‐patterned die successfully produced extruded cast‐films with hill‐like micro‐texture. Such films displayed static and kinetic coefficients of friction (COF_s and COF_k) values of 0.247 ± 0.028 and 0.245 ± 0.003, respectively, for a steel fixture sliding along the micro‐texture of the film. The equivalent COF_s and COF_k values for non‐textured (NT) films were 0.369 ± 0.036 and 0.340 ± 0.024, respectively, confirming that textured films displayed a reduction in COF of about 30%. For textured and NT films sliding on textured films, the COF_k values were even lower at 0.161 ± 0.013 and 0.113 ± 0.004, which represents about 20–40% reduction as compared with that for the NT‐NT counterparts. Films coated with a silicone lubricant displayed COF_s and COF_k values of 0.334 ± 0.042 and 0.099 ± 0.012, respectively, for NT films sliding over lubricated NT films, and 0.426 ± 0.031 and 0.063 ± 0.006, respectively, for textured films sliding over lubricated textured films. The COF_k values for textured/non‐lubricated films approach those of NT/lubricated films, indicating that micro‐textured polypropylene films may be used in environmentally sensitive applications where lubricants and fluorinated additives may not be used for reducing friction. POLYM. ENG. SCI., 54:2147–2154, 2014. © 2013 Society of Plastics Engineers     

Novel Tacrine‐Grafted Ugi Adducts as Multipotent Anti‐Alzheimer Drugs: A Synthetic Renewal in Tacrine–Ferulic Acid Hybrids

Herein we describe the design, multicomponent synthesis, and biological, molecular modeling and ADMET studies, as well as in vitro PAMPA‐blood–brain barrier (BBB) analysis of new tacrine–ferulic acid hybrids (TFAHs). We identified (E)‐3‐(hydroxy‐3‐methoxyphenyl)‐N‐{8[(7‐methoxy‐1,2,3,4‐tetrahydroacridin‐9‐yl)amino]octyl}‐N‐[2‐(naphthalen‐2‐ylamino)2‐oxoethyl]acrylamide (TFAH 10 n ) as a particularly interesting multipotent compound that shows moderate and completely selective inhibition of human butyrylcholinesterase (IC₅₀=68.2 nM ), strong antioxidant activity (4.29 equiv trolox in an oxygen radical absorbance capacity (ORAC) assay), and good β‐amyloid (Aβ) anti‐aggregation properties (65.6 % at 1:1 ratio); moreover, it is able to permeate central nervous system (CNS) tissues, as determined by PAMPA‐BBB assay. Notably, even when tested at very high concentrations, TFAH 10 n easily surpasses the other TFAHs in hepatotoxicity profiling (59.4 % cell viability at 1000 μM ), affording good neuroprotection against toxic insults such as Aβ_1–40, Aβ_1–42, H₂O₂, and oligomycin A/rotenone on SH‐SY5Y cells, at 1 μM . The results reported herein support the development of new multipotent TFAH derivatives as potential drugs for the treatment of Alzheimer′s disease.     

Investigation of pre-reaction and cure temperature on multiscale dispersion in POSS–epoxy nanocomposites

Dispersion of monoamine-functionalized polyhedral oligomeric silsesquioxane (POSS) in an epoxy network was improved by pre-reacting the POSS with excess epoxide and employing a high-temperature cure. DGEBA/DDS networks were formulated with 2.5 and 10 wt% POSS. In some samples, POSS was pre-reacted with DGEBA. The hybrid materials were characterized via SEM, TEM, and DMA. The microscopy and DMA results evinced a multiscale morphology with POSS-rich glassy domains, nano- and microcrystallites, and crystallite agglomerations. For a loading level of 2.5 wt% POSS, the sample with unmodified POSS cured at 125 °C had inorganic crystallites on the order of 1–5 μm and agglomerations on the order of 10–20 μm, whereas the sample with pre-reacted POSS cured at 180 °C had near-perfect dispersion with no agglomerations and very few POSS crystallites. The 10 wt% POSS epoxies also showed improved dispersion with pre-reaction and increasing cure temperature. The dispersion improvements were attributed to the enhanced miscibility of the pre-reacted POSS and the increased rate of POSS reaction into the growing epoxy network at a higher cure temperature.     

Synthesis and characterization of PVA/PES thin film composite nanofiltration membrane modified with TiO2 nanoparticles for better performance and surface properties

Novel polyethersulfone (PES)/poly (vinyl alcohol) (PVA)/titanium dioxide (TiO₂) composite nanofiltration membranes were prepared by dip-coating of PES membrane in PVA and TiO₂ nanoparticles aqueous solution. Glutaraldehyde (GA) was used as a cross-linker for the composite polymer membrane in order to enhance the chemical, thermal as well as mechanical stabilities. TiO₂ nanoparticles with different concentrations (0, 0.05, 0.1, 0.5 wt.%) were coated on the surface of PVA/PES composite membrane. The morphological study was investigated by atomic force microscopy (AFM), scanning surface microscopy (SEM) and along with X-ray diffraction (XRD). In addition, the membranes performances, in terms of permeate flux, ion rejection and swelling factor were also investigated. It was found that the increase in TiO₂ solution concentration can highly affect the surface morphology and filtration performance of coated membranes. The contact angle measurement and XRD studies indicated that the TiO₂ nanoparticles successfully were coated on the surface of PVA/PES composite membranes. However, rougher surface was obtained for membranes by TiO₂ coating. The filtration performance data showed that the 0.1 wt.% TiO₂-modified membrane presents higher performance in terms of flux and NaCl salt rejection. Finally, TiO₂ modified membranes demonstrated the lower degree of swelling.