How the risk of failure in lifetime of tempered glass depends on the size of NiS inclusions and heat soak test duration

The probability of breakage in service lifetime of heat-tempered glass panes contaminated by nickel sulfide inclusions is estimated with a multiscale micromechanically motivated statistical theory, which considers the effects of the heat soak test (HST). Short and long HSTs differently affect the phase transformation of NiS of diverse chemical composition, whose increase in volume can break the glass. The main hypothesis, corroborated by experiments, is that there is a lower limit for the size of NiS stones below which no crack can be initiated from the volumetric expansion. The catastrophic propagation of nucleated fractures in the long term is modeled through a rescaled critical stress intensity factor, which accounts for the subcritical crack propagation and the slow phase transformation of NiS. A parametric analysis evidences how the failure probability is strongly affected by these parameters, depending on the holding time in the HST. Tailored experimental activity is suggested for the proper calibration of the model.     

A Small Cyclic β-Hairpin Peptide Mimics the Rbfox2 RNA Recognition Motif and Binds to the Precursor miRNA 20b

The RNA recognition motif (RRM), which is the most abundant RNA-binding motif in eukaryotes, is a well-structured domain of about 90 amino acids, yet the β2β3 hairpin, corresponding to strands 2 and 3 of the β-sheet, and the intervening loop make essential interactions with RNA in many RRM complexes. A series of small cyclic peptide mimics of the β2β3 hairpin of Rbfox2 protein that recognize the terminal loop of precursor miR-20b have been designed to investigate whether the full RNA-binding protein can be mimicked with a minimal structurally preorganized peptide. Within a small library of seven cyclic peptides, a peptide with low-micromolar affinity for the miR-20b precursor was found. NMR spectroscopy titration data suggest that this peptide specifically targets the apical loop of pre-miR-20b. This work shows that it is possible to mimic RNA-binding proteins with designed stable peptides, which provide a starting point for designing or evolving small peptide mimetics of RRM proteins.     

Polydialkylphosphazenes: New synthetic efforts and protonation reactions

Some dialkyl-or diaryl-phosphoranimines are so thermally stable that their thermal polymerization cannot be pursued: it follows that an alternative route to the synthesis of said polymers is to be found. The polymerization ofN-silyldiethylphosphoranimine with the aid of anionic initiators was studied. This reaction. compared with thermal polymerization. proceeded at a lower temperature and with a shorter completion time. Low molecular weights and often bimodal distributions were found.M _m values obtained with Bu₄NF and NaOPh were in the range 1000 10.000, with very narrow polydispersities. Since symmetrical disubstituted polyalkylphosphazenes with alkyl chains from C₂ up to C₈ are insoluble in organic solvents, their solution characterization in usual solvents was prevented. For this purpose, protonation reactions with organic and mineral acids were studied. The protonated polymers were found to be soluble in organic acids and in water, NMR spectra were registered. The molecular weights of the polymers were determined in 20% (v/v) acetic acid. The method, tested on samples of polydimethylphosphazene whose molecular weight was determined independently by membrane osmometry in chloroform solutions, was found to be reliable.Presented at the 1st Italian Workshop on Cyclo- and Polytphosphazene Materials. February 15, 16, 1996, at the CNR Research Area in Padova, Italy.     

Effect of different titania phases on the hydrogen gas sensing features of polyaniline/TiO2 nanocomposite

This paper presents a resistance-based hydrogen gas sensor using polyaniline (emeraldine)/TiO₂ nanocomposite (PT–NC) thin film. It is demonstrated that different gas sensing features can arise when various TiO₂ phases (anatase and rutile) are applied. The different wt% of TiO₂ phases were dispersed into an acidic solution of aniline monomers and PT–NCs were synthesized by an in-situ self-assembly chemical oxidative polymerization method of aniline. PT–NCs deposited on an epoxy glass substrate having Cu-interdigited electrodes for hydrogen gas sensing at air pressure and room temperature. Our results show that the better sensitivity of the sensor strongly depends on the sensor surface morphology and its components. Furthermore, hydrogen gas sensing mechanism of the sensor based contact areas between Pani chains and TiO₂ grains was studied.     

Synthesis,Pharmacological Evaluation,and Docking Studies of Novel Pyridazinone‐Based Cannabinoid Receptor Type 2 Ligands

In recent years, cannabinoid type 2 receptors (CB₂R) have emerged as promising therapeutic targets in a wide variety of diseases. Selective ligands of CB₂R are devoid of the psychoactive effects typically observed for CB₁R ligands. Based on our recent studies on a class of pyridazinone 4‐carboxamides, further structural modifications of the pyridazinone core were made to better investigate the structure–activity relationships for this promising scaffold with the aim to develop potent CB₂R ligands. In binding assays, two of the new synthesized compounds [6‐(3,4‐dichlorophenyl)‐2‐(4‐fluorobenzyl)‐cis‐N‐(4‐methylcyclohexyl)‐3‐oxo‐2,3‐dihydropyridazine‐4‐carboxamide ( 2 ) and 6‐(4‐chloro‐3‐methylphenyl)‐cis‐N‐(4‐methylcyclohexyl)‐3‐oxo‐2‐pentyl‐2,3‐dihydropyridazine‐4‐carboxamide ( 22 )] showed high CB₂R affinity, with K_i values of 2.1 and 1.6 nm , respectively. In addition, functional assays of these compounds and other new active related derivatives revealed their pharmacological profiles as CB₂R inverse agonists. Compound 22 displayed the highest CB₂R selectivity and potency, presenting a favorable in silico pharmacokinetic profile. Furthermore, a molecular modeling study revealed how 22 produces inverse agonism through blocking the movement of the toggle‐switch residue, W6.48.     

Structural Determination and Occurrence in Ahiflower Oil of Stearidonic Acid Trans Fatty Acids

Several marine oils and seed oils on the market contain relevant quantities of stearidonic acid (18:4n‐3, SDA). The formation of 18:4n‐3 trans fatty acids (tFA) during the refining of these oils necessitates the development of a method for their quantification. In this study, 18:4n‐3 was isolated from Ahiflower and isomerized to obtain its 16 geometric isomers. The geometric isomers of 18:4n‐3 were isolated by silver ion HPLC (Ag⁺‐HPLC) and characterized by partial reduction with hydrazine followed by gas chromatography analysis. The elution order of all 16 isomers was established using a 100 m × 0.25 mm 100% poly(biscyanopropyl siloxane) capillary column and at the elution temperature of 180 °C. The 4 mono‐trans‐18:4n‐3 isomers produced during the refining of oils rich in 18:4n‐3 were chromatographically resolved from each other, but c6,t9,c12,c15‐18:4 coeluted with the tetra‐cis isomer. These 2 fatty acids (FA) were resolved by reducing the separation temperature to 150 °C, but this change caused tetra‐cis‐18:4n‐3 to coelute with t6,c9,c12,c15–18:4. Combining the results from 2 isothermal separations (180 and 150 °C) was necessary to quantify the 4 mono‐trans 18:4n‐3 FA in Ahiflower oil.     

Targeting Serotonin 2A and Adrenergic α1 Receptors for Ocular Antihypertensive Agents: Discovery of 3,4‐Dihydropyrazino[1,2‐b]indazol‐1(2H)‐one Derivatives

Glaucoma affects millions of people worldwide and causes optic nerve damage and blindness. The elevation of the intraocular pressure (IOP) is the main risk factor associated with this pathology, and decreasing IOP is the key therapeutic target of current pharmacological treatments. As potential ocular hypotensive agents, we studied compounds that act on two receptors (serotonin 2A and adrenergic α₁) linked to the regulation of aqueous humour dynamics. Herein we describe the design, synthesis, and pharmacological profiling of a series of novel bicyclic and tricyclic N2‐alkyl‐indazole‐amide derivatives. This study identified a 3,4‐dihydropyrazino[1,2‐b]indazol‐1(2H)‐one derivative with potent serotonin 2A receptor antagonism, >100‐fold selectivity over other serotonin subtype receptors, and high affinity for the α₁ receptor. Moreover, upon local administration, this compound showed superior ocular hypotensive action in vivo relative to the clinically used reference compound timolol.     

Bio-ethanol production by fermentation of ricotta cheese whey as an effective alternative non-vegetable source

The aim of the present paper is to investigate the feasibility of bio-ethanol production by batch fermentation of ricotta cheese whey (“Scotta”), a dairy industry waste characterized by lactose concentration ranging from 4.5% to 5.0% (w/w) and, with respect to traditional (raw) whey, by much lower protein content. Scotta, therefore, could represent an effective non-vegetable source for renewable energy production. The microrganism used to carry out the fermentation processes was the yeast Kluyveromyces marxianus. Preliminary experiments, performed in aerobic conditions on different volumes of scotta, have shown the actual growth of the yeast. The subsequent fermentation experiments were carried out, in anaerobic conditions, on three different substrates: scotta, raw cheese whey and deproteinized whey. The experimental data have demonstrated the process feasibility: scotta is an excellent substrate for fermentation and exhibits better performance with respect to both raw cheese whey and deproteinized whey. Complete lactose consumption, indeed, was observed in the shortest time (13 h) and with the highest ethanol yield (97% of the theoretical value).     

Internal and external algorithms for the points-in-regions problem—the inside join of geo-relational algebra

We consider the problem of collectively locating a set of points within a set of disjoint polygonal regions when neither for points nor for regions preprocessing is allowed. This problem arises in geometric database systems. More specifically it is equivalent to computing theinside join of geo-relational algebra, a conceptual model for geo-data management. We describe efficient algorithms for solving this problem based on plane-sweep and divide-and-conquer, requiringO(n(logn) +t) andO(n(log² n) +t) time, respectively, andO(n) space, wheren is the total number of points and edges, and (is the number of reported (point, region) pairs. Since the algorithms are meant to be practically useful we consider as well as the internal versions-running completely in main memory-versions that run internally but use much less than linear space and versions that run externally, that is, require only a constant amount of internal memory regardless of the amount of data to be processed. Comparing plane-sweep and divide-and-conquer, it turns out that divide-and-conquer can be expected to perform much better in the external case even though it has a higher internal asymptotic worst-case complexity. An interesting theoretical by-product is a new general technique for handling arbitrarily large sets of objects clustered on a singlex-coordinate within a planar divide-and-conquer algorithm and a proof that the resulting “unbalanced” dividing does not lead to a more than logarithmic height of the tree of recursive calls.     

Bicyclo‐orthoester as a low‐shrinkage additive in cationic UV curing

A commercially available bicyclo‐orthoester (BOE) was used as low‐shrinkage additive for cationic UV curing of epoxy resins. A high reactivity of BOE by ring‐opening homopolymerization has been observed under cationic UV curing conditions. The BOE and trimethylolpropane triglycidyl ether monomers are compatible and give rise to a cured copolymeric network, under UV irradiation, with a flexibilization increase by increasing the BOE content in the photocurable formulation. Shrinkage after photopolymerization shows a linear reduction by increasing the BOE content in the photocurable formulation; a volume expansion upon polymerization is reached in the presence of 50 wt% of the additive. Copyright © 2007 Society of Chemical Industry