Optimization of Green Multiple Emulsions Processing to Improve Their Physical Stability

The effect of processing protocol on physical stability and the microstructure of water‐in‐oil‐in‐water multiple emulsions containing a mixture of two amphiphilic copolymers with opposed hydrophilic‐lipophilic balance as emulsifiers and a green solvent, 2‐ethylhexyl lactate, as the dispersed phase, has been assessed. Emulsions were obtained in at least two steps: a homogenization step by using a rotor‐stator device, followed by one or two homogenization steps carried out in a high‐pressure device that used microfluidizer technology. To study the microstructure and physical stability of these emulsions, a combination of different techniques, such as transmitted‐light optical microscopy, globule size distribution, viscous flow tests, and multiple light scattering measurements, were performed.     

Incorporation of chloramphenicol and captopril into poly(GL)‐b‐poly(GL‐co‐TMC‐co‐CL)‐b‐poly(GL) monofilar surgical sutures

Incorporation of chloramphenicol and captopril into coated and uncoated monofilament sutures was evaluated, as well as the derived bactericide and wound healing effects. To this end, a commercially available suture and an amorphous random copolymer constituted by trimethylene carbonate and lactide units were considered. The suture had a segmented architecture based on polyglycolide hard blocks and a soft block constituted by glycolide, trimethylene carbonate and ε‐caprolactone units. Chloramphenicol was better loaded when the coating copolymer was employed due to its protective effect whereas captopril showed an opposite behavior due to partial solubilization during immersion in the coating bath. Interestingly, the release behavior was very different for the two studied drugs since a significant retention of chloramphenicol was always detected, suggesting the establishment of interactions between drug and copolymers. On the other hand, delivery of captopril showed a typical dose dependent behavior. A low in vitro toxicity of the two drugs was determined considering both epithelial‐like and fibroblast‐like cells. Bactericide effect of chloramphenicol against Gram‐negative and Gram‐positive bacteria was demonstrated at a dose that was non‐toxic for all assayed cells. An accelerating wound healing effect of captopril was also demonstrated for early events. In this case, the use of a coating copolymer was fundamental to avoid cytotoxic effects on highly loaded sutures. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44762.     

Preparation of random poly(butylene alkylate-co-terephthalate)s with different methylene group contents: crystallization and degradation kinetics

Random copolyesters having 1,4-butanediol units were synthesized from a transesterification process between homopolymers constituted by aliphatic dicarboxylates (i.e. succinate, adipate or sebacate) and the aromatic therephthalate derivative, as verified by NMR spectroscopy. Biodegradability of resulting copolyesters was studied via enzymatic hydrolysis using Pseudomonas cepacia lipase at pH = 7.2 and 37 °C. Kinetics of degradation showed that in all cases the degradation rate decreased after 19 days of exposure. The observed glass transition temperatures, T _g, of the random copolyesters showed a non-linear dependence on composition, a feature that was explained in terms of the internal stiffening effect of butylene terephthalate units. Copolymers with higher aliphatic (i.e. 50 and 70 mol-%) and methylene (i.e. adipate and sebacate units) contents showed double melting peaks in DSC thermograms. These copolyesters resulted in two different crystalline rich phases after melt-crystallization and subsequent cooling. The ratio between these phases logically depended on the predominant aliphatic or aromatic dicarboxylate content. The copolymers initially crystallized via the aromatic units through a heterogeneous nucleation and a spherulitic growth. The presence of aliphatic dicarboxylate units hindered the beginning of the crystallization process, but the overall growth kinetic constant was similar for all samples. The secondary nucleation constants were determined and showed higher values for samples with higher adipate and sebacate contents.     

Characterization of laser energy consumption in sintering of polymer based powders

This paper presents an analysis of Laser Sintering (LS) process from an energy standpoint. LS has a potential as an environmental benign alternative to traditional processes but only few authors deal with the process optimization including the energy aspects. This work evaluates the effect of the energy density in processing of two polymeric materials: polyamide powder and a phenolic resin coated sand. The different behaviour of the two materials is studied by analysing the geometrical features (depth and width) of linear sintered structures. In particular the volumetric productivity and the energy intensity of the process are calculated to characterize the sintering process.It is shown how an upper limit to the energy consumption can be remarked. Measurements reveal that within the energy density range of 0.02-0.1 J/mm² the whole energy input is useful for the agglomeration process. The use of higher energy density produces different results for both the cases analysed. A proper selection of energy density maintains the energy requirement below the level of 10⁶ J/kg which is considered a lower limit for manufacturing process.     

Analytical modeling of stress-induced martensitic transformation in the crack tip region of nickel–titanium alloys

A novel analytical method, which predicts the extent of the stress-induced martensitic transformation (SIM) in the crack tip vicinity of nickel–titanium (NiTi)-based shape memory alloys, as well as describing the stress distribution in both transformed and untransformed regions, is presented. The method has been validated by comparisons with results from finite-element simulations with good agreement. Furthermore, the method has been used to analyze the effects of various thermomechanical parameters on the extent of the transformation region near the crack tip. Finally, the effects of several thermomechanical loading conditions, in terms of both applied stress and temperature, on the crack tip transformation behavior have been analyzed. The results highlight a marked effect of temperature on the extent of the transformation region and, consequently, on the crack tip stress distribution. As a consequence, temperature plays a role in the fracture process of NiTi alloys.     

On the Acetylation of Phenanthrene and 9-chlorophenanthrene

Friedel-Crafts acetylation of phenanthrene ( 1a ) in sym-tetrachloroethane yields mixtures of 2-, 3- and 9-acetylphenanthrenes ( 2a, 3a, 4 ). The distribution of isomers is found to depend strongly upon the method of mixing the reagents. Acetylation of 9-chlorophenanthrene ( 1b ), performed by a variety of methods and solvents, led mainly to 3-acetyl-9-chlorophenanthrene ( 3b ) (≥85%). Previously unreported 2-acetyl-9-chlorophenanthrene ( 2b ) was found to form up to a maximum 11% in nitrobenzene.     

Molecular Modeling and Molecular Dynamics Studies of Hydralazine with Human DNA Methyltransferase 1

A series of DNA methyltransferase 1 (DNMT1) inhibitors were modeled by docking and molecular dynamics studies to rationalize their activity. Our findings will be valuable in guiding research efforts toward the rational design and virtual screening of novel DNMT inhibitors.

     

Design and performance of two-stage reverse osmosis plant

Simple explicit equations are derived for the design of permeate-staged and reject-staged reverse osmosis plants. Their accuracy has been tested against iterative numerical procedures. Errors in the membrane area of both stages are below 10% under normal operating conditions. Therefore, the method can be usefully applied for quick initial estimates and for discriminating between competing processes. Two design examples are presented: sea-water desalination and sugar solution concentration. Recoveries of up to 40% can be expected even for highly concentrated sea-water (50 000 ppm). Concentrations of more than 35 wt.% can also be obtained with relatively low energy. In both cases reverse osmosis proves to be competitive with evaporative processes.     

Structure-activity relationship study of 16 a-thiocamptothecins: an integrated in vitro and in silico approach

The instability of the hydroxylactone E ring represents a critical drawback of camptothecins, because the lactone ring is recognized to be essential for stabilization of topoisomerase I‐mediated DNA cleavage. In an attempt to investigate the effect of the thiopyridone pharmacophofore on the molecular and pharmacological features of the drug, we prepared a series of novel 16 a‐thiocamptothecin analogues. Due to the sulfur atom, a destabilization of the hydrogen bond between the hydroxy group in position 17 of the opened E ring and the carbonyl of the pyridone moiety is predicted, thus shifting the equilibrium toward the closed lactone form and increasing the lipophilic properties of the compounds. This feature was associated with superior antiproliferative potency, with reduced interaction with the human serum albumin and with substantial increase of the persistence of the topoisomerase I–DNA cleavable complex. These effects were prominent for thio‐SN38, the most active compound of the series. The favorable interactions at the molecular and cellular level of the reported thiocamptothecins confer promising features, and these compounds warrant preclinical development.