Further developments of a damage theory for filled polymers

This paper investigates matrix debonding from filler particles as a mechanism for weakening of a filled polymer. We analyze several simplified models of debonding. Our main concern is its effect on the overall elastic instants; for each debonding model, we calculate the change ΔW in overall strain energy density due to debonding. The resulting formulas for ΔW are all special cases of one general expression. Accordingly, we propose that this expression describes a broad class of debonding models, including some for which a detailed stress and strain analysis is not possible.     

Sequencing, Scheduling and Tooling Single-Stage Multifunctional Machines in a Small Batch Environment

Single-Stage multifunctional Machining Systems (SSMSs) are an important integral part of automated, flexible manufacturing systems. However, the SSMS frequently becomes the bottleneck of the entire manufacturing system by virtue of protracted internal set-up requirements. A key aspect of achieving full SSMS utilization is the ability to reduce as much as possible these demands at the expense of increasing external set-up. As of today, fixturing devices have not received much attention in the modeling literature. Nevertheless, fixturing devices are in some cases a limited resource which, may affect the shop scheduling decisions and the shop performance and as such can not be omitted. This study presents a {0–1} programming model which takes the fixturing device's limitation in to consideration when determining the weekly sequence of jobs to be produced. The model tries to minimize the non-productive machine time. Based on this model, a heuristic procedure is developed and tested using data of four production weeks obtained from a hi-tech company that produces medical imaging systems.     

Fast randomized algorithm for 2-hops clustering in vehicular ad-hoc networks

Vehicular Ad-Hoc Networks (VANETs) enable inter vehicle wireless communication as well as communication with road side equipment. Warning messages can be exchanged among nearby vehicles, helping to predict dangerous situations, and thus improving road safety. Such safety messages require fast delivery and minimal delay to local areas, in order for them to be effective. Therefore, a fast and efficient channel access scheme is required. A feasible solution, derived from the Mobile Ad-Hoc Networks (MANETs) field, groups nodes into smaller manageable sections called clusters. Such an approach can be beneficial for locally delivering messages under strict time constraints. In this paper, a Hierarchical Clustering Algorithm (HCA) is presented. HCA is a distributed randomized algorithm, which manages channel access by forming three hierarchy clusters. The proposed channel access scheme enables delay bounded reliable communication. Unlike other common clustering algorithm for VANETs, HCA does not require the knowledge of the vehicles’ locations. This feature guarantees accurate operation even when localization systems such as GPS are not available. The running time and message complexity were analyzed and simulated. Simulation results show that the algorithm behaves well especially under realistic mobility patterns; therefore, it is a suitable solution for channel access scheme for VANETs.     

Photo-Polymerization Damage Protection by Hydrogen Sulfide Donors for 3D-Cell Culture Systems Optimization

Photo-polymerized hydrogels are ideally suited for stem-cell based tissue regeneration and three dimensional (3D) bioprinting because they can be highly biocompatible, injectable, easy to use, and their mechanical and physical properties can be controlled. However, photo-polymerization involves the use of potentially toxic photo-initiators, exposure to ultraviolet light radiation, formation of free radicals that trigger the cross-linking reaction, and other events whose effects on cells are not yet fully understood. The purpose of this study was to examine the effects of hydrogen sulfide (H₂S) in mitigating cellular toxicity of photo-polymerization caused to resident cells during the process of hydrogel formation. H₂S, which is the latest discovered member of the gasotransmitter family of gaseous signalling molecules, has a number of established beneficial properties, including cell protection from oxidative damage both directly (by acting as a scavenger molecule) and indirectly (by inducing the expression of anti-oxidant proteins in the cell). Cells were exposed to slow release H₂S treatment using pre-conditioning with glutathione-conjugated-garlic extract in order to mitigate toxicity during the photo-polymerization process of hydrogel formation. The protective effects of the H₂S treatment were evaluated in both an enzymatic model and a 3D cell culture system using cell viability as a quantitative indicator. The protective effect of H₂S treatment of cells is a promising approach to enhance cell survival in tissue engineering applications requiring photo-polymerized hydrogel scaffolds.     

Improved blocking properties of short-chain alkanethiol monolayers self-assembled on gold

Blocking of gold surfaces by self-assembled monolayers (SAMs) of n-octanethiol (OT) was investigated. Short-chain alkanethiols such as OT are known to form loosely-packed SAMs with abundant defects and pinholes, exhibiting poor blocking of the gold surface. Hence, gold substrates subjected to 20 h OT adsorption manifested excessive electrochemical penetrability, low contact angles with a large hysteresis, and extensive exchange of functional disulfide molecules into the OT SAM. It is shown that a single electrochemical cycle in H₂SO₄ solution after 1 h OT adsorption, followed by another 20 h adsorption, results in a dramatic improvement of the coverage and blocking properties of the SAM, showing considerably lower electrochemical penetrability, improved contact angles, and sluggish exchange of the functional molecules into the OT SAM. Insertion of the latter molecules into the monolayer was monitored by their ability to coordinatively attach ligand-substituted gold nanoparticles.     

In vivo degradation of semi-rigid polymeric films made of alginate and polyethylene glycol

Alginate-based biomaterials can form naturally derived polymeric hydrogels with sufficient structural integrity to readily be used in many clinical applications. However, ionically cross-linked alginate gels do not always possess structural properties suitable for application as erodable polymeric films for controlled release of drugs and growth factors. In this study, semi-rigid polymeric films were constructed of sodium alginate and polyethylene glycol (PEG) by means of a rehydration cross-linking technique. The films were assembled by dehydrating a solution of alginate and PEG and cross-linking the alginate during its rehydration with a solution of calcium chloride. The product is a highly dense polymeric network that prevents in vivo cellular infiltration and disassembles primarily by surface erosion. By implanting the PEG-alginate films into the subcutis of rats, the mechanism of polymer degradation was demonstrated to occur via inflammation-mediated erosion of the material rather than by means of cellular infiltration. There were extensive areas of foamy macrophages at the site of the implant, indicating a likely mechanism of removal and disposal of the disassembled PEG and alginate polymer. The eroded fragments of the film that remained after six weeks did not exhibit signs of a cellular infiltrate but rather stayed intact, appearing as small, dense fragments of polymer. Our observations that nearly all the PEG-alginate material was cleared from the implantation site by the sixth postoperative week highlight the potential exploitation of these films as bioresorbable wound dressings with prospective utilization as a drug delivery device. Moreover, the employment of polymeric films made of functionalized PEG, which enables covalent attachment of biological molecules, potentiates their use for growth factor delivery applications.     

RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels

Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG-b-DEG₉₅TMA₅) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG₉₈TMA₂-b-OEG-b-DEG₉₈TMA₂) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels.     

Camptothecin in sterically stabilized phospholipid nano-micelles: a novel solvent pH change solubilization method

Camptothecin (CPT) is a topoisomerase I inhibitor that acts against a broad spectrum of cancers. Unfortunately clinical application of CPT is limited by insolubility, instability, and toxicity problems. To circumvent these delivery problems of CPT, we propose biocompatible, targeted sterically stabilized micelles (SSM) as nanocarriers for CPT (CPT-SSM). SSM composed of polyethylene glycol (PEGylated) phospholipids are attractive nanocarriers for CPT delivery because they are sufficiently small to extravasate through the leaky microvasculature of tumor and inflamed tissues for passive targeting. The purpose of this study was to develop a novel method of preparing CPT-SSM based on its pH dependent, reversible carboxylate-lactone conversion chemistry. CPT carboxylate was added to SSM at pH 5 that favored the formation of active but hydrophobic CPT lactone for spontaneous association with SSM. The kinetics of CPT conversion and CPT-SSM formation, and the effect of varying CPT-PEGylated phospholipid molar ratio on CPT-SSM properties and CPT solubilization were evaluated. CPT converted gradually from the carboxylate form to lactone, and CPT-SSM were formed after 12 h incubation. The mean size of CPT-SSM was approximately 14 nm. CPT solubilization (approximately 12 microg/ml) and other CPT-SSM micelle properties did not change significantly with increasing CPT to PEGylated hospholipid molar ratios using this novel method, unlike the coprecipitation/reconstitution technique previously reported. This reproducible CPT solubilization in SSM was attributed to avoidance of drug aggregate formation by this method. The advantages of our solvent pH change method to prepare CPT-SSM support further investigations of this approach to other hydrophobic drugs similar to CPT in chemistry and also CPT molecular solubilization in other nanocarriers.