Critical phenomenon during photoinitiated gelation at different temperatures: A Photo-DSC study

The behaviour of photoinitiated radical polymerization of an 80 wt% epoxy diacrylate (EA) and 20 wt% tripropyleneglycoldiacrylate (TPGDA) mixture with 2-mercaptothioxanthone (TX-SH) photoinitiator was studied at different temperatures by using photo-differential scanning calorimetric (Photo-DSC) technique. All photopolymerization reactions were carried out under the same conditions. It was observed that all conversion curves during gelation at different temperatures present nice sigmoidal behaviour which suggests the application of the percolation model. Observations around the critical time, called the glass transition point (t_g), taken to reach the maximum rate of polymerization (Rp_max) show that the gel fraction exponent (β) obeyed the percolation model. The produced β values were found to be around 0.50, predicting that the system under consideration belongs to the same universality class. However, Rp_max and the final conversion (C_s) values were found to increase when the temperature was increased up to a certain value. On the other hand, t_g values decreased and became saturated as the temperature was increased.     

Acidolysis Reaction of Terebinth Fruit Oil with Palmitic and Caprylic Acids to Produce Low Caloric Spreadable Structured Lipid

The lipase (Lipozyme IM from Rhizomucor miehei) catalyzed acidolysis reaction of terebinth (Pistacia terebinthus L.) fruit oil with caprylic and palmitic acid in hexane was investigated in a batch system. The effect of reaction conditions and relationship among them were analyzed and optimized by response surface methodology with a four-factor five-level central composite rotatable experimental design. The four major factors chosen were enzyme load (10–20 wt%), reaction time (12–20 h), reaction temperature (45–60 °C) and substrate mol ratio (TO:PA:CA, 1:2.3–4.1:1.15–2.05). Optimum reaction conditions for reaction time, temperature, enzyme load and substrate mole ratio were 12 h, 45 °C, 10 wt% and 1:4.1:2.05, respectively. The maximum yield of desired triacylglycerols (TAG) obtained at these optimum conditions was 50.87 %. Produced structured lipid had a caloric value which was 1.5 % lower than that of terebinth fruit oil. Its solid fat content was found comparable with commercially available margarines. The relative activity of lipase was well maintained in up to 10 repeated cycles.     

Favorable scaffolds: proteins with different sequence, structure and function may associate in similar ways

Proteins with similar structures may have different functions. Here, using a non-redundant two-chain protein-protein interface dataset containing 103 clusters, we show that this paradigm extends to interfaces. Whereas usually similar interfaces are obtained from globally similar chains, this is not always the case. Remarkably, in some interface clusters, although the interfaces are similar, the overall structures and functions of the chains are different. Hence, our work suggests that different folds may combinatorially assemble to yield similar local interface motifs. The preference of different folds to associate in similar ways illustrates that the paradigm is universal, whether for single chains in folding or for protein-protein association in binding. We analyze and compare the two types of clusters. Type I, with similar interfaces, similar global structures and similar functions, is better packed, less planar, has larger total and non-polar buried surface areas, better complementarity and more backbone-backbone hydrogen bonds than Type II (similar interfaces, different global structures and different functions). The dataset clusters may provide rich data for protein-protein recognition, cellular networks and drug design. In particular, they should be useful in addressing the difficult question of what the favorable ways for proteins to interact are.     

Kinetics of polyurethane formation between glycidyl azide polymer and a triisocyanate

Kinetics of the polyurethane formation between glycidyl azide polymer (GAP) and a polyisocyanate, Desmodur N‐100, were studied in the bulk state by using quantitative FTIR spectroscopy. The reaction was followed by monitoring the change in intensity of the absorption band at 2270 cm^?1 for NCO stretching in the IR spectrum, and was shown to obey second‐order kinetics up to 50% conversion. The activation parameters were obtained from the evaluation of kinetic data at different temperatures in the range of 50–80°C. The enthalpy and entropy of activation were found to be ΔH^? = 44.1 ± 0.5 kJ · mol^?1 and ΔS^? = ?196 ± 2 J · mol^?1l · K^?1, respectively. Dibutyltin dilaurate (DBTDL) was used as the curing catalyst. The kinetic study of the polyurethane formation between GAP and Desmodur N‐100 showed that the reaction is enormously speeded up in the presence of the catalyst, and the reaction obeys second‐order kinetics, provided that the catalyst concentration is kept constant. An investigation on the rate of the catalysed reaction depending on the catalyst concentration provided the order of the reaction, with respect to the DBTDL catalyst concentration, and the rate constant for the catalytic pathway of the reaction. The rate constant for the catalytic pathway was established to be 4.37 at 60°C, while the uncatalyzed reaction has a rate constant of 3.88 × 10^?6 L · mol^?1 · s^?1 at the same temperature. A rate enhancement factor of 23 was achieved by using 50 ppm catalyst. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 918–923, 2001     

Microhardness and morphologic characteristics of rapidly solidified Al-12Si-8Ni-5Nd alloy

Al-Si-Ni-Nd alloys with a nominal composition of Al-12 wt.% Si-8 wt.% Ni-5 wt.% Nd alloy are prepared by a conventional casting (ingot) and melt spinning technique at different cooling rates (ν). The effects of the rapid solidification rate on the microstructures and microhardness performances of the specimen alloys are investigated in detail. The results obtained by the XRD, SEM and DSC show that the ingot and melt spun alloys have a multiphase structure. When ν is 5 m/s, the alloy consists of four phases namely α-Al, intermetallic Al₃Ni, Al₁₁Nd₃, and fcc Si. The melt-spun ribbons are completely composed of α-Al and eutectic Si phases, and primary silicon is not observed when ν increases to 20 m/s, 25 m/s, 30 m/s and 35 m/s. The XRD analysis indicated that the solubility of Si in the α-Al matrix increases greatly with the rapid solidification. The change in microhardness is discussed based on the microstructural observations. The microhardness values of the melt spun ribbons are about three times higher than those of ingot counterparts.     

Impacts of impregnation with boron compounds on surface roughness of woods and varnished surfaces

This study determines the effects of the process of impregnation of boron compounds on the surface roughness of Oriental beech, Scotch pine, Oriental spruce, and Uluda? fir woods and varnished surfaces. For this purpose, samples are prepared according to ASTM D 358 and impregnated according to ASTM D 1413‐99 with a 5.5% solution of boric acid (Ba), borax (Bx), and Ba with Bx (Ba + Bx) and varnished with synthetic varnish (Sv) and water‐based varnish (Wb) in accordance with ASTM D 3023. The surface roughness is determined according to ISO 4287 and TS 930 standards. The results indicate that the surface roughness is the highest in Uluda? fir, Wb, and Bx and the lowest in Oriental spruce, Sv, and Ba + Bx. For the combination of wood, impregnation material, and varnish, the surface roughness is the highest in Oriental beech with Bx and Wb and the lowest in Scotch pine with Ba + Bx and Sv. The surface roughness is less in impregnated samples than unimpregnated samples and in impregnated and varnished samples than impregnated and unvarnished samples. According to these results, boron compounds decrease the surface roughness of varnishes and wood materials. Thus, impregnation of wood with boron compounds decreases the surface roughness. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4952–4957, 2006     

In vitro and in vivo evaluation of the effects of demineralized bone matrix or calcium sulfate addition to polycaprolactone–bioglass composites

The objective of this study was to improve the efficacy of polycaprolactone/bioglass (PCL/BG) bone substitute using demineralized bone matrix (DBM) or calcium sulfate (CS) as a third component. Composite discs involving either DBM or CS were prepared by compression moulding. Bioactivity of discs was evaluated by energy dispersive X-ray spectroscopy (ESCA) and scanning electron microscopy (SEM) following simulated body fluid incubation. The closest Calcium/Phosphate ratio to that of hydroxyl carbonate apatite crystals was observed for PCL/BG/DBM group (1.53) after 15 day incubation. Addition of fillers increased microhardness and compressive modulus of discs. However, after 4 and 6-week PBS incubations, PCL/BG/DBM discs showed significant decrease in modulus (from 266.23 to 54.04 and 33.45 MPa, respectively) in parallel with its highest water uptakes (36.3 and 34.7%). Discs preserved their integrity with only considerable weight loss (7.5–14.5%) in PCL/BG/DBM group. In vitro cytotoxicity tests showed that all discs were biocompatible. Composites were implanted to defects on rabbit humeri. After 7 weeks, new tissue formation and mineralization at bone-implant interface were observed for all implants. Bone mineral densities at interface were higher than that of implant site and negative controls (defects left empty) but lower than healthy bone level. However, microhardness of implant sites was higher than in vitro results indicating in vivo mineralization of implants. Addition of DBM or CS resulted with higher microhardness values at interface region (ca. 650 μm from implant) compared to PCL/BG and negative control. Histological studies revealed that addition of DBM enhanced bone formation around and into implant while CS provided cartilage tissue formation around the implant. From these results, addition of DBM or CS could be suggested to improve bone healing efficacy of PCL/BG composites.     

A simulation-optimization approach for integrated sourcing and inventory decisions

In this paper, we study a generalized vendor selection problem that integrates vendor selection and inventory replenishment decisions of a firm. In addition to vendor-specific procurement and management costs, we consider inventory replenishment, holding, and backorder costs explicitly to meet stationary stochastic demand faced by the firm. Our goal is to select the best set of vendors along with the optimum inventory decisions at each plant of the firm so that we minimize the system-wide total costs and achieve desired service and reliability levels. Due to uncertainties inherent in the problem related to demand observed by the firm, quality provided by vendors, and disruptions observed by vendors, we utilize a simulation-optimization approach to solve the problem. More specifically, we build a discrete-event simulation model to evaluate the objective function of the problem that works in concert with a scatter search-based metaheuristic optimization approach to search the solution space. Computational results not only provide managerial insights and measure the significance of intangible factors in the vendor selection process but also highlight the importance of computational tools such as simulation-optimization for the vendor selection problem.     

Capacitated Refueling Station Location Problem with Traffic Deviations Over Multiple Time Periods

In this paper, we consider the problem of locating refueling stations in a transportation network via mathematical programming. The proposed model is applicable for several alternative fuel types and is particularly suitable for hydrogen fuel. We assume that a central planner, a hydrogen manufacturer or a government agency, determines the locations of the refueling stations for a given intra-city transportation network while accounting for multi-period travel demand, nonlinear refueling station operational cost, and the deviations of travelers from their shortest routes to refuel. Incorporating demand patterns over multiple periods allows us to account for both short- and long-term variation in hydrogen refueling demand (the former due to time of day, and the latter future hydrogen fuel cell vehicle growth). It also helps us model the changes in user preferences (station and route choices) and traffic conditions over different periods. To account for refueling station operational cost in making investment decisions, we introduce a staircase marginal cost function. In addition, the model explicitly considers station and route choices of travelers as they may deviate from their original paths to refuel, incurring additional costs and affecting the number and locations of refueling stations. We formulate this problem as a multi-period, mixed-integer model with constant link travel time and staircase operational cost at refueling stations. We applied two well-known solution algorithms, branch-and-bound and Lagrangian relaxation, to solve the problem. Our analysis shows that although we are able to solve the refueling station location problem to optimality with branch-and-bound, the Lagrangian relaxation approach provides very good results with less computational time. Additionally, our numerical example of Mashhad, Iran demonstrates that locating refueling stations with considering multi-period traffic patterns (as opposed to single-period) results in minimum network-wide traffic congestion and lower user and agency costs over a planning horizon.     

Determining the effect of trace elements on biohydrogen production from fruit and vegetable wastes

Trace elements are one of the important parameters for dark fermentative H₂ production because they work as co-factors in H₂ formation biochemistry. Lack or excess of trace element and its concentrations could be an important reason for the low yield of H₂ production. In this study, the effects of 11 different trace elements (Fe, Ni, Zn, Co, Cu, Mn, Al, B, Se, Mo and W) were tested at two levels in terms of biohydrogen production from Fruit and Vegetable Wastes (FVW) with Biochemical Hydrogen Potential (BHP) Tests using Plackett-Burman statistical design. 1.1–2.8 times enhancement of biohydrogen production was determined with its addition. The most effective trace elements were found as Zn and Ni. In order to reveal the resident microbial flora, Denaturing Gradient Gel Electrophoresis (DGGE) analysis was carried out on all BHP effluent samples. Results of DGGE analysis, four microbial sequences evaluated as Clostridium sp., Clostridium baratii, Uncultured bacterium, Uncultured Streptococcus sp., and their similarity rates were 99%, 100%, 89%, 98%, respectively.