(29)Si NMR shifts and relative stabilities calculated for hypercoordinated silicon-polyalcohol complexes: role in sol-gel and biogenic silica synthesis

Penta- and hexa-coordinated silicon is rare, occurring as a transient species in some glasses, nonaqueous organosilicon solutions and organosilicon gels such as silicone, and is stable at high pressures within the earth in dense phases such as stishovite. The stable form expected in aqueous solution is quadra-coordinated silicon. A recent study proposed the existence of hypercoordinated silicon-polyalcohol complexes in aqueous solution, based on (29)Si NMR shifts at -102 to -103 ppm and -145 to -147 ppm. Here, we report ab initio molecular orbital calculations of (29)Si NMR chemical shifts and relative stabilities of silicon-polyalcohol monocyclic and spirocyclic complexes, from ethylene glycol (C(2)H(6)O(2)) to arabitol (C(5)H(12)O(5)) with Si in quadra-, penta- and hexa-coordination ((Q)Si, (P)Si, (H)Si), calculated at the HF/6-311+G(2d,p)//HF/6-31G* level. Calculated shifts are accurate with a 1-8% error for (Q)Si and 2-9% for (P)Si. Shifts calculated for the hypercoordinated silicon complexes having structures proposed in the literature are much more negative (-128 and -180 ppm for (P)Si and (H)Si) than observed. We propose that cyclic trimers complexed by polyalcohols can explain the -102 ppm shift, where the Si atoms are all (Q)Si, or where two silicons are (Q)Si and one is (P)Si with rapid exchange between the Si sites. The -145 ppm resonance results from structures similar to those proposed in the experimental NMR study for the -102 ppm peak. Our relative stability calculations indicate that structures proposed in the literature for hypercoordinated silicon complexes are thermodynamically unstable in aqueous solution at acidic to neutral conditions but may exist in degrading silicone-gel breast-implants. Thus, aqueous hypercoordinated silicon-polyalcohol complexes are unlikely to play an important role in biological silicon uptake and hold little promise for novel silica synthesis routes from aqueous solutions under nonextreme conditions.     

Synchronization and control of spatiotemporal chaos using time-series data from local regions

In this paper we show that the analysis of the dynamics in localized regions, i.e., sub-systems can be used to characterize the chaotic dynamics and the synchronization ability of the spatiotemporal systems. Using noisy scalar time-series data for driving along with simultaneous self-adaptation of the control parameter representative control goals like suppressing spatiotemporal chaos and synchronization of spatiotemporally chaotic dynamics have been discussed. (c) 1998 American Institute of Physics.     

An integrated economic lot-size model for vendor–buyer inventory system when input is random

An integrated strategy is discussed for both vendor and buyer when the input is random. It is shown numerically that the cooperative approach is beneficial to reduce the cost when compared with an independent decision by both the parties. Though the integrated total cost decreases, the buyer’s cost increases due to random input in his inventory. To encourage the buyer to order a large quantity, a trade credit is offered by the vendor to the buyer to settle the account. A conciliation factor is suggested to share the benefits.     

An analysis of the complexation between poly(aspartic acid) and poly(ethylene glycol)

The compatibility between poly(aspartic acid) and poly(ethylene glycol) for the formation of an interpolymer complex (IPC) was investigated by dynamic rheology and evaluation of zeta potential values. The homogeneity of the realized IPC was observed by near infrared chemical imagistic (NIR-CI) technique. The data were sustained and underlined by the assessment of the compatibility between the polymeric compounds.     

Modulation of the nucleation rate preexponential in a low-temperature Ising system

A metastable lattice gas with nearest-neighbor interactions and continuous-time dynamics is studied using a generalized Becker-D?ring approach in the multidimensional space of cluster configurations. The preexponential of the metastable-state lifetime (inverse of nucleation rate) is found to exhibit distinct peaks at integer values of the inverse supersaturation. Peaks are unobservable (infinitely narrow) in the strict limit T-->0, but become detectable and eventually dominate at higher temperatures.     

Stimuli Responsive Scaffolds Based on Carboxymethyl Starch and Poly(2‐Dimethylaminoethyl Methacrylate) for Anti‐Inflammatory Drug Delivery

The purpose of the study is to obtain multicomponent polyelectrolyte hydrogels with optimal synergistic properties by combining a modified starch with a synthetic one. Thus, new low‐cost and biocompatible semi‐interpenetrating polymer network (semi‐IPN) hydrogels of carboxymethyl starch and poly(2‐dimethylaminoethyl methacrylate) are prepared and investigated. The synthesized hydrogels are studied with respect to the specific characteristics of the gels: swelling kinetics, thermal analysis, viscoelastic characteristics, and their ability to be used as a matrix in drug delivery systems. Therefore, the semi‐IPN gels are loaded with ibuprofen, followed by additional tests to assess the in vitro drug release. The cytocompatibility of the hydrogels with respect to their composition is evaluated in vitro on fibroblast cell culture. The investigations confirm the obtainment of new semi‐IPN hydrogels with pH and temperature responsiveness, good mechanical strength, and potential for use as drug delivery systems or transdermal patches.     

Single Supplier�CBuyer Integrated Inventory Model Under Multiple JIT Delivery and Stock-Dependent Demand

In this paper, an integrated inventory model for a supply chain comprising of single buyer and single supplier is studied when demand is stock-dependent and units in inventory deteriorate at a constant rate. The total cost of the integrated system consists of the transportation cost, inspection cost and the cost of less flexibility under the assumption of JIT deliveries. The total integrated cost of single-supplier and single-buyer is minimized with respect to number of inspections and deliveries, the cycle time of deliveries and the delivery size for the replenishment time. A numerical example is given to validate the model. The sensitivity analysis carried out suggests that the unit inspection cost, deterioration rate of units in inventory and stock-dependent parameter are the critical factors.     

A Multi-Objective Production Inventory Model with Backorder for Fuzzy Random Demand Under Flexibility and Reliability

In this paper, an Economic Production Quantity (EPQ) model is developed with flexibility and reliability consideration of production process in an imprecise and uncertain mixed environment. The model has incorporated fuzzy random demand, an imprecise production preparation time and shortage. Here, the setup cost and the reliability of the production process along with the backorder replenishment time and production run period are the decision variables. Due to fuzzy-randomness of the demand, expected average demand is a fuzzy quantity and also imprecise preparation time is represented by fuzzy number. Therefore, both are first transformed to a corresponding interval number and then using the interval arithmetic, the single objective function for expected profit over the time cycle is changed to respective multi-objective functions. Due to highly nonlinearity of the expected profit functions it is optimized using a multi-objective genetic algorithm (MOGA). The associated profit maximization problem is illustrated by numerical examples and also its sensitivity analysis is carried out.     

Assessment of 210Po deposition in moss species and soil around coal-fired power plant

In the present study, the depositions of ²¹⁰Po were assessed in the surface soil and some mosses species found in the area around coal fired power plant using radiochemical deposition and alpha spectrometry counting system. The purposes of the study were to determine activity concentrations of ²¹⁰Po in mosses and surface soil collected around coal-fired power plant in relation to trace the potential source of ²¹⁰Po and to identify most suitable moss species as a bio-indicator for ²¹⁰Po deposition. In this study, different species of mosses, Orthodontium imfractum, Campylopus serratus and Leucobryum aduncum were collected in May 2011 at the area around 15 km radius from Tanjung Bin coal-fired power plant located in Pontian, Johor. The ²¹⁰Po activity concentrations in mosses and soil varied in the range 102 ± 4 to 174 ± 8 Bq/kg dry wt. and 37 ± 2 to 184 ± 8 Bq/kg dry wt., respectively. Corresponding highest activity concentration of ²¹⁰Po observed in L. aduncum, therefore, this finding can be concluded this species was the most suitable as a bio-indicator for ²¹⁰Po deposition. On the other hand, it is clear the accumulation of ²¹⁰Po in mosses might be supplied from various sources of atmospheric deposition such as coal-fired power plant operation, industrial, plantation, agriculture and fertilizer activities, burned fuel fossil and forest; and other potential sources. Meanwhile, the main source of ²¹⁰Po in surface soil is supplied from the in situ deposition of radon decay and its daughters in the soil itself.     

Synthesis of hydrogels based on poly(NIPAM) inserted into collagen sponge

The study presents the preparation of a semi-synthetic hydrogel based on poly(N-isopropyl acrylamide-co-diethylene glycol diacrylate) inserted onto the collagen porous membrane. The synthesis of the hydrogels was performed through radical copolymerization of N-isopropyl acrylamide (NIPAM) with diethylene glycol diacrylate (DEGDA) also as crosslinking agent, using ammonium persulfate as initiator and N,N,N',N'-tetramethylethylene diamine as activator, and it was achieved in the presence of the collagen matrix. The prepared hydrogels were characterized by Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy. The swelling behaviour of the semi-interpenetrated polymer network related on the hydrogel composition, it was also evaluated. The pore sizes of the synthesized hydrogels, much larger than the typical mesh size of a conventional hydrogel, allow to consider the hybrid hydrogel based on the inserted poly(NIPAM-co-DEGDA) onto collagen fibrils as a super-porous hydrogel.