Investigation of CL‐20 and RDX Nanocomposites

Nanocrystalline explosives offer a number of advantages in comparison to conventional energetics including reduced sensitivity and improved mechanical properties. In this study, formulations consisting of 90 % hexanitro‐hexaazaisowurtzitane (CL‐20) or cyclotrimethylene trinitramine (RDX) and 10 % polyvinyl alcohol (PVOH) were prepared with mean crystal sizes ranging from 200 nm to 2 μm. The process to create these materials used a combination of aqueous mechanical crystal size reduction and spray drying. The basic physical characteristics of these formulations were determined using a variety of techniques, including scanning electron microscopy, X‐ray diffraction, and Raman spectroscopy. Compressive stress‐strain tests on pressed pellets revealed that the mechanical properties of the compositions improved with decreasing crystal size, consistent with Hall‐Petch mechanics. In the most extreme case (involving CL‐20/PVOH formulations), crystal size reduction from 2 μm to 300 nm improved compressive strength and Young’s modulus by 126 % and 61 %, respectively. These results serve to highlight the relevance of structure‐property relationships in explosive compositions, and particularly elucidate the substantial benefits of reducing the high explosive crystal size to nanoscale dimensions.     

Liver-Specific Pyruvate Dehydrogenase Complex Deficiency Upregulates Lipogenesis in Adipose Tissue and Improves Peripheral Insulin Sensitivity

The pyruvate dehydrogenase complex (PDC) plays a critical role in lipid synthesis and glucose homeostasis in the fed and fasting states. The central role of the liver in the maintenance of glucose homeostasis has been established by studying changes in key enzymes (including PDC) and the carbon-flux via several pathways under different metabolic states. In the present study we have developed a murine model of liver-specific PDC deficiency using Cre-loxP technology to investigate its consequences on lipid and carbohydrate metabolism. There was no incorporation of glucose-carbon into fatty acids by liver in vitro from liver-specific Pdha1 knockout (L-PDHKO) male mice due to absence of hepatic PDC activity. Interestingly, there was a compensatory increase in lipogenic capacity in epididymal adipose tissue from L-PDHKO mice. Both fat and lean body mass were significantly reduced in L-PDHKO mice, which might be explained by an increase in total energy expenditure compared with wild-type littermate mice. Furthermore, both liver and peripheral insulin sensitivities measured during a hyperinsulinemic-euglycemic clamp were improved in L-PDHKO mice. The findings presented here demonstrate (i) the indispensable role of PDC for lipogenesis from glucose in liver and (ii) specific adaptations in lipid and glucose metabolism in the liver and adipose tissue to compensate for loss of PDC activity in liver only.     

Novel thermo‐responsive semi‐interpenetrating network microspheres of gellan gum‐poly(N‐isopropylacrylamide) for controlled release of atenolol

Thermoresponsive microspheres of gellan gum‐poly(N‐isopropylacrylamide), i.e., GG‐P(NIPAAm) semi‐interpenetrating polymer networks (semi‐IPNs) have been prepared by ionic crosslinking and used to study the controlled release (CR) of atenolol (ATL), an antihypertensive drug. Interaction of the drug with polymers was studied by Fourier transform infrared (FTIR) spectroscopy. Differential scanning calorimetry (DSC) was used to confirm the polymorphism and molecular level dispersion of ATL. Scanning electron microscopy (SEM) indicated spherical nature and smooth surfaces of the microspheres with some debris attached on their surfaces. Mean particle size measured by laser light diffraction ranged between 34 and 76 μm. Equilibrium swelling performed at 25°C and 37°C in pH 7.4 phosphate buffer exhibited thermoresponsive nature of the polymers. In vitro drug release performed at 25°C and 37°C indicated temperature‐dependency of ATL release, which was extended up to 12 h. In vitro release profiles at both the temperatures confirmed thermoresponsive nature of the polymers giving pulsatile trends. The % cumulative release data have been fitted to an empirical equation to estimate transport parameters and to understand the nature of drug release. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Identification of mixing parameters in agitated pulp chests: A continuous time domain approach

Parameter identification is quite challenging in mixing, which is extensively employed in chemical process industry. Agitated pulp chests are more difficult to characterize because they handle non-Newtonian pulp suspensions and non-ideal flows such as short circuiting, recirculation and channeling. In the present study, we characterize the agitated pulp chests in the continuous time domain, which obviates the restrictions imposed by the discrete time approach. For this purpose, a robust and efficient hybrid genetic algorithm is utilized along with a differential-algebraic model of mixing. Necessary derivatives including auxiliary differential equations are obtained for gradient search. Using realistic large sets of mixing data, both the algorithm and the model are successfully validated before characterizing laboratory-scale agitated pulp chests. Superior characterizations are obtained compared to those yielded by the discrete time domain approach. This outcome highlights the benefit of the continuous time domain approach developed in this work.     

Choked flow and importance of Mach I in freeze-drying process design

Occasionally the freeze drying cycle conditions are developed on a small scale dryer that result in a water vapor flux during primary drying that the full-scale equipment cannot handle, resulting in loss of the ability to control chamber pressure. A primary cause of loss of pressure control is a phenomenon commonly described as “choked flow”, where the required mass transfer through the duct connecting the drying and condenser chamber cannot be maintained at the control pressure. Water vapor flow rate increases as the condenser pressure decreases, but it can continue to do so only until the velocity of water vapor reaches speed of sound (i.e., Mach I) at the duct exit. The flow is then said to be choked, and any further increase in water vapor flow rate results in an increase in chamber pressure (i.e., loss in chamber pressure control). Sublimation tests were carried out in Lyostar II freeze-dryer (SP Industries, NY) to predict the occurrence of choked flow. A capacitance manometer was installed in the “condenser chamber” and differential pressure (P_c?P_cd) was measured as a function of sublimation rate (P_c=chamber pressure and P_cd=condenser pressure). Water vapor flow rate was measured by Tunable Diode Laser Absorption Spectroscopy (TDLAS) methodology, with a check by gravimetric data. Flow of water vapor in the duct connecting chamber and the condenser was modeled using computational fluid dynamics software (Fluent 6.3). The critical pressure ratio (K?=P_c/P_cd) has been identified as an important variable that determines the onset of choked flow during primary drying. This ratio can be calculated given the mass flux. For our freeze-dryer, K* greater than 2.5 (for P_c<150 mTorr) resulted in choked flow. The gas velocity indeed reaches Mach I limit at the duct exit under the choked flow conditions, as modeled by Fluent. Using the differential pressure measurements, the throat connecting the chamber and the condenser can be used as an “in process” mass flow meter to measure sublimation rate under non-choked flow conditions during primary drying without interrupting the process. Also, TDLAS is a useful tool for determination of sublimation rate even at very high mass flux.     

Nanofibrous Patches for Spinal Cord Regeneration

The difficulty in spinal cord regeneration is related to the inhibitory factors for axon growth and the lack of appropriate axon guidance in the lesion region. Here scaffolds are developed with aligned nanofibers for nerve guidance and drug delivery in the spinal cord. Blended polymers including poly(L ‐lactic acid) (PLLA) and poly(lactide‐co‐glycolide) (PLGA) are used to electrospin nanofibrous scaffolds with a two‐layer structure: aligned nanofibers in the inner layer and random nanofibers in the outer layer. Rolipram, a small molecule that can enhance cAMP (cyclic adenosine monophosphate) activity in neurons and suppress inflammatory responses, is immobilized onto nanofibers. To test the therapeutic effects of nanofibrous scaffolds, the nanofibrous scaffolds loaded with rolipram are used to bridge the hemisection lesion in 8‐week old athymic rats. The scaffolds with rolipram increase axon growth through the scaffolds and in the lesion, promote angiogenesis through the scaffold, and decrease the population of astrocytes and chondroitin sulfate proteoglycans in the lesion. Locomotor scale rating analysis shows that the scaffolds with rolipram significantly improved hindlimb function after 3 weeks. This study demonstrates that nanofibrous scaffolds offer a valuable platform for drug delivery for spinal cord regeneration.     

The First Example of Saccharin‐Lithium Bromide Catalysis: Direct Synthesis of N‐Tosylimines from Alcohols

The first procedure to access N‐tosylimines directly from alcohols under mild and neutral conditions is reported. The protocol involves saccharin‐lithium bromide‐catalyzed oxidation of alcohols to aldehydes/ketones with chloramine‐T followed by their condensation with the in situ generated oxidation by‐product p‐toluenesulfonamide in the same reaction vessel to afford N‐tosylimines in 40–90% overall yields. The present work opens up a new and efficient synthetic route to N‐tosyimines directly from alcohols in a one‐pot procedure.     

Improving the Effectiveness of Isinglass Finings for Beer Clarification by Optimisation of the Mixing Process. Part 1: Laboratory Scale Experiments

In order to optimise the process of fining beer there is a need to model the process in terms of addition, mixing and flocculation. Mixing of beer and finings has been achieved in a small laboratory stirred vessel that enables exact characterisation of the shear conditions and residence time. The performance of the finings was evaluated after settling in Imhoff cones. Results identified an optimum mixing regime comprising two stages; a relatively vigorous and short duration first mix followed by a longer more gentle mix.