Thermal conductivity measurements on ferrofluids

The thermal conductivity of a number of ferrofluids consisting of colloidally dispersed Fe₃O₄ particles in diester, hydrocarbon, water and fluorcarbon carriers have been measured at 38°C. The variation in thermal conductivity with particle concentration is well described by Tareef's equation (1940). This has enabled the ratio of the physical to magnetic size to be determined and compared with estimates of the ratio obtained from electron micrographs and magnetic measurements.The fit between theory and experiment is particularly good for hydrocarbon carrier fluids giving the ratio of solid to magnetic radiusR _i/R _m=1.24±0.03 compared with the value obtained from magnetic data and electron micrographs of 1.19±0.07. The corresponding value from the fluids with a diester carrier ranges between 1.1<R _d/R _m<1.3 which is again consistent with microscopy and magnetic data.The application of a magnetic field of 0.1 T had no noticeable effect on the thermal conductivities of ferrofluids.     

ENERGY TRANSFER AND PHOTOOXIDATION KINETICS IN REACTION CENTERS ON THE PICOSECOND TIME SCALE

Abstract— Picosecond 530 nm actinic and 1242 nm probe light pulses have been used to measure the kinetics of energy transfer and photooxidation in Rhodopseudomonas sphaeroides R-26 reaction centers. The energy transfer rate between bacteriopheophytin and the bacteriochlorophyll dimer is 1.0 ± 0.3 ± 10¹¹s^-land photooxidation of the dimer occurs within 5 ps after the dimer reaches the first excited singlet state. Using these parameters in a simple model we are able to explain the odd result that the number of reaction centers oxidized by a saturating 530 nm actinic picopulse is only 60% of the number oxidized by a saturating CW light source.     

Versatile self-complexing compounds based on covalently linked donor-acceptor cyclophanes

A range of covalently linked donor-acceptor compounds which contain 1) a hydroquinone (HQ) unit, 2) a 1,5-dioxynaphthalene (DNP) ring system, or 3) a tetrathiafulvalene (TTF) unit as the pi-donor, and 4) cyclobis(paraquat-p-phenylene) (CBPQT(4+)) as the pi-accepting tetracationic cyclophane were prepared and shown to operate as simple molecular machines. The pi-donating arms can be included inside the cyclophane in an intramolecular fashion by virtue of stabilizing noncovalent bonding interactions. What amounts to self-complexing/decomplexing equilibria were shown to be highly temperature dependent when the pi-donating arm contains either an HQ or DNP moiety. The thermodynamic parameters associated with the equilibria have been unraveled by using variable-temperature (1)H NMR spectroscopy. The negative DeltaH degrees and DeltaS degrees values account for the fact that the "uncomplexed" conformation becomes the dominant species, since the entropy gain associated with the decomplexation process overcomes the enthalpy loss resulting from the breaking of the donor-acceptor interactions. The arm's in-and-out movements with respect to the linked cyclophanes can be arrested by installing a bulky substituent at the end of the arm. In the case of compounds carrying a DNP ring system in their side arm, two diastereoisomeric, self-complexing conformations are observed below 272 K in hexadeuterioacetone. By contrast, control over the TTF-containing arm's movement is more or less ineffective through the thermally sensitive equilibrium although it can be realized by chemical and electrochemical ways as a result of TTF's excellent redox properties. Such self-complexing compounds could find applications as thermo- and electroswitches. In addition, the thermochromism associated with the arm's movement could lead to some of the compounds finding uses as imaging and sensing materials.     

New Synthetic Route to Pummerer's Ketone

Pummerer's ketone 1 is obtained with an overall yield of 55 % by the following sequence: Claisen rearrangement of an arylcyclohexylether 3; allylic oxidation of the methylcycloalkylphenolic derivative 4b, then spontaneous cyclisation during demethylation to give 2. 1 is obtained by dehydrogenation of 2. NMR data agree with a cis stereochemistry at C_4a and C _9b.     

Os(VIII)-catalysed oxidation of sulfides by sodium salt of N-chlorobenzenesulfonamide

Catalytic activity of Os(VIII) in the oxidation of some twenty organic sulfides with sodium salt of N-chlorobenzenesulfonamide (CAB) has been investigated in alkaline (pH8.7) t-butanol–water (1:1 v/v) medium. Significant retarding influence of [OH⁻] on the reactivity is exhibited. The catalysed reaction is strongly accelerated in the presence of Hg(II). Imperfections are observed in the linear Hammett relationship in the case of –NO₂ substituents.     

Dual functional polyelectrolyte multilayer coatings for implants: permanent microbicidal base with controlled release of therapeutic agents

Here we present a new bifunctional layer-by-layer (LbL) construct made by combining a permanent microbicidal polyelectrolyte multilayered (PEM) base film with a hydrolytically degradable PEM top film that offers controlled and localized delivery of therapeutics. Two degradable film architectures are presented: (1) bolus release of an antibiotic (gentamicin) to eradicate initial infection at the implant site, or (2) sustained delivery of an anti-inflammatory drug (diclofenac) to cope with inflammation at the site of implantation due to tissue injury. Each degradable film was built on top of a permanent base film that imparts the implantable device surface with microbicidal functionality that prevents the formation of biofilms. Controlled-delivery of gentamicin was demonstrated over hours and that of diclofenac over days. Both drugs retained their efficacy upon release. The permanent microbicidal base film was biocompatible with A549 epithelial cancer cells and MC3T3-E1 osteoprogenitor cells, while also preventing bacteria attachment from turbid media for the entire duration of the two weeks studied. The microbicidal base film retains its functionality after the biodegradable films have completely degraded. The versatility of these PEM films and their ability to prevent biofilm formation make them attractive as coatings for implantable devices.     

Modeling and optimizing a vendor managed replenishment system using machine learning and genetic algorithms

Using a supply chain network, we demonstrate the feasibility, viability, and robustness of applying machine learning and genetic algorithms to respectively model, understand, and optimize such data intensive environments. Deployment of these algorithms, which learn from and optimize data, can obviate the need to perform more complex, expensive, and time consuming design of experiments (DOE), which usually disrupt system operations. We apply and compare the behavior and performance of the proposed machine learning algorithms to that obtained via DOE in a simulated Vendor Managed Replenishment system, developed for an actual firm. The results show that the models resulting from the proposed algorithms had strong explanatory and predictive power, comparable to that of DOE. The optimal system settings and profit were also similar to that obtained from DOE. The virtues of using machine learning and evolutionary algorithms to model and optimize data rich environments thus seem promising because they are automatic, involving little human intervention and expertise. We believe and are exploring how they can be made adaptive to improve parameter estimates with increasing data, as well as seamlessly detecting system (and therefore model) changes, thus being capable of recursively updating and reoptimizing a modified or new model.