Kinetic studies on fluvastatin photodegradation in solutions

Summary The effect of solvent on the photodegradation kinetics of fluvastatin was evaluated. The degradation rate of fluvastatin was estimated on the basis of the quantum yields and kinetic parameters determination. The photodegradation appeared to follow first-order kinetics. In order to establish the light intensity absorbed by a system, Reinecke’s salt was used as a chemical actinometer.     

Polarisation characteristics of a 12 fibre coupler under femtosecond pulsed and continuous wave illumination

We report on the experimental investigation carried out in the polarisation characteristics of femtosecond pulsed and continuous wave beams propagating through a 1×2 fibre coupler. It is demonstrated that the polarisation states of pulsed and continuous wave illumination over the broad wavelength range can be preserved in a conventional fused fibre coupler. Furthermore, the fibre coupler acts as a low-pass spectral filter in the visible wavelength range with a splitting ratio between 99.6/0.4 and 99.7/0.3. The result is of importance for fibre-optic second harmonic generation microscopy which requires the polarisation preservation to extract molecular organization of a sample.     

How simple can a thermotropic mesogenic molecule be? Supramolecular layers through a network of hydrogen bonds

The supramolecular approach was applied to obtain a thermotropic liquid crystalline phase from the smallest possible molecules. Diaminobenzene derivatives are able to form smectic layers through a network of interconnected hydrogen bonded rings. The observed smectic A phase exhibits unusually small optical birefringence, comparable with that of lyotropic lamellar phases.     

Formation of radical anions and not deprotonation starts the reaction of gamma-butyrolactone with potassium anions

A mechanism is proposed for the reaction of gamma-butyrolactone with the potassium anion as a two-electron-transfer reagent. Potassium hydride and potassium 4-potassiobutyrate are formed in this process as intermediates. These compounds deprotonate gamma-butyrolactone. Potassium lactone enolate, potassium butyrate, and hydrogen are the final reaction products.     

Cucurbituril binding of trans-[{PtCl(NH3)2}2(micro-NH2(CH2)8NH2)]2+ and the effect on the reaction with cysteine

The effect of encapsulation by cucurbiturils Q[7] and Q[8] on the rate of reaction of the anti-cancer dinuclear platinum complex trans-[{PtCl(NH3)2}2(micro-NH2(CH2)8NH2)]2+ with the model biological nucleophiles glutathione and cysteine has been examined by NMR spectroscopy. It was expected that the octamethylene linking chain would fold inside the cucurbituril host and hence position the reactive platinum centres close to the cucurbituril portals, and thereby, confer resistance to degradation by biological nucleophiles. The upfield shifts of the resonances from the methylene protons in the linking ligand observed in 1H NMR spectra of the platinum complex upon addition of either Q[7] or Q[8] indicate that the cucurbituril is positioned over the linking ligand, with the Pt(II) centres projecting out of the portal. Furthermore, the relative changes in chemical shift of the methylene resonances suggest that the octamethylene linking chain folds within the cucurbituril cavity, particularly in Q[8]. Simple molecular models, based on the observed relative changes in chemical shift, could be constructed that were consistent with the proposed folding of the linking ligand within the cucurbituril cavity. Encapsulation by Q[7] was found to reduce the rate of reaction of the platinum complex with glutathione. Encapsulation by Q[7] and Q[8] was also found to reduce the rate of reaction of the platinum complex with cysteine, with Q[8] slowing the reaction to a greater extent than Q[7], consistent with the inferred encapsulation geometries. Encapsulation of dinuclear platinum complexes within the cucurbituril cavity may provide a novel way of reducing the reactivity and degradation of these promising chemotherapeutic agents with blood plasma proteins.     

Construction of a side pumped double-clad fiber using polished couplers

The paper presents a new way of side pumping double-clad fibers. Elaborated asymmetric polished couplers are presented. By using these couplers in pumping power set-ups of double-clad fiber very good pumping efficiency a very good efficiency was attained. The experimental and numerical optimizations of designed couplers are presented.     

Approximating Time to Extinction for Endemic Infection Models

Approximating the time to extinction of infection is an important problem in infection modelling. A variety of different approaches have been proposed in the literature. We study the performance of a number of such methods, and characterise their performance in terms of simplicity, accuracy, and generality. To this end, we consider first the classic stochastic susceptible-infected-susceptible (SIS) model, and then a multi-dimensional generalisation of this which allows for Erlang distributed infectious periods. We find that (i) for a below-threshold infection initiated by a small number of infected individuals, approximation via a linear branching process works well; (ii) for an above-threshold infection initiated at endemic equilibrium, methods from Hamiltonian statistical mechanics yield correct asymptotic behaviour as population size becomes large; (iii) the widely-used Ornstein-Uhlenbeck diffusion approximation gives a very poor approximation, but may retain some value for qualitative comparisons in certain cases; (iv) a more detailed diffusion approximation can give good numerical approximation in certain circumstances, but does not provide correct large population asymptotic behaviour, and cannot be relied upon without some form of external validation (eg simulation studies).     

Effect of counterions on the interactions of charged oligothiophenes

The functionality of conjugated polymer systems often relies on oxidations or reductions, in most cases mediated by the presence of counterions. The effect that the common counterion hexafluorophosphate (PF6-) has on the intermolecular interactions between charged oligothiophenes is investigated here using ab initio quantum chemistry methods. Counterions are explicitly included in the simulations of oxidized oligothiophenes and in the dimerization process. Our calculations provide quantitative and qualitative insight into the intermolecular interactions in oligothiophene-counterion systems and show that the intermolecular pi-stacking of oligothiophenes is not adversely affected by the presence of counterions and that in fact oligothiophene dimerization is further stabilized by their presence.     

Cis and trans selective 1,4-addition of a lithium dithioester enolate to 4-O-TBS-2-cyclohexenone

The 1,4-addition of the lithium enolate of methyldithioacetate (LMDTA) to (+/-)-4-O-TBS-2-cyclohexenone (3) can be varied from being highly 3,4-trans selective to being highly 3,4-cis selective simply by varying the reaction temperature. This stereodivergency allows expedient syntheses of the corresponding trans and cis methyl esters 6t and 6c and derived bicyclic ketolactones 7t and 7c.