Phase-transfer-catalyzed asymmetric acylimidazole alkylation

2-Acylimidazoles are alkylated under phase-transfer conditions with cinchonidinium catalysts at -40 degrees C with allyl and benzyl electrophiles in high yield with excellent enantioselectivity (79 to >99% ee). The acylimidazole substrates are made in three steps from bromoacetic acid via the N-acylmorpholine adduct. The catalyst is made in high purity allowing for S-product formation (6-20 h) under mild conditions, consistent with an ion-pair mechanism. The products are readily converted to useful ester products using methyltriflate and sodium methoxide, via a dimethylacylimidazolium intermediate without racemization. The process is efficient, direct, and amenable to other electrophiles and transformations that proceed through an enolate intermediate.     

Bulk and adsorbed monolayer phase behavior of binary mixtures of undecanoic acid and undecylamine: catanionic monolayers

Differential scanning calorimetry (DSC) and X-ray powder diffraction (PXRD) have been used to determine the phase behavior of the binary mixtures of undecanoic acid (A) and undecylamine (B) in the bulk. In addition, we report DSC data that indicates very similar behavior for the solid monolayers of these materials adsorbed on the surface of graphite. The two species are found to form a series of stoichiometric complexes of the type AB, A(2)B, and A(3)B on the acid rich side of the phase diagram. Interestingly, no similar series of complexes is evident on the amine rich side. As a result of this complexation, the solid monolayers of the binary mixtures exhibit a very pronounced enhancement in stability relative to the pure adsorbates.     

Combining discrete-event simulation and system dynamics in a healthcare setting: A composite model for Chlamydia infection

This paper presents a composite model in which two simulation approaches, discrete-event simulation (DES) and system dynamics (SD), are used together to address a major healthcare problem, the sexually transmitted infection Chlamydia. The paper continues an on-going discussion in the literature about the potential benefits of linking DES and SD. Previous researchers have argued that DES and SD are complementary approaches and many real-world problems would benefit from combining both methods. In this paper, a DES model of the hospital outpatient clinic which treats Chlamydia patients is combined with an SD model of the infection process in the community. These two models were developed in commercial software and linked in an automated fashion via an Excel interface. To our knowledge this is the first time such a composite model has been used in a healthcare setting. The model shows how the prevalence of Chlamydia at a community level affects (and is affected by) operational level decisions made in the hospital outpatient department. We discuss the additional benefits provided by the composite model over and above the benefits gained from the two individual models.     

Secure key distribution over a 500 km long link using a Raman ultra‐long fiber laser

In traditional communication systems the transmission medium is considered as a given characteristic of the channel, which does not depend on the properties of the transmitter and the receiver. Recent experimental demonstrations of the feasibility of extending the laser cavity over the whole communication link connecting the two parties, forming an ultra‐long fiber laser (UFL), have raised groundbreaking possibilities in communication and particularly in secure communications. Here, a 500 km long secure key distribution link based on Raman gain UFL is demonstrated. An error‐free distribution of a random key with an average rate of 100 bps between the users is demonstrated and the key is shown to be unrecoverable to an eavesdropper employing either time or frequency domain passive attacks.     

Click chemistry in mesoporous materials: functionalization of porous silicon rugate filters

In this paper we report the use of the optical properties of porous silicon photonic crystals, combined with the chemical versatility of acetylene-terminated SAMs, to demonstrate the applicability of "click" chemistry to mesoporous materials. Cu(I)-catalyzed alkyne-azide cycloaddition reactions were employed to modify the internal pore surfaces through a two-step hydrosilylation/cycloaddition procedure. A positive outcome of this catalytic process, here performed in a spatially confined environment, was only observed in the presence of a ligand-stabilized Cu(I) species. Detailed characterization using Fourier transform infrared spectroscopy and optical reflectivity measurements demonstrated that the surface acetylenes had reacted in moderate to high yield to afford surfaces exposing chemical functionalities of interest. The porous silicon photonic crystals modified by the two-step strategy, and exposing oligoether moieties, displayed improved resistance toward the nonspecific adsorption of proteins as determined with fluorescently labeled bovine serum albumin. These results demonstrate that "click" immobilization offers a versatile, experimentally simple, and modular approach to produce functionalized porous silicon surfaces for applications as diverse as porous silicon-based sensing devices and implantable biomaterials.     

Discrete Conditional Phase-type models utilising classification trees: Application to modelling health service capacities

Discrete Conditional Phase-type models (DC-Ph) consist of a process component (survival distribution) preceded by a set of related conditional discrete variables. This paper introduces a DC-Ph model where the conditional component is a classification tree. The approach is utilised for modelling health service capacities by better predicting service times, as captured by Coxian phase-type distributions, interfaced with results from a classification tree algorithm. To illustrate the approach, a case-study within the healthcare delivery domain is given, namely that of maternity services. The classification analysis is shown to give good predictors for complications during childbirth. Based on the classification tree predictions, the duration of childbirth on the labour ward is then modelled as either a two or three-phase Coxian distribution. The resulting DC-Ph model is used to calculate the number of patients and associated bed occupancies, patient turnover, and to model the consequences of changes to risk status.     

Quantum-state resolved reaction dynamics at the gas-liquid interface: direct absorption detection of HF(v,J) product from F(2P)+squalane

Exothermic reactive scattering of F atoms at the gas-liquid interface of a liquid hydrocarbon (squalane) surface has been studied under single collision conditions by shot noise limited high-resolution infrared absorption on the nascent HF(v,J) product. The nascent HF(v,J) vibrational distributions are inverted, indicating insufficient time for complete vibrational energy transfer into the surface liquid. The HF(v=2,J) rotational distributions are well fit with a two temperature Boltzmann analysis, with a near room temperature component (T(TD) approximately equal to 290 K) and a second much hotter scattering component (T(HDS) approximately equal to 1040 K). These data provide quantum state level support for microscopic branching in the atom abstraction dynamics corresponding to escape of nascent HF from the liquid surface on time scales both slow and fast with respect to rotational relaxation.     

Tedanolide C: a potent new 18-membered-ring cytotoxic macrolide isolated from the Papua New Guinea marine sponge Ircinia sp

Cytotoxicity-guided fractionation of the crude methanol extract of a marine sponge, Ircinia sp., yielded tedanolide C (1), a new 18-membered macrolide. The structure was solved by interpreting NMR and MS data, and the relative stereochemistry was determined from a combination of homo- and heteronuclear coupling constants in conjunction with molecular modeling. Compound 1 exhibited potent cytotoxicity against HCT-116 cells in vitro. Cell cycle analysis showed that treatment of cells with compound 1 arrested cells in the S-phase.     

Locational analysis: highlights of growth to maturity

Locational analysis has grown to maturity over the last decades, from its earliest roots, to fruitfulness in a wide-ranging number of strands that join with other disciplines and applications such as environmental planning and supply chain management. This paper charts the progress of location theory in three stages: a period of early contributions, when a number of seminal geometrical and geographical problems were studied; a ‘coming of age’ with the development of defining or classical problems that have proved fundamental to much later research and a third period of new models and new applications.