Studies on quinazolinones. 2. Synthesis of 2-(4-benzylpiperazin-1-ylmethyl)-2,3-dihydro-5H-oxazolo[2,3–6]quinazolin-5-one and -2,3-dihydro-5H-thiazolo[2,3-b]quinazolin-5-one

To search for novel antihypertensive heterocycles in the condensed quinazoline series, two representative compounds were synthesized via a suitable reaction sequences. Treating anthranilonitrile with allyl isocyanate gave 2-(allylureido)benzonitrile ( 10 ) in a quantitative yield. Compound 10 was cyclized to 3-allylquinazoline-2(1H, 4(3H)-dione ( 11 ). Bromination of 11 in carbon tetrachloride converted it into the corresponding 3-(2,3-dibromopropyl) derivative ( 12 ) in 92% yield. Ring closure of 12 was effected by the action of alkali to afford 2-bromomethyl-2,3-dihydro-5H-oxazolo[2,3-b]quinazolin-5-one ( 13 ). The title compound, 2-(4-benzylpiperazin-1-ylmethyl)-2,3-dihydro-5H-oxazolo[2,3-b]quinazolin-5-one ( 7 ) could be obtained by a reaction of either 12 or 13 with 1-benzylpiperazine respectively. Starting from the readily available 3-allyl-2H-thioxoquinazolin-4(3H)-one ( 16 ) via the analogous reactions gave the 2-bromomethyl-2,3-dihydro-5H-thiazolo[2,3-b]-quinazolin-5-one ( 19 ) in good yield. However, the reaction of 19 with 1-benzylpiperazine provided another target compound, 2-(4-benzylpiperazin-1-ylmethyl)-2,3-dihydro-5H-thiazolo[2,3-b]quinazolin-5-one ( 8 ) only in poor yield (8%). As major product, the dehydrobrominated compound, 2-methylene-2,3-dihydro-5H-thiazolo[2,3-b]quinazolin-5-one ( 22 ) was isolated. A preliminary pharmacological evaluation revealed that both compounds 7 and 8 are devoid of the antihypertensive activity.     

Effects of mucin addition on the stability of oil–water emulsions

In this work, bovine submaxillary gland mucin (BSM) was used as an emulsifier to stabilize oil–water emulsion systems. Prior to use, commercial BSM was purified by jacalin affinity chromatography. Emulsions consisting of 5% mineral oil in phosphate buffered saline (PBS) were prepared through the addition of different amounts of purified mucin followed by sonication using either of two methods: (1) low energy input for a long time (2 h), or (2) high energy input for a short time (20 s). The surfactancy property of mucin was investigated by surface tension measurements, which showed the BSM to greatly reduce the surface tension of PBS. Compared to several synthetic surfactants of the Pluronic® type, mucin showed comparable or better surface activity than F68, F88 and F108 products in dilute solutions. The formed emulsions had a mean droplet size that decreased monotonically with increasing concentration of mucin until a plateau was reached at concentrations around 0.1% by weight. The stability of these emulsions was evaluated by monitoring their average droplet size during a 33-day period. Emulsions with more than 0.25% mucin showed a constant mean size throughout the period. Specifically, an emulsion produced with 0.95% mucin showed a stable mean droplet size of about 300 nm. The stability of the mucin-emulsified systems was also evaluated by measuring turbidity changes with time, which allowed a comparison with similar emulsions stabilized by the Pluronic® surfactants in the same concentration. Thus, mucin showed its ability to establish more stable and more efficient oil–water emulsion systems. Since mucin is a glycoprotein, and hence biodegradable, our results suggest that mucin might serve as an ideal biological surfactant for the stabilization of emulsion systems intended for biomedical and pharmaceutical applications.     

A New Series of Proton/Charge Transfer Molecules: Synthesis and Spectral Studies of 2-(5-Aryl-1-carbomethoxy-1H-pyrazol-3-yl)phenols

Abstract. The carbomethoxyhydrazone of 2'-hydroxyacetophenone was trilithiated with excess lithium diisopropylamide and C-acylated with a variety of benzoate esters followed by acid cyclization of the intermediates to 2-(5-aryl-l-car-bomethoxy-lHpyrazol-3-yl)phenols [3-(2-hydroxyphen-yl)-lH-pyrazoles]. The products were characterized by Fourier transform-IR, ^lH NMR, ¹³C NMR, UV-visible absorption and fluorescence. All the derivatives in n -heptane have an absorption maximum at ˜304 nm and an extremely weak (φ_r= 10 ⁴) fluorescence with maxima in the range of 335–460 nm. The broad range of fluorescence maxima and fluorescence quantum yields is attributed to varying contributions of charge transfer that are dependent on both the identity of the substituent and solvent polarity. A phenomenally large Stokes-shifted fluorescence maximum at 620 nm was observed for 2-(l-car-bomethoxy-5-[4-dimethylaminophenyl]-lff-pyrazol-3-y1)phenol in n-heptane and attributed to excited-state intramolecular proton transfer. As a result, competitive excited-state proton/charge transfer properties have been observed in the pyrazoles studied, of which the spectral properties can be fine tuned by substituent as well as solvent effects.     

Some Optimal Strategies for Bandit Problems with Beta Prior Distributions

A bandit problem with infinitely many Bernoulli arms is considered. The parameters of Bernoulli arms are independent and identically distributed random variables from a common distribution with beta(a, b). We investigate the k-failure strategy which is a modification of Robbins's stay-with-a-winner/switch-on-a-loser strategy and three other strategies proposed recently by Berry et al. (1997, Ann. Statist., 25, 2103–2116). We show that the k-failure strategy performs poorly when b is greater than 1, and the best strategy among the k-failure strategies is the 1-failure strategy when b is less than or equal to 1. Utilizing the formulas derived by Berry et al. (1997), we obtain the asymptotic expected failure rates of these three strategies for beta prior distributions. Numerical estimations and simulations for a variety of beta prior distributions are presented to illustrate the performances of these strategies.     

On powers associated with Sierpiński numbers, Riesel numbers and Polignac's conjecture

We address conjectures of P. Erd?s and conjectures of Y.-G. Chen concerning the numbers in the title. We obtain a variety of related results, including a new smallest positive integer that is simultaneously a Sierpiński number and a Riesel number and a proof that for every positive integer r, there is an integer k such that the numbers k,k²,k³,…,kr are simultaneously Sierpiński numbers.     

Symmetry and bifurcation in vestibular system

The vestibular system in almost all vertebrates, humans included, controls balance by employing a set of six semicircular canals, three in each inner ear, to detect angular accelerations of the head. Signals from the canals are transmitted to neck motoneurons and activate eight corresponding muscle groups. These signals may be either excitatory or inhibitory, depending on the direction of acceleration. McCollum and Boyle have observed that in the cat the network of neurons concerned possesses octahedral symmetry, a structure deduced from the known innervation patterns (connections) from canals to muscles. We re-derive the octahedral symmetry from mathematical features of the probable network architecture, and model the movement of the head in response to the activation patterns of the muscles concerned. We assume that connections among neck muscles can be modeled by a ‘coupled cell network’, a system of coupled ODEs whose variables correspond to the eight muscles, and that network also has octahedral symmetry. The network and its symmetries imply that these ODEs must be equivariant under a suitable action of the octahedral group. Using results of Ashwin and Podvigina, we show that with the appropriate group actions, there are six possible spatiotemporal patterns of time-periodic states that can arise by Hopf bifurcation from an equilibrium corresponding to natural head motions. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Finite temperature formalism for composite quantum particles

This Letter provides the missing part of the newly constructed many-body formalism for composite quantum particles: the introduction of a finite temperature. The finite T formalism we propose deeply relies on the existence of a compact closure relation for the (overcomplete) set of N-composite-particle states. As a first application, we here calculate the energy mean value of the exciton gas outside the condensation regime. We show that carrier exchanges increase its temperature dependence compared to elementary bosons, a signature of the degree-of-freedom increase resulting from the particle composite nature.     

Mixed-metal Pt monolayer electrocatalysts with improved CO tolerance

Using a combination of periodic, self-consistent, density functional theory (DFT) calculations and CO-stripping voltammetry experiments, we have designed a new class of Pt-M bimetallic monolayer catalysts supported on a non-Pt metal, which exhibit improved stability against CO poisoning and might be suitable for proton-exchange membrane fuel cell anodes. These surfaces help in reducing the overpotential associated with anodic CO oxidation and minimize the amount of Pt used, thereby reducing materials cost. DFT calculations predict highly repulsive interactions between adsorbed CO molecules on these surfaces, leading to weaker binding and lower coverage of CO than on pure Pt, which in turn facilitates oxidative removal of CO from these catalytic surfaces.     

An Aggregation‐Induced‐Emission Platform for Direct Visualization of Interfacial Dynamic Self‐Assembly

An in‐depth understanding of dynamic interfacial self‐assembly processes is essential for a wide range of topics in theoretical physics, materials design, and biomedical research. However, direct monitoring of such processes is hampered by the poor imaging contrast of a thin interfacial layer. We report in situ imaging technology capable of selectively highlighting self‐assembly at the phase boundary in real time by employing the unique photophysical properties of aggregation‐induced emission. Its application to the study of breath‐figure formation, an immensely useful yet poorly understood phenomenon, provided a mechanistic model supported by direct visualization of all main steps and fully corroborated by simulation and theoretical analysis. This platform is expected to advance the understanding of the dynamic phase‐transition phenomena, offer insights into interfacial biological processes, and guide development of novel self‐assembly technologies.     

Cohort Analysis Technique for Long-Term Manpower Planning: the Case of a Hong Kong Tertiary Institution

This paper considers the problem of long-term manpower planning on the number of teaching staff for the case of a tertiary institution—the City Polytechnic of Hong Kong (CPHK). Due to the high turnover experienced in recent years, it is found necessary to study the wastage pattern of staff, defined as the number of new appointees who have left CPHK employment, rather than simply addressing just the issue of strength (namely number in post). A cohort analysis technique is therefore applied to characterize statistically the wastage rate as related to the length of service of individual cohorts of staff, being groups of newcomers joining CPHK in the same periods of time. This results in a log-normal model, showing a significant cohort specific effect on the wastage behaviour. Extending this cohort analysis technique, together with double exponential smoothing forecasts, to future retention rates (1 — cumulative wastage rates), a long-term planning model is constructed to study the relation between expected yearly recruitment levels and the target manpower requirements for the future five-year planning horizon. While the idea and model developed here are generally applicable, the present computational results provide valuable decision supports for an actual case study, for CPHK in particular.