Surface and aggregation behavior of aqueous solutions of Ru(II) metallosurfactants: 4. Effect of chain number and orientation on the aggregation of [Ru(bipy)2(bipy')]Cl2 complexes

The structure of aggregates formed by eight surfactant [Ru(bipy)2(p,p'-dialkyl-2,2'-bipy)]Cl2 complexes-which we express as Ru(p)(q)Cn, where n (=12 or 19) is the alkyl chain length, p (=4 or 5) refers to the substitution position on the bipyridine ligand, and q (=1 or 2) is the number of substituted alkyl chains-in aqueous solutions has been examined using small-angle neutron scattering for a range of concentrations close to the critical micelle concentration and for several combinations of n, p, and q. A number of general results emerge. The double-chain surfactants possess a smaller headgroup charge but a larger aggregate size than their single-chain analogues. Over the concentration range studied, the micelles of the single-chain surfactants grow as the concentration is increased, whereas for the double-chain systems, the aggregate size remains unchanged. For both single- and double-chain surfactants, an increase in alkyl chain length is accompanied by an expected increase in aggregate size and an increase in average headgroup charge. The aggregates formed in solutions of resolved double-chain complexes are larger than those found in solutions of racemic mixtures. The Ru(4)(1)C12 and Ru(5)(1)C12 systems form aggregates with high water content. Variation of the substitution position for the single-chain surfactants produces dramatic changes in the structure of the micelles. The aggregates formed in solutions of Ru(4)(1)C19 and Ru(5)(1)C19 display particularly different structures. The Ru(4)(1)C19 system forms essentially spherical aggregates. In contrast, in the Ru(5)(1)C19 system, wormlike aggregates are formed in which the rigid rodlike sections appear to undergo a transition from a noninterdigitated to an interdigitated structure as the concentration is increased. For double-chain surfactants, the aggregation number for p = 4 surfactants is considerably larger than that for p = 5 surfactants.     

Landing of size-selected Agn+ clusters on single crystal TiO2 (110)-(1x1) surfaces at room temperature

Mass-selected Ag(n) (+) (n=1,2,3) clusters with impact energy less than 2 eV per atom were deposited from the gas phase onto rutile titania (110)-(1x1) single crystal surfaces at room temperature and imaged using ultra-high vacuum scanning tunneling microscopy. Upon reaching the surface, Ag monomers sintered to form three-dimensional islands of approximately 50 atoms in size, with an average measured height of 7.5 A and diameter of 42 A. This suggests that the monomers are highly mobile on the titania surface at room temperature. Dimers also sintered to form large clusters upon deposition, approximately 30 atoms in size, with an average height of 6.2 A and diameter of 33 A. Clusters formed from monomer deposition appeared approximately three times more frequently at step edges than clusters formed from dimer deposition, indicating that the surface mobility of deposited monomers is higher than that of deposited dimers. In sharp contrast to the deposition of monomers and dimers, the deposition of trimers resulted in a high density of very small clusters on the order of a few atoms in size, indicative of intact trimers on the surface, implying that deposited trimers have very limited mobility on the surface at room temperature.     

Development of analytical and preparative chromatographic separations of novel growth hormone secretagogue compounds

Chromatographic separations of new growth hormone secretagogue compounds were developed to support structure-activity relationship (SAR) studies in conjunction with lead optimization. These new compounds differed from Merck's MK-677 by having two chiral centers and thus diastereomeric mixtures were generated. Separation of initial compounds in the SAR was achieved on a Kromasil C18 column using an ammonium acetate buffer and acetonitrile. However, additional candidates were not separable on C18 columns and a chiral Kromasil CHI-DMB column was used to resolve the diastereomeric compounds. The Kromasil CHI-DMB packing was also used in a preparative chromatographic system to resolve multigram quantities of secretagogue candidates for testing. Chiral separations of different intermediates were also developed in support of evolution of an asymmetric synthetic route. This report summarizes development of the preparative chromatographic system used to purify diastereomeric mixtures and chiral separations of intermediates in the synthesis.     

A stochastic cellular automata model of tautomer equilibria

ABSTRACT

Many chemical substances, including drugs and biomolecules, exist in solution not as a single species, but as a collection of tautomers and related species. Importantly, each of these species is an independent compoundwith its own specific biochemical and physicochemical properties. The species interconvert in a dynamic and often complicated manner, making modelling the overall species composition difficult. Agent-based cellular automata models are uniquely suited to meet this challenge, allowing the equilibria to be simulated using simple rulesand at the same time capturing the inherent stochasticity of the natural phenomenon. In the present example a stochastic cellular automata model is employed to simulate the tautomer equilibria of 9-anthrone and 9-anthrol in the presence of their common anion. The observed K_E of the 9-anthrone ? 9-anthrol tautomerisation along with the measured tautomer pK_a values were used to model the equilibria at pH values 4, 7 and 10. At pH 4 and 7, the anthrone comprises >99% of the total species population, while at pH 10the anthrone and the anion each represent just under half of the total population. The advantages of the cellular automata approach over the customary coupled differential equation approach are discussed.     

Location of services and the impact on healthcare quality: insights from a simulation of a musculoskeletal physiotherapy service

Many healthcare systems are being redesigned to deliver local care with more services within the community. Relocation may enhance access but other aspects of healthcare quality should also be considered, notably waiting times and equity of care. This study examined a musculoskeletal physiotherapy service using a discrete-event simulation with simple heuristics to model patient behaviour. This combination provided an effective mechanism for incorporating the individuality of the patients in the flows along the patient pathways, subject to the varying availabilities of key resources. In particular, it captured the feedback that is critical in system performance, especially where waiting times are important. The model recognised the heterogeneity of patient attitudes and demonstrated how the behaviour of a relatively small proportion can affect the experience of all patients. The study suggested that, with careful operational management, more care could be delivered locally while exploiting many of the benefits of a centralised service.     

Frequency comb generation in the green using silicon nitride microresonators

Optical frequency combs enable precision measurements in fundamental physics and have been applied to a growing number of applications, such as molecular spectroscopy, LIDAR and atmospheric trace‐gas sensing. In recent years, the generation of frequency combs has been demonstrated in integrated microresonators. Extending their spectral range to the visible is generally hindered by strong normal material dispersion and scattering losses. In this paper, we report the first realization of a green‐light frequency comb in integrated high‐Q silicon nitride (SiN) ring microresonators. Third‐order optical non‐linearities are utilized to convert a near‐infrared Kerr frequency comb to a broadband green light comb. The 1‐THz frequency spacing infrared comb covers up to 2/3 of an octave, from 144 to 226 THz (or 1327‐2082 nm), and the simultaneously generated green‐light comb is centered around 570‐580 THz (or 517‐526 nm), with comb lines emitted down to 517 THz (or 580 nm) and up to 597 THz (or 502 nm). The green comb power is estimated to be as high as −9.1 dBm in the bus waveguide, with an on‐chip conversion efficiency of −34 dB. The proposed approach substantiates the feasibility of on‐chip optical frequency comb generation expanding to the green spectral region or even shorter wavelengths.

     

Homogeneously alloyed CdSxSe1-x nanocrystals: synthesis, characterization, and composition/size-dependent band gap

Alloy nanocrystals provide an additional degree of freedom in selecting desirable properties for nanoscale engineering because their physical and optical properties depend on both size and composition. We report the pyrolytic synthesis of homogeneously alloyed CdS(x)Se(1-x) nanocrystals in all proportions. The nanocrystals are characterized using UV-visible absorption spectroscopy, transmission electron microscopy, X-ray diffractrometry, and Rutherford backscattering spectrometry to determine precisely structure, size, and composition. The dependence of band gap on nanocrystal size and composition is elucidated, yielding a bowing constant of 0.29, in agreement with bulk values. In addition, the morphology of the resultant nanocrystals can be altered by changing the reaction conditions, generating structures ranging from homogeneous, spherical nanocrystals to one-dimensional gradient nanorods.     

Measurement of the alpha-secondary kinetic isotope effect for the reaction catalyzed by mammalian protein farnesyltransferase

Protein farnesytransferase (FTase) catalyzes the transfer of a 15-carbon prenyl group from farnesyl diphosphate (FPP) to the cysteine residue of target proteins and is a member of the newest class of zinc metalloenzymes that catalyze sulfur alkylation. Common substrates of FTase include oncogenic Ras proteins, and therefore inhibitors are under development for the treatment of various cancers. An increased understanding of the salient features of the chemical transition state of FTase may aid in the design of potent inhibitors and enhance our understanding of the mechanism of this class of zinc enzymes. To investigate the transition state of FTase we have used transient kinetics to measure the alpha-secondary 3H kinetic isotope effect at the sensitive C1 position of FPP. The isotope effect for the FTase single turnover reaction using a peptide substrate that is farnesylated rapidly is near unity, indicating that a conformational change, rather than farnesylation, is the rate-limiting step. To look at the chemical step, the kinetic isotope effect was measured as 1.154 +/- 0.006 for a peptide that is farnesylated slowly, and these data suggest that FTase proceeds via a concerted mechanism with dissociative character.     

Analysis of the effects of doping and barrier design on the small-signal modulation characteristics of long-wavelength multiple quantum well lasers

This theoretical work has modelled the small signal response of InGaAsP and InGaAlAs multiple quantum well (MQW) lasers based on an ambipolar carrier transport model. The MQW parameters such as barrier bandgap, barrier width and the number of quantum wells have been optimized for high-speed modulation. The effect of the p-type doping and the strain of the InGaAs well have also been investigated.For the InGaAsP-based system, the optimization for maximum 3 dB bandwitdth shows that the optimum width is about 5 nm for 1.1 m barriers and 7 nm for 1.2 m barriers. The optimum barrier bandgap wavelength is about 1.1 m for the barrier width of 6 nm, about 1.15 m for 8 nm and 10 nm barriers. The p-doped MQW exhibits a higher modulation bandwidth because of its high differential gain and improved carrier distribution among the MQWs. The compressively strained InGaAs quantum well system has the potential for a higher modulation bandwidth. For the InGaAlAs-based system, the optimization for maximum 3 dB bandwidth shows that the optimum width is about 4 nm for a barrier wavelength of 1.10 m, and 6 nm for 1.2 m. The optimum barrier bandgap wavelength is about 1.1 m for a barrier width of 4 nm, and about 1.2 m for 6, 8 and 10 nm.     

Duplex formation and the onset of helicity in poly d(CG)n oligonucleotides in a solvent-free environment

The gas-phase conformations of a series of cytosine/guanine DNA duplexes were examined by ion mobility and molecular dynamics methods. Deprotonated duplex ions were formed by electrospray ionization, and their collision cross sections measured in helium were compared to calculated cross sections of theoretical models generated by molecular dynamics. The 4-mer (dCGCG) and 6-mer (dCGCGCG) duplexes were found to have globular conformations. Globular and helical structures were observed for the 8-mer (dCGCGCGCG) duplex, with the globular form being the more favored conformer. For the 10-mer (dCGCGCGCGCG), 14-mer (dCGCGCGCGCGCGCG), and 18-mer (dCGCGCGCGCGCGCGCGCG) duplexes, only helical structures were observed in the ion mobility measurements. Theory predicts that the helical structures are less stable than the globular forms in the gas phase and should collapse into the globular form given enough time. However, molecular dynamics simulations at 300 K indicate the helical structures are stable in aqueous solution and will retain their conformations for a limited time in the gas phase. The presence of helical structures in the ion mobility experiments indicates that the duplexes retain "solution structures" in the gas phase on the millisecond time scale.