The 2D IR responses of amide and carbonyl modes in water cannot be described by Gaussian frequency fluctuations

The two-dimensional (2D) IR spectral shapes seen for aqueous amide-I' or carbonyls having apparently single bands are not those predicted by Gaussian frequency fluctuations. Their population evolution exposes discrete distributions undergoing picosecond time scale exchange. The energy transfer to other modes provides a clear view of this underlying structure, which is largely attributed to exchanging water configurations. The results suggest new approaches to examine protein-bound water at the residue level.     

Molecular packing in amorphous carbohydrate matrixes

The molecular packing of bidisperse matrixes of amorphous carbohydrates consisting of a fractionated maltopolymer supplemented with various amounts of the disaccharide maltose is investigated by combining Positron Annihilation Lifetime Spectroscopy (PALS) with specific volume measurements. The maltopolymer-maltose blends are equilibrated at a range of water activities between 0 and 0.75 at 25 degrees C in order to investigate the effect of water content and carbohydrate molecular weight distribution on the size of the molecular free volume holes in both the glassy and rubbery states. In the rubbery state, the size of the intermolecular holes is only very weakly dependent on the carbohydrate molecular weight, provided that the carbohydrate blends are analyzed at the same water content. In contrast, in the glassy state, significant differences in the size of the free volume holes are observed between the various blends at constant water content. Both the specific volume and the hole volume decrease with increasing maltose content, initially rapidly up to a maltose content of about 40 wt % on total carbohydrate. In addition, we find that the role of water as a plasticizer and matrix constituent is a complex one. At very low water contents, water acts by filling the free volume holes between the carbohydrate molecules. This hole-filling mechanism could well be related to the phenomenon of anti-plasticization observed before. At higher water contents, corresponding generally to water activities above 0.11 at 25 degrees C, water conversely increases the average hole volume in the carbohydrate matrixes, most likely caused by water interfering with the hydrogen bonding between the carbohydrate molecules, leading to a local expansion of the molecular packing.     

Force coefficients and Strouhal numbers of three circular cylinders subjected to a cross-flow

In this paper, wind tunnel experiments were conducted to measure the mean force coefficients and Strouhal numbers for three circular cylinders of equal diameters in an equilateral-triangular arrangement when subjected to a cross-flow. These experiments were carried out at five subcritical Reynolds numbers ranging from 1.26 × 10⁴ to 6.08 × 10⁴. The pressure distributions on the surface of the cylinders were measured using pressure transducers. Furthermore, the hot-wire anemometer was employed to measure the vortex shedding frequencies behind each cylinder. Six spacing ratios (l/d) varying from 1.5 to 4 were investigated. It is observed that for l/d > 2, the upstream cylinder experiences a lower mean drag coefficient compared with the downstream cylinders. The minimum values of the drag coefficient for the downstream cylinders occur at l/d = 1.5 and l/d = 2, because there is no vortex shedding from the foregoing cylinders. Also, the value of the pressure coefficient behind the upstream cylinder reduces by increasing l/d. Moreover, by decreasing the value of l/d, the Strouhal number for the upstream cylinder increases. It can be concluded that the flow pattern and aerodynamic coefficients are basically dependent on l/d; in other words, decreasing l/d results in an increase in the effects of the flow interference between the cylinders.     

Encapsulation of conventional and unconventional water dimers by water-binding foldamers

Water-binding foldamers have been rarely studied. By orienting both H-bond donors and acceptors toward their interior, two pyridine-derived crescent-shaped folding oligoamides were found to be capable of trapping both conventional and unconventional water dimer clusters in their cavity (～2.5 ? radius). In the unconventional water dimer cluster, the two water molecules stay in contact via an unusual H-H interaction (2.25 ?) rather than the typical H-bond.     

Nonparametric estimation of the anisotropic probability density of mixed variables

The problem of nonparametric estimation of the joint probability density of a vector of continuous and ordinal/nominal categorical random variables with bounded support is considered. There are numerous publications devoted to the cases of either continuous or categorical variables, and the curse of dimensionality and strong regularity assumptions are the two familiar issues in the literature. Mixed variables occur in practically all applications of the statistical science and, nonetheless, the literature devoted to the joint density estimation is practically next to none. This paper develops the theory of estimation of the density of mixed variables which is on par with results known for simpler settings. Specifically, a data-driven estimator is developed that adapts to unknown anisotropic smoothness of the joint density and, whenever the density depends on a smaller number of variables, performs a dimension reduction that implies the corresponding optimal rate of the mean integrated squared error (MISE) convergence. The results hold without traditional, in the density estimation literature, minimal regularity assumptions like differentiability or continuity of the density. The procedure of estimation is based on mimicking an oracle-estimator that knows the underlying density, and the main theoretical result is the oracle inequality which relates the MISEs of the estimator and the oracle-estimator. The proof is based on a new exponential inequality for Sobolev statistics which is of interest on its own merits.     

Asymmetric electrocyclic reactions

This critical review offers an overview of asymmetric electrocyclic processes, where diastereo- or enantioselectivity is a consequence of the influence of a chiral component (be it substrate or catalyst) on the electrocyclic bond-forming process (195 references).     

A new angle on pluronic additives: advancing droplets and understanding in digital microfluidics

Biofouling in microfluidic devices limits the type of samples which can be handled and the duration for which samples can be manipulated. Despite the cost of disposing fouled devices, relatively few strategies have been developed to tackle this problem. Here, we have analyzed a series of eight amphiphilic droplet additives, Pluronic coblock polymers of poly(propylene oxide) (PPO) and poly(ethylene oxide) (PEO), as a solution to biofouling in digital microfluidics using serum-containing cell culture media as a model fluid. Our analysis shows that species with longer PPO chains are superior for enabling droplet motion and reducing biofouling. Two of the tested species, L92 and P105, were found to lengthen device lifetimes by 2-3 times relative to additives used previously when used at optimal concentrations. Pluronics with low PEO content such as L92 were found to be cytotoxic to an immortalized mammalian cell line, and therefore we recommend that Pluronic additives with greater or equal to 50% PEO composition, such as P105, be used for digital microfluidic applications involving cells. Finally, contact angle measurements were used to probe the interaction between Pluronic-containing droplets and device surfaces. Strong correlations were found between various types of contact angle measurements and the capacity of additives to reduce biofouling, which suggests that contact angle measurements may be useful as a tool for rapidly screening new candidates for the potential to reduce biofouling. We propose that this study will be useful for scientists and engineers who are developing digital microfluidic platforms for a wide range of applications involving protein-containing solutions, and in particular, for applications involving cells.     

Synthesis, improved antisense activity and structural rationale for the divergent RNA affinities of 3'-fluoro hexitol nucleic acid (FHNA and Ara-FHNA) modified oligonucleotides

The synthesis, biophysical, structural, and biological properties of both isomers of 3'-fluoro hexitol nucleic acid (FHNA and Ara-FHNA) modified oligonucleotides are reported. Synthesis of the FHNA and Ara-FHNA thymine phosphoramidites was efficiently accomplished starting from known sugar precursors. Optimal RNA affinities were observed with a 3'-fluorine atom and nucleobase in a trans-diaxial orientation. The Ara-FHNA analog with an equatorial fluorine was found to be destabilizing. However, the magnitude of destabilization was sequence-dependent. Thus, the loss of stability is sharply reduced when Ara-FHNA residues were inserted at pyrimidine-purine (Py-Pu) steps compared to placement within a stretch of pyrimidines (Py-Py). Crystal structures of A-type DNA duplexes modified with either monomer provide a rationalization for the opposing stability effects and point to a steric origin of the destabilization caused by the Ara-FHNA analog. The sequence dependent effect can be explained by the formation of an internucleotide C-F···H-C pseudo hydrogen bond between F3' of Ara-FHNA and C8-H of the nucleobase from the 3'-adjacent adenosine that is absent at Py-Py steps. In animal experiments, FHNA-modified antisense oligonucleotides formulated in saline showed a potent downregulation of gene expression in liver tissue without producing hepatotoxicity. Our data establish FHNA as a useful modification for antisense therapeutics and also confirm the stabilizing influence of F(Py)···H-C(Pu) pseudo hydrogen bonds in nucleic acid structures.     

Stabilization and tracking control for a class of nonlinear systems

This paper discusses stabilization and tracking control using linear matrix inequalities for a class of systems with Lipschitz nonlinearities. A nonlinear state feedback stabilization control is proposed for systems containing a more general case of Lipschitz nonlinearity. The main objective of the present study is to provide, for multi-input multi-output nonlinear systems, a tracking control approach based on nonlinear state feedback, which guarantees global asymptotic output and state tracking with zero tracking error in the steady state. Further, the tracking control is formulated for optimal disturbance rejection, using $L_2$ gain reduction based performance criteria. The proposed methodologies are illustrated herein using two simulation examples of chaotic and unstable dynamical systems.