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.     

Aharonov-Bohm effect in a draining bathtub vortex

We study planar waves in a circulating, draining fluid flow, which: (i) exhibit an analogue of the Aharonov-Bohm (AB) effect in Quantum Mechanics; (ii) obey a Klein-Gordon equation on an ‘effective spacetime’ which resembles the Kerr spacetime of General Relativity; and (iii) may be observed in the laboratory using gravity waves in a shallow basin. We describe a modified AB effect which depends on two dimensionless parameters, associated with the circulation α and draining β rates; we call this the ‘αβ effect’. We show that the αβ effect is inherently asymmetric even in the low-frequency limit, and that it leads to novel interference patterns which carry the signature of both rotation and absorption.     

Single-molecule elasticity measurements of the onset of excluded volume in poly(ethylene glycol)

A polymer must reach a certain size to exhibit significant excluded-volume interactions and adopt a swollen random-walk configuration. We show that single-molecule measurements can sense the onset of swelling by modulating the effective chain size with force: as the force is reduced from a large value, the polymer is first highly aligned, then a Gaussian coil, then finally a swollen chain, with each regime exhibiting a distinct elasticity. We use this approach to quantify the structural parameters of poly(ethylene glycol) and show that they vary in the expected manner with changes in solvent.     

Kondo temperature in multilevel quantum dots

We develop a general method to evaluate the Kondo temperature in a multilevel quantum dot that is weakly coupled to conducting leads. Our theory reveals that the Kondo temperature is strongly enhanced when the intradot energy-level spacing is comparable or smaller than the charging energy. We propose an experiment to test our result, which consists of measuring the size dependence of the Kondo temperature.     

Optical fiber-coupled InGaAs-based terahertz time-domain spectroscopy system

The successful demonstration of an optical fiber-coupled terahertz time-domain spectroscopy (THz-TDS) system is described in this study. The terahertz output power of the emitter with two optical band rejection filters was 132 nW, which is an improvement of 70% over the output power without any filters. This improvement is due to the suppression of an optical modulated signal that is reverse-generated when an alternating current bias exceeding a certain threshold is applied to the emitter. Under the optimal alignment conditions, the terahertz detector in a fiber-coupled THz-TDS system clearly measured water vapor dips in the free space.