Stochastic resonance and nonlinear response using NMR spectroscopy

We revisit the phenomenon of quantum stochastic resonance in the regime of validity of the Bloch equations. We find that a stochastic resonance behavior in the steady-state response of the system is present whenever the noise-induced relaxation dynamics can be characterized via a single relaxation time scale. The picture is validated by a simple nuclear magnetic resonance experiment on water.     

9-donor-substituted acridizinium salts: versatile environment-sensitive fluorophores for the detection of biomacromolecules

The absorption and steady-state emission properties of a series of N-alkyl- and N-aryl-9-aminoacridizinium derivatives and two 9-sulfanyl-substituted acridizinium derivatives were investigated. The N-alkyl derivatives and the 9-methylsulfanylacridizinium have an intense intrinsic fluorescence (phi(f) = 0.2-0.6), whereas the N-aryl-substituted compounds are virtually nonfluorescent in liquid solutions (phi(f) < or = 0.01). The emission intensity of the latter compounds significantly increases with increasing viscosity of the medium. It is demonstrated that the excited-state deactivation of the N-aryl-9-aminoacridizinium derivatives is due to two nonradiative processes: (i) torsional relaxation by rotation about the N-aryl bond and (ii) an electron-transfer process from an electron-donor substituted phenyl ring to the photoexcited acridizinium chromophore. The binding of several representative acridizinium derivatives to double-stranded DNA was studied by the spectrophotometric titrations and linear dichroism spectroscopy. The results give evidence that the prevailing binding mode is intercalation with binding constants in the range (0.5-5.0) x 10(5) M(-1) (in base pairs). Notably, the binding of most of the N-aryl-9-aminoacridizinium derivatives leads to a fluorescence enhancement by a factor of up to 50 upon binding to the biomacromolecules. Moreover, the addition of selected proteins, namely albumins, to N-(halogenophenyl)-9-aminoacridizinium ions in the presence of an anionic surfactant (sodium dodecyl sulfate) results in a 20-fold fluorescence enhancement. In each case, the emission enhancement is supposed to result from the hindrance of the torsional relaxation in the corresponding binding site of the biomacromolecule, which in turn suppresses the excited-state deactivation pathway.     

The communication complexity of addition

Suppose each of k≤n ^o(1) players holds an n-bit number x _i in its hand. The players wish to determine if ∑ _i≤k x _i =s. We give a public-coin protocol with error 1% and communication O(k logk). The communication bound is independent of n, and for k≥3 improves on the O(k logn) bound by Nisan (Bolyai Soc. Math. Studies; 1993).     

Ageing and thermal stability studies on quasi-solid composite electrolytes for Grätzel-type solar cells

Loss of volatile components from two types of quasi-solid gel electrolytes to be used in Grätzel (or dye-sensitized, DSSC)-type alternative solar cells are checked time to time by thermogravimetry (TG) to follow the stability or changes of composites during storage at ambient. One of the gel samples, labeled as P2000 and based on UreaSil 2000, a 3D-cage precursor compound, has been found quite stable, while the related P230 sample based on UreaSil 230 seems to have a bit higher deviation in heterogeneity and some tendencies losing gradually from its volatile content, time to time. In addition, two online coupled evolved gas analytical tools (TG–EGA–FTIR and TG/DTA–EGA–MS) are applied to check the gel electrolytes for thermal vaporization, degradation, and decomposition processes as a function of temperature during dynamic heating in air. Initial minor elimination of ethyl acetate has been detected by both in situ coupled mass spectroscopy and FTIR spectroscopic gas cell. According to both evolved gas analytical systems, the other liquid ingredients, acetic acid (AcOH) and sulfolane are also released in the order of their volatility. Above 300 °C, an oxidative thermal degradation of UreaSil-type host matrices is indicated by the occurrence of, among others, formaldehyde or ammonia for electrolyte samples P2000 and P230, respectively. Evolution of various alkyl iodides with short chain length has only been detected by the mass spectroscopic evolved gas analysis method only.     

Using mesoscopic models to design strong and tough biomimetic polymer networks

Using computational modeling, we investigate the mechanical properties of polymeric materials composed of coiled chains, or "globules", which encompass a folded secondary structure and are cross-linked by labile bonds to form a macroscopic network. In the presence of an applied force, the globules can unfold into linear chains and thereby dissipate energy as the network is deformed; the latter attribute can contribute to the toughness of the material. Our goal is to determine how to tailor the labile intra- and intermolecular bonds within the network to produce material exhibiting both toughness and strength. Herein, we use the lattice spring model (LSM) to simulate the globules and the cross-linked network. We also utilize our modified Hierarchical Bell model (MHBM) to simulate the rupture and reforming of N parallel bonds. By applying a tensile deformation, we demonstrate that the mechanical properties of the system are sensitive to the values of N(in) and N(out), the respective values of N for the intra- and intermolecular bonds. We find that the strength of the material is mainly controlled by the value of N(out), with the higher value of N(out) providing a stronger material. We also find that, if N(in) is smaller than N(out), the globules can unfold under the tensile load before the sample fractures and, in this manner, can increase the ductility of the sample. Our results provide effective strategies for exploiting relatively weak, labile interactions (e.g., hydrogen bonding or the thiol/disulfide exchange reaction) in both the intra- and intermolecular bonds to tailor the macroscopic performance of the materials.     

Computational analysis of bending strain in single chains of β‐PVDF

Hartree–Fock calculations on 20 carbon atom chains of β‐phase poly(vinylidene fluoride) (PVDF) were done as a function of bending strain. The results can be modeled in terms of a classical energy versus strain curve resulting in a pseudomodulus (310 GPa) comparable to the Young's modulus calculated for stretching along carbon atom chain (199 GPa). The model also shows that the minimum energy state of a single chain of the polymer is not linear in the all‐trans geometry and that a significant strain energy is stored in natural thin films. This suggests that energy can be captured from bending motions in β‐PVDF. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1493–1495, 2011     

Electronic compressibility of a graphene bilayer

We calculate the electronic compressibility arising from electron-electron interactions for a graphene bilayer within the Hartree-Fock approximation. We show that, due to the chiral nature of the particles in this system, the compressibility is rather different from those of either the two-dimensional electron gas or ordinary semiconductors. We find that an inherent competition between the contributions coming from intraband exchange interactions (dominant at low densities) and interband interactions (dominant at moderate densities) leads to a nonmonotonic behavior of the compressibility as a function of carrier density.