The infrared spectrum of cyclic-N3: theoretical prediction

We have carried out the first calculations of the infrared absorption spectrum of cyclic-N(3). Accurate vibrational energies and wave functions computed with incorporation of the geometric phase effect (via gauge theory) and using an ab initio potential energy surface were employed in this work. A sophisticated fully dimensional dipole moment function was constructed using accurate ab initio calculations and a three-dimensional-spline interpolation. Transformation of the dipole moment vector function from the reference frame associated with instantaneous principal axes of inertia to the laboratory-fixed reference frame was carried out using hyperspherical coordinates. We found that the permanent dipole moment of cyclic-N(3) in the ground vibrational state is relatively small (170 mD). The excited vibrational states show permanent dipole moments in the 10-25 mD range. The most intense part of the infrared absorption spectrum is observed in the deep infrared part of spectrum, 75-275?cm(-1), where five lines exhibit absolute absorption intensities in the range between 0.5 and 1.2 km/mol. These transitions correspond to excitation of the pseudorotational progression of states. Several unique spectroscopic features discussed in the paper should help to identify cyclic-N(3) in the laboratory.     

A spectroscopic and computational study of Al(III) complexes in sodium cryolite melts: Ionic composition in a wide range of cryolite ratios

The structure of sodium cryolite melts was studied using Raman spectroscopy and quantum chemical calculations performed at the density functional theory level. The existence of bridged forms in the melts was argued first from the analysis of experimental Raman spectra. In the quantum chemical modelling emphasis was put on the construction of potential energy surfaces describing the formation/dissociation of certain complex species. Effects of the ionic environment were found to play a crucial role in the energetics of model processes. The structure of the simplest possible polymeric forms involving two Al centres linked through F atoms (“dimers”) was thoroughly investigated. The calculated equilibrium constants and model Raman spectra yield additional evidence in favour of the dimers. This agrees with a self-consistent analysis of a series of Raman spectra for a wide range of the melt composition.     

Hydrophilization of Magnetic Nanoparticles with Modified Alternating Copolymers. Part 1: The Influence of the Grafting

Iron oxide nanoparticles (NPs) with a diameter 21.6 nm were coated with poly(maleic acid-alt-1-octadecene) (PMAcOD) modified with grafted 5,000 Da poly(ethyelene glycol) (PEG) or short ethylene glycol (EG) tails. The coating procedure utilizes hydrophobic interactions of octadecene and oleic acid tails, while the hydrolysis of maleic anhydride moieties as well as the presence of hydrophilic PEG (EG) tails allows the NP hydrophilicity. The success of the NP coating was found to be independent of the degree of grafting which was varied between 20 and 80% of the -MacOD-units, but depended on the length of the grafted tail. The NP coating and hydrophilization did not occur when the modified copolymer contained 750 Da PEG tails independently of the grafting degree. To explain this phenomenon the micellization of the modified PMAcOD copolymers in water was analyzed by small angle x-ray scattering (SAXS). The PMAcOD molecules with the grafted 750 Da PEG tails form compact non-interacting disk-like micelles, whose stability apparently allows for no interactions with the NP hydrophobic shells. The PMAcOD containing the 5,000 Da PEG and EG tails form much larger aggregates capable of an efficient coating of the NPs. The coated NPs were characterized using transmission electron microscopy, dynamic light scattering, ζ-potential measurements, and thermal gravimetry analysis. The latter method demonstrated that the presence of long PEG tails in modified PMAcOD allows the attachment of fewer macromolecules (by a factor of ~20) compared to the case of non-modified or EG modified PMAcOD, emphasizing the importance of PEG tails in NP hydrophilization. The NPs coated with PMAcOD modified with 60% (towards all -MAcOD- units) of the 5,000 PEG tails bear a significant negative charge and display good stability in buffers. Such NPs can be useful as magnetic cores for virus-like particle formation.     

Observation of size-dependent thermalization in CdSe nanocrystals using time-resolved photoluminescence spectroscopy

We report heat dissipation times in semiconductor nanocrystals of CdSe. Specifically, a previously unresolved, subnanosecond decay component in the low-temperature photoluminescence decay dynamics exhibits longer decay lifetimes (tens to hundreds of picoseconds) for larger nanocrystals as well as a size-independent, ~25-meV spectral shift. We attribute the fast relaxation to transient phonon-mediated relaxation arising from nonequilibrium acoustic phonons. Following acoustic phonon dissipation, the dark exciton state recombines more slowly via LO-phonon assistance resulting in the observed spectral shift. The measured relaxation time scales agree with classical calculations of thermal diffusion, indicating that interfacial thermal conductivity does not limit thermal transport in these semiconductor nanocrystal dispersions.     

Quantum anonymous voting with anonymity check

We propose a new protocol for quantum anonymous voting having serious advantages over the existing protocols: it protects both the voters from a curious tallyman and all the participants from a dishonest voter in unconditional way. The central idea of the protocol is that the ballots are given back to the voters after the voting process, which gives a possibility for two voters to check the anonymity of the vote counting process by preparing a special entangled state of two ballots. Any attempt of cheating from the side of the tallyman results in destroying the entanglement, which can be detected by the voters.     

Near-field optical polarimetry of plasmonic nanowires

Local polarization properties of a gold subwavelength grating with plasmon-induced linear dichroism are studied by scanning near-field optical dynamic polarimetry. Periodic modulation of linear dichroism with the period corresponding to the period of the grating and the contrast of 0.3 is found at the distance of λ/20 from the sample.     

Metallic glass electronic structure peculiarities revealed by UHV STM/STS

We present the results of ultrahigh vacuum scanning tunneling microscopy/spectroscopy investigation of metallic glass surface. The topography and electronic structure of Ni_63.5Nb_36.5 have been studied. A great number of clusters with size about 5–10 nm have been found on constant current scanning tunneling microscopy images. The tunneling spectra of normalized tunneling conductivity revealed the energy pseudogap in the vicinity of Fermi energy. For energy values above 0.1 eV the normalized tunneling conductivity changes linearly with increasing of tunneling bias. The obtained results can be understood within suggested theoretical model based on the interplay of elastic electron scattering on random defects and weak intra-cluster Coulomb interaction. The effects of the finite edges of electron spectrum of each cluster have to be taken into account to explain the experimental data. The tunneling conductivity behavior and peculiarities in current images of individual clusters can also be qualitatively analyzed in the framework of suggested model.     

On the Possibility of Recovery of Heavy Metals from Excess Activated Sludge at 6-37°C

A method for recovery of heavy metals (Fe, Zn, Cu, Cr, Ni, Pb, Co) from excess activated sludge is proposed, based on substitution of heavy metals in the cells of microorganisms by calcium after introducing poorly soluble calcium salts into the system at 6-37°C.