Adduct formed by chromium trioxide and zwitterionic quinolinic acid

Chromium trioxide forms an adduct with zwitterionic quinolinic acid. The structure of the product was found to be (quinolinium-3-carboxylato-O)trioxidochromium(VI), determined by single-crystal X-ray diffraction methods. To evaluate the bonding properties of the compound, its structure was optimized at the B3LYP/6-311G* level of theory. The electronic characteristics were investigated by topological methods applied to the total charge density in various model compounds including the title compound, title compound with a HF molecule presenting a hydrogen bonding and anionic moiety. Calculated aromaticity indices indicate that the quinolinic rings tend to conserve their degree of aromaticity against hydrogen bonding. However, when there is hydrogen bonding involving an N-H bond or when the quinolinium zwitterion is deprotonated, there are clear changes in the interaction between chromium trioxide and the quinolinic moiety.      

What nonlinear-IR experiments can tell you about water that the IR spectrum cannot

Frequently, the IR spectrum of water is used to characterize the structure and strength of the associated hydrogen bond network. Here, we use nonlinear-IR spectroscopy to investigate the dynamics of four aqueous systems that have very similar absorption spectra. We address the question: to what extent can the dynamics of water vary in systems with very similar absorption spectra? The results illustrate that the vibrational lifetimes and orientational relaxation time scales vary dramatically between the four samples and do not correlate with the amount of water relative to surfactant or solute in solution. Nonlinear-IR spectroscopies are therefore important for providing detailed information necessary to understand hydrogen bonded systems.     

The carrier gas pressure effect in a laminar flow diffusion chamber, homogeneous nucleation of n-butanol in helium

Homogeneous nucleation rate isotherms of n-butanol+helium were measured in a laminar flow diffusion chamber at total pressures ranging from 50 to 210 kPa to investigate the effect of carrier gas pressure on nucleation. Nucleation temperatures ranged from 265 to 280 K and the measured nucleation rates were between 10(2) and 10(6) cm(-3) s(-1). The measured nucleation rates decreased as a function of increasing pressure. The pressure effect was strongest at pressures below 100 kPa. This negative carrier gas effect was also temperature dependent. At nucleation temperature of 280 K and at the same saturation ratio, the maximum deviation between nucleation rates measured at 50 and 210 kPa was about three orders of magnitude. At nucleation temperature of 265 K, the effect was negligible. Qualitatively the results resemble those measured in a thermal diffusion cloud chamber. Also the slopes of the isothermal nucleation rates as a function of saturation ratio were different as a function of total pressure, 50 kPa isotherms yielded the steepest slopes, and 210 kPa isotherms the shallowest slopes. Several sources of inaccuracies were considered in the interpretation of the results: uncertainties in the transport properties, nonideal behavior of the vapor-carrier gas mixture, and shortcomings of the used mathematical model. Operation characteristics of the laminar flow diffusion chamber at both under-and over-pressure were determined to verify a correct and stable operation of the device. We conclude that a negative carrier gas pressure effect is seen in the laminar flow diffusion chamber and it cannot be totally explained with the aforementioned reasons.     

HXeCCH in Ar and Kr matrices

HXeCCH molecule is prepared in Ar and Kr matrices and characterized by IR absorption spectroscopy. The experiments show that HXeCCH can be made in another host than the polarizable Xe environment. The H-Xe stretching absorption of HXeCCH in Ar and Kr is blueshifted from the value measured in solid Xe. The maximum blueshifts are +44.9 and +32.3 cm(-1) in Ar and Kr, respectively, indicating stabilization of the H-Xe bond. HXeCCH has a doublet H-Xe stretching absorption measured in Xe, Kr, and Ar matrices with a splitting of 5.7, 13, and 14 cm(-1), respectively. Ab initio calculations for the 1:1 HXeCCHcdots, three dots, centeredNg complexes (Ng = Ar, Kr, or Xe) are used to analyze the interaction of the hosts with the embedded molecule. These calculations support the matrix-site model where the band splitting observed experimentally is caused by specific interactions of the HXeCCH molecule with noble-gas atoms in certain local morphologies. However, the 1:1 complexation is unable to explain the observed blueshifts of the H-Xe stretching band in Ar and Kr matrices compared to a Xe matrix. More sophisticated computational approach is needed to account in detail the effects of solid environment.     

Systematic study of the physicochemical properties of a homologous series of aminobisphosphonates

Aminobisphosphonates, e.g., alendronate and neridronate, are a well known class of molecules used as drugs for various bone diseases. Although these molecules have been available for decades, a detailed understanding of their most important physicochemical properties under comparable conditions is lacking. In this study, ten aminobisphosphonates, H₂N(CH₂)_nC(OH)[P(O)(OH)₂]₂, in which n = 2-5, 7-11 and 15 have been synthesized. Their aqueous solubility as a function of temperature and pH, pK_a-values, thermal stability, IR absorptions, and NMR spectral data for bothliquid (¹H, ¹³C, ³¹P-NMR) and solid state (¹³C, ¹⁵N and ³¹P-CPMAS NMR) were determined.     

Programmable processor implementations of -best list sphere detector for MIMO receiver

An increasing number of standards in wireless communications have encouraged to study programmable processors as platforms for flexible receivers. A multiple-input multiple-output (MIMO) antenna system combined with orthogonal frequency division multiplexing (OFDM) technique has been introduced in many wireless communications standards, such as in the third generation long term evolution (3G LTE). The MIMO-OFDM system requires an efficient detector and a platform support for parallel processing of multiple subcarriers. A K-best list sphere detector (LSD) provides for near optimal decoding performance and a fixed throughput making it an interesting algorithm from the point of view of practical implementations.In this paper, we compare the implementations of the K-best LSD on four processor platforms: a digital signal processor (DSP), software defined radio (SDR), application-specific processor (ASP) and application-specific instruction-set processor (ASIP). The DSP is a popular very long instruction word (VLIW) device (TMS320C6455), the SDR processor employs multithreading and multiple cores (SB3500 core processor), the ASP is based on transport triggered architecture (TTA), while the ASIP is the SDR processor enhanced with a special instruction-set extension for sorting.A 2×2 MIMO antenna system with 64-quadrature amplitude modulation (64-QAM) is assumed. The chosen list sizes K=8 and 16 are based on simulation results carried out in MATLAB environment with the third generation long term evolution (3G LTE) parameters. The proposed ASIP achieved a promising throughput of 32.0 Mbps, where the software defined radio (SDR) implementation on the SB3500 core processor suffers from an inefficient software sorter. The ASP, in which the minimized hardware complexity has been the goal, achieves a throughput of 7.6 Mbps. However, more essential examination is related to the symbol time, which sets strict parallel processing requirements to the programmable processors.     

Cluster analysis of infrared spectra of rabbit cortical bone samples during maturation and growth

Bone consists of an organic and an inorganic matrix. During development, bone undergoes changes in its composition and structure. In this study we apply three different cluster analysis algorithms [K-means (KM), fuzzy C-means (FCM) and hierarchical clustering (HCA)], and discriminant analysis (DA) on infrared spectroscopic data from developing cortical bone with the aim of comparing their ability to correctly classify the samples into different age groups. Cortical bone samples from the mid-diaphysis of the humerus of New Zealand white rabbits from three different maturation stages (newborn (NB), immature (11 days-1 month old), mature (3-6 months old)) were used. Three clusters were obtained by KM, FCM and HCA methods on different spectral regions (amide I, phosphate and carbonate). The newborn samples were well separated (71-100% correct classifications) from the other age groups by all bone components. The mature samples (3-6 months old) were well separated (100%) from those of other age groups by the carbonate spectral region, while by the phosphate and amide I regions some samples were assigned to another group (43-71% correct classifications). The greatest variance in the results for all algorithms was observed in the amide I region. In general, FCM clustering performed better than the other methods, and the overall error was lower. The discriminate analysis results showed that by combining the clustering results from all three spectral regions, the ability to predict the correct age group for all samples increased (from 29-86% to 77-91%). This study is the first to compare several clustering methods on infrared spectra of bone. Fuzzy C-means clustering performed best, and its ability to study the degree of memberships of samples to each cluster might be beneficial in future studies of medical diagnostics.     

Theoretical and experimental study on phase transitions and mass fluxes of supersaturated water vapor onto different insoluble flat surfaces

The heterogeneous nucleation and condensation of water vapor onto three different surfaces (newsprint paper, Teflon, cellulose film) was studied theoretically and experimentally. The theoretical framework included the use of the classical theory of heterogeneous nucleation, diffusion theory corrected with transition regime correction factors, and the theory of heat transfer. Experiments were carried out using an environmental scanning electron microscope (ESEM). The experimental results for newsprint paper were investigated more closely. Our results show that the measured onset supersaturations were smaller than the modeled ones when the experimentally determined contact angle was used. Furthermore, the measured condensational growth rates were smaller than the modeled ones, presumably resulting from the approximations that had to be made in the calculations.     

Layer-by-layer electrostatic self-assembly of single-wall carbon nanotube polyelectrolytes

We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness.     

Protons solvated in noble-gas matrices: interaction with nitrogen

The interaction of a (NgHNg)(+) cation (Ng = Ar and Kr) with a nitrogen molecule is studied. The structure, energetics, and vibrational properties of these complexed systems are computationally studied at the MP2/6-311++G(2d,2p) level of theory. The computations reveal two stable structures, linear and T-shaped configurations, with BSSE corrected interaction energies of the order of -1000 cm(-1). The (NgHNg)(+)[dot dot dot]N(2) complexes are characterized experimentally by IR absorption spectroscopy in solid Ar and Kr matrices. The spectra show that only one complex structure is present, as evidenced by the single nitrogen-induced nu(3) band. According to the computational results, the linear structure is more probable in the experiments. However, our results show that the one-to-one complex at the present computational level does not accurately agree with the matrix-isolation experiments, the differences originating possibly from the influence of the surrounding matrix. Based on the current data, the mechanism of cation decay in noble-gas matrices is discussed. The observed similar decay of (NgHNg)(+) and its N(2) complex indicates that the solvated proton is unable to tunnel and is therefore immobile in noble-gas matrices. The observations for the cation decay are consistent with the electron neutralization mechanism.