Synthesis and characterization of 1,1-di-tert-butyldiazene

The synthesis and direct observation of 1,1-di-tert-butyldiazene (16) at -127°C is described. The absorption spectrum of a red solution of 1,1-diazene 16 reveals a structured absorption band with λ max at 506 run (Me_2O, -125°C). The vibrational spacing in S_1 is about 1200 cm^(-1). The excited state of 16 emits weakly with a single maximum at 715 run observed in the fluorescence spectrum (Me_2O:CD_2Cl_2, -196°C). The proton NMR spectrum of 16 occurs as a singlet at 1.41 ppm. Monitoring this NMR absorption at -94^0 ± 2°C shows that 1,1-diazene 16 decomposes with a first-order rate of 1.8 x 10^(-3) sec(-1) to form isobutane, isobutylene and hexarnethylethane. This rate is 10^8 and 10^(34) times faster than the thermal decomposition of the corresponding cis and trans 1,2-di-tert-butyldiazene isomers. The free energy of activation for decomposition of 1,1-diazene 16 is found to be 12.5 ± 0.2 kcal/mol at -94°C which is much lower than the values of 19.1 and 19.4 kcal/lmole calculated at -94°C for N-(2,2,6,6- tetramethylpiperidyl)nitrene (3) and N-(2,2,5,5- tetrarnethylpyrrolidyl)nitrene (4), respectively. This difference between 16 and the cyclic-1,1-diazenes 3 and 4 can be attributed to a large steric interaction between the tert-butyl groups in 1,1-diazene 16.

In order to investigate the nature of the singlet-triplet gap in 1,1-diazenes, 2,5-di-tert-butyl-N-pyrrolynitrene (22) was generated but was found to be too reactive towards dimerization to be persistent. In the presence of dimethylsulfoxide, however, N-pyrrolynitrene (22) can be trapped as N-(2,5-di-tert-butyl- N'-pyrrolyl)dimethylsulfoxirnine (38). N-(2,5-di-tert-butyl-N'-pyrrolyl)dimethylsulfoximine (38-d^6) exchanges with free dimethylsulfoxide at 50°C in solution, presumably by generation and retrapping of pyrrolynitrene 22.

Study on the dynamics of the population of a copepod (Eudiaptomus vulgaris Schmeil). [Translation from: Memorie dell'Istituto Italiano di Idrobiologia Dott.Marco de Marchi 13 179-202, 1961. ]

Eudiaptomus vulgaris Schmeil is the most abundant copepod in Lake Maggiore and forms also, in respect to other entomostraca, the most important element, through its average biomass and because it is fairly numerous throughout the year. Plankton samples collected in a systematic and quantitative way, gave the opportunity to study some aspects of the dynamics of the population of this copepod, in safety in view of the uncertainty which in this kind of study can ensue when samples are taken only at a single station - in consequence of the changes in size of population between different water masses. The results of the biometrical observations are of the population of Eudiaptomus vulgaris is presented.

Transverse target single-spin asymmetry in inclusive electroproduction of charged pions and kaons

Single-spin asymmetries were investigated in inclusive electroproduction of charged pions and kaons from transversely polarized protons at the HERMES experiment. The asymmetries were studied as a function of the azimuthal angle psi about the beam direction between the target-spin direction and the hadron production plane, the transverse hadron momentum P-T relative to the direction of the incident beam, and the Feynman variable x(F). The sin psi* amplitudes are positive for pi(+) and K+ slightly negative for pi(-) and consistent with zero for K-, with particular P-T but weak x(F) dependences. Especially large asymmetries are observed for two small subsamples of events, where also the scattered electron was recorded by the spectrometer. (C) 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Joint modelling of voicing label and continuous F0 for HMM based speech synthesis

Fundamental frequency, or F0 is critical for high quality speech synthesis in HMM based speech synthesis. Traditionally, F0 values are considered to depend on a binary voicing decision such that they are continuous in voiced regions and undefined in unvoiced regions. Multi-space distribution HMM (MSDHMM) has been used for modelling the discontinuous F0. Recently, a continuous F0 modelling framework has been proposed and shown to be effective, where continuous F0 observations are assumed to always exist and voicing labels are explicitly modelled by an independent stream. In this paper, a refined continuous F0 modelling approach is proposed. Here, F0 values are assumed to be dependent on voicing labels and both are jointly modelled in a single stream. Due to the enforced dependency, the new method can effectively reduce the voicing classification error. Subjective listening tests also demonstrate that the new approach can yield significant improvements on the naturalness of the synthesised speech. A dynamic random unvoiced F0 generation method is also investigated. Experiments show that it has significant effect on the quality of synthesised speech. © 2011 IEEE.

Motor learning of novel dynamics is not represented in a single global coordinate system: evaluation of mixed coordinate representations and local learning.

Successful motor performance requires the ability to adapt motor commands to task dynamics. A central question in movement neuroscience is how these dynamics are represented. Although it is widely assumed that dynamics (e.g., force fields) are represented in intrinsic, joint-based coordinates (Shadmehr R, Mussa-Ivaldi FA. J Neurosci 14: 3208-3224, 1994), recent evidence has questioned this proposal. Here we reexamine the representation of dynamics in two experiments. By testing generalization following changes in shoulder, elbow, or wrist configurations, the first experiment tested for extrinsic, intrinsic, or object-centered representations. No single coordinate frame accounted for the pattern of generalization. Rather, generalization patterns were better accounted for by a mixture of representations or by models that assumed local learning and graded, decaying generalization. A second experiment, in which we replicated the design of an influential study that had suggested encoding in intrinsic coordinates (Shadmehr and Mussa-Ivaldi 1994), yielded similar results. That is, we could not find evidence that dynamics are represented in a single coordinate system. Taken together, our experiments suggest that internal models do not employ a single coordinate system when generalizing and may well be represented as a mixture of coordinate systems, as a single system with local learning, or both.

One-legged locomotion with a compliant passive joint

There is an increasing attention of exploiting compliant materials for the purpose of legged locomotion, because they provide significant advantages in locomotion performance with respect to energy efficiency and stability. Toward establishing a fundamental basis for this line of research, a minimalistic locomotion model of a single legged system is explored in this paper. By analyzing the dynamic behavior of the system in simulation and a physical robotic platform, it is shown that a stable locomotion process can be achieved without the necessity of sensory feedback. In addition, further analysis characterizes the relation between motor control and the natural body dynamics determined by morphological properties such as body mass and spring constant. © 2006 The authors.

A Single-Fundamental-Mode Photonic Crystal Vertical Cavity Surface Emitting Laser

Single-fundamental-mode photonic crystal (PhC) vertical cavity surface emitting lasers (VCSEL) are produced and their single-fundamental-mode performances are investigated and demonstrated. A two-dimensional PhC with single-point-defect structure is fabricated using UV photolithography and inductive coupled plasma reactive ion etching on the surface of the VCSEL's top distributed Bragg-reflector. The PhC VCSEL maintains single-fundamental-mode operating with output power 1.7 mW and threshold current 2.5 mA. The full width half maximum of the lasing spectrum is less than 0.1 nm, the far field divergence angle is less than 10 degrees and the side mode suppression ratio is over 35 dB. The device characteristics are analyzed based on the effective index model of the photonic crystal fiber. The experimental results agree well with the theoretical expectation.

Density Gradient Ultracentrifugation of Nanotubes: Interplay of Bundling and Surfactants Encapsulation

Density gradient ultracentrifugation (DGU) has emerged as a promising tool to prepare chirality enriched nanotube samples. Here, we assess the performance of different surfactants for DGU. Bile salts (e.g., sodium cholate (SC), sodium deoxycholate (SDC), and sodium taurodeoxycholate (TDC)) are more effective in individualizing Single Wall Carbon Nanotubes (SWNTs) compared to linear chain surfactants (e.g., sodium dodecylbenzene sulfonate (SDBS) and sodium dodecylsulfate (SDS)) and better suited for DGU. Using SC, a narrower diameter distribution (0.69-0.81 nm) is achieved through a single DGU step on CoMoCAT tubes, when compared to SDC and TDC (0.69-0.89 nm). No selectivity is obtained using SDBS. due to its ineffectiveness in debundling. We assign the reduce selectivity of dihydroxy bile salts (S DC and TDC) in comparison with trihydroxy SC to the formation of secondary micelles. This is determined by the number and position of hydroxyl ( OH) groups on the a-side of the steroid backbone. We also enrich CoMoCAT SWNT in the 0.84-0.92 nm range using the Pluronic F98 triblock copolymer. Mixtures of bile salts (SC) and linear chain surfactants (SOS) are used to enrich metallic and semiconducting laser-ablation grown SWNTs. We demonstrate enrichment of a single chirality, (6,5), combining diameter and metallic versus semiconductillg separation on CoMoCAT samples.

Single- and double-electron processes in collisions of Xe23+ ions with helium

We report the measurements of relative cross sections for single capture (SC), double capture (DC), single ionization (SI), double ionization (DI), and transfer ionization (TI) in collisions of Xe23+ ions with helium atoms in the velocity range of 0.65-1.32 a.u. The relative cross sections show a weak velocity dependence. The cross-section ratio of double-(DE) to single-electron (SE) removal from He, sigma(DE)/sigma(SE), is about 0.45. Single capture is the dominant reaction channel which is followed by transfer ionization, while only very small probabilities are found for pure ionization and double capture. The present experimental data are in satisfactory agreement with the estimations by the extended classical over-barrier (ECB) model..

Studies on the Interaction between Single-strand Oligonucleotide and Ginsenosides by Electrospray Ionization Mass Spectrometry

Oligonucleotide from SARS virus was selected as a target molecule in the paper. The noncovalent complexes of ginsenosides with the target molecule were investigated by electrospray ionization mass spectrometry. The effects of experimental conditions were examined firstly on the formation of noncovalent complexes. Based on the optimized experimental conditions, the interaction of different ginsenosides with the target molecule was researched, finding that the interaction orders are relative with the structure of aglycons, the length and terminal sugar types of saccharide chains in the ginsenosides. There are certain rules for the interaction between the ginsenosides and DNA target molecule. For different type ginsenosides, the interaction intensity takes the orders 20-S-protopanaxatriol > 20-S-protopanaxadiol, and panaxatriol ginsenosides > panaxadiol ginsenosides. For the ginsenosides with the same type aglycone, tri-saccharide chain > di-saccharide chain > tetra-saccharide chain and single-saccharide chain > panaxatriol. For the ginsenosides with the same tetra-saccharide chain, the ginsenosides with smaller molecule masses > the ginsenosides with larger molecule masses.

Kinetics and Statistical Distributions of Single-Molecule Conformational Dynamics

We developed a coarse-grained yet microscopic detailed model to study the statistical fluctuations of single-molecule protein conformational dynamics of adenylate kinase. We explored the underlying conformational energy landscape and found that the system has two basins of attractions, open and closed conformations connected by two separate pathways. The kinetics is found to be nonexponential, consistent with single-molecule conformational dynamics experiments. Furthermore, we found that the statistical distribution of the kinetic times for the conformational transition has a long power law tail, reflecting the exponential density of state of the underlying landscape. We also studied the joint distribution of the two pathways and found memory effects.

Synergistic extraction of rare earths(III) from chloride medium with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and di-(2-ethylhexyl)-2-ethylhexylphosphonate

The synergistic effect of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 (HPMBP, HA) and di-(2ethylhexyl)-2-ethylhexylphosphonate (DEHEHP, B) in the extraction of rare earths (RE) from chloride solutions has been investigated. Under the experimental conditions used, there was no detectable extraction when DEHEHP was used as a single extractant while the amount of RE(III) extracted by HPMBP alone was also low. But mixtures of the two extractants at a certain ratio had very high extractability for all the RE (III). For example, the synergistic enhancement coefficient was calculated to be 9.35 for Y3+, and taking Yb3+ and Y3+ as examples, RE3+ is extracted as RE(OH)A(2).B. The stoichiometry, extraction constants and thermodynamic functions such as Gibbs free energy change Delta G (-17.06kJmol(-1)), enthalpy change Delta H (-35.08kjmol(-1)) and entropy change Delta S (-60.47JK(-1)mol(-1)) for Y3+ at 298 K were determined. The separation factors (SF) for adjacent pairs of rare earths were calculated. Studies show that the binary extraction system not only enhances the extraction efficiency of RE(III) but also improves the selectivity, especially between La(III) and the other rare earth elements.

Extraction of rare earths(III) from nitrate medium with di-(2-ethylhexyl) 2-ethylhexyl phosphonate and synergistic extraction combined with 1-phenyl-3-methyl-4-benzoy l-pyrazolone-5

The extraction of trivalent rare earths ( RE) from nitrate solutions with di-(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP, B) and synergistic extraction combined with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP, HA) were investigated. The extraction distribution ratios demonstrate a distinct "tetra effect," and Y lies between Tb and Dy when DEHEHP is used as a single extractant for RE. According to the corresponding separation factors (SF12) for adjacent pairs of rare earths, it could be concluded that DEHEHP could be employed for the separation of La from the other rare earths, and Y from light rare earths. The present work has also found that mixtures of HPMBP and DEHEHP have an evident synergistic effect for RE(III). Taking Y( III) as an example, a possible synergistic extraction mechanism is proposed. The enhancement of extraction in the binary system can be explained due to the species Y(NO3) (.) A(2) (.) HA (.) B formed. The synergistic enhancement coefficients ( R), extraction constants, formation constants and thermodynamic functions of the reaction were calculated.