Refractive index measurements of solid parahydrogen

Solid para-H2 is a promising gain medium for stimulated Raman scattering, due to its high number density and narrow Raman linewidth. In preparation for the design of a cw solid hydrogen Raman laser, we have made the first measurements, to our knowledge, of the index of refraction of a solid para-H2 crystal, in the wavelength range of 430-1100?nm. For a crystal stabilized at 4.4?K, this refractive index is measured to be n(p-H2)=1.130±0.001 at 514?nm. A slight, but significant, dependence on the final crystal-growth temperature is observed, with higher n(p-H2) at higher crystal-growth temperatures. Once a crystal is grown, it can be heated up to 10?K with no change in n(p-H2). The refractive index varies only slightly over the observed wavelength range, and no significant birefringence was observed.     

Bis-N-heterocyclic carbene palladium(IV) tetrachloride complexes: synthesis, reactivity, and mechanisms of direct chlorinations and oxidations of organic substrates

This Article describes the preparation and isolation of novel octahedral CH(2)-bridged bis-(N-heterocyclic carbene)palladium(IV) tetrachlorides of the general formula LPd(IV)Cl(4) [L = (NHC)CH(2)(NHC)] from LPd(II)Cl(2) and Cl(2). In intermolecular, nonchelation-controlled transformations LPd(IV)Cl(4) reacted with alkenes and alkynes to 1,2-dichlorination adducts. Aromatic, benzylic, and aliphatic C-H bonds were converted into C-Cl bonds. Detailed mechanistic investigations in the dichlorinations of alkenes were conducted on the 18VE Pd(IV) complex. Positive solvent effects as well as kinetic measurements probing the impact of cyclohexene and chloride concentrations on the rate of alkene chlorination support a Pd(IV)-Cl ionization in the first step. Product stereochemistry and product distributions from various alkenes also support Cl(+)-transfer from the pentacoordinated Pd(IV)-intermediate LPd(IV)Cl(3)(+) to olefins. 1-Hexene/3-hexene competition experiments rule out both the formation of π-complexes along the reaction coordinate as well as in situ generated Cl(2) from a reductive elimination process. Instead, a ligand-mediated direct Cl(+)-transfer from LPd(IV)Cl(3)(+) to the π-system is likely to occur. Similarly, C-H bond chlorinations proceed via an electrophilic process with in situ formed LPd(IV)Cl(3)(+). The presence of a large excess of added Cl(-) slows cyclohexene chlorination while the presence of stoichiometric amounts of chloride accelerates both Pd(IV)-Cl ionization and Cl(+)-transfer from LPd(IV)Cl(3)(+). (1)H NMR titrations, T1 relaxation time measurements, binding isotherms, and Job plot analysis point to the formation of a trifurcated Cl(-)···H-C bond in the NHC-ligand periphery as a supramolecular cause for the accelerated chemical events involving the metal center.     

The Rb7Bi3−3xSb3xCl16 Family: A Fully Inorganic Solid Solution with Room-Temperature Luminescent Members

Low-dimensional ns²-metal halide compounds have received immense attention for applications in solid-state lighting, optical thermometry and thermography, and scintillation. However, these are based primarily on the combination of organic cations with toxic Pb²⁺ or unstable Sn²⁺, and a stable inorganic luminescent material has yet to be found. Here, the zero-dimensional Rb₇Sb₃Cl₁₆ phase, comprised of isolated [SbCl₆]³⁻ octahedra and edge-sharing [Sb₂Cl₁₀]⁴⁻ dimers, shows room-temperature photoluminescence (RT PL) centered at 560 nm with a quantum yield of 3.8±0.2 % at 296 K (99.4 % at 77 K). The temperature-dependent PL lifetime rivals that of previous low-dimensional materials with a specific temperature sensitivity above 0.06 K⁻¹ at RT, making it an excellent thermometric material. Utilizing both DFT and chemical substitution with Bi³⁺ in the Rb₇Bi_3−3xSb_3xCl₁₆ (x≤1) family, we present the edge-shared [Sb₂Cl₁₀]⁴⁻ dimer as a design principle for Sb-based luminescent materials.     

CHAOS AND MULTIPLE PERIODS IN AN UNSYMMETRICAL SPRING AND DAMPING SYSTEM WITH CLEARANCE

Chaos and multiple periods are presented for the harmonically excited unsymmetrical spring and damping system with clearance. This paper demonstrates the non-linear behaviour of the motion through simulation and experiment. Intensive care and caution are taken in the experiments to observe the chaos and the multiple periods properly. The focus in this paper is mainly on the change of the bilinear spring stiffness ratio as a prime factor by which chaotic motions occur from quasi-periodic motion. Other investigations and effects on motion are also discussed for the changing of the extent of clearance. The investigations are based on frequency response curves. To understand the dynamics of the non-linearity of this model, all possible data processing and displaying techniques are taken into account. To observe the overall phenomena of this bilinear system, the resonance curves and the bifurcation diagrams are taken thoroughly for a wide frequency region.     

Classical gravity does not refract negatively

We appraise recent claims that classical gravitation can induce negative refraction of electromagnetic radiation in vacuum. By recasting the previous literature in covariant notation, we show that the criterion used hitherto for determining negative refraction in vacuum is inappropriate, and can even be satisfied by parametrized transformations in Minkowski spacetime. Using instead a covariantly acceptable definition, we find that in classical vacuum the power flux of a plane electromagnetic wave points in the direction of phase advance.     

Analysis of Voice and Quantitative Measurement of Glottal Gap After Thyroplasty Type I in the Treatment of Unilateral Vocal Paralysis

Thyroplasty type I is one of several surgical treatments in which improving the voice of unilateral vocal fold paralysis is the ultimate objective. The goal of the surgery is the medialization of the paralyzed vocal fold. The purpose of this study is to evaluate the effectiveness of thyroplasty type I through acoustical analysis, aerodynamic measures, and quantitative videostroboscopic measurements. We report on 20 patients with unilateral vocal cord paralysis who underwent thyroplasty type I. We performed preoperative and postoperative video image analysis (normalized glottal gap area) and computer-assisted voice analysis (fundamental frequency, jitter, shimmer, noise-to-harmonic ratio, mean phonation time, mean flow rate, mean subglottic pressure) in all patients. The glottal gap was significantly reduced after thyroplasty type I. Postoperative voice quality was characterized by an improved pitch and amplitude pertubation (jitter and shimmer), phonation time (mean phonation time), and subglottic pressure (mean subglottic pressure). Thyroplasty type I is an effective method for regaining glottal closure and vocal function.     

Hyaluronic Acid: Its Role in Voice

The extracellular matrix (ECM), once regarded simply as a structural scaffold, is now recognized as an important modulator of cellular behavior and function. One component that plays a prominent role in this process is hyaluronic acid (HA)--a molecule found in many different tissues. Research into the roles of HA indicates that it plays a key role in tissue viscosity, shock absorption, and space filling. Specifically, research into the role of HA in laryngology indicates that it has profound effects on the structure and viscosity of vocal folds. This article provides an introduction to the structure and biological functions of HA and its importance in voice. In addition, an overview of the pharmaceutical applications of HA is discussed.     

Expanding Mg-Zn hybrid chemistry: inorganic salt effects in addition reactions of organozinc reagents to trifluoroacetophenone and the implications for a synergistic lithium-magnesium-zinc activation

Numerous organic transformations rely on organozinc compounds made through salt-metathesis (exchange) reactions from organolithium or Grignard reagents with a suitable zinc precursor. By combining X-ray crystallography, NMR spectroscopy and DFT calculations, this study sheds new light on the constitution of the organometallic species involved in this important synthetic tool. Investigations into the metathesis reactions of equimolar amounts of Grignard reagents (RMgX) and ZnCl(2) in THF led to the isolation of novel magnesium-zinc hybrids, [{(thf)(2)Mg(μ-Cl)(3)ZnR}(2)] (R=Et, tBu, nBu or o-OMe-C(6)H(4)), which exhibit an unprecedented structural motif in mixed magnesium-zinc chemistry. Furthermore, theoretical modelling of the reaction of EtMgCl with ZnCl(2) reveals that formation of the mixed-metal compound is thermodynamically preferred to that of the expected homometallic products, RZnCl and MgCl(2). This study also assesses the alkylating ability of hybrid 3 towards the sensitive ketone trifluoroacetophenone, revealing a dramatic increase in the chemoselectivity of the reaction when LiCl is introduced as an additive. This observation, combined with recent related breakthroughs in synthesis, points towards the existence of a trilateral Li/Mg/Zn synergistic effect.     

Chemical Synthesis of Magnetically Hard and Strong Rare Earth Metal Based Nanomagnets

We report a general chemical approach to synthesize strongly ferromagnetic rare‐earth metal (REM) based SmCo and SmFeN nanoparticles (NPs) with ultra‐large coercivity. The synthesis started with the preparation of hexagonal CoO+Sm₂O₃ (denoted as SmCo‐O) multipods via decomposition of Sm(acac)₃ and Co(acac)₃ in oleylamine. These multipods were further reduced with Ca at 850 °C to form SmCo₅ NPs with sizes tunable from 50 to 200 nm. The 200 nm SmCo₅ NPs were dispersed in ethanol, and magnetically aligned in polyethylene glycol (PEG) matrix, yielding a PEG‐SmCo₅ NP composite with the room temperature coercivity (H_c) of 49.2 kOe, the largest H_c among all ferromagnetic NPs ever reported, and saturated magnetic moment (M_s) of 88.7 emu g^?1, the highest value reported for SmCo₅ NPs. The method was extended to synthesize other ferromagnetic NPs of Sm₂Co₁₇, and, for the first time, of Sm₂Fe₁₇N₃ NPs with H_c over 15 kOe and M_s reaching 127.9 emu g^?1. These REM based NPs are important magnetic building blocks for fabrication of high‐performance permanent magnets, flexible magnets, and printable magnetic inks for energy and sensing applications.