The microwave spectrum of 1-phosphabut-3-ene-1-yne, CH2=CHCP

The new molecule 1-phosphabut-3-ene-1-yne, CH₂=CHCP, produced by pyrolyzing prop-1-ene-3-phosphorus dichloride, CH₂=CHCH₂PCl₂, was detected by microwave spectroscopy. The analysis of the rotational transitions indicates that the molecule is planar with constants: A₀ = 46 694(24), B₀ = 2807.7100(21), and C₀ = 2645.8356(21) MHz. These rotational constants indicate that the structure of the vinyl group is essentially the same as that in CH₂=CHCN and CH₂=CHCCH; r(C---C) = 1.432 Å and (C=C---C) = 123.9°. The dipole moment parameters are μ_A = 1.181(2), μ_B = 0.074(1), and μ = 1.183(2) D. The vibrational satellite spectra for the C---CP bending modes indicate that ν₁₁(a′) = 184 ± 30 cm⁻¹ and ν₁₅(a″) = 263 ± 30 cm⁻¹.     

Crystal and molecular structures of cis-dichlorobis(trifluorophosphine)bis(triphenylphosphine)ruthenium(II), cis-RuCl2(PF3)2(PPh3)3, and dichloro(2,7-dimethylocta-2,6-diene-1,8-diyl)(trifluorophosphine)ruthenium(IV), RuCl2(PF3)(C10H16)

The first structures of trifluorophosphine complexes of transition metals in an oxidation state greater than +1 are reported.     

Comparative tests to improve the gas chromatographic analysis of chlorobornanes in fish samples

A comparison was made between electron capture negative ionization quadrupole mass spectrometry (ECNI-MS) and electron capture detection (ECD) with regard to repeatability and reproducibility for the gas chromatographic (GC) analysis of toxaphene congeners [chlorobornanes (CHBs)]. The tests, including standard solutions and several cleaned fish extracts, showed larger relative standard deviations (RSDs) for the repeatability of ECNI-MS but no differences in the reproducibility of the 2 techniques. The sensitivity of the GC-ECNI-MS was considerably better than that of GC/ECD. Four stepwise-designed comparative tests were also conducted on GC analysis, cleanup, and the complete method. The results showed that, according to the current state-of-the-art, coefficients of variation for the between-laboratory performance were not < 20% and were usually between 20 and 30%. In spite of separation problems, e.g., for CHB 26, which cannot be separated into a single-component peak, a 95% methyl 5% phenyl polysiloxane (CP Sil 8) column was preferred to more polar columns for the analysis of CHBs 26, 40, 41, 44, 50, and 62. CHB 62 was more difficult to determine than CHB 26 and 50. Addition of the CHBs 40, 41, and 44 to the standard set of 3 chlorobornanes (26, 50, and 62) resulted in more separation problems. A 3-step cleanup method was recommended.     

Synthesis of a eta 2-2,3-diphosphabutadiene complex of zerovalent platinum from the corresponding eta 2-phosphaalkyne complex

Hydrozirconation of the eta 2-phosphaalkyne complex [Pt(dppe)(eta 2-tBuCP)] with [ZrHCl(eta 5-C5H5)2], followed by treatment with the chlorophosphaalkene ClP=C(SiMe3)2 affords the eta 2-2,3-diphosphabutadiene complex [Pt(dppe)(eta 2-tBuC(H)=PP=C(SiMe3)2]. In the presence of [Pt(PPh3)2] the latter undergoes an addition reaction with water to afford the structurally characterised Pt(II) complex [Pt(dppe)(tBuCH2P(O)HPC(SiMe3)2].     

Microwave-assisted acylation of 7-amino-5-aryl-6-cyanopyrido[2,3-d]pyrimidines

A microwave-assisted method is described for monoacylating 7-amino-5-aryl-6-cyanopyrido[2,3-d]pyrimidines using excess acid chlorides in pyridine. A diacylated intermediate is effectively deacylated to the product amide by a macroporous-Tris resin. A small library of 17 amides was prepared to validate the method. The integration of commercial microwave technology into the ArQule chemistry platform is also discussed.     

The Discretized Generalized Korteweg-de Vries Equation with Fourth Order Nonlinearity

In this paper, we study a discretized version of the (generalized) Korteweg-de Vries equation, _t u + _x ³ u + u ⁴ _x u = 0. After a number of estimates, we utilize the Contraction Mapping Principle to prove the global well-posedness of this equation in a certain discrete Banach space. Our results are analogous to those of Kenig, Ponce, and Vega in the continuous setting. However, due to the nature of the Fourier multipliers, the proofs of several of these estimates in the discrete setting require new techniques. Our results yield a numerical procedure for computing the solution. We present a numerical algorithm which is based on successive iterations to obtain a fixed point guaranteed by the Contraction Mapping Principle. This fixed point is the desired solution to the discrete equation.     

A Novel Treatment for Hypophonic Voice: Twang Therapy

A hypophonic voice, characterized perceptually as weak and breathy, is associated with voice disorders such as vocal fold atrophy and unilateral vocal fold paralysis. Although voice therapy programs for hypophonia typically address the vocal folds or the sound source, twang voice quality was examined in this study as an alternative technique for increasing vocal power by altering the epilarynx or the sound filter. OBJECTIVE: This study investigated the effect of twang production on physiologic, acoustic, and perceived voice handicap measures in speakers with hypophonia. DESIGN/METHODS: This prospective pilot study compared the vocal outcomes of six participants with hypophonia at pre- and posttreatment time points. Outcome measures included mean airflow rate, intensity in dB sound pressure level (SPL), maximum phonation time, and self-report of voice handicap. RESULTS: All subjects improved in at least three of the four vocal outcome measures. Wilcoxon signed-rank test of paired differences revealed significant differences between pre- and posttherapy group means for airflow rate, SPL, and Voice Handicap Index scores. CONCLUSION: The twang voice quality as a manipulation of the sound filter offers a clinical complement to traditional voice therapies that primarily address the sound source.     

Synchronized cluster formation in coupled laser networks

We experimentally investigate the phase dynamics of laser networks with homogenous time-delayed mutual coupling and establish the fundamental rules that govern their state of synchronization. We identified a specific substructure that imposes its synchronization state on the entire network and show that for any coupling configuration the network forms at most two synchronized clusters. Our results indicate that the synchronization state of the network is a nonlocal phenomenon and cannot be deduced by decomposing the network into smaller substructures, each with its individual synchronization state.     

Dark solitons in mode-locked lasers

Dark soliton formation in mode-locked lasers is investigated by means of a power-energy saturation model that incorporates gain and filtering saturated with energy, and loss saturated with power. It is found that general initial conditions evolve (mode-lock) into dark solitons under appropriate requirements also met in experimental observations. The resulting pulses are essentially dark solitons of the unperturbed nonlinear Schr?dinger equation. Notably, the same framework also describes bright pulses in anomalous and normally dispersive lasers.     

Sample Treatment Approaches for Trace Level Determination of Cesium in Hepatitis B Vaccine by Suppressed Ion Chromatography

The hepatitis B surface antigen manufactured by recombinant DNA technology is extracted from the culture media by density gradient centrifugation using cesium salts. Cesium is considered to be toxic, because it affects active ion transport by blocking potassium channels. The residual trace levels of cesium in hepatitis B vaccine samples are determined by suppressed ion chromatography. Hepatitis B vaccines contain various buffer salts, aluminum-containing adjuvants, proteins and traces of iron. The polyvalent cations (Al³⁺, Fe³⁺) and proteins degrade the chromatographic performance in terms of decreased retention time and poor reproducibility. Different sample preparation approaches were evaluated with the aim of eliminating these foulants: (1) filtration, (2) digestion and (3) digestion-protein precipitation. Quantitative elimination of these foulants was achieved in the digestion-protein precipitation sample clean-up approach. Cesium was separated on the IonPac CS17 column with suppressed conductivity detection. The results of the ion chromatography (IC) method were compared with ICP-MS analysis. The precision of determination was better than 6.5% (relative standard deviation) with a method detection limit of 45 ng mL⁻¹. The expanded uncertainty in the measurement at 95% confidence level (coverage factor 2) is better than 16.3%.