Unusual Hydrogen-bonding Networks Consisting of π-Extended 4,4′-Bipyridines and Chloranilic Acid

Hydrogen-bonding networks of π-extended 4,4′-bipyridines, 2,5-di(4-pyridyl)thiophene (1), 2,5-di(4-pyridyl)furan (2) and 1,4-di(4-pyridyl)benzene (3) with 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid, CA) have been investigated. The dipyridyl compounds afforded complexes 4 [(dication of 1)·(monoanion of CA)²], 5 [(dication of 2)·(dianion of CA)·(MeOH)] and 6 [(3)·(dication of 3)·(dianion of CA)·(H²O)⁶] with CA. X-ray structure analyses revealed the formation of unusual molecular tape and sheet structures involving N–H ?O, O–H ?O, C–H ?O and N–H ?N hydrogen bonds, where the aromatic spacer groups play an important role in constructing the unique crystal structures.     

Effect of Electron Beam Irradiation on the Kinetics of Non-isothermal Crystallization of Nylon 66

The non-isothermal crystallization kinetics was studied by differential scanning calorimetric analysis on nylon 66 and e-beam irradiated nylon 66 at different cooling rates. The Modified Avrami equation, the Ozawa equation and the Combined Avrami-Ozawa equation were applied to study the kinetics of non-isothermal crystallization of nylon 66. The crystallization behavior of pristine nylon 66 polymer was compared with that of e-beam irradiated nylon 66 and observed that the kinetics of non-isothermal crystallization of nylon66 was affected largely upon e-beam irradiation. E-beam irradiation not only decreased the crystallization temperature of nylon 66, but influenced the mechanism of nucleation and crystal growth and reduced the overall crystallization rate of nylon 66 also. The crystallization activation energy calculated by the Kissinger method for irradiated nylon 66 was lower than that of pristine nylon 66.     

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.     

Microwave absorption studies of MgB2 superconductor

Microwave absorption studies have been carried out on MgB₂ superconductor using a standard X-band EPR spectrometer. The modulated low-field microwave absorption signals recorded for polycrystalline (grain size ∼ 10 μm) samples suggested the absence of weak-link character. The field dependent direct microwave absorption has been found to obey a ✓H dependence with two different slopes, which indicated a transition from strongly pinned lattice to flux flow regime.     

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.     

Laryngeal Gestures During Stop Production Using High-Speed Digital Images

On acoustic and fiberscopic studies of stop consonants, voice onset time and glottal width have been shown to be greatest in heavily aspirated stops, next greater for slightly aspirated stops, and least for unaspirated stops. Integrated activity of the thyroarytenoid and posterior cricoarytenoid muscles has been reported to be involved in differentiating aspirate characteristics of the stops. However, the fine movement of mucosal edges of vocal folds during the production of stops has not been well documented. In recent years, a new method for high-speed digital recording of laryngeal dynamics has made this possible. In the current study, the movements of vocal fold edges were documented during the period of stop production using a fiberscopic system of high-speed digital images. By observing the glottal width and the visual vibratory movements of vocal folds before voice onset, the heavily aspirated stop was characterized as being more prominent and dynamic than the slightly aspirated and unaspirated stops.     

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.     

Vocal Nodules and Laryngeal Morphology

Our purpose was to study the occurrence of vocal fold nodules under conditions of habitual vocal abuse associated with increased laryngeal muscle tension, to identify the existence of a relationship between vocal nodules and laryngeal morphology. We studied one group of 30 subjects with vocal nodules, 18 to 50 years old, who were compared with two control groups, one of females and one of males, consisting of 30 subjects each. The parameters evaluated were: type of vocal folds coaptation, glottic proportion (GP) and abduction angle (AA), obtained by videotelelaryngoscopy. In the nodules group, the larynges presented a mean value of GP similar to that of the female group, both of which were lower than the mean GP value of the male group. On the other hand, the mean AA was lower than the one in the female group, and closer to the one in the male group. We concluded that vocal nodules were present only in larynges with a predominantly young female morphology, with functional limitations of abduction.     

A simple and selective kinetic spectrophotometric method for the determination of kanamycin using acetylacetone-formaldehyde reagent in N,N′-dimethylformamide medium

A simple, sensitive, and selective kinetic spectrophotometric method for the determination of kanamycin in pure form and pharmaceutical formulations is described. The method is based on the measurement of the intensity of the yellow chromogen formed by the reaction between kanamycin and acetylacetone-formaldehyde reagent in a N,N′-dimethyl formamide medium. The variable-time method was used to evaluate the rate of reaction of the colored chromogen formed at 410 nm. The reaction conditions were optimized and the calibration graph was found to be linear in the range 60–160 μg/mL. The results obtained by the developed and reference methods are in good agreement. Various statistical parameters were evaluated to establish the precision, accuracy, repeatability, and reproducibility of the proposed method. The text was submitted by the authors in English.     

Reactions of vinyl acetate and vinyl trifluoroacetate with cationic diimine Pd(II) and Ni(II) alkyl complexes: identification of problems connected with copolymerizations of these monomers with ethylene

Vinyl acetate (VA) and vinyl trifluoroacetate (VA(f)) react with [(NwedgeN)Pd(Me)(L)][X] (M = Pd, Ni, (NwedgeN) = N,N'-1,2-acenaphthylenediylidene bis(2,6-dimethyl aniline), Ar(f) = 3,5-trifluoromethyl phenyl, L = Ar(f)CN, Et2O; X = B(Ar(f))4-, SbF6-) to form pi-adducts 3 and 5 at -40 degrees C. Binding affinities relative to ethylene have been determined. Migratory insertion occurs in a 2,1 fashion (DeltaG++ = 19.4 kcal/mol, 0 degrees C for VA, and 17.4 kcal/mol, -40 degrees C for VA(f)) to yield five-membered chelate complexes [(NwedgeN)Pd(kappa2-CH(Et)(OC(O)-CH3))]+, 4, and [(NwedgeN)Pd(kappa2-CH(Et)(OC(O)CF3))]+, 6. When VA is added to [(NwedgeN)Ni(CH3)]+, an equilibrium mixture of an eta2 olefin complex, 8c, and a kappa-oxygen complex, 8o, results. Insertion occurs from the eta2 olefin complex, 8c (DeltaG++ = 15.5 kcal/mol, -51 degrees C), in both a 2,1 and a 1,2 fashion to generate a mixture of five- and six-membered chelates, 9(2,1) and 9(1,2). VA(f) inserts into the Ni-CH3 bond (-80 degrees C) to form a five-membered chelate with no detectable intermediate. Thermolysis of the Pd chelates results in beta-acetate elimination from 4 (DeltaG++ = 25.5 kcal/mol, 60 degrees C) and beta-trifluoroacetate elimination from 6 (DeltaG = 20.5 kcal/mol, 10 degrees C). The five-membered Ni chelate, 9(2,1), is quite stable at room temperature, but the six-membered chelate, 9(1,2), undergoes beta-elimination at -34 degrees C. Treatment of the OAc(f) containing Pd chelate 6 with ethylene results in complete opening to the pi-complex [(NwedgeN)Pd(kappa2-CH(Et)(OAc(f)))(CH2CH2)]+ (OAc(f) = OC(O)CF3), 18, while reaction of the OAc containing Pd chelate 4 with ethylene establishes an equilibrium between 4 and the open form 16, strongly favoring the closed chelate 4 (DeltaH = -4.1 kcal/mol, DeltaS = -23 eu, K = 0.009 M(-1) at 25 degrees C). The open chelates undergo migratory insertion at much slower rates relative to those of the simple (NwedgeN)Pd(CH3)(CH2CH2)+ analogue. These quantitative studies provide an explanation for the behavior of VA and VA(f) in attempted copolymerizations with ethylene.