Laryngeal adduction in resonant voice

The primary question in this study was whether subjects with nodules and subjects with healthy larynges would produce “resonant voice” with a similar laryngeal configuration. A second question regarded whether the electroglottographic closed quotient (EGG CQ) could be used to noninvasively distinguish resonant from other voice types. Twelve adult singers and actors served as subjects, including 6 persons with healthy larynges and 6 persons with nodules. Performers were used as an attempt to maximize token validity and stability. Subjects produced repeated tokens of resonant, pressed, normal, and breathy voice during sustained vowels. Laryngeal adduction was directly estimated using blinded, ordinal, visual-perceptual ratings based on videoscopic views of the larynx. EGG CQs were further calculated based on separate trials. The perceptual ratings indicated that subjects in both groups produced resonant voice with a barely adducted or barely abducted laryngeal configuration that was distinct from configurations for pressed and breathy (but not normal) voice. Previous literature suggests that this configuration may be relevant in many cases of voice therapy (I). Average CQs distinguished resonant from pressed voice, but inconsistently distinguished resonant from breathy voice. Further CQs were reliably different across healthy subjects and subjects with nodules. Thus, the utility of this measure to noninvasively estimate resonant voice may be limited, particularly without ongoing subject-specific calibration procedures.     

Nanoparticle assisted laser desorption/ionization mass spectrometry for small molecule analytes

Nanoparticle assisted laser desorption/ionization mass spectrometry (NPs-ALDI-MS) shows remarkable characteristics and has a promising future in terms of real sample analysis. The incorporation of NPs can advance several methods including surface assisted LDI-MS, and surface enhanced LDI-MS. These methods have advanced the detection of many thermally labile and nonvolatile biomolecules. Nanoparticles circumvent the drawbacks of conventional organic matrices for the analysis of small molecules. In most cases, NPs offer a clear background without interfering peaks, absence of fragmentation of thermally labile molecules, and allow the ionization of species with weak noncovalent interactions. Furthermore, an enhancement in sensitivity and selectivity can be achieved. NPs enable straightforward analysis of target species in a complex sample. This review (with 239 refs.) covers the progress made in laser-based mass spectrometry in combination with the use of metallic NPs (such as AuNPs, AgNPs, PtNPs, and PdNPs), NPs consisting of oxides and chalcogenides, silicon-based NPs, carbon-based nanomaterials, quantum dots, and metal-organic frameworks.

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Graphical abstract An overview is given on nanomaterials for use in surface-assisted laser desorption/ionization mass spectrometry of small molecules.

     

Probing the photochemical mechanism in photoactive yellow protein

Selectively bridged model compounds related to the chromophore in photoactive yellow protein have been synthesized where the single bond adjacent to the benzene ring (bond 1) and where both bond 1 and the adjacent double bond (bond 2) are bridged. They were compared to the nonbridged reference compound regarding their photophysical properties using steady-state and time-resolved fluorescence at various temperatures. Quantum chemical calculations were additionally performed and showed that several conformers are populated in the ground state. The neutral model compounds show that the nonradiative deactivation channel is linked to both single- and double-bond twisting. The relative importance of single-bond twisting is increased for the corresponding deprotonated hydroxy compounds with an enhanced donor character. The simultaneous photochemical activity of both single and double bonds explains the ease of photochemical isomerization in the confined environment of the natural PYP protein and also of the primary step in the vision process in rhodopsin.     

VISCOMETRIC STUDY OF POLY(METHYL METHACRYLATE) AND POLYSTYRENE BLENDS IN DIFFERENT SOLVENTS

The intermolecular interaction between poly(methyl methacrylate) (PMMA) and polystyrene (PS) intetrahydrofuran (THF) and N,N'-dimethyl formamide (DMF) solvents was studied at 28℃ using a dilute solution viscometrymethod. Solvent is believed to play a key role in characterizing the viscosity behavior of the polymer solution. The intrinsicviscosity and viscosity interaction parameter were experimentally measured for the binary (solvent/polymer) and for theternary systems in two solvents. The compatibility of the polymer mixture was discussed in terms of the sign of △b_m. Theresults show that the compatibility of PMMA/PS blend in DMF is larger than that in THF.     

A water-stable lanthanide metal-organic framework for fluorimetric detection of ferric ions and tryptophan

Microchimica Acta - The preparation of a highly water stable and porous lanthanide metal-organic framework (MOF) nanoparticles (denoted SUMOF-7II; SU refers to Stockholm University) is described....     

NUMERICAL METHOD FOR SOLVING LINEAR BOUNDARY VALUE PROBLEMS BY THE CHEBYSHEV τ-METHOD

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On modeling the advertising-operations interface under asymmetric competition

Using a market share attraction structure of advertising competition and following a supermodular game approach, this article demonstrates for an asymmetric oligopoly, the directional impact of changes in model parameters on the marketing controlled variables of all rivals (advertising budgets) and the operations controlled variables of all rivals (ordered quantities). Importantly, the various changes are examined analytically, empirically and numerically in both non-dominated and dominated asymmetric oligopolies.     

A general RNA-capping ribozyme retains stereochemistry during cap exchange

Numerous natural and artificial ribozymes have been shown to facilitate reactions that invert stereochemistry. Here, we demonstrate that an RNA-capping ribozyme retains stereochemistry at a phosphorus reaction center. The ribozyme synthesizes a broad range of 5'-5' RNA caps by exchanging phosphate groups around the alpha-phosphate found at the 5' terminus of the ribozyme. A ribozyme prepared with an Rp adenosine(5')alpha-thiotetraphosphate cap was found to exchange this cap for an Rp 4-thiouridine(5')alpha-thiotetraphosphate cap when incubated with 4-thiouridine triphosphate. The same Rp capped construct, when incubated with [gamma-(32)P]-ATP, exchanged the unlabeled ATP for a radiolabeled one while maintaining the same stereoconfiguration. In contrast, ribozymes prepared with an Sp cap failed to react even in the presence of thiophilic metal ions such as manganese. The kinetics of capping was also unusual as compared to inverting ribozymes. When the ribozyme was prepared with a triphosphate, capping was found to follow Michaelis-Menten-type kinetics even though the rate of pyrophosphate release was completely independent of nucleotide substrate concentration. Interestingly, the rate of capping and hydrolysis, when summed, was found to be indistinguishable from the rate of pyrophosphate release, indicating that an early rate-limiting step precedes both capping and hydrolysis. Together the retention of stereochemistry and kinetics imply that capping utilizes two inverting chemical steps that are separated by the transient formation of a rate-limiting covalent intermediate. As all protein enzymes that mediate similar capping reactions utilize a covalent intermediate, chemical necessity may have strongly guided the evolution of both protein and RNA-capping catalysts.     

On optimal service capacity allocation policy in an advance selling environment in continuous time

Based on some general reasonable assumptions, this paper employs the techniques of calculus of variations and optimal control theory to derive 10 main propositions associated with a service provider who aims at maximizing the present value of revenues/profits over a planning horizon in continuous time. Employing an aggregate pricing-response function that is dependent on excess capacity and a convex service cost formulation, the results show that (i) for a zero discount rate and unanticipated competitive entry, units of service capacity are allocated evenly over time, (ii) for a zero discount rate and anticipated competitive entry, units of allocated service capacity are increasing over time, (iii) for a positive discount rate and unanticipated competitive entry, units of allocated service capacity are decreasing over time, and (iv) for a positive discount rate and anticipated competitive entry, units of allocated service capacity are increasing over time, or are decreasing at first then increasing later. In addition, the questions of how deep a service firm should advance sell, whether advance selling is optimal in continuous time, and whether excess capacity could be an optimal strategy have been addressed. Furthermore, related sensitivity analyses are performed and endpoint constraints together with alternative shapes of the service-cost function are discussed. The managerial implications of the study’s results have been demonstrated.     

Crucial role of the counteranion on the templation of metallomacrocycles and a 3D network: synthesis,characterization, and structural analysis

Two novel supramolecular architectures, [[Ag(2)L(1)(2)][X](2)] with X = CF(3)SO(3)(-) (2a) or X = NO(3)(-) (2b) and [[AgL(1)(2)][X]](n) with X = BF(4)(-) (3), were constructed by self-assembly and obtained in quantitative yields, using AgX as a building block and L(1) as the bridging ligand (L(1) = 1,3-bis(benzimidazol-1-ylmethyl)benzene). The X-ray molecular structures of 2a and 3 are reported. Complex 2a was identified as a metallomacrocycle in which one ligating triflate anion is coordinated to each of the two unsaturated Ag(I) ions. 2a crystallizes in monoclinic unit cell P2(1)/n with a = 9.728(6) A, b = 17.303(4) A, c = 13.268(3) A, beta = 92.52(4) degrees, V = 2231(2) A(3), and Z = 2. Remarkably, the X-ray structure of 2a shows a layered network structure consisting of infinite metallomacrocycles held together through pi-pi interactions between benzimidazole rings. In dramatic contrast, the product 3 prepared from AgBF(4) and L(1) lacks metal-counterion bonding, leading to a supramolecular 3D network with the following three outstanding features: (i) in one dimension, metallomacrocycles containing two Ag centers and two bridging ligands form infinite, double-stranded chains; (ii) neighboring chains are arranged by two distinct pi-pi interactions, one between substituted benzene rings and the other between benzimidazole rings, leading to a 3D structure; (iii) cavities within the 3D network contain BF(4)(-) counteranions. 3 crystallizes in monoclinic unit cell C2/c with a = 25.33(3) A, b = 11.655(6) A, c = 18.466(8) A, beta = 123.00(8) degrees, V = 4572(8) A(3), and Z = 4. Interestingly, electrospray mass spectroscopy suggests in either case that the identified elemental subunit [AgL(1)(2)](+) is the key building block which self-assembles and subsequent anion templation provides either the macrocycles 2a, b or the inorganic polymer 3. Remarkably, in dichloromethane solvent ligand-to-metal stoichiometries of 2:1 in 3 and 1:1 in 2a, b are obtained even with excess ligand, showing the power of metal-anion interactions in determining the overall supramolecular structure. Anion metathesis, showing supramolecular structural rearrangements from 2a to 2b and more spectacularly from 3 to 2b, smoothly occurred. The crucial effect and the nature of coordinating counteranions (BF(4)(-), CF(3)SO(3)(-), NO(3)(-)) on the supermolecule design are presented and discussed.