Insights into Structure Direction of Microporous Aluminophosphates: Competition between Organic Molecules and Water

A combination of experimental characterisation techniques and computational modelling has allowed us to gain insight into the molecular features governing structure direction in the synthesis of microporous aluminophosphates. The occlusion of three different structure‐directing agents (SDAs), triethylamine (TEA), benzylpyrrolidine (BP) and (S )‐(?)‐N‐benzylpyrrolidine‐2‐methanol (BPM), within the AFI structure during its crystallisation, together with the simultaneous incorporation of water, has been experimentally measured. We found a higher incorporation of organic molecules in the structure obtained with BPM, while a higher water (and lower organic) content is found for the ones obtained with TEA and BP as SDAs. The computational study provides a thermodynamic explanation for the observed behaviour in terms of the relative stabilisation energy of the SDAs and water molecules within the AFI framework compared with when they are in aqueous solution, and demonstrates that a competition for preferential occupation exists between water and organic SDAs, which is a function of the interaction with the inorganic framework. The lower interaction of TEA and BP molecules with the AFI structure promotes the simultaneous incorporation of water molecules in the 12‐membered‐ring (MR) channel, to increase the host–guest interaction energy and thus the thermodynamic stability. The presence of strongly interacting methanol groups in the BPM molecules leads to the incorporation of only organic molecules within the 12‐MR channels. Our results demonstrate the essential role that water molecules play in the stabilisation of hydrophilic microporous aluminophosphates; a minimum amount of organic SDA is, however, essential for a templating role of the microporous architecture.     

Mimicking the atmospheric OH-radical-mediated photooxidation of isoprene: formation of cloud-condensation nuclei polyols monitored by electrospray ionization mass spectrometry

Recently, it has been proposed (M. Claeys et al., Science 2004; 303: 1173) that the atmospheric OH-radical-mediated photooxidation of isoprene is a source of two major secondary organic aerosol (SOA) components, that is, 2-methylthreitol and 2-methylerythritol. These diastereoisomeric tetrols, which were characterized for the first time in the fine size fraction (<2.5 microm aerodynamic diameter) of aerosols collected in the Amazon rain forest during the wet season, were proposed to enhance the capability of the aerosols to act as cloud-condensation nuclei. In the present study, we performed the oxidation of isoprene in aqueous solution under conditions that attempted to mimic atmospheric OH-radical-induced photooxidization, and monitored and characterized on-line the reaction products via electrospray ionization mass (and tandem mass) spectrometry in the negative ion mode. The results show that the reaction of isoprene with photo- or chemically generated hydroxyl radicals indeed yields 2-methyltetrols. Other polyols were also detected, and they may therefore be considered as plausible SOA components eventually formed in normal or more extreme OH-radical-mediated photooxidation of biogenic isoprene.     

Quantum chemical mass spectrometry: ab initio prediction of electron ionization mass spectra and identification of new fragmentation pathways

The electron ionization mass spectra of four organic compounds are predicted based on the results of quantum chemical calculations at the DFT/B3LYP/6‐311 + G* level of theory. This prediction is performed ‘ab initio’, i.e. without any prior knowledge of the thermodynamics or kinetics of the reactions under consideration. Using a set of rules determining which routes will be followed, the fragmentation of the molecules' bonds and the complete resulting fragmentation pathways are studied. The most likely fragmentation pathways are identified based on calculated reaction energies ΔE when bond cleavage is considered and on activation energies ΔE^? when rearrangements are taken into account; the final intensities of the peaks in the spectrum are estimated from these values. The main features observed in the experimental mass spectra are correctly predicted, as well as a number of minor peaks. In addition, the results of the calculations allow us to propose fragmentation pathways new to empirical mass spectrometry, which have been experimentally verified using tandem mass spectrometry measurements. Copyright © 2016 John Wiley & Sons, Ltd.     

Outcome of laryngeal and velopharyngeal biofeedback treatment in children and young adults: A pilot study

A relatively new management strategy for the treatment of voice disorders is the use of laryngeal (LB) and velopharyngeal biofeedback (VB). The main purpose of the present pilot study is to document the outcome of vocal and velopharyngeal performances after a well-defined LB and VB treatment. Four subjects were studied pretreatment (1 week before LB or VB treatment) and posttreatment (1 week after the LB or VB treatment). To measure and compare the effect of LB and VB, objective and subjective assessment techniques were used. Perceptual voice assessment included a perceptual rating of the voice using the GRBAS scale. Furthermore, the vocal quality in this population is modeled by means of the Dysphonia Severity Index. For the objective assessment of nasal resonance, the Nasometer and the Glatzel test were used. A perceptual evaluation of speech, the Gutzmann test, and the tests from Bzoch were used as subjective assessment techniques. Both patients selected for LB and VB treatment showed improvement of their performances. The resulting improvement, as measured by means of an objective approach, is in agreement with the perceived (auditory) improvement of voice and resonance. The use of LB and VB treatment in patients, especially in some subjects who are not responding to traditional voice or velopharyngeal therapy, must be encouraged.     

A two-class discrete-time queueing model with two dedicated servers and global FCFS service discipline

This paper considers a simple discrete-time queueing model with two types (classes) of customers (types 1 and 2) each having their own dedicated server (servers A and B resp.). New customers enter the system according to a general independent arrival process, i.e., the total numbers of arrivals during consecutive time slots are i.i.d. random variables with arbitrary distribution. Service times are deterministically equal to 1 slot each. The system uses a “global FCFS” service discipline, i.e., all arriving customers are accommodated in one single FCFS queue, regardless of their types. As a consequence of the “global FCFS” rule, customers of one type may be blocked by customers of the other type, in that they may be unable to reach their dedicated server even at times when this server is idle, i.e., the system is basically non-workconserving. One major aim of the paper is to estimate the negative impact of this phenomenon on the queueing performance of the system, in terms of the achievable throughput, the system occupancy, the idle probability of each server and the delay. As it is clear that customers of different types hinder each other more as they tend to arrive in the system more clustered according to class, the degree of “class clustering” in the arrival process is explicitly modeled in the paper and its very direct impact on the performance measures is revealed. The motivation of our work are systems where this kind of blocking is encountered, such as input-queueing network switches or road splits.     

Universality of the double scaling limit in random matrix models

We study unitary random matrix ensembles in the critical case where the limiting mean eigenvalue density vanishes quadratically at an interior point of the support. We establish universality of the limits of the eigenvalue correlation kernel at such a critical point in a double scaling limit. The limiting kernels are constructed out of functions associated with the second Painlevé equation. This extends a result of Bleher and Its for the special case of a critical quartic potential. The two main tools we use are equilibrium measures and Riemann‐Hilbert problems. In our treatment of equilibrium measures we allow a negative density near the critical point, which enables us to treat all cases simultaneously. The asymptotic analysis of the Riemann‐Hilbert problem is done with the Deift‐Zhou steepest‐descent analysis. For the construction of a local parametrix at the critical point we introduce a modification of the approach of Baik, Deift, and Johansson so that we are able to satisfy the required jump properties exactly. © 2005 Wiley Periodicals, Inc.     

Proposal of a new model for the modulated structure of α-uranium

The modulated structure of α-uranium is analysed in the framework of the theory of superspace groups. Arguments are given which lead to the (3 + 2)D superspace group Pmcm($\text{1}\text{2}$βγ) as the most probable one. The consequences for the structure are derived. The most important one is, that there are two independent atoms in the unit-cell, one with a displacement along b and c and the other with a displacement only along a. This model is quite different from that previously found, which has only one independent atom, and a modulation in all three directions.     

Strong solutions of stationary equations in abstract kinetic theory

An abstract differential equation with partial range boundary conditions, modelling a variety of plane-symmetric stationary transport phenomena, is studied in Hilbert space. The collision operator is assumed to be a positive compact perturbation of the identity. A complete existence and uniqueness theory for the abstract equation is presented and two examples from rarefied gas dynamics are detailed.Work supported in part by D.O.E. grant No. DE-AS05 80ER10711 and N.S.F. grant No. DMS-8312451.The research was carried out while the author was visiting the Department of Physics and Astronomy of the Free University of Amsterdam, The Netherlands.     

Study of the enzymatic degradation of vasostatin I and II and their precursor chromogranin A by dipeptidyl peptidase IV using high-performance liquid chromatography/electrospray mass spectrometry

The interaction of dipeptidyl peptidase IV with structurally related proteins differing in chain length, namely vasostatin I and II and their precursor protein chromogranin A, was examined using high-performance liquid chromatography in combination with electrospray mass spectrometry. Suitable analytical procedures were developed involving the use of reversed-phase high-performance liquid chromatography for purification of the enzymatic degradation products and a peptide mapping procedure for evaluating the enzymatic degradation of the large precursor protein chromogranin A. While vasostatin I was found to be a substrate for dipeptidyl peptidase IV, no N-terminal cleavage of Leu-Pro could be noted for chromogranin A. With respect to vasostatin II, N-terminal degradation was only observed after degradation in the C-terminal domain to proteins containing < or = 78 amino acids. The specificity of the N-terminal release of Leu-Pro was proved by addition of a DPP IV specific inhibitor.     

A stationary criticality problem in generalL p -space for energy dependent neutron transport in cylindrical geometry

The energy-dependent neutron transport integral equation in a homogeneous cylinder of radiusR and infinite height with isotropic scattering is studied as an abstract equationf=K f in the spaceL ₁((0, 1)×(E _m ,E _M )). By means of techniques based on the theory of positive operators in Banach spaces, we prove that the eigenvalue problem for the integral operatorK admits as a solution a unique a. e. positive eigenfunction to which the leading eigenvalue _o corresponds.After establishing continuity and strictly increasing monotonicity of _o inR we discuss and solve the criticality problem under the assumption of subcriticality for a non-multiplying medium.The formulation of the eigenvalue problem forK is finally extended to anyL _p space, 1p< . Recalling thatK is a Riesz operator inL _p , we prove, as a general result, that the spectrum ofK, acting onL _p , is independent ofp.

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Résumé On étudie un faisceau de neutrons d'une énergieE (comprise entre deux bornesM _e ), dans un cylindre de rayon 0rR de hauteur infinie; on considère la diffraction comme isotrope. L'èquation intègrale du transport de neutrons est formuleeé abstraitement parf=K f, oùK est un opèrateur dans l'espaceL ₁ (r,E) des fonctions intégrables. La théorie des opérateurs positifs dans les espaces de Banach nous permet de démontrer que l'opérateur intégralK possède une fonction propre unique, positive presque partout, correspondant à la valeur propre dominante _o.Après avoir démontré que _o est continue et strictement croissante par rapport àR, on discute et résout le problème critique sous une hypothèse bien motivée physiquement.La formulation du problème aux valeurs propres est généralisée dans un espaceL _p ,p quelconque,K étant un opérateur de Riesz; on obtient comme résultat que le spectre deK dansL _p est indépendant dep.

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Work performed under the auspices of C. N. R. (Gruppo Nazionale per la Fisica-Matematica) and partially supported by M. P. I.

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The research leading to this article was completed while the third author was visiting the University of Florence in the summer of 1983.