Enhanced stabilization and deposition of Pt nanocrystals on carbon by dumbbell-like polyethyleniminated poly(oxypropylene)diamine

Pseudo-dendritic polyethyleniminated poly(oxypropylene)diamine (D400(EI)(20)) was used as a stabilizer and promoter to prepare Pt nanoparticles in aqueous solution, which was then deposited on carbon surface followed by calcination. After being deposited on carbon surface, no Pt(0) could be detected in the solution phase. In all steps, the increasing molar ratio of the amino groups of D400(EI)(20) to H(2)PtCl(6) ([N]/[Pt]) drastically reduced the size and the polydispersity and kept a constant low value after [N]/[Pt] = 20. Under a [N]/[Pt] ratio of 20, the particle sizes obtained from transmission electron microscopy (TEM) were very small in solution (2.7-2.4 nm) and remained the same after being deposited on carbon surface (2.7-2.4 nm), and were only slightly increased to 3.6-3.0 nm after calcination. The stabilizing ability of D400(EI)(20) to Pt on carbon surface before and after calcination can be interpreted by the existence of binding energy between Pt and amine nitrogen. The X-ray diffraction (XRD) pattern together with the TEM image reveals that the obtained Pt nanoparticles exist in single-crystal form. The results of photoelectron spectroscopy (XPS) evidence that the metallic Pt(0) rather than the oxidized Pt is the predominant species in the Pt/C catalysts. The electrochemical active surface (EAS) area of the Pt/C catalyst is only slightly higher than that of the E-TEK Pt/C catalyst, but the utilization factor (93.4%) is remarkably higher than the latter (62.8%). The increasing time of thermal treatment increases the crystallinity of Pt(0) on carbon, accompanied by the increasing EAS areas, which corresponds to its enhanced electrocatalytic performance to methanol oxidation.     

Infrared spectral changes with crystallization in poly(vinylchloride): Correlations with X-ray and density data

The influence of crystallinity and stereoregularity on the infrared (IR) spectrum of atactic PVC in the solid state has been studied by many researchers [1-12]. Although the molecules in commercial PVC consist of both syndiotactic and isotactic sequences, the bulk polymer is not highly stereoregular, having approximately 50% syndiotacticity. Its infrared spectrum is different from that of highly syndiotactic PVC [3,5,7,9,10-12], particularly in the carbon-to-chlorine stretching region where there are three bands located at 610(615), 635, and 690 cm^?1. These three bands are known to be of complex origin, since each band consists of more than one absorption frequency and its relative intensity depends on the physical state or history of the specimen [3,5,7,9,10-12]. The spectrum in this region is most rigorously interpreted in terms of chain conformational structure, the spatial arrangement of the atoms around the C-C1 bond. Thus, while changes in absorbance intensities for the bands with history do not necessarily reflect changes in crystallinity, their history dependence renders these bands potentially useful as crystallinity indicators.     

Raman Scattering Tensors in Biological Molecules and Their Assemblies

INTRODUCTION

The tensor associated with a Raman band plays an important role in determining the band intensity and its structural significance. Each Raman tensor interrelates two electric vectors, that of the exciting radiation (i.e. laser photon) and that of the Raman scattered radiation (i.e. the inelastically scattered photon which results from the exchange of a vibrational quantum between the exciting photon and the molecule). The Raman tensor is obtained formally as the first derivative of the molecular polarizability tensor, the derivative being taken with respect to the vibrational normal coordinate. In other words, the Raman tensor associated with a vibrational Raman band is an indicator of how the polarizability of the molecule oscillates with the molecular normal mode of vibration.     

On σ(·, W)-Holomorphic Functions and Theorems of Vitali-Type

The aim of this paper is to give some criterions for holomorphy of F-valued σ(F, W)-holomorphic functions which are bounded on bounded sets in a domain D of Fréchet spaces E (resp. ${\mathbb{C}^n}$ ) where ${W \subset F'}$ defines the topology of Fréchet space F. Base on these results we consider the problem on holomorphic extension of F-valued σ(F, W)-holomorphic functions from non-rare subsets of D and from subsets of D which determines uniform convergence in H(D). As an application of the above, some theorems of Vitali-type for a locally bounded sequence ${\{f_i\}_{i \in \mathbb{N}}}$ of Fréchet-valued holomorphic functions are also proved.     

Investigating the mechanisms of diamond polishing using Raman spectroscopy

Recent research has shown that a phase transformation of diamond to a different form of carbon is involved when diamonds are polished in the traditional fashion. The question as to how this phase transformation is activated and maintained to produce high wear rates is of great technological interest since it may radically change the way we view the processing of diamond. This paper describes the use of Raman spectroscopy to examine debris produced on the diamond polishing wheel, both during its preparation and during polishing. In addition, polished diamond surfaces were examined for the possible existence of non-diamond surface layers in an attempt to identify material removal mechanisms. Raman spectroscopy proves ideal for these analyses because its relatively high spatial resolution is well suited to the analysis of small wear features and debris particles, and because of the wealth of information it reveals about chemical structure. This level of structural information has been lacking in previous analyses of diamond polishing debris. In addition to the non-diamond carbon found in the wear debris, significant quantities of two iron oxides, magnetite (Fe₃O₄) and haematite (α-Fe₂O₃), were also found. An interesting observation was that a transformation from magnetite to haematite could be induced either by using high power laser excitation or by frictional heating during polishing. It is suggested that some of the Raman peaks previously attributed to lonsdaleite might better be explained by the presence of these oxides.     

Infrared Absorption Study of Some Cyclic Ureas,Cyclic Thioureas and Their N,N′-Dialkyl Derivatives

Abstract

In his communication on the detection limits for thermal emission spectroscopy of metallic species in flame media, Fassel (¹) attacks our previous statement that detection limits for Al, Be and Mo were available only for turbulent oxygen-supported hydrogen or acetylene flames. It should be borne in mind that he was referring to a preliminary communication (²) which naturally does not carry an extensive bibliography. It should also be noted that we were concerned, in context, with a comparison of the separated flame with conventional flames, not with highly unconventional flames such as those to which he refers. Whilst the point with which he takes issue was a very minor one, incorporated in our preliminary communication mainly as an “aside”, we firmly disagree with his observation. The flame he refers to (³) (⁴) is, in fact, a diluted oxy-acetylene flame which is supported by venting some air (and therefore nitrogen) to dilute the fuel-oxygen mixture. Fassel's communication (¹) erroneously refers to this as a 'premixed oxy-acetylene flame', whereas elsewhere (⁵) it is described more correctly as an oxygen-nitrogen-acetylene flame. The burner he long-pathlength carbonaceous flames (¹⁰). They also allow more sensitive molecular emission spectroscopy of sulphur in an air-hydrogen flame (¹¹), etc. We hope that this unfortunate correspondence will not distract attention from the main issue of our previous or previous preliminary communication on the separated nitrous oxide-acetylene flime.     

Benchmark calculations with correlated molecular wavefunctions. XIII. Potential energy curves for He2, Ne2 and Ar2 using correlation consistent basis sets through augmented sextuple zeta

The potential energy curves of the rare gas dimers He2, Ne2, and Ar2 have been computed using correlation consistent basis sets ranging from singly augmented aug-cc-pVDZ sets through triply augmented t-aug-cc-pV6Z sets, with the augmented sextuple basis sets being reported herein. Several methods for including electron correlation were investigated, namely Møller—Plesset perturbation theory (MP2, MP3 and MP4) and coupled cluster theory [CCSD and CCSD(T)]. For He2 CCSD(T)/d-aug-cc-pV6Z calculations yield a well depth of 7.35 cm-1 (10.58 K), with an estimated complete basis set (CBS) limit of 7.40 cm-1 (10.65 K). The latter is smaller than the 'exact' well depth (Aziz, R. A., Janzen, A. R., and Moldover, M. R., 1995, Phys. Rev. Lett., 74, 1586) by about 0.2 cm-1 (0.35 K). The Ne2 well depth, computed with the CCSD(T)/d-aug-cc-pV6Z method, is 28.31 cm-1 and the estimated CBS limit is 28.4 cm-1, approximately 1 cm-1 smaller than the empirical potential of Aziz, R. A., and Slaman, M., J., 1989, Chem. Phys., 130, 187. Inclusion of core and core—valence correlation effects has a negligible effect on the Ne2 well depth, decreasing it by only 0.04 cm-1. For Ar2, CCSD(T)/d-aug-cc-pV6Z calculations yield a well depth of 96.2 cm-1. The corresponding HFDID potential of Aziz, R. A., 1993, J. chem. Phys., 99, 4518 predicts of De of 99.7 cm-1. Inclusion of core and core-valence effects in Ar2 increases the well depth and decreases the discrepancy by approximately 1 cm-1.     

Water and oil signal assignment in low-moisture mozzarella as determined by time-domain NMR T2 relaxometry

A time-domain ¹H nuclear magnetic resonance relaxometry method was elaborated for the rapid microstructural characterization of mozzarella cheese. For this purpose, there is a strong need to know how the experimentally determined T₂ relaxation time distribution can be related to specific constituents in mozzarella. In this study, a detailed investigation is offered for fresh and aged low-moisture mozzarella cheese, often applied as a pizza cheese, by application of both a conventional Carr–Purcell–Meiboom–Gill (CPMG) sequence and a free-induction decay CPMG (FID-CPMG) sequence. The relaxation behavior was further elucidated by addition of deuterium oxide and by mild heat treatment of samples. The relaxation times of water protons in mozzarella were found to range from a few microseconds to some tens of milliseconds (in aged mozzarella) or to about hundred milliseconds (in fresh mozzarella). The upper limit of the T₂ distribution can even be extended to the seconds range upon releasing water protons from the mozzarella matrix using a mild heat treatment or upon addition of deuterated water. Both stimuli also provided evidence for the absorption of water into the cheese matrix. The potential release and uptake of water demonstrated that mozzarella acts as a very dynamic system during production and storage. The detected differences in the behavior of the water fraction between fresh and aged low-moisture mozzarella might be utilized to study the influence of either production and/or storage conditions on the cheese ripening process.     

Polymerizable derivatives of long-chain fatty acids. IV. Vinyl esters

Contrary to some published reports, the vinyl esters of saturated fatty acids polymerize readily and rapidly. Vinyl oleate, when present in excess of 5%, and oxygen exert marked retarding effects. Techniques are described for the free-radical-initiated polymerization of the vinyl esters of caprylic, capric, lauric, myristic, palmitic, and stearic acids in bulk, dispersion, solution, and emulsion. Some data are given for polymerization in the presence of chain-transfer agents, such as carbon tetrachloride, dodecylmercaptan, and ethylbenzene. Conditions are reported for obtaining degrees of polymerization from about 2 (when chain-transfer agents are employed) to 10,000 (weight average). The weight average degree of polymerization increases markedly as the conversion increases, particularly above 80%. Even up to extremely high conversions, soluble polymers are obtained in most cases. Solubility characteristics, transition point data, molecular weights (osmometric and light-scattering), and isolation and purification techniques are also reported.     

OPTIMAL FISH HARVESTING FOR A POPULATION MODELED BY A NONLINEAR PARABOLIC PARTIAL DIFFERENTIAL EQUATION

As the human population continues to grow, there is a need for better management of our natural resources in order for our planet to be able to produce enough to sustain us. One important resource we must consider is marine fish populations. We use the tool of optimal control to investigate harvesting strategies for maximizing yield of a fish population in a heterogeneous, finite domain. We determine whether these solutions include no‐take marine reserves as part of the optimal solution. The fishery stock is modeled using a nonlinear, parabolic partial differential equation with logistic growth, movement by diffusion and advection, and with Robin boundary conditions. The objective for the problem is to find the harvest rate that maximizes the discounted yield. Optimal harvesting strategies are found numerically.