Compositional and 2H NMR studies of bis(benzene)chromium composites of mesoporous vanadium-niobium mixed oxides

New mesoporous niobium oxides with 5, 10, and 15 mol% vanadium(V) doped into the walls of the structure were synthesized by the ligand-assisted templating method with an octadecylamine template. These materials were characterized by XRD, XPS, EPR, elemental analysis, and nitrogen adsorption before being treated with excess bis(benzene)chromium to give new composites with an organometallic phase in the walls. All materials were also characterized by EPR, XRD, nitrogen adsorption, XPS, SQUID magnetometry, and elemental analysis. The materials with higher percentages of vanadium absorbed more bis(benzene)chromium, because this process depends largely on the electron transfer between the organometallic and the walls of the mesostructure and vanadium(V) is a stronger oxidant than niobium(V). Conductivity studies on these materials revealed that the ratio of Cr(0) to Cr(l) in the pores was more important than the absolute Cr loading level in governing electron transport properties but that increasing the V content led to more insulating behavior regardless of the Cr concentration. Solid-state 2H NMR studies on perdeuteriobenzene analogues of these composites showed the presence of the neutral and cationic Cr species in different ratios depending on the loading. Tumbling of these species was also slow on the NMR time scale, indicating that the charge-carrying Cr species are not rapidly moving through the pore channels of the mesostructure. This suggests that the walls of the structure may play a key role in charge transfer in these composites, contrary to what was previously believed.     

X-ray photoelectron spectroscopy and magnetic studies on the effect of pore size, wall thickness, and wall composition on superparamagnetic cobaltocene mesoporous Nb, Ta, and Ti composites

Recent results in our group demonstrated that mixed oxidation state mesoporous niobium oxide cobaltocene composites display superparamagnetism at certain composition ratios. This was the first report of superparamagnetism in nanoscale molecular ensembles. A series of mesoporous niobium oxide materials were synthesized in order to understand the role of pore size and thickness of the walls in the mesostructure on the magnetic properties. Mesoporous Ti oxide and Ta oxide composites were also synthesized in order to investigate the effect of changing the wall composition on the magnetic properties of this new series of materials. All samples were characterized by X-ray diffraction, nitrogen adsorption, ultraviolet spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and superconducting quantum interference device magnetometry. The results of this study showed that variation of wall thickness or pore size in the Nb system had little effect on the properties and that superparamagnetism most likely arises from mixed oxidation state cobaltocene grains residing in the individual pores and not from the free electrons in the mesostructure or much larger domains. The Langevin function was applied to the isothermal magnetic data from the Nb composites and gave mean superparamagnetic particle sizes of ca. 14 nm in each system. The Co(II) to Co(III) ratios in these materials were approximately 1:1. The Ti and Ta materials showed no sign of superparamagnetism and only very low levels of neutral cobaltocene in the pores. This suggests that a critical amount of cobaltocene is required to bring about superparamagnetic behavior.     

Cash flow optimization in delivery scheduling

The paper examines the inventory routing problem from the perspective of the present value of the cash flow associated with the distribution of a commodity such as propane. We analyze this problem for both deterministic and stochastic customer demands and validate our results on data from a real life distribution operation of propane. The analysis based on the present value of the cash flow indicates that optimization of propane deliveries based on efficiency/cost criteria alone will generate inferior solutions and it would be more advantageous for the company to set deliveries for a large percentage of the customers based on the present value of cash flow. In addition, in the case of stochastic demands, deliveries based on the cash flow consideration will tend to reduce the number of stockouts (i.e. improve both profit and service).     

Endoscopic and stroboscopic description of adults with paradoxical vocal fold dysfunction

The purpose of this study was to determine if endoscopic and stroboscopic parameters of voice were normal between attacks of paradoxical vocal fold dysfunction (PVFD). Fifty adults (38 females, 12 males) and 54 adult controls (40 females, 14 males) were examined via endoscopy with and without stroboscopy. Endoscopy indicated paradoxical adduction of the folds during the respiratory cycle of all 50 participants with PVFD, although they were asymptomatic. Atypical laryngeal configurations were observed including abnormality of the anterior-posterior dimension and ventricular fold medialization in both groups of subjects. Stroboscopy demonstrated abnormalities including unstable zero phase, decreased amplitude of vibration, decreased mucosal waves, and phase asymmetry primarily for the PVFD subjects alone. Results indicate that persons with PVFD demonstrate subtle laryngeal abnormality endoscopically and stroboscopically when dyspnea is not reported. This supports the hypothesis that PVFD is not episodic but exists as a continuum of laryngeal instability that may, due to various precipitating factors, be exacerbated to breathing attacks.     

Consistency requirements and pattern methods in cost sharing problems with technological cooperation

Using the discrete cost sharing model with technological cooperation, we investigate the implications of the requirement that demand manipulations must not affect the agents’ shares. In a context where the enforcing authority cannot prevent agents (who seek to reduce their cost shares) from splitting or merging their demands, the cost sharing methods used must make such artifices unprofitable. The paper introduces a family of rules that are immune to these demand manipulations, the pattern methods. Our main result is the characterization of these methods using the above requirement. For each one of these methods, the associated pattern indicates how to combine the technologies in order to meet the agents’ demands. Within this family, two rules stand out: the public Aumann–Shapley rule, which never rewards technological cooperation; and the private Aumann–Shapley rule, which always rewards technology providers. Fairness requirements imposing natural bounds (for the technological rent) allow to further differentiate these two rules.     

High‐Pressure Raman and Calorimetry Studies of Vanadium(III) Alkyl Hydrides for Kubas‐Type Hydrogen Storage

Reversible hydrogen storage under ambient conditions has been identified as a major bottleneck in enabling a future hydrogen economy. Herein, we report an amorphous vanadium(III) alkyl hydride gel that binds hydrogen through the Kubas interaction. The material possesses a gravimetric adsorption capacity of 5.42 wt % H₂ at 120 bar and 298 K reversibly at saturation with no loss of capacity after ten cycles. This corresponds to a volumetric capacity of 75.4 kgH₂ m^?3. Raman experiments at 100 bar confirm that Kubas binding is involved in the adsorption mechanism. The material possesses an enthalpy of H₂ adsorption of +0.52 kJ mol^?1 H₂, as measured directly by calorimetry, and this is practical for use in a vehicles without a complex heat management system.