Room Temperature Synthesis and Size Control of HKUST‐1

We report the synthesis of HKUST‐1 (Cu₃(btc)₂; btc=benzene‐1,3,5‐tricarboxylate) and its growth kinetics by dynamic light scattering completely at room temperature without prior nucleation‐induction steps. Upon an increase in concentration of the starting solutions, the generation of a pure phase requires adjustment of the H₂O/EtOH ratio. The presence of DMF is important to avoid competitive side phases. Replacement of DMF by a minimal amount of diethylamine resulted in the instantaneous formation of pure HKUST‐1 upon mixing at room temperature. Additionally, the synthesis parameters strongly influence the final crystallite size and porous properties.     

Quantum-dynamics study of the H5+ cluster: full dimensional benchmark results on its vibrational states

A full-dimensional quantum dynamics study is carried out for the highly fluxional H(5)(+) cation on a recent reference potential energy surface by using the multi configuration time-dependent Hartree method. With five equivalent light atoms and shallow barriers between various low-lying stationary points on the surface, the spectroscopic characterization of H(5)(+) represents a huge challenge for accurate quantum dynamics simulations. The present calculation is the first such a study on this cation, which together with its isotope analogies are of primary importance in the interstellar chemistry. The vibrational ground state properties and several vibrationally excited states corresponding to low vibrational frequency motions, not yet directly observable by the experiment, are presented and analyzed.     

<Emphasis Type="Italic">T</Emphasis> = 0 phase diagram of the 1<Emphasis Type="Italic">D</Emphasis> Hubbard model with magnetic interactions in the narrow band limit

In this paper we study a generalization of the Hubbard model by considering spin-spin interactions described by the exchange constant J. An external magnetic field his also taken into account. In the narrowband limit and for the 1D case, we present the exact solution obtained in the framework of the Green’s function formalism, using the Composite Operator Method. We report the T = 0 phase diagram for both ferro (J > 0) and anti-ferro (J < 0) couplings. The competition of the different energy scales (U, J, and h; being U the local charge interaction) generates a variety of phases and different charge and spin orderings.     

Determination of the rates of formation and hydrolysis of the Schiff bases formed by pyridoxal 5′-phosphate and hydrazinic compounds

The macroscopic rate constants of formation (k₁) and hydrolysis (k₂) for the reactions of pyridoxal 5′-phosphate (PLP) with hydrazine (PLP-HY system), carbidopa (-hydrazino--methyl-β-(3,4-dihydroxyphenyl)propionic acid, PLP-CD system), hydralazine (1-hydrazinophthalazine, PLP-HL system) and isoniazid (4-pyridinecarboxylic acid hydrazide, PLP-ISO system) were fitted to a kinetic scheme that considers the different ionic species present in the medium, their protonation constants, and their individual rates of formation (k₁ⁱ) and hydrolysis (k₂ⁱ). The results obtained for the molecules bearing the hydrazine group are compared with those for the reactions of PLP with n-hexylamine (PLP-NHA system) and poly- -lysine (PLP-LYS system). Some structural effects on the individual rate constants are also examined.     

Plant-Derived Pesticides as an Alternative to Pest Management and Sustainable Agricultural Production: Prospects,Applications and Challenges

Pests and diseases are responsible for most of the losses related to agricultural crops, either in the field or in storage. Moreover, due to indiscriminate use of synthetic pesticides over the years, several issues have come along, such as pest resistance and contamination of important planet sources, such as water, air and soil. Therefore, in order to improve efficiency of crop production and reduce food crisis in a sustainable manner, while preserving consumer’s health, plant-derived pesticides may be a green alternative to synthetic ones. They are cheap, biodegradable, ecofriendly and act by several mechanisms of action in a more specific way, suggesting that they are less of a hazard to humans and the environment. Natural plant products with bioactivity toward insects include several classes of molecules, for example: terpenes, flavonoids, alkaloids, polyphenols, cyanogenic glucosides, quinones, amides, aldehydes, thiophenes, amino acids, saccharides and polyketides (which is not an exhaustive list of insecticidal substances). In general, those compounds have important ecological activities in nature, such as: antifeedant, attractant, nematicide, fungicide, repellent, insecticide, insect growth regulator and allelopathic agents, acting as a promising source for novel pest control agents or biopesticides. However, several factors appear to limit their commercialization. In this critical review, a compilation of plant-derived metabolites, along with their corresponding toxicology and mechanisms of action, will be approached, as well as the different strategies developed in order to meet the required commercial standards through more efficient methods.     

Pricing policies for selling indivisible storable goods to strategic consumers

Annals of Operations Research - We study the dynamic pricing problem faced by a monopolistic retailer who sells a storable product to forward-looking consumers. In this framework, the two major...     

A fuzzy approach to a municipality grouping model towards creation of synergies

In recent years, a trend for accelerating the economic, social and environmental development of cities through associations, organization and creation of synergies has been identified. Our investigation applies a grouping model in order to identify municipalities that could create optimal synergies towards the construction of competitive advantages. In order to achieve this task, we use tools of Fuzzy Logic to evaluate subjective and qualitative characteristic elements of different municipalities under Galois’ group theory. Results conclude on 32 different groups ordered in 7 different levels, relating 12 municipalities of a specific region according to 8 competitive variables. This work seeks to shed light in the conformation of groups under uncertain conditions and the deep examination of the characteristic competitive elements in a specific region for further policy and decision-making processes.     

Numerical investigation of transient heat and mass transfer in a parallel-flow liquid-desiccant absorber

Liquid desiccant systems have received significant attention as a way to reduce latent loads. Tests of liquid desiccant systems in humid climates have shown significant reductions in energy consumption. As moisture in the air is absorbed at the dehumidifier, the temperature of the liquid desiccant increases due to the addition of heat from the enthalpy of condensation of the water vapor. Thus, the coupled effects of heat and mass transfer are relevant for these applications. A two-dimensional mathematical model of the transient heat and mass transfer for an absorber where a thin film of liquid desiccant flows down its walls and dehumidifies the air in parallel-flow configuration is developed and the dynamics of the modeled system are analyzed.     

The aggregation of sodium dehydrocholate in water

 We used a battery of different methods to study the association in aqueous sodium dehydrocholate (NaDHC) solutions. This salt associates by a stepwise mechanism. Below (9.6 ± 4.2) × 10⁻⁴ mol dm⁻³ there is a molecular solution with some strongly insoluble dehydrocholic acid produced by hydrolysis. Between (9.6 ± 4.2) × 10⁻⁴ and (5.2 ± 2.2) × 10⁻³ mol dm⁻³, an aggregate similar to acid soap (NaDHC.HDHC) appears and its amount and the aggregate's size increase with concentration. At =(2.20 ± 0.85) × 10⁻² mol dm⁻³ the aggregates formed have properties usually associated with true micelles, such as solubilisation of water-insoluble dyes. These aggregates increase in size with concentration and change their shape at 8 × 10⁻² mol dm⁻³, giving nonsymmetrical aggregates. The changes in the solution physicochemical properties at these concentrations may be misinterpreted and this explains the different values of the critical micelle concentration reported in the literature for substances with similar structure, such as bile salts. Received: 14 May 2001 Accepted: 10 August 2001