Molecular dynamics simulation of the reaction of hydration of formaldehyde using a potential based on solute-solvent interaction energy components

Molecular dynamics simulations of aqueous solutions at infinite dilution of the reaction of water with formaldehyde, H(2)O + H(2)CO --> H(2)C(OH)(2), were performed using Lennard-Jones 12-6-1 potentials to describe the solute-solvent interactions, and TIP3P to describe the water-water interactions. The Morokuma decomposition scheme of ab initio interaction energies at the SCF level and the dispersion component at MP2 level were used to reproduce the molecular parameters of the solute-water interaction potential. The results show that the functions that use the EX-PL-DIS-ES interaction model to describe the solvation of the reactant and product systems lead to good values of the reaction (DeltaG) and activation (DeltaG(#)) free energy as compared with those from using AMBER-derived parameters, and with the available theoretical and experimental data.     

Molecular simulation of the hydration of ethene to ethanol using ab initio potentials and free energy curves

Molecular dynamics simulations of aqueous solutions at infinite dilution of the reaction of water with ethene: H2O + CH2CH2 --> CH3CH2OH were performed using Lennard-Jones 12-6-1 potentials to describe the solute-solvent interactions, and TIP3P to describe the water-water interactions. The Morokuma decomposition scheme of ab initio interaction energies at the SCF level and the dispersion component at the MP2 level were used to reproduce the molecular parameters of the solute-water interaction potentials. The results show that the functions that use the EX-PL-DIS-ES interaction model to describe the solvation of the reactant, transition state, and product systems lead to good values of the reaction (Delta G) and acceptable values of the activation (Delta G#) free energy as compared with those from using AMBER-derived parameters, using the available theoretical and experimental data as referents.     

Applied biological and physicochemical activity of isoquinoline alkaloids: oxoisoaporphine and boldine

The aim of this study was to determine the electronic influence of substituent groups and annelated rings such as oxazole-oxazinone on the physicochemical and photoprotection, antioxidant capacity, toxicity and singlet oxygen photosensitization biological properties of isoquinoline alkaloid frameworks. Thus, oxoisoaporphine derivatives 1-5 and 3-azaoxoisoaporphine (6), some of them with phenolic structures, did not present any antioxidant capacity, possibly either by formation of keto-enol tautomerism species or the formation of unstable free radicals. Due to the singlet oxygen quantum yields (F_D) near to unity, and greater photostability than phenalenone, oxoisoaporphines 4-6 may be considered as photosensitizers for singlet oxygen production and can be used as new universal study tools. The biological application as antibacterial agents is an important and possible tool in the study of compounds with low cytotoxicity and high reactivity in antineoplastic chemotherapy. On the other hand, when boldine and its annelated derivatives B1-4 are irradiated, a photoprotector effect is observed (SPF = 2.35), even after 30 minutes of irradiation. They also act as photoprotectors in cell fibroblast cultures. No hemolysis was detected for boldine hydrochloride and its salts without irradiation. In solutions irradiated before incubation (at concentrations over 200 ppm) photoproducts were toxic to the nauplii of Artemia salina.     

Weierstrass weight of the hyperosculating points of generalized Fermat curves

Let $(S,H)$ be a generalized Fermat pair of the type $(k,n)$. If $F?S$ is the set of fixed points of the non-trivial elements of the group H, then F is exactly the set of hyperosculating points of the standard embedding $S?{\mathbb{P}}^n$. We provide an optimal lower bound (this being sharp in a dense open set of the moduli space of the generalized Fermat curves) for the Weierstrass weight of these points.     

Langmuir and Langmuir-Blodgett (LB) films of tetrapyridyl metalloporphyrins

We report on the formation of Langmuir films of 5,10,15,20-tetra(4-pyridyl) 21H,23H-porphine, hereafter named tetrapyridyl porphyrins with distinct central ions (2H⁺, Zn²⁺, Cu²⁺, Ni²⁺). The films were characterized with surface pressure and surface potential isotherms and in situ UV-vis absorbance. The measurements indicated strong aggregation of porphyrin monomers at the air-water interface, with a red shift of the Soret band in comparison with the spectrum obtained from CHCl₃ solutions. The shift was larger for the non-substituted H₂TPyP, and depended on the metal ion. Significantly, aggregation occurred right after spreading of the Langmuir film, with no further shifts in the UV-vis spectra upon compression of the film, or even after transferring them onto solid substrates in the form of Langmuir-Blodgett (LB) films. The buildup of LB films from H₂TPyP and ZnTPyP was monitored with UV-vis spectroscopy, indicating an equal amount of material deposited in each deposition step. Using FTIR in the transmission and reflection modes, we inferred that the H₂TPyP molecules exhibit no preferential orientation in the LB films, while for ZnTPyP there is preferential orientation, with the porphyrin molecules anchored to the substrate by the lateral pyridyl groups.     

Uniformization of conformal involutions on stable Riemann surfaces

Let S be a closed Riemann surface of genus g. It is well known that there are Schottky groups producing uniformizations of S (Retrosection Theorem). Moreover, if τ: S → S is a conformal involution, it is also known that there is a Kleinian group K containing, as an index two subgroup, a Schottky group G that uniformizes S and so that K/G induces the cyclic group 〈τ〉. Let us now assume S is a stable Riemann surface and τ: S → S is a conformal involution. Again, it is known that S can be uniformized by a suitable noded Schottky group, but it is not known whether or not there is a Kleinian group K, containing a noded Schottky group G of index two, so that G uniformizes S and K/G induces 〈τ〉. In this paper we discuss this existence problem and provide some partial answers: (1) a complete positive answer for genus g ≤ 2 and for the case that S/〈τ〉 is of genus zero; (2) the existence of a Kleinian group K uniformizing the quotient stable Riemann orbifold S/〈τ〉. Applications to handlebodies with orientation-preserving involutions are also provided.     

Thermal behaviour and characterization of an iron aluminum arsenate mineral

It has been determined the thermal behaviour at high temperatures of an iron aluminum arsenate mineral first described in the location of La Serena Valley, Extremadura, Spain, which expands until 1173 K contracting later and softening at 1653 K and full melting at 1773 K. The DTA/TG experiment only detects some rearrangement with an endothermic at 1173 K due to the mica mixing. The mineral is a scorodite variety mixed with micaceous clay which has been found as aggregates of pyramidal crystals associated with quartz, wolframite, molibdenite, cassiterite and other secondary minerals in the pegmatite of the San Nicolas mine. The chemical composition, the physico- chemical characteristics such as density and hardness, as well as the thermal behaviour has allowed to conclude that this mineral can be an Al-enriched scorodite (mansfieldite): (Fe, Al) AsO₄·2H₂O mixed with illite from the scorodite-mansfieldite series. This revised version was published online in July 2006 with corrections to the Cover Date.