Electronic Properties of Water in Liquid Environment. A Sequential QM/MM Study Using the Free Energy Gradient Method

There is a continuous search for theoretical methods that are able to describe the effects of the liquid environment on molecular systems. Different methods emphasize different aspects, and the treatment of both the local and bulk properties is still a great challenge. In this work, the electronic properties of a water molecule in liquid environment is studied by performing a relaxation of the geometry and electronic distribution using the free energy gradient method. This is made using a series of steps in each of which we run a purely molecular mechanical (MM) Monte Carlo Metropolis simulation of liquid water and subsequently perform a quantum mechanical/molecular mechanical (QM/MM) calculation of the ensemble averages of the charge distribution, atomic forces, and second derivatives. The MP2/aug-cc-pV5Z level is used to describe the electronic properties of the QM water. B3LYP with specially designed basis functions are used for the magnetic properties. Very good agreement is found for the local properties of water, such as geometry, vibrational frequencies, dipole moment, dipole polarizability, chemical shift, and spin-spin coupling constants. The very good performance of the free energy method combined with a QM/MM approach along with the possible limitations are briefly discussed.

A theoretical study of the characterization and the absorption spectrum of Mg: Tetracycline complexes in aqueous environment.

The complex formed by the tetracycline (TC) molecule with the Mg ion is able to prevent the replication of the genetic material in the bacterial ribosome, making an excellent antibiotic. In general, the absorption and emission spectra of TC are very sensitive to the host ions and the pH of the solvent that the set is immersed. However, the theoretical absorption spectrum available in the literature is scarce and limited to simple models that do not consider the fluctuations of the liquid. Our aim is to obtain the electronic absorption spectrum of TC and the complex Mg:TC in the ratio 1:1 and 2:1. Moreover, we analyze the changes in intensity and shifts of the bands in the systems listed. We performed the simulation using the classical Monte Carlo technique with the Lennard-Jones plus Coulomb potential applied to each atom of the both TC molecule and the Mg:TC complexes in water. The electronic absorption spectrum was obtained from the time-dependent density functional theory using different solvent models. In general, we obtained a good qualitative description of the spectra when compared with the experimental results. The Mg atom shifts the first band by 4 nm in our models, in excellent agreement to the experimental result of 4 nm. The second absorption band is found here to be useful for the characterization of the position where the ion attaches to the TC.

Realistic fluids as source for dynamically accreting black holes in a cosmological background

We show that a single imperfect fluid can be used as a source to obtain a mass-varying black hole in an expanding universe. This approach generalizes the well-known McVittie spacetime, by allowing the mass to vary thanks to a novel mechanism based on the presence of a temperature gradient. This fully dynamical solution, which does not require phantom fields or fine-tuning, is a step forward in a new direction in the study of systems whose local gravitational attraction is coupled to the expansion of the universe. We present a simple but instructive example for the mass function and briefly discuss the structure of the apparent horizons and the past singularity.

Experimental investigations of heat transfer coefficients of cutting fluids in metal cutting processes: analysis of workpiece phenomena in a given case study

This paper reports an experimental method to estimate the convective heat transfer of cutting fluids in a laminar flow regime applied on a thin steel plate. The heat source provided by the metal cutting was simulated by electrical heating of the plate. Three different cooling conditions were evaluated: a dry cooling system, a flooded cooling system and a minimum quantity of lubrication cooling system, as well as two different cutting fluids for the last two systems. The results showed considerable enhancement of convective heat transfer using the flooded system. For the dry and minimum quantity of lubrication systems, the heat conduction inside the body was much faster than the heat convection away from its surface. In addition, using the Biot number, the possible models were analyzed for conduction heat problems for each experimental condition tested.

Consistency of the mass variation formula for black holes accreting cosmological fluids

We address the spherical accretion of generic fluids onto black holes. We show that, if the black hole metric satisfies certain conditions, in the presence of a test fluid it is possible to derive a fully relativistic prescription for the black hole mass variation. Although the resulting equation may seem obvious due to a form of it appearing as a step in the derivation of the Schwarzschild metric, this geometrical argument is necessary to fix the added degree of freedom one gets for allowing the mass to vary with time. This result has applications on cosmological accretion models and provides a derivation from first principles to serve as a basis to the accretion equations already in use in the literature.

Turbidimetric Spectroscopy for the Evaluation of Metalworking Fluids Stability

The stability of oil-in-water (O/W) emulsions used as metalworking fluids is a key factor for the economical and environmental balance of the entire metalworking process because used and broken fluids must be recycled or disposed. In this study, the ability of turbidimetric spectroscopy in the ultraviolet and visible light range to detect metalworking fluids destabilization was evaluated. Destabilization was achieved by adding calcium chloride, thus achieving accelerated aging, which leads to coalescence, creaming, and complete emulsion separation. The stability of the metalworking fluids at 5% volumetric concentration in deionized water was monitored using a spectroscopic turbidimeter composed of an optical probe for in-line measurements. Destabilization was also monitored by measuring the vertical profile of backscattered and transmitted light. The results of this offline measurement system were compared with those from the in-line spectroscopic sensor, indicating that the latter can provide local, real-time information on emulsion destabilization, thus enabling control actions.

Derivation and characterization of progenitor stem cells from canine allantois and amniotic fluids at the third trimester of gestation

Fetal tissues are frequently discarded before (amniocentesis) or after birth, which both facilitates stem cell access and helps to overcome ethical concerns. In the present study, we aimed to isolate and characterize stem cells from the allantoic and amniotic fluids (ALF; AMF) of third trimester canine fetuses. This gestation age has not been previously explored for stem cells isolation. The gestational age, cell culture conditions and method of isolation used in this study allowed for the establishment and efficient expansion of ALF and AMF cells. We showed that the majority of ALF and ALF cells express the stem cell markers, such as vimentin, nestin and cytokeratin 18 (CK18). Under appropriate culture conditions AMF derived cells can undergo differentiation into osteogenic, adipogenic, chondrogenic and neuron-like lineages. ALF derived cells showed adipogenic, and chondrogenic potential. Therefore, ALF and AMF cells derived at the third gestation trimester can be qualified as progenitor stem cells, accordingly referred as (alantoic fluid progenitor/stem) ALF PS cells and (amniotic fluid progenitor/stem) AMF PS cells. (C) 2012 Elsevier Ltd. All rights reserved.