Unruh–DeWitt Detectors in Spherically Symmetric Dynamical Space-Times

In the present paper, Unruh–DeWitt detectors are used in order to investigate the issue of temperature associated with a spherically symmetric dynamical space-times. Firstly, we review the semi-classical tunneling method, then we introduce the Unruh–DeWitt detector approach. We show that for the generic static black hole case and the FRW de Sitter case, making use of peculiar Kodama trajectories, semiclassical and quantum field theoretic techniques give the same standard and well known thermal interpretation, with an associated temperature, corrected by appropriate Tolman factors. For a FRW space-time interpolating de Sitter space with the Einstein–de Sitter universe (that is a more realistic situation in the frame of ΛCDM cosmologies), we show that the detector response splits into a de Sitter contribution plus a fluctuating term containing no trace of Boltzmann-like factors, but rather describing the way thermal equilibrium is reached in the late time limit. As a consequence, and unlike the case of black holes, the identification of the dynamical surface gravity of a cosmological trapping horizon as an effective temperature parameter seems lost, at least for our co-moving simplified detectors. The possibility remains that a detector performing a proper motion along a Kodama trajectory may register something more, in which case the horizon surface gravity would be associated more likely to vacuum correlations than to particle creation.     

Six-month-old infants discriminate voicing on the basis of temporal envelope cues (L)

Young deaf children using a cochlear implant develop speech abilities on the basis of speech temporal-envelope signals distributed over a limited number of frequency bands. A Headturn Preference Procedure was used to measure looking times in 6-month-old, normal-hearing infants during presentation of repeating or alternating sequences composed of different tokens of /aba/and /apa/ processed to retain envelope information below 64 Hz while degrading temporal fine structure cues. Infants attended longer to the alternating sequences, indicating that they perceive the voicing contrast on the basis of envelope cues alone in the absence of fine spectral and temporal structure information.     

Is tetrahedral H42+ a minimum? Anomalous behavior of popular basis sets with the standard p exponents on hydrogen

The nature of the tetrahedral H₄²⁺ stationary point (minimum or triply degenerate saddle) depends remarkably upon the theoretical level employed. Harmonic vibrational analyses with, e.g., the 6-31G** (and 6-31 + +G**) and Dunning's [4s2p1d;2s1p] [D95(d,p)] basis sets using the standard p exponent suggest (erroneously) that the T_d geometry is a minimum at both the HF and MP2 levels. This is not the case at definitive higher levels. The C₃H₄²⁺ structure with an apical H is another example of the failure of the calculations with the 6-31G**, 6-311G**, and D95(d,p) basis sets. Even at MP2/6-31G** and MP2/ cc-pVDZ levels, the C_3v structure has no negative eigenvalues of the Hessian. Actually, this form is a second-order saddle point as shown by the MP2/6-31G** calculation with the optimized exponent. The D_4h methane dication structure is also an example of the misleading performance of the 6-31G** basis set. In all these cases, energy-optimized hydrogen p exponents give the correct results, i.e., those found with more extended treatments. Optimized values of the hydrogen polarization function exponents eliminate these defects in 6-31G** calculations. Species with higher coordinate hydrogens may also be calculated reliably by using more than one set of p functions on hydrogen [e.g., the 6-31G(d,2p) basis set]. Not all cases are critical. A survey of examples, also including some boron compounds, provides calibration. © 1993 John Wiley & Sons, Inc.     

Bifurcations and global stability of families of gradients

Dedicated to René Thom on his sixty fifth anniversary.     

Density functional theory study of the adsorption of formaldehyde on Pd4 and on Pd4/gamma-Al2O3 clusters

B3LYP/LANL2DZ and B3LYP/6-31G(d)-restricted and -unrestricted calculations are employed to calculate energies and adsorption forms of formaldehyde adsorbed on planar and on tetrahedral Pd4 clusters and on a Pd4 cluster supported on Al10O15. Formaldehyde adsorbs on planar Pd4 in the eta(2)(C,O)-di-sigma adsorption mode, while on tetrahedral Pd4, it adsorbs in the eta(2)(C,O)-pi adsorption mode. The adsorption energy on planar Pd4 is -21.4 kcal x mol(-1), whereas for the tetrahedral Pd4 cluster, the adsorption energy is -13.2 kcal x mol(-1). The latter value is close to experimental findings (-12 to -14 kcal x mol(-1)). Adsorption of formaldehyde on Pd4 supported on an Al10O15 cluster leads essentially to the same result as that found for adsorption on the tetrahedral Pd4 cluster. Charge density analysis for the interaction between formaldehyde and the Pd4 clusters indicates strong backdonation in the eta(2) adsorption mode, leading to positive charge on the Pd4 cluster. NBO analysis shows that the highly coordinated octahedral aluminum atoms of Al10O15 donate electron density to the supported Pd4 cluster, while tetrahedral aluminum atoms with lower coordination number have acidic nature and therefore act as electron acceptors.     

Correlation between Enterococcus faecalis biofilms development stage and quantitative surface roughness using atomic force microscopy.

Biofilms are assemblages of microorganisms and their associated extracellular products at an interface and typically with an abiotic or biotic surface. The study of the morphology of biofilms is important because they are associated with processes of biofouling, corrosion, catalysis, pollutant transformation, dental caries, drug resistance, and so forth. In the literature, biofilms have been examined by atomic force microscopy (AFM), which has proven to be a potent tool to study different aspects of the biofilm development on solid surfaces. In this work, we used AFM to investigate topographical changes during the development process of Enterococcus faecalis biofilms, which were generated on sterile cellulose nitrate membrane (CNM) filters in brain heart infusion (BHI) broth agar blood plates after 24, 36, 72, 192, and 360 h. AFM height images showed topographical changes due to biofilm development, which were used to characterize several aspects of the bacterial surface, such as the presence of extracellular polymeric substance, and the biofilm development stage. Changes in the development stage of the biofilm were shown to correlate with changes in the surface roughness as quantified through the mean roughness.     

Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO2 Capture from Air: Roles of Atmospheric Water

Direct air capture (DAC) processes for extraction of CO₂ from ambient air are unique among chemical processes in that they operate outdoors with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al₂O₃, is explored in detail. By combining CO₂ adsorption measurements, oxidative degradation rates, elemental analyses, solid-state NMR and in situ IR spectroscopic analysis in conjunction with ¹⁸O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. We demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.     

Determination of low‐molecular‐weight amines and ammonium in saline waters by ion chromatography after their extraction by steam distillation

A new method was developed for the determination of ammonium ion, monomethylamine and monoethylamine in saline waters by ion chromatography. Steam distillation was used to eliminate matrix interferences. Variables such as distillation time, concentration of sodium hydroxide solution and analyte mass were optimized by using a full two‐level factorial (2³) design. The influence of steam distillation on the analytical curves prepared in different matrices was also investigated. Limits of detection of 0.03, 0.05 and 0.05 mg/L were obtained for ammoniumion, monomethylamine and monoethylamine, respectively. Saline water samples from the Brazilian oil industry, containing sodium and potassium concentrations between 2.0–5.2% w/v and 96–928 mg/L, respectively, were analyzed. Satisfactory recoveries (90–105%) of the analytes were obtained for all spiked samples, and the precision was ≤ 7% (n = 3). The proposed method is adequate for analyzing saline waters containing sodium to ammoniumion, monomethylamine and monoethylamine concentration ratios up to 28 000:1 and potassium to ammonium, monomethylamine and monoethylamine concentration ratios up to 12 000:1.     

Ultrasound-Assisted Synthesis of 4-Alkoxy-2-methylquinolines: An Efficient Method toward Antitubercular Drug Candidates

Tuberculosis (TB) has been described as a global health crisis since the second half of the 1990s. Mycobacterium tuberculosis (Mtb), the etiologic agent of TB in humans, is a very successful pathogen, being the main cause of death in the population among infectious agents. In 2019, it was estimated that around 10 million individuals were contaminated by this bacillus and about 1.2 million succumbed to the disease. In recent years, our research group has reported the design and synthesis of quinoline derivatives as drug candidates for the treatment of TB. These compounds have demonstrated potent and selective growth inhibition of drug-susceptible and drug-resistant Mtb strains. Herein, a new synthetic approach was established providing efficient and rapid access (15 min) to a series of 4-alkoxy-6-methoxy-2-methylquinolines using ultrasound energy. The new synthetic protocol provides a simple procedure utilizing an open vessel system that affords the target products at satisfactory yields (45–84%) and elevated purities (≥95%). The methodology allows the evaluation of a larger number of molecules in assays against the bacillus, facilitating the determination of the structure–activity relationship with a reduced environmental cost.