[Neonatal hypoglycemia: glucose gel efficacy in the treatment of early hypoglycemia in newborns with risk factors. Randomized clinical trial].

Unlabelled: Hypoglycemia is the most frequent metabolic disorder in newborns; the administration of 40% glu cose gel in the oral mucosa could be as effective in its correction as the administration of formula milk, not interfering with breastfeeding.

Objective: To evaluate the efficacy of 40% glucose gel com pared with formula milk in the treatment of early asymptomatic hypoglycemia in newborns with risk factors.

Patients And Method: Randomized clinical trial, non-inferiority, conducted in a private hos pital.

Plasmon-induced excitation energy transfer in silver nanoparticle dimers: A real-time TDDFTB investigation.

Using real-time quantum dynamics calculations, we perform theoretical investigations of light-induced interactions and electronic excitation transfer in a silver nanoparticle dimer. Real-time time-dependent density functional tight-binding (RT-TDDFTB) calculations provide details of the quantum dynamical processes at an electronic/atomistic level with attosecond resolution. The computational efficiency of RT-TDDFTB allows us to examine electronic dynamics up to picosecond time scales.

Field Programmable Gate Arrays for Enhancing the Speed and Energy Efficiency of Quantum Dynamics Simulations.

We present the first application of field programmable gate arrays (FPGAs) as new, customizable hardware architectures for carrying out fast and energy-efficient quantum dynamics simulations of large chemical/material systems. Instead of tailoring the software to fixed hardware, which is the typical case for writing quantum chemistry code for central processing units (CPUs) and graphics processing units (GPUs), FPGAs allow us to directly customize the underlying hardware (even at the level of specific electrical signals in the circuit) to give a truly optimized computational performance for quantum dynamics calculations. By offloading the most intensive and repetitive calculations onto an FPGA, we show that the computational performance of our real-time electron dynamics calculations can even exceed that of optimized commercial mathematical libraries running on high-performance GPUs.

Confined Lithium-Sulfur Reactions in Narrow-Diameter Carbon Nanotubes Reveal Enhanced Electrochemical Reactivity.

We demonstrate an unusual electrochemical reaction of sulfur with lithium upon encapsulation in narrow-diameter (subnanometer) single-walled carbon nanotubes (SWNTs). Our study provides mechanistic insight on the synergistic effects of sulfur confinement and Li ion solvation properties that culminate in a new mechanism of these sub-nanoscale-enabled reactions (which cannot be solely attributed to the lithiation-delithiation of conventional sulfur). Two types of SWNTs with distinct diameters, produced by electric arc (EA-SWNTs, average diameter 1.

Real-Time Quantum Dynamics of Long-Range Electronic Excitation Transfer in Plasmonic Nanoantennas.

Using large-scale, real-time, quantum dynamics calculations, we present a detailed analysis of electronic excitation transfer (EET) mechanisms in a multiparticle plasmonic nanoantenna system. Specifically, we utilize real-time, time-dependent, density functional tight binding (RT-TDDFTB) to provide a quantum-mechanical description (at an electronic/atomistic level of detail) for characterizing and analyzing these systems, without recourse to classical approximations. We also demonstrate highly long-range electronic couplings in these complex systems and find that the range of these couplings is more than twice the conventional cutoff limit considered by Förster resonance energy transfer (FRET)-based approaches.

Accurate Electron Affinities and Orbital Energies of Anions from a Nonempirically Tuned Range-Separated Density Functional Theory Approach.

The treatment of atomic anions with Kohn-Sham density functional theory (DFT) has long been controversial because the highest occupied molecular orbital (HOMO) energy, E, is often calculated to be positive with most approximate density functionals. We assess the accuracy of orbital energies and electron affinities for all three rows of elements in the periodic table (H-Ar) using a variety of theoretical approaches and customized basis sets. Among all of the theoretical methods studied here, we find that a nonempirically tuned range-separated approach (constructed to satisfy DFT-Koopmans' theorem for the anionic electron system) provides the best accuracy for a variety of basis sets, even for small basis sets where most functionals typically fail.

Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks.

We present a detailed analysis of nonempirically tuned range-separated functionals, with both short- and long-range exchange, for calculating the static linear polarizability and second hyperpolarizabilities of various polydiacetylene (PDA) and polybutatriene (PBT) oligomers. Contrary to previous work on these systems, we find that the inclusion of some amount of short-range exchange does improve the accuracy of the computed polarizabilities and second hyperpolarizabilities. Most importantly, in contrast to prior studies on these oligomers, we find that the lowest-energy electronic states for PBT are not closed-shell singlets, and enhanced accuracy with range-separated DFT can be obtained by allowing the system to relax to a lower-energy broken-symmetry solution.

Optical properties of graphene nanoflakes: Shape matters.

In recent years there has been significant debate on whether the edge type of graphene nanoflakes (GNFs) or graphene quantum dots (GQDs) are relevant for their electronic structure, thermal stability, and optical properties. Using computer simulations, we have proven that there is a fundamental difference in the absorption spectra between samples of the same shape, similar size but different edge type, namely, armchair or zigzag edges. These can be explained by the presence of electronic structures near the Fermi level which are localized on the edges.

Photoinduced charge-transfer dynamics simulations in noncovalently bonded molecular aggregates.

The rational design of new materials as prototype systems for organic solar cells remains challenging. Perylene diimide has emerged as a promising material to replace fullerene derivatives because of its synthetic flexibility, leading to the manipulation of their optical properties. As a result of their fused aromatic core that favors π-π stacking interactions, the aggregation of these molecules can reach highly ordered nanostructures as one-dimensional nanofibers, with a fast photoinduced charge transfer mechanism.

Real-Time Quantum Dynamics Reveals Complex, Many-Body Interactions in Solvated Nanodroplets.

Electronic excitations in the liquid phase are surprisingly rich and considerably more complex than either gas-phase or solid-state systems. While the majority of physical and biological processes take place in solvent, our understanding of nonequilibrium excited-state processes in these condensed phase environments remains far from complete. A central and long-standing issue in these solvated environments is the assessment of many-body interactions, particularly when the entire system is out of equilibrium and many quantum states participate in the overall process.

Giant Raman Response to the Encapsulation of Sulfur in Narrow Diameter Single-Walled Carbon Nanotubes.

Encapsulation of sulfur in HiPCO-SWNTs leads to large changes in the Raman spectra with the appearance of new peaks at 319, 395, and 715 cm(-1) which originate from the sulfur species within the SWNTs, while the high frequency SWNT bands (ν > 1200 cm(-1)) are decreased in intensity. The encapsulated species also shifts the near-IR interband electronic transitions to lower energy by more than 10%. These effects seem to originate with the van der Waals interaction of the confined sulfur species with the walls of the SWNTs which are not expected to be significant in the case of the previously studied large diameter SWNTs.

Isolation of Pristine Electronics Grade Semiconducting Carbon Nanotubes by Switching the Rigidity of the Wrapping Polymer Backbone on Demand.

Conjugated polymers are among the most selective carbon nanotube sorting agents discovered and enable the isolation of ultrahigh purity semiconducting singled-walled carbon nanotubes (s-SWCNTs) from heterogeneous mixtures that contain problematic metallic nanotubes. The strong selectivity though highly desirable for sorting, also leads to irreversible adsorption of the polymer on the s-SWCNTs, limiting their electronic and optoelectronic properties. We demonstrate how changes in polymer backbone rigidity can trigger its release from the nanotube surface.

Bioelectrochemical sensing of promethazine with bamboo-type multiwalled carbon nanotubes dispersed in calf-thymus double stranded DNA.

We report the quantification of promethazine (PMZ) using glassy carbon electrodes (GCE) modified with bamboo-like multi-walled carbon nanotubes (bCNT) dispersed in double stranded calf-thymus DNA (dsDNA) (GCE/bCNT-dsDNA). Cyclic voltammetry measurements demonstrated that PMZ presents a thin film-confined redox behavior at GCE/bCNT-dsDNA, opposite to the irreversibly-adsorbed behavior obtained at GCE modified with bCNT dispersed in ethanol (GCE/bCNT). Differential pulse voltammetry-adsorptive stripping with medium exchange experiments performed with GCE/bCNT-dsDNA and GCE modified with bCNTs dispersed in single-stranded calf-thymus DNA (ssDNA) confirmed that the interaction between PMZ and bCNT-dsDNA is mainly hydrophobic.

Electron dynamics in complex environments with real-time time dependent density functional theory in a QM-MM framework.

This article presents a time dependent density functional theory (TDDFT) implementation to propagate the Kohn-Sham equations in real time, including the effects of a molecular environment through a Quantum-Mechanics Molecular-Mechanics (QM-MM) hamiltonian. The code delivers an all-electron description employing Gaussian basis functions, and incorporates the Amber force-field in the QM-MM treatment. The most expensive parts of the computation, comprising the commutators between the hamiltonian and the density matrix-required to propagate the electron dynamics-, and the evaluation of the exchange-correlation energy, were migrated to the CUDA platform to run on graphics processing units, which remarkably accelerates the performance of the code.

A theoretical study of the optical properties of nanostructured TiO2.

Optical properties of TiO(2) nanoclusters (with more than 30 TiO(2) units) were calculated within a fully atomistic quantum dynamic framework. We use a time dependent tight-binding model to describe the electronic structure of TiO(2) nanoclusters in order to compute their optical properties. We present calculated absorption spectra for a series of nanospheres of different radii and crystal structures.

Quantum Dynamical Simulations as a Tool for Predicting Photoinjection Mechanisms in Dye-Sensitized TiO2 Solar Cells.

On the basis of a time-dependent self-consistent density functional tight-binding (TD-DFTB) approach, we present a novel method able to capture the differences between direct and indirect photoinjection mechanisms in a fully atomistic picture. A model anatase TiO2 nanoparticle (NP) functionalized with different dyes has been chosen as the object of study. We show that a linear dependence of the rate of electron injection with respect to the square of the applied field intensity can be viewed as a signature of a direct electron injection mechanism.

Transition dipole moments of the Qy band in photosynthetic pigments.

From studying the time evolution of the single electron density matrix within a density functional tight-binding formalism we calculate the Q(y) transition dipole moments vector direction and strength for a series of important photosynthetic pigments. We obtain good agreement with first-principles and experimental results and provide insights into the detailed nature of these excitations from the time evolving populations of molecular orbitals involved as well as correlations between pigment chemistry and dipole strength.

Dynamical simulation of the optical response of photosynthetic pigments.

From time integration of the electron dynamics under a density functional tight binding Hamiltonian in the presence of external time varying electric fields, we obtain the absorption spectra of a series of chlorophylls and bacteriochlorophylls. We obtain good agreement with the observed experimental energies as well as with fully ab initio results in the literature for the main absorption bands. As a first step towards an atomistic description of energy transfer between chromophores in photosynthetic antenna systems we calculate the coupling energy between the excitations of two chlorophyll a molecules as a function of the distance as well as the transfer of energy between these when one of them is subjected to laser illumination.