Testing standard basis sets for direct ionizations: H+ + H at ELab = 0.1-100 keV.

With the simplest-level electron nuclear dynamics (SLEND) method, we test standard Slater-type-orbital/contracted-Gaussian-functions (STO/CGFs) basis sets for the simulation of direct ionizations (DIs), charge transfers (CTs), and target excitations (TEs) in H+ + H at ELab = 0.1-100 keV. SLEND is a time-dependent, variational, on-the-fly, and nonadiabatic method that treats nuclei and electrons with classical dynamics and a Thouless single-determinantal state, respectively. While previous tests for CTs and TEs exist, this is the first SLEND/STO/CGFs test for challenging DIs. Spin-orbitals with negative/positive energies are treated as bound/unbound states for bound-to-bound (CT and TE) and bound-to-unbound (DI) transitions. SLEND/STO/CGFs simulations correctly reproduce all the features of DIs, CTs and TEs over all the considered impact parameters and energies. SLEND/STO/CGFs simulations correctly predict CT integrals cross-sections (ICSs) over all the considered energies and predict satisfactory DI and TE ICSs within some energy ranges. Strategies to improve SLEND/STO/CGFs for DI predictions are discussed.

Electron Nuclear Dynamics of H+ + C2H2 at ELab = 30, 200, and 450 eV.

We present a complete simplest-level electron nuclear dynamics (SLEND) investigation of H+ + C2H2 at collision energies ELab = 30, 200, and 450 eV. This reaction is relevant in astrophysics and provides a computationally feasible prototype for proton cancer therapy reactions. SLEND is a time-dependent, variational, direct, and nonadiabatic method that adopts a classical-mechanics description for the nuclei and a Thouless single-determinantal wave function for the electrons. We perform this study with our code PACE, which incorporates the One Electron Direct/Electron Repulsion Direct (OED/ERD) atomic integrals package developed by the Bartlett group. Current SLEND simulations with the 6-31G** basis set involves 2,646 trajectory calculations from 9 nonredundant, symmetry-inequivalent projectile-target orientations. For H+ + C2H2 at ELab = 30 eV, SLEND/6-31G** simulations predict one simple scattering process, and three reactive ones: C2H2 hydrogen substitution, C2H2 fragmentation into two CH moieties, and C2H2 fragmentation into CHC and H moieties, respectively. We reveal and analyze the mechanisms of these processes through computer animations; this valuable chemical information is inaccessible by experiments. The SLEND/6-31G** scattering angle functions exhibit primary and secondary rainbow scattering features that vary with the projectile-target orientations and collision energies. SLEND/6-31G** predicts 1-electron-transfer (1-ET) integral cross sections at ELab = 30, 200, and 450 eV in good agreement with their experimental counterparts. SLEND/6-31-G** predicts 1-ET differential cross sections (DCSs) at ELab = 30 eV that agree well with their experimental counterparts over all the measured scattering angles. In addition, SLEND/6-31G** predicts 0-ET DCSs at ELab = 30 eV that agree well with their experimental counterparts at low scattering angles, but less satisfactorily at higher ones. Remarkably, both the 0- and 1-ET DCSs from SLEND/6-31G** exhibit distinct primary rainbow scattering signatures in excellent agreement with their experimentally inferred counterparts. Furthermore, both SLEND/6-31G** and the experiment indicate that the primary rainbow scattering angles from the 0- and 1-ET DCSs are identical (an unusual fact in proton-molecule collisions). Through these rainbow scattering predictions, SLEND has also validated a procedure to extract primary rainbow angles from structureless DCSs. We analyze the obtained theoretical results in comparison with available experimental data and discuss forthcoming developments in the SLEND method.

Loss of Cognitive Function in Mexican children due to lead exposure and the associated economic costs.

BACKGROUND: Lead exposure reduces the cognitive development and future economic prospects of children. While previous studies in high-income settings have explored productivity losses associated with lead exposure, limited research has focused on low and middle-income countries like Mexico. OBJECTIVES: This study aims to provide a comprehensive assessment of the economic implications of lead exposure on Mexican children using, for the first time, nationally representative Blood lead levels (BLLs) measurements in children aged 1-4, specifically focusing on the costs of forgone lifetime income due to cognitive losses. METHODS: BLLs of children aged 1-4 were extracted from the 2018-2019 National Health and Nutrition Survey (ENSANUT). Estimations of cognitive losses were derived from a log-linear relationship between BLLs and IQ loss. Lost lifetime economic productivity per child was calculated, assuming a 2% reduction in lifetime potential productivity for each IQ point lost due to lead exposure, based on previous literature (Attina and Trasande, 2013; Larsen and Sanchez-Triana, 2023). Productivity data were obtained from representative sources for Mexico. RESULTS: The estimated economic loss amounted to US $33.02 billion, equivalent to 2.76% of Mexico's Gross Domestic Product (GDP) in 2019 (calculated for a 1-year cohort). On a national scale, the long-term loss of cognition for children 1-4 years old is 4.14 IQ points per child due to lead exposure, with significant variability across States (range: 3.26 to 5.26). Lead-poisoned children (≥5 µg/dL) suffered an average loss of 6.42 IQ points (range: 0 to 6.97). In terms of economic impact, some States like Chiapas experienced losses of 7.08% of its GDP, while others had losses as low as 0.67%. Intriguingly, states with lower Human Development Indexes (HDIs) exhibited relatively higher economic losses despite lower average blood lead levels. DISCUSSION: The heterogeneous impact of lead exposure across Mexican states underscores the necessity for tailored regional policies. These findings emphasize the urgency for targeted interventions and informed policy measures to mitigate the socioeconomic consequences of lead exposure on Mexican children.

Anthelmintic efficacy of an organic fraction from Guazuma ulmifolia leaves and evaluation of reactive oxidative stress on Haemonchus contortus.

This study describes the anthelmintic efficacy of an organic fraction (EtOAc-F) from Guazuma ulmifolia leaves and the evaluation of its reactive oxidative stress on Haemonchus contortus. The first step was to assess the anthelmintic effect of EtOAc-F at 0.0, 3.5, 7.0 and 14 mg kg of body weight (BW) in gerbil's (Meriones unguiculatus) artificially infected with H. contortus infective larvae (L3). The second step was to evaluate the preliminary toxicity after oral administration of the EtOAc-F in gerbils. Finally, the third step was to determine the relative expression of biomarkers such as glutathione (GPx), catalase (CAT), and superoxide dismutase (SOD) against H. contortus L3 post-exposition to EtOAc-F. Additionally, the less-polar compounds of EtOAc-F were identified by gas mass spectrophotometry (GC-MS). The highest anthelmintic efficacy (97.34%) of the organic fraction was found in the gerbils treated with the 14 mg/kg of BW. Histopathological analysis did not reveal changes in tissues. The relative expression reflects overexpression of GPx (p<0.05, fold change: 14.35) and over expression of SOD (p≤0.05, fold change: 0.18) in H. contortus L3 exposed to 97.44 mg/mL of EtOAc-F compared with negative control. The GC-MS analysis revealed the presence of 4-hydroxybenzaldehyde (1), leucoanthocyanidin derivative (2), coniferyl alcohol (3), ferulic acid methyl ester acetate (4), 2,3,4-trimethoxycinnamic acid (5) and epiyangambin (6) as major compounds. According to these results, the EtOAc-F from G. ulmifolia leaves exhibit anthelmintic effect and increased the stress biomarkers on H. contortus.

Electron nuclear dynamics of time-dependent symmetry breaking in H+ + H2O at ELab = 28.5-200.0 eV: a prototype for ion cancer therapy reactions.

Following our preceding research [P. M. McLaurin, R. Merritt, J. C. Domínguez, E. S. Teixeira and J. A. Morales, Phys. Chem. Chem. Phys., 2019, 21, 5006], we present an electron nuclear dynamics (END) investigation of H+ + H2O at ELab = 28.5-200.0 eV in conjunction with a computational procedure to induce symmetry breaking during evolution. The investigated system is a computationally feasible prototype to simulate water radiolysis reactions in ion cancer therapy. END is a time-dependent, variational, non-adiabatic, and on-the-fly method, which utilizes classical mechanics for nuclei and a Thouless single-determinantal state for electrons. In this study, a procedure inherent to END introduces low degrees of symmetry breaking into the reactants' restricted Hartree-Fock (RHF) state to induce a higher symmetry breaking during evolution. Specifically, the Thouless exponential operator acting on the RHF reference generates an axial spin density wave (ASDW) state according to Fukutome's analysis of HF symmetry breaking; this state exhibits spatial and spin symmetry breaking. By varying a Thouless parameter, low degrees of symmetry breaking are introduced into ASDW states. After starting the dynamics from those states, higher degrees of symmetry breaking may subsequently emerge as dictated by the END equations without ad hoc interventions. Simulations starting from symmetry-conforming states preserve the symmetry features during dynamics, whereas simulations starting from symmetry-broken states display an upsurge of symmetry breaking once the reactants collide. Present simulations predict three types of reactions: (I) projectile scattering, (II) hydrogen substitution, and (III) water radiolysis into H + OH and 2H + O fragments. Remarkably, symmetry breaking considerably increases the extent of the target-to-projectile electron transfers (ETs) occurring during the above reactions. Then, with symmetry breaking, 1-ET differential and integral cross sections increase in value, whereas 0-ET differential cross sections and primary rainbow scattering angles decrease. More importantly, END properties calculated from symmetry-breaking simulations exhibit better agreement with the experimental data. Notably, END 1-ET integral cross sections with symmetry breaking compare better with their experimental counterparts than 1-ET integral cross sections from high-level close-coupling calculations; moreover, END validates an undetected rainbow scattering peak inferred from the experimental data. A discussion of our symmetry-breaking procedure in the context of Fukutome's analysis of HF symmetry breaking is also presented.

Investigating bone resorption in Atlantic herring fish intermuscular bones with solid-state NMR.

Bones are connective tissues mainly made of collagen proteins with calcium phosphate deposits. They undergo constant remodeling, including destroying existing bones tissues (known as bone resorption) and rebuilding new ones. Bone remodeling has been well-described in mammals, but it is not the case in fish. Here, we focused on the mobile phase of the bone vascular system by carefully preserving moisture in adult Atlantic herring intermuscular bones. We detected pore water with high ionic strength and soluble degraded peptides whose 1H-transverse relaxation times, T2s, exceed 15 milliseconds. With favorable T2s, we incorporated a solution state spinlock scheme into the INEPT techniques to unequivocally demonstrate collagen degradation. In addition, we detected a substantial amount of inorganic phosphate in solution with 31P-NMR in the considerable background of solid hydroxyapatite calcium phosphate by saturation recovery experiment. It is consistent with the idea that bone resorption degrades bone collagen and releases calcium ions and phosphate ions in the pore water with increased ionic strength. Our report is the first to probe the resorption process in the heterogenous bone microstructure with a rigorous characterization of 1H and 13C relaxation behavior and direct assignments. In addition, we contribute to the fish bones literature by investigating fish bone remodeling using NMR for the first time.

Meta-analysis on the efficacy and safety of anterior vertebral body tethering in adolescent idiopathic scoliosis.

PURPOSE: In this meta-analysis, we analyzed the efficacy and safety of anterior vertebral body tethering in patients with adolescent idiopathic scoliosis. METHODS: We performed a literature search and analyzed the following data: baseline characteristics, efficacy measures (corrections of the main thoracic curve, proximal thoracic curve, and thoracolumbar curve, thoracic kyphosis, lumbosacral lordosis, rib hump, lumbar prominence and SRS-22 scores, and complications. Analyses were performed with Cochrane's Review Manager version 5.4. RESULTS: Twelve studies met the inclusion criteria. Significant corrections of the main thoracic (MD 22.51, 95% CI 12.93 to 32.09) proximal thoracic (MD 10.14°, 95% CI 7.25° to 13.02°), and thoracolumbar curve (MD 12.16, 95% CI 9.14 to 15.18) were found. No statistically significant corrections were observed on the sagittal plane assessed by thoracic kyphosis (MD - 0.60°, 95% CI - 2.45 to 1.26; participants = 622; studies = 4; I2 = 36%) and lumbosacral lordosis (MD 0.19°, 95% CI - 2.16° to 2.54°). Significant corrections were identified for rib hump (MD 5.26°, 95% CI 4.19° to 6.32°) and lumbar prominence (MD 1.20°, 95% CI 0.27° to 2.13°) at final follow-up. Significant improvements of total SRS-22 score (MD - 0.96, 95% CI - 1.10 to - 0.83) were achieved at final follow-up. The most common complication was overcorrection (8.0%) and tether breakage (5.9%), with a reoperation rate of 10.1%. CONCLUSIONS: Anterior vertebral body tethering is effective to reduce the curve in the coronal plane and clinical deformity. Maximum correction is achieved at one year. The method should, however, be optimized to reduce the rate of complications.

Estimating the cost of HIV services for key populations provided by the LINKAGES program in Kenya and Malawi.

BACKGROUND: Data remain scarce on the costs of HIV services for key populations (KPs). The objective of this study was to bridge this gap in the literature by estimating the unit costs of HIV services delivered to KPs in the LINKAGES program in Kenya and Malawi. We estimated the mean total unit costs of seven clinical services: post-exposure prophylaxis (PEP), pre-exposure prophylaxis (PrEP), HIV testing services (HTS), antiretroviral therapy (ART), sexually transmitted infection (STI) services, sexual and reproductive health (SRH) services, and management of sexual violence (MSV). These costs take into account the costs of non-clinical services delivered alongside clinical services and the pre-service and above-service program management integral to the LINKAGES program. METHODS: Data were collected at all implementation levels of the LINKAGES program including 30 drop-in-centers (DICs) in Kenya and 15 in Malawi. This study was conducted from the provider's perspective. We estimated economic costs for FY 2019 and cost estimates include start-up costs. Start-up and capital costs were annualized using a discount rate of 3%. We used a combination of top-down and bottom-up costing approaches. Top-down methods were used to estimate the costs of headquarters, country offices, and implementing partners. Bottom-up micro-costing methods were used to measure the quantities and prices of inputs used to produce services in DICs. Volume-weighted mean unit costs were calculated for each clinical service. Costs are presented in 2019 United States dollars (US$). RESULTS: The mean total unit costs per service ranged from US$18 (95% CI: 16, 21) for STI services to US$635 (95% CI: 484, 785) for PrEP in Kenya and from US$41 (95% CI: 37, 44) for STI services to US$1,240 (95% CI 1156, 1324) for MSV in Malawi. Clinical costs accounted for between 21 and 59% of total mean unit costs in Kenya, and between 25 and 38% in Malawi. Indirect costs-including start-up activities, the costs of KP interventions implemented alongside clinical services, and program management and data monitoring-made up the remaining costs incurred. CONCLUSIONS: A better understanding of the cost of HIV services is highly relevant for budgeting and planning purposes and for optimizing HIV services. When considering all service delivery costs of a comprehensive HIV service package for KPs, costs of services can be significantly higher than when considering direct clinical service costs alone. These estimates can inform investment cases, strategic plans and other budgeting exercises.

Sustained representation of perspectival shape.

Arguably the most foundational principle in perception research is that our experience of the world goes beyond the retinal image; we perceive the distal environment itself, not the proximal stimulation it causes. Shape may be the paradigm case of such "unconscious inference": When a coin is rotated in depth, we infer the circular object it truly is, discarding the perspectival ellipse projected on our eyes. But is this really the fate of such perspectival shapes? Or does a tilted coin retain an elliptical appearance even when we know it's circular? This question has generated heated debate from Locke and Hume to the present; but whereas extant arguments rely primarily on introspection, this problem is also open to empirical test. If tilted coins bear a representational similarity to elliptical objects, then a circular coin should, when rotated, impair search for a distal ellipse. Here, nine experiments demonstrate that this is so, suggesting that perspectival shapes persist in the mind far longer than traditionally assumed. Subjects saw search arrays of three-dimensional "coins," and simply had to locate a distally elliptical coin. Surprisingly, rotated circular coins slowed search for elliptical targets, even when subjects clearly knew the rotated coins were circular. This pattern arose with static and dynamic cues, couldn't be explained by strategic responding or unfamiliarity, generalized across shape classes, and occurred even with sustained viewing. Finally, these effects extended beyond artificial displays to real-world objects viewed in naturalistic, full-cue conditions. We conclude that objects have a remarkably persistent dual character: their objective shape "out there," and their perspectival shape "from here."

Thermal niche breadth and their relationship with sturnira bat species diversification.

The interaction between climatic conditions and the ability of organisms to maintain homeostasis regulates the distribution of species on the planet. However, its influence on macroevolutionary dynamics is not well understood. It has been suggested that diversification rates will be different in lineages with narrow thermal niches (specialists) to diversification rates in generalist lineages, but the evidence for this is elusive. Here, we tested this hypothesis by using the most diverse (in species richness and geographic range variation) tropical bat genus within the Phyllostomidae family. We estimated the realized thermal niche breadth of Sturnira species from their geographic range and categorized them as generalists, cold specialists, or warm specialists. We compared dynamic evolutionary models that differ in 1) niche breadth evolution, 2) parental niche breadth inheritance, and 3) whether niche breadth evolution is associated with shifts in diversification rates. Our best-performing model indicates that most Sturnira species arose as specialists in warm climates and that over time, their niche breadth broadens, and just a subset of those species becomes specialists in cold environments. We found that the evolution of realized thermal niche breadth causes fluctuations in per-lineage rates of diversification, where warm specialists boast the highest speciation rates. However, we found no evidence of these changes in niche neither triggering nor being a result of speciation events themselves; this suggests that diversification events in Sturnira could instead depend on allopatric speciation processes such as the development of geographic barriers.

Insights about levels and sources of organic pollution in an urbanized Amazon estuary (Belém, PA, Northern Brazil).

Amazon aquatic systems have been affected by organic pollution from urbanized regions. This study was conducted to determine the levels, sources, and distribution patterns of 16 polycyclic aromatic hydrocarbons (PAHs) and 6 steroid markers in surficial sediments from an important urbanized Amazon estuarine system (Belém, PA, Northern Brazil). Total PAH concentration (∑PAH) ranged from 878.2 to 9905.7 ng g-1, 3295.2 ng g-1 on average, suggesting a highly contaminated environment. PAH molecular ratios and statistical analysis indicated that PAH originated from a mixture of local sources emissions, mainly related to the combustion of fossil fuels and biomass. Coprostanol levels (maximum concentration = 292.52 ng g-1) could be compared to the mid-range reported in the literature. Studied stations, except for one, presented sterol ratio data indicating organic matter related to untreated sewage. Sterols indicative of sewage contamination showed a correlation with pyrogenic PAH amounts which are transported by the same channels where sewage is discharged.

Temporally stable rotational coherent states for molecular simulations. II. Symmetric rotor case.

Following our preceding work on spherical and linear rotors [C. Stopera and J. A. Morales, J. Chem. Phys. 152, 134112 (2020)], we reformulate an earlier rotational coherent state (CS) set to obtain a temporally stable (TS) CS set for symmetric rotors. Being TS, the new CSs remain within its own set during dynamics by evolving exclusively through their parameters. The TS CS set is now appropriate to reconstruct quantum rotational properties from classical-mechanics simulations of chemical reactions. Following literature precedents, we enforce temporal stability by incorporating action-angle-related phase factors into two parameters of the original CS set. Proofs and final expressions of the symmetric-rotor CS turn out more intricate than those of its spherical-rotor counterpart. We demonstrate and examine the key properties of the new CS set: continuity, resolution of unity, temporal stability, action identity, minimum uncertainty relationships, and quasi-classical behavior. Regarding the last property, we demonstrate that the body-fixed z-component of the CS angular momentum average evolves exactly as its classical counterpart, and that the x- and y-components display an astonishing analogy with their classical counterparts in terms of functional form, precession angular velocities, amplitudes, and phases. We elucidate some of these properties via computer simulations of a rotating benzene molecule represented with the CS set. We discuss the utilization of this CS set to reconstruct quantum rotational properties of symmetric-rotor molecules from classical-mechanics simulations. The new CS set is appropriate to establish quantum-classical connections for rotational properties in chemical dynamics, statistical mechanics, spectroscopy, nuclear physics, and quantum computing.

Meta-analysis of the efficacy of ketamine in postoperative pain control in adolescent idiopathic scoliosis patients undergoing spinal fusion.

PURPOSE: In this meta-analysis, we aim to compare ketamine use versus a control group (saline solution) during induction of anesthesia in adolescent idiopathic scoliosis patients undergoing fusion surgery in terms of postoperative opioid consumption, pain control, and side effects. METHODS: A PubMed search of studies published over the last 20 years using the descriptor/terms "ketamine AND scoliosis" was performed. Baseline characteristics of each article were obtained and efficacy measures analyzed (morphine equivalent treatment at 24, 48, and 72 h postoperatively, complications (vomiting/nausea and pruritus), length of hospital stay (days); and pain score (VAS)) (Review Manager 5.4 software package). RESULTS: Five randomized clinical trials were included. Morphine administration showed statistically significant differences at 24 and 48 h (MD - 0.15, 95% CI - 0.18 to - 0.12) and (MD - 0.26, 95% CI - 0.31 to - 0.21) between the ketamine and control (saline solution), respectively. No intergroup differences were found regarding nausea/vomiting and pruritus (OR 0.77, 95% CI 0.35 to 1.67) and (OR 0.71, 95% CI 0.31 to 1.62), respectively, same as for the pain score (MD - 0.75, 95% CI - 1.71 to 0.20). CONCLUSIONS: The use intraoperative and postoperative continuous low doses of ketamine significantly reduces opioid use throughout the first 48 h in patients with AIS who undergo posterior spinal fusion.

Effect of a prioritization score on the inter-hospital transfer time management of severe COVID-19 patients: a quasi-experimental intervention study.

BACKGROUND: The overburdening of the healthcare system during the coronavirus disease 19 (COVID-19) pandemic is driving the need to create new tools to improve the management of inter-hospital transport for patients with a severe COVID-19 infection. OBJECTIVE: The aim of this study was to analyse the usefulness of the application of a prioritization score (IHTCOVID-19) for inter-hospital transfer of patients with COVID-19 infection. METHODS: The study has a quasi-experimental design and was conducted on the Medical Emergency System, the pre-hospital emergency department of the public company belonging to the Autonomous Government of Catalonia that manages urgent healthcare in the region. Patients with a severe COVID-19 infection requiring inter-hospital transport were consecutively included. The pre-intervention period was from 1 to 31 March 2020, and the intervention period with the IHTCOVID-19 score was from 1 to 30 April 2020 (from 8 am to 8 pm). The prioritization score comprises four priority categories, with Priority 0 being the highest and Priority 3 being the lowest. Inter-hospital transfer (IHT) management times (alert-assignment time, resource management time and total central management time) and their variability were evaluated according to whether or not the IHTCOVID-19 score was applied. RESULTS: A total of 344 IHTs were included: 189 (54.9%) in the pre-intervention period and 155 (45.1%) in the post-intervention period. The majority of patients were male and the most frequent age range was between 50 and 70 years. According to the IHTCOVID-19 score, 12 (3.5%) transfers were classified as Priority 0, 66 (19.4%) as Priority 1, 247 (71.8%) as Priority 2 and 19 (5.6%) as Priority 3. Overall, with the application of the IHTCOVID-19 score, there was a significant reduction in total central management time [from 112.4 (inter-quartile range (IQR) 281.3) to 89.8 min (IQR 154.9); P = 0.012]. This significant reduction was observed in Priority 0 patients [286.2 (IQR 218.5) to 42.0 min (IQR 58); P = 0.018] and Priority 1 patients [130.3 (IQR 297.3) to 75.4 min (IQR 91.1); P = 0.034]. After applying the IHTCOVID-19 score, the average time of the process decreased by 22.6 min, and variability was reduced from 618.1 to 324.0 min. CONCLUSION: The application of the IHTCOVID-19 score in patients with a severe COVID-19 infection reduces IHT management times and variability.

Evaluation of Adding Natural Gum to Pectin Extracted from Ecuadorian Citrus Peels as an Eco-Friendly Corrosion Inhibitor for Carbon Steel.

The production and use of eco-friendly corrosion inhibitors allows valuable compounds contained in plant waste to be identified and repurposed while reducing the use of polluting synthetic substances. Pectin extracted from Tahiti limes (Citrus latifolia) and King mandarin (Citrus nobilis L.) in addition to natural gums-xanthan gum and latex from the "lechero" plant (Euphorbia laurifolia)-were used to create an eco-friendly corrosion inhibitor. The optimal extraction conditions for pectin were determined from different combinations of pH, temperature, and time in a 23 factorial design and evaluated according to the obtained pectin yield. The highest pectin extraction yields (38.10% and 41.20% from King mandarin and lime, respectively) were reached at pH = 1, 85 °C, and 2 h. Extraction of pectic compounds was confirmed using Fourier-transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetry analyses. Subsequently, a simplex-centroid mixture design was applied to determine the formulation of extracted pectin and natural gums that achieved the highest corrosion inhibitor effect (linear polarization and weight loss methods in NACE 1D-196 saline media using API-5LX52 carbon steel). Impedance spectroscopy analysis showed that the addition of xanthan gum to pectin (formulation 50% pectin-50% xanthan gum) improved the corrosion inhibitor effect from 29.20 to 78.21% at 400 ppm due to higher adsorption of inhibitory molecules on the metal surface.

Statistical-law formulas for zero- to two-electron-transfer probabilities in proton-molecule and proton cancer therapy reactions from electron nuclear dynamics theory.

We present the first quantum-mechanical derivation of statistical-law formulas to calculate zero- to two-electron transfers (ETs) in proton-molecule reactions. The original statistical derivation assumed that the n-ET probabilities of N electrons in a shell obey an N-trial binomial distribution with success probability equal to an individual one-ET probability; the latter was heuristically identified with the number of transferred electrons from the integrated charge density. The obtained formulas proved accurate to calculate ET cross sections in proton-molecule and proton cancer therapy (PCT) reactions. We adopt the electron nuclear dynamics (END) theory in our quantum-mechanical derivation due to its versatile description of ETs via a Thouless single-determinantal state. Since non-orthogonal Thouless dynamical spin-orbitals pose mathematical difficulties, we first present a derivation for a model system with N ≥ 2 electrons where only two with opposite spins are ET active; in that scheme, the Thouless dynamical spin-orbitals become orthogonal, a fact that facilitates a still intricate derivation. In the end, we obtain the number of transferred electrons from the Thouless state charge density and the ETs probabilities from the Thouless state resolution into projectile-molecule eigenstates describing ETs. We prove that those probabilities and numbers of electrons interrelate as in the statistical-law formulas via their common dependency on the Thouless variational parameters. We review past ET results of proton-molecule and PCT reactions obtained with these formulas in the END framework and present new results of H+ + N2O. We will present the derivation for systems with N > 2 electrons all active for ETs in a sequel.

Molecular Pathogenesis and Peripheral Monitoring of Adult Fragile X-Associated Syndromes.

Abnormal trinucleotide expansions cause rare disorders that compromise quality of life and, in some cases, lifespan. In particular, the expansions of the CGG-repeats stretch at the 5'-UTR of the Fragile X Mental Retardation 1 (FMR1) gene have pleiotropic effects that lead to a variety of Fragile X-associated syndromes: the neurodevelopmental Fragile X syndrome (FXS) in children, the late-onset neurodegenerative disorder Fragile X-associated tremor-ataxia syndrome (FXTAS) that mainly affects adult men, the Fragile X-associated primary ovarian insufficiency (FXPOI) in adult women, and a variety of psychiatric and affective disorders that are under the term of Fragile X-associated neuropsychiatric disorders (FXAND). In this review, we will describe the pathological mechanisms of the adult "gain-of-function" syndromes that are mainly caused by the toxic actions of CGG RNA and FMRpolyG peptide. There have been intensive attempts to identify reliable peripheral biomarkers to assess disease progression and onset of specific pathological traits. Mitochondrial dysfunction, altered miRNA expression, endocrine system failure, and impairment of the GABAergic transmission are some of the affectations that are susceptible to be tracked using peripheral blood for monitoring of the motor, cognitive, psychiatric and reproductive impairment of the CGG-expansion carriers. We provided some illustrative examples from our own cohort. Understanding the association between molecular pathogenesis and biomarkers dynamics will improve effective prognosis and clinical management of CGG-expansion carriers.

Efficacy of the bivalent HPV vaccine against HPV 16/18-associated precancer: long-term follow-up results from the Costa Rica Vaccine Trial.

BACKGROUND: Oncogenic human papillomavirus (HPV) infections cause most cases of cervical cancer. Here, we report long-term follow-up results for the Costa Rica Vaccine Trial (publicly funded and initiated before licensure of the HPV vaccines), with the aim of assessing the efficacy of the bivalent HPV vaccine for preventing HPV 16/18-associated cervical intraepithelial neoplasia grade 2 or worse (CIN2+). METHODS: Women aged 18-25 years were enrolled in a randomised, double-blind, controlled trial in Costa Rica, between June 28, 2004, and Dec 21, 2005, designed to assess the efficacy of a bivalent vaccine for the prevention of infection with HPV 16/18 and associated precancerous lesions at the cervix. Participants were randomly assigned (1:1) to receive an HPV 16/18 AS04-adjuvanted vaccine or control hepatitis A vaccine. Vaccines were administered intramuscularly in three 0·5 mL doses at 0, 1, and 6 months and participants were followed up annually for 4 years. After the blinded phase, women in the HPV vaccine group were invited to enrol in the long-term follow-up study, which extended follow-up for 7 additional years. The control group received HPV vaccine and was replaced with a new unvaccinated control group. Women were followed up every 2 years until year 11. Investigators and patients were aware of treatment allocation for the follow-up phase. At each visit, clinicians collected cervical cells from sexually active women for cytology and HPV testing. Women with abnormal cytology were referred to colposcopy, biopsy, and treatment as needed. Women with negative results at the last screening visit (year 11) exited the long-term follow-up study. The analytical cohort for vaccine efficacy included women who were HPV 16/18 DNA-negative at vaccination. The primary outcome of this analysis was defined as histopathologically confirmed CIN2+ or cervical intraepithelial neoplasia grade 3 or worse associated with HPV 16/18 cervical infection detected at colposcopy referral. We calculated vaccine efficacy by year and cumulatively. This long-term follow-up study is registered with ClinicalTrials.gov, NCT00867464. FINDINGS: 7466 women were enrolled in the Costa Rica Vaccine Trial; 3727 received the HPV vaccine and 3739 received the control vaccine. Between March 30, 2009, and July 5, 2012, 2635 women in the HPV vaccine group and 2836 women in the new unvaccinated control group were enrolled in the long-term follow-up study. 2635 women in the HPV vaccine group and 2677 women in the control group were included in the analysis cohort for years 0-4, and 2073 women from the HPV vaccine group and 2530 women from the new unvaccinated control group were included in the analysis cohort for years 7-11. Median follow-up time for the HPV group was 11·1 years (IQR 9·1-11·7), 4·6 years (4·3-5·3) for the original control group, and 6·2 years (5·5-6·9) for the new unvaccinated control group. At year 11, vaccine efficacy against incident HPV 16/18-associated CIN2+ was 100% (95% CI 89·2-100·0); 34 (1·5%) of 2233 unvaccinated women had a CIN2+ outcome compared with none of 1913 women in the HPV group. Cumulative vaccine efficacy against HPV 16/18-associated CIN2+ over the 11-year period was 97·4% (95% CI 88·0-99·6). Similar protection was observed against HPV 16/18-associated CIN3-specifically at year 11, vaccine efficacy was 100% (95% CI 78·8-100·0) and cumulative vaccine efficacy was 94·9% (73·7-99·4). During the long-term follow-up, no serious adverse events occurred that were deemed related to the HPV vaccine. The most common grade 3 or worse serious adverse events were pregnancy, puerperium, and perinatal conditions (in 255 [10%] of 2530 women in the unvaccinated control group and 201 [10%] of 2073 women in the HPV vaccine group). Four women in the unvaccinated control group and three in the HPV vaccine group died; no deaths were deemed to be related to the HPV vaccine. INTERPRETATION: The bivalent HPV vaccine has high efficacy against HPV 16/18-associated precancer for more than a decade after initial vaccination, supporting the notion that invasive cervical cancer is preventable. FUNDING: US National Cancer Institute.

Electron nuclear dynamics of H+ + CO2 (000) → H+ + CO2 (v1v2v3) at ELab = 20.5-30 eV with coherent-states quantum reconstruction procedure.

The simplest-level electron nuclear dynamics (SLEND) method with the coherent-states (CSs) quantum reconstruction procedure (CSQRP) is applied to the scattering system H+ + CO2 (000) → H+ + CO2 (v1v2v3) at ELab = 20.5-30 eV. Relevant for astrophysics, atmospheric chemistry and proton cancer therapy, this system undergoes collision-induced vibrational excitations in CO2. SLEND is a time-dependent, variational, direct, and non-adiabatic method that adopts a classical-mechanics description for nuclei and a single-determinantal wavefunction for electrons. The CSQRP employs the canonical CS to reconstruct quantum state-to-state vibrational properties from the SLEND classical nuclear dynamics. Overall, the calculated collision-induced vibrational properties agree well with experimental data. SLEND total differential cross sections (DCSs) agree remarkably well with their experimental counterparts and accurately display rainbow scattering angles structures. SLEND averaged target excitation energies for vibrational + rotational and rotational motions exhibit reasonable and good agreements with experimental data, respectively. These properties show that rotational excitation is low and that the asymmetric stretch normal mode of CO2 is much more excited than the others. SLEND/CSQRP state-to-state vibrational DCSs agree reasonably well with the sparse experimental data for final states v1v2v3 = 000-002, but less satisfactorily for 003. These DCSs also accurately display rainbow scattering angles structures. Finally, SLEND/CSQRP vibrational proton energy loss spectra agree remarkably well with their experimental counterparts for various final vibrational states of CO2, collisions energies and scattering angles. Present results demonstrate the accuracy of SLEND/CSQRP to predict state-to-state vibrational properties in scattering systems with multiple normal modes.

Temporally stable rotational coherent states for molecular simulations. I. Spherical and linear rotor cases.

We reformulate a previous rotational coherent state (CS) to obtain temporally stable (TS) CSs for the spherical rotor (SR) and linear rotor (LR): TSSR and TSLR CSs, respectively. Being TS, the new CSs remain within their own classes during dynamics by evolving exclusively through their CS parameters. The new TS CSs are now appropriate to reconstruct quantum rotational properties from classical-mechanics simulations of chemical reactions. Following literature precedents, we enforce temporal stability by incorporating action-angle-related phase factors into the parameters of the original CS. In addition, to elucidate CS quantum reconstruction procedures, we derive one more rotational CS from a quantum electron nuclear dynamics description of a diatomic rotor (DR). The DR CS and the TSLR CS are not identical but display similar structures and properties. We rigorously demonstrate and examine the key properties of the three CSs: continuity, resolution of unity, temporal stability, action identity, minimum uncertainty relationships, and quasi-classical behavior. Finally, we present computer simulations of the CSs dynamics and an application of them to predict CO rotational excitation probabilities in the Li+ + CO reaction. CS results agree satisfactorily with experimental ones and encourage future applications in chemical dynamics, statistical mechanics, spectroscopy, nuclear physics, quantum coherence, and quantum computing.