Discovery and Optimization of Tambjamines as a Novel Class of Antileishmanial Agents.

Leishmaniasis is a neglected tropical disease that is estimated to afflict over 12 million people. Current drugs for leishmaniasis suffer from serious deficiencies, including toxicity, high cost, modest efficacy, primarily parenteral delivery, and emergence of widespread resistance. We have discovered and developed a natural product-inspired tambjamine chemotype, known to be effective against Plasmodium spp, as a novel class of antileishmanial agents. Herein, we report in vitro and in vivo antileishmanial activities, detailed structure-activity relationships, and metabolic/pharmacokinetic profiles of a large library of tambjamines. A number of tambjamines exhibited excellent potency against both Leishmania mexicana and Leishmania donovani parasites with good safety and metabolic profiles. Notably, tambjamine 110 offered excellent potency and provided partial protection to leishmania-infected mice at 40 and/or 60 mg/kg/10 days of oral treatment. This study presents the first account of antileishmanial activity in the tambjamine family and paves the way for the generation of new oral antileishmanial drugs.

SERS-Based Sensor Using Subnanometric Copper-Silver Mixed Clusters Ag(8-n)Cun (n = 0-8) for Pyridine: A DFT Study.

Surface-enhanced Raman spectroscopy (SERS) is a powerful Raman technique that provides high selectivity and sensitivity in analyzing the intermolecular interaction of a target compound adsorbed on the surface of a noble nanomaterial, i.e., silver, gold, or copper. Although copper presents a better SERS enhancement than gold and silver, its oxidation in the air is much easier than that of gold and silver. A mixed material between these metals may potentially improve the SERS signal enhancement in this context. In this work, we evaluated the SERS spectra of pyridine (Py) adsorbed on the copper-silver mixed clusters Ag(8-n)Cun (n = 0-8) using density functional theory (DFT) at the PBE functional. The cc-pVDZ-PP basis set was chosen for Ag and Cu, while the cc-pVDZ basis set was used for C, N, and H atoms. Geometrical and electronic structures of the mixed clusters and the Py adsorption configuration on these clusters were computed. The calculated SERS spectra then revealed the influence of the Ag/Cu mixing ratio on the SERS enhancement. As a result, the substituted copper atoms on the silver cluster turned out to be favorable adsorption sites for Py. Interestingly, when the number of Cu atoms increased from n = 0 (pure Ag8 cluster) to n = 5 (Ag3Cu5 cluster), the ring stretching peak (1590 cm-1) of Py significantly increased from 20 to 120 au and then saturated around this value despite increasing the Cu atom number to 8 (pure Cu8 cluster). This observation was extended for other ligands such as pyrazine and 3H-pyrrole. TD-DFT was then employed to clarify the chemical enhancement mechanism. The results obtained hopefully provide helpful information for the design of analytical sensors with lower costs.

Morphological Characteristics of the Vietnamese Adult Human Acetabulum Using Multiplanar Reconstruction Computed Tomography in Total Hip Replacement Surgery.

Background: The anatomical parameters of the acetabulum vary among races and geographical regions. Multislice Computed Tomography (CT) has proven to be a practical approach to assess morphological parameters of the acetabulum. The purpose of this study was to explore morphological characteristics of the acetabulum measured by CT scans in Vietnamese adults. Methods: Thirty-five consecutive patients aged 18 years and older received indications and eligibility for total hip replacement surgery. Sixty-three acetabulum were examined with multislice computed tomographic system (CT) with multiplanar reconstruction (MPR). Measured morphometric parameters of acetabulum included acetabular inclination angle (AIA), acetabular anteversion angle (AAA), acetabular angle of sharp (AAS), sagittal acetabular angle (SAA), acetabular horizontal offset (AHO), transverse acetabular ligament anteversion (TALA), transverse acetabular ligament inclination (TALI), acetabular depth (ADe), acetabular depth ratio (ADr) and acetabular diameter (ADi). Results: The mean values of acetabular diameter, femoral head diameter, AIA, AAA, AAS, SAA, TALA, TALI, AHO, ADe, ADr were 50.22±3.56 mm, 43.54±3.68 mm, 40.27±5.09 mm, 13.30±5.54 mm, 39.46±5.41 mm, 26.38±9.01 mm, 9.49±3.92 mm, 47.70±6.73 mm, 3.06±0.37 mm, 18.62±2.95 mm and 309.60±41.87 mm. Conclusion: Our initial data has showed morphological characteristics of the acetabulum in Vietnamese adults, different from the populations from other parts of world. Also, significant correlation between the orientation of the acetabulum and the transverse acetabular ligament was documented.

Diagnostic algorithm for glioma grading using dynamic susceptibility contrast­enhanced magnetic resonance perfusion and proton magnetic resonance spectroscopy.

The present retrospective study aimed to investigate the diagnostic capacity of and design a diagnostic algorithm for dynamic susceptibility contrast-enhanced MRI (DSCE-MRI) and proton magnetic resonance spectroscopy (1H-MRS) in grading low-grade glioma (LGG) and high-grade glioma (HGG). This retrospective study enrolled 57 patients, of which 14 had LGG and 43 had HGG, five had World Health Organization grade 1, nine had grade 2, 20 had grade 3 and 23 had grade 4 glioma. All subjects underwent a standard 3T MRI brain tumor protocol with conventional MRI (cMRI) and advanced techniques, including DSCE-MRI and 1H-MRS. The associations of grade categorization with parameters in tumor and peritumor regions in the DSCE-MRI were examined, including tumor relative cerebral blood volume (TrCBV) and peripheral relative (Pr)CBV, as well as Tr and Pr cerebral blood flow (CBF) and 1H-MRS, including the creatine (Cr) and N-acetyl aspartate (NAA) ratios of choline (Cho), i.e. the TCho/NAA, PCho/NAA, TCho/Cr and PCho/Cr metabolite ratios. The data were compared using the Mann-Whitney U-test, independent samples t-test, Chi-square test, Fisher's exact test and receiver operating characteristic curve analyses. Decision tree analysis established an algorithm based on cutoffs for specified significant parameters. The PrCBF had the highest performance in the preoperative prediction of histological glioma grading, followed by the TrCBV, PrCBF, TrCBV, PCho/NAA, PCho/Cr, TCho/NAA and TCho/Cr. An algorithm based on TrCBV, PrCBF and TCho/Cr had a diagnostic accuracy of 100% for LGG and 90.7% for HGG and a misclassification risk of 7%. The cutoffs (sensitivity and specificity) were 2.48 (86 and 100%) for TrCBV, 1.26 (83.7 and 100%) for PrCBF and 3.18 (69.8 and 78.6%) for TCho/Cr. In conclusion, the diagnostic algorithm using TrCBV, PrCBF and TCho/Cr values, which were obtained from DSCE-MRI and 1H-MRS, increased diagnostic accuracy to 100% for LGGs and 90.7% for HGGs compared to previous studies using conventional MRI. This non-invasive advanced MRI diagnostic algorithm is recommended for clinical application for constructing preoperative strategies and prognosis of patients with glioma.

Theoretical insights into the HO●-induced oxidation of chlorpyrifos pesticide: Mechanism, kinetics, ecotoxicity, and cholinesterase inhibition of degradants.

The oxidation of the common pesticide chlorpyrifos (CPF) initiated by HO● radical and the risks of its degradation products were studied in the gaseous and aqueous phases via computational approaches. Oxidation mechanisms were investigated, including H-, Cl-, CH3- abstraction, HO●-addition, and single electron transfer. In both phases, HO●-addition at the C of the pyridyl ring is the most energetically favorable and spontaneous reaction, followed by H-abstraction reactions at methylene groups (i.e., at H19/H21 in the gas phase and H22/H28 in water). In contrast, other abstractions and electron transfer reactions are unfavorable. However, regarding the kinetics, the significant contribution to the oxidation of CPF is made from H-abstraction channels, mostly at the hydrogens of the methylene groups. CPF can be decomposed in a short time (5-8 h) in the gas phase, and it is more persistent in natural water with a lifetime between 24 days and 66 years, depending on the temperature and HO● concentration. Subsequent oxidation of the essential radical products with other oxidizing reagents, i.e., HO●, NO2●, NO●, and 3O2, gave primary neutral products P1-P15. Acute and chronic toxicity calculations estimate very toxic levels for CPF and two degradation products, P7w and P12w, in aquatic systems. The neurotoxicity of these products was investigated by docking and molecular dynamics. P7w and P12w show the most significant binding scores with acetylcholinesterases, while P8w and P13w are with butyrylcholinesterase enzyme. Finally, molecular dynamics illustrate stable interactions between CPF degradants and cholinesterase enzyme over a 100 ns time frame and determine P7w as the riskiest degradant to the neural developmental system.

Prospective association of attachment style with suicide attempts among US Army soldiers.

BACKGROUND: Insecure attachment styles are associated with retrospectively reported suicide attempts (SAs). It is not known if attachment styles are prospectively associated with medically documented SAs. METHODS: A representative sample of US Army soldiers entering service (n = 21 772) was surveyed and followed via administrative records for their first 48 months of service. Attachment style (secure, preoccupied, fearful, dismissing) was assessed at baseline. Administrative medical records identified SAs. Discrete-time survival analysis examined associations of attachment style with future SA during service, adjusting for time in service, socio-demographics, service-related variables, and mental health diagnosis (MH-Dx). We examined whether associations of attachment style with SA differed based on sex and MH-Dx. RESULTS: In total, 253 respondents attempted suicide. Endorsed attachment styles included secure (46.8%), preoccupied (9.1%), fearful (15.7%), and dismissing (19.2%). Examined separately, insecure attachment styles were associated with increased odds of SA: preoccupied [OR 2.5 (95% CI 1.7-3.4)], fearful [OR 1.6 (95% CI 1.1-2.3)], dismissing [OR 1.8 (95% CI 1.3-2.6)]. Examining attachment styles simultaneously along with other covariates, preoccupied [OR 1.9 (95% CI 1.4-2.7)] and dismissing [OR 1.7 (95% CI 1.2-2.4)] remained significant. The dismissing attachment and MH-Dx interaction was significant. In stratified analyses, dismissing attachment was associated with SA only among soldiers without MH-Dx. Other interactions were non-significant. Soldiers endorsing any insecure attachment style had elevated SA risk across the first 48 months in service, particularly during the first 12 months. CONCLUSIONS: Insecure attachment styles, particularly preoccupied and dismissing, are associated with increased future SA risk among soldiers. Elevated risk is most substantial during first year of service but persists through the first 48 months. Dismissing attachment may indicate risk specifically among soldiers not identified by the mental healthcare system.

New insight into environmental oxidation of phosmet insecticide initiated by HO˙ radicals in gas and water - a theoretical study.

Phosmet is an organophosphorus insecticide widely used in agriculture to control a range of insects; recently, it was banned by the European Union in 2022 due to its harmful effects. However, its environmental degradation and fate have not yet been evident. Thus, phosmet oxidation by HO˙ radicals was theoretically studied in this work using the DFT approach at the M06-2X/6-311++G(3df,3pd)//M06-2X/6-31+G(d,p) level of theory. Three different mechanisms were considered, including formal hydrogen transfer (FHT), radical adduct formation (RAF), and single electron transfer (SET). The mechanisms, kinetics, and lifetime were studied in the gas and aqueous phases, in addition to its ecotoxicity evaluation. The results show that FHT reactions were dominant in the gas phase, while RAF was more favourable in the aqueous phase at 298 K, while SET was negligible. The branching ratio indicated that H-abstractions at the methyl and the methylene groups were the most predominant, while the most favourable HO˙-addition was observed at the phosphorus atom of the dithiophosphate group. The overall rate constant values varied from 1.2 × 109 (at 283 K) to 1.40 × 109 M-1 s-1 (at 323 K) in the aqueous phase and from 6.29 × 1010 (at 253 K) to 1.32 × 1010 M-1 s-1 (at 323 K) in the gas phase. The atmospheric lifetime of phosmet is about 6 hours at 287 K, while it can persist from a few seconds to several years depending on the temperature and [HO˙] concentration in the aqueous environment. The QSAR-based ecotoxicity evaluation indicates that phosmet and its degradation products are all dangerous to aquatic organisms, although the products are less toxic than phosmet. However, they are generally developmental toxicants and mutagenicity-negative compounds.

Security-Reliability Analysis of AF Full-Duplex Relay Networks Using Self-Energy Recycling and Deep Neural Networks.

This paper investigates the security-reliability of simultaneous wireless information and power transfer (SWIPT)-assisted amplify-and-forward (AF) full-duplex (FD) relay networks. In practice, an AF-FD relay harvests energy from the source (S) using the power-splitting (PS) protocol. We propose an analysis of the related reliability and security by deriving closed-form formulas for outage probability (OP) and intercept probability (IP). The next contribution of this research is an asymptotic analysis of OP and IP, which was generated to obtain more insight into important system parameters. We validate the analytical formulas and analyze the impact on the key system parameters using Monte Carlo simulations. Finally, we propose a deep learning network (DNN) with minimal computation complexity and great accuracy for OP and IP predictions. The effects of the system's primary parameters on OP and IP are examined and described, along with the numerical data.

Predictors of suicide attempt within 30 days of first medically documented major depression diagnosis in U.S. army soldiers with no prior suicidal ideation.

BACKGROUND: Understanding mental health predictors of imminent suicide attempt (SA; within 30 days) among soldiers with depression and no prior suicide ideation (SI) can inform prevention and treatment. The current study aimed to identify sociodemographic and service-related characteristics and mental disorder predictors associated with imminent SA among U.S. Army soldiers following first documented major depression diagnosis (MDD) with no history of SI. METHODS: In this case-control study using Army Study to Assess Risk and Resilience in Servicemembers (STARRS) administrative data, we identified 101,046 active-duty Regular Army enlisted soldiers (2010-2016) with medically-documented MDD and no prior SI (MDD/No-SI). We examined risk factors for SA within 30 days of first MDD/No-SI using logistic regression analyses, including socio-demographic/service-related characteristics and psychiatric diagnoses. RESULTS: The 101,046 soldiers with documented MDD/No-SI were primarily male (78.0%), < 29 years old (63.9%), White (58.1%), high school-educated (74.5%), currently married (62.0%) and < 21 when first entering the Army (56.9%). Among soldiers with MDD/No-SI, 2,600 (2.6%) subsequently attempted suicide, 16.2% (n = 421) within 30 days (rate: 416.6/100,000). Our final multivariable model identified: Soldiers with less than high school education (χ23 = 11.21, OR = 1.5[95%CI = 1.2-1.9]); combat medics (χ22 = 8.95, OR = 1.5[95%CI = 1.1-2.2]); bipolar disorder (OR = 3.1[95%CI = 1.5-6.3]), traumatic stress (i.e., acute reaction to stress/not PTSD; OR = 2.6[95%CI = 1.4-4.8]), and "other" diagnosis (e.g., unspecified mental disorder: OR = 5.5[95%CI = 3.8-8.0]) diagnosed same day as MDD; and those with alcohol use disorder (OR = 1.4[95%CI = 1.0-1.8]) and somatoform/dissociative disorders (OR = 1.7[95%CI = 1.0-2.8]) diagnosed before MDD were more likely to attempt suicide within 30 days. Currently married soldiers (χ22 = 6.68, OR = 0.7[95%CI = 0.6-0.9]), those in service 10 + years (χ23 = 10.06, OR = 0.4[95%CI = 0.2-0.7]), and a sleep disorder diagnosed same day as MDD (OR = 0.3[95%CI = 0.1-0.9]) were less likely. CONCLUSIONS: SA risk within 30 days following first MDD is more likely among soldiers with less education, combat medics, and bipolar disorder, traumatic stress, and "other" disorder the same day as MDD, and alcohol use disorder and somatoform/dissociative disorders before MDD. These factors identify imminent SA risk and can be indicators for early intervention.

Revisiting the HO●-initiated oxidation of L-proline amino acid in the aqueous phase: influence of transition metal ions.

The oxidation of L-proline (Pro) by HO● radical in water and the influence of transition metal ions on this process has been revisited by using the density functional theory (DFT) method at the M05-2X/6-311 + + G(3df,3pd)//M05-2X/6-311 + + G(d,p) level of theory at the temperature of 298.15 K. The main reactive sites of the HO●-initiated oxidation of Pro via hydrogen atom transfer (HAT) reactions are at the ß- and γ-carbon, with the branching ratios being 44.6% and 39.5%, respectively. The overall rate constant at 298.15 K is 6.04 × 108 M-1 s-1. In addition, Pro tends to form stable complexes with both Fe and Cu ions via the -COO functional group of dipole-salt form. The most stable Cu(II)-Pro complexes have high oxidant risks in enhancing the HO● formation in the presence of reducing agents. Besides this, the high oxidation state metal complexes, i.e. Fe(III)-Pro and Cu(II)-Pro, may be oxidized by HO● radical via HAT reactions but with a lower rate constant than that of free-Pro. By contrast, the low oxidation state metal complexes (i.e. Fe(II)-Pro and Cu(I)-Pro) have higher oxidation risks than the free ligands, and thus, the complexation enhances the oxidation of Pro amino acid.

Understanding a Time of High Risk for Suicide: Adversities Associated with Separation from Military Service among National Guard and Reserve Service Members.

OBJECTIVE: The purpose was to examine five types of adversity and their associations with separating from military service among a nationally representative sample of U.S. National Guard and Reserve (NGR) service members. METHODS: Multivariate logistic regression analyses were conducted to examine the association between separating from the service and adversities, and demographic differences in adversities experienced among those who had separated from the service and those who stayed in the service. RESULTS: Those who left the military were more likely to report financial (OR = 1.65, 95% CI = 1.01-2.70) and healthcare access problems (OR = 2.21, 95% CI = 1.10-4.46). Among those who left the military, female service members were more likely to experience interpersonal adversity (OR = 4.28, 95% CI = 1.15-15.87), and Army and Marine service members were more likely to experience job-employment adversity (OR = 4.92, 95% CI = 1.50-16.12) and financial adversity (OR = 6.46, 95% CI = 1.22-34.33). CONCLUSION: Separating service members experience financial adversity and challenges with healthcare access. Interpersonal difficulties are particularly experienced by female service members, and job/employment difficulties experienced by Army and Marine veterans. Continued efforts are needed to facilitate service delivery for NGR separating service members who need them.

Predictive Value of Preoperative Diffusion Tensor Imaging for Evaluating Postoperative Outcomes of Supratentorial Glioma in the Motor Function Area.

Objective: This study aimed to assess the predictive value of preoperative diffusion tensor imaging (DTI) data for surgical outcomes of patients with supratentorial glioma in the motor function area. Patients and Methods: This is a retrospective study of 43 patients receiving navigation-guided surgery for histopathologically demonstrated supratentorial glioma in the motor function area. All patients underwent preoperative 3 Tesla magnetic resonance imaging examinations with conventional and DTI sequences. Data on preoperative imaging and pre- and postoperative clinical characteristics of patients were retrospectively collected. Univariate and multivariate linear regressions were applied to analyze the relationships between preoperative parameters and pre- and postoperative muscle strength and the Karnofsky Performance Status (KPS) score. Results: Fourteen patients had low-grade gliomas and 29 had high-grade gliomas. Although the corticospinal tract (CST) score did not differ significantly between tumor grades, edema and deviation were common in low-grade gliomas (64.3%), while destroyed and infiltrated lesions were common in high-grade gliomas (58.6%). Muscle strength improved after surgery in the deviated tract group (40%) more than in the infiltrated tract group (33.3%). Two independent indices, preoperative muscle strength (p = 0.000) and glioma-to-CST distance (p = 0.001), were linearly related to postoperative muscle strength. The preoperative KPS score was the only indicator that affected the postoperative KPS score (p = 0.000). Conclusion: DTI should be considered in surgical management of supratentorial gliomas in the motor function area to determine the appropriate surgical strategy and predict the nature of the tumor and postoperative motor function.

Neutralization Short-Circuiting with Weak Electrolytes Erodes the Efficiency of Bipolar Membranes.

Bipolar membranes (BPMs) are critical components of a variety of electrochemical energy technologies. Many electrochemical applications require the use of buffers to maintain stable, nonextreme pH environments, yet the impact of buffers or weak acids/bases on the electrochemical behavior of BPMs remains poorly understood. Our data for a cell containing weak electrolytes is consistent with internal pH gradients within the anion exchange membrane (AEM) or cation exchange membrane (CEM) component of the BPM that form via ionic short-circuiting processes at open-circuit. Short-circuiting results from the coupling of co-ion crossover and parasitic neutralization and leads to buffering of the bipolar interface. This phenomenon, which we term neutralization short-circuiting, serves to erode BPM efficiency by attenuating the open-circuit membrane voltage and introducing parasitic reverse bias currents associated with weak acid/base dissociation at the interface. These findings establish a mechanistic basis for the operation of BPM cells in the presence of weak acid/base electrolytes.

Hydroxyl radical-initiated decomposition of metazachlor herbicide in the gaseous and aqueous phases: Mechanism, kinetics, and toxicity evaluation.

The oxidation of widely-used herbicide metazachlor (MTZ) by hydroxyl radical (HO•) in the gas and the aqueous phases was investigated in terms of mechanistic and kinetic behaviors using the M06-2X/6-311++G (3df, 3pd)//M06-2X/6-31 + G (d,p) level of theory over the temperature range 250-400 K. The formal hydrogen transfer, HO•-addition, and single electron transfer mechanisms were considered. The overall rate constants in the gas phase range from 8.40 × 1010 to 8.31 × 109 M-1 s-1 at the temperature from 250 to 400 K, respectively, while the ones in the aqueous phase are close to diffusion-controlled rates, with diffusion-corrected rate constants being 1.31 × 109 to 1.27 × 109 M-1 s-1. The formal hydrogen transfer mechanism is the most dominant in the gas phase, whereas the HO•-addition is the most favorable in the aqueous phase. The H-abstraction at two methyl groups and the HO•-addition to C11 and C12 atoms (pyrazole ring), C16 and C18 atoms (benzyl ring) are significant. The short lifetime in the environment, equal to only 4.16 h, requires more attention to this herbicide compound, whereas its lifetime in the aqueous condition varies sharply from half second to several thousand days depending on the HO• concentration. The ecotoxicity estimation of MTZ and its principal transformation products to aquatic organisms suggests that they are harmful or toxic substances. Moreover, the MTZ is a developmental toxicant and mutagenicity-positive, while its decomposed products are developmental toxicants with no mutagenic toxicity. Their bioaccumulation in aquatic organisms is negligible.

Prospective associations of emotion reactivity and risk behaviors with suicide attempts in US Army soldiers.

BACKGROUND: Emotion reactivity and risk behaviors (ERRB) are transdiagnostic dimensions associated with suicide attempt (SA). ERRB patterns may identify individuals at increased risk of future SAs. METHODS: A representative sample of US Army soldiers entering basic combat training (n = 21 772) was surveyed and followed via administrative records for their first 48 months of service. Latent profile analysis of baseline survey items assessing ERRB dimensions, including emotion reactivity, impulsivity, and risk-taking behaviors, identified distinct response patterns (classes). SAs were identified using administrative medical records. A discrete-time survival framework was used to examine associations of ERRB classes with subsequent SA during the first 48 months of service, adjusting for time in service, socio-demographic and service-related variables, and mental health diagnosis (MH-Dx). We examined whether associations of ERRB classes with SA differed by year of service and for soldiers with and without a MH-Dx. RESULTS: Of 21 772 respondents (86.2% male, 61.8% White non-Hispanic), 253 made a SA. Four ERRB classes were identified: 'Indirect Harming' (8.9% of soldiers), 'Impulsive' (19.3%), 'Risk-Taking' (16.3%), and 'Low ERRB' (55.6%). Compared to Low ERRB, Impulsive [OR 1.8 (95% CI 1.3-2.4)] and Risk-Taking [OR 1.6 (95% CI 1.1-2.2)] had higher odds of SA after adjusting for covariates. The ERRB class and MH-Dx interaction was non-significant. Within each class, SA risk varied across service time. CONCLUSIONS: SA risk within the four identified ERRB classes varied across service time. Impulsive and Risk-Taking soldiers had increased risk of future SA. MH-Dx did not modify these associations, which may therefore help identify risk in those not yet receiving mental healthcare.

Detection of Arterial Injuries in Blunt Abdominopelvic Trauma: The Value of Computed Tomography.

Background: This study aims to evaluate the value of computed tomography (CT) in detecting arterial injuries in abdominopelvic trauma compared with digital subtraction angiography (DSA). Methods: A retrospective study was performed on 83 patients (67 men, 16 women with a mean age of 38.2 years) who were hospitalized with abdominopelvic trauma and were diagnosed by CT with arterial injuries including active extravasation (AE), pseudoaneurysm (PA), and arteriovenous fistula (AVF). The findings on the CT images were interpreted and its value as a diagnostic modality was analyzed compared with images taken from patients who underwent DSA from June 2020 to November 2021. Results: A total of 94 arterial lesions were observed on CT (54 AE, 37 PA, and 3 AVF). The sensitivity (Se), specificity (Sp), positive predictive values (PPV), and negative predictive values (NPV) on the arterial phase when diagnosing AE were 88.9%, 90%, 92.3%, and 85.7%, respectively, and 86.1%, 91.4 %, 86.1%, and 91.4%, respectively, when diagnosing PA. On the portal venous phase, the Se, Sp, PPV, NPV for AE were 88.9%, 92.5%, 94.1%, and 86.0%, respectively, and 75%, 91.4%, 84.4%, and 85.5%, respectively, for PA. On the dual phase, the Se, Sp, PPV, and NPV for AE were 92.6%, 90%, 92.6%, and 90%, respectively, 88.9%, 91.4%. 86.5%, and 93%, respectively, for PA, and 75%, 100%, 100%, and 98.9%, respectively for AVF. Conclusions: Our study showed that CT is a useful, non-invasive modality for detecting arterial injuries in abdominopelvic trauma. A dual-phase scan combined with arterial and portal venous phases gives the optimal performance.

Oxidation of l-leucine amino acid initiated by hydroxyl radical: are transition metal ions an enhancement factor?

Hydroxyl radical (HO·) formation initiated by the Fenton-type reactions of Fe and Cu complexes of l-leucine (Leu) amino acid as well as its oxidation reaction by HO· was computationally investigated by using the density functional theory method at the M05-2X/6-311++G(3df,2pd)//M05-2X/6-311++G(d,p) level of theory in the aqueous phase. The results showed that dipole-salt is the main form of Leu in the physiological condition. Leu exhibits high chelating potential towards both Fe(III)/Fe(II) and Cu(II)/Cu(I) ions with the most favourable coordinating positions at two oxygen atoms of the -COO functional group. Furthermore, the Leu-ions complexes show a high risk of HO· formation via Fenton-like reactions, especially when ascorbate anion exists in the environment as a reducing agent. Finally, the oxidation reaction of l-leucine by HO· demonstrated a relatively high overall apparent reaction rate, k overall, being 1.18 × 109 M-1 s-1, in which formal hydrogen transfer reactions of the dipole-salt form occur as the primary mechanism. Consequently, the Leu oxidation by HO· radical can be promoted by the Fenton reaction enhancement of its transition metal complexes.

Association of Premilitary Mental Health With Suicide Attempts During US Army Service.

Importance: Approximately one-third of US soldiers who attempt suicide have not received a mental health diagnosis (MH-Dx) before their suicide attempt (SA), yet little is known about risk factors for SA in those with no MH-Dx. Objective: To examine whether premilitary mental health is associated with medically documented SA among US Army soldiers who do not receive an MH-Dx before their SA. Design, Setting, and Participants: This cohort study used data from a representative survey of soldiers in the US Army entering basic combat training from April 1, 2011, to November 30, 2012, who were followed up via administrative records for the first 48 months of service. Analyses were conducted from April 5, 2021, to January 21, 2022. Regular Army enlisted soldiers (n = 21 772) recruited from 3 US Army installations during the first week of service who agreed to have their administrative records linked to their survey responses were included. Exposures: Preenlistment lifetime history of mental disorder, suicide ideation, SA, and nonsuicidal self-injury (NSSI) as reported during the baseline survey. Service-acquired MH-Dx and sociodemographic and service-related variables were identified using administrative records. Main Outcomes and Measures: Documented SAs were identified using administrative medical records. Using a discrete-time survival framework, linear splines examined the pattern of SA risk over the first 48 months of service. Logistic regression analysis examined associations of lifetime baseline survey variables with subsequent, medically documented SA among soldiers who did vs did not receive an MH-Dx during service. Models were adjusted for time in service and sociodemographic and service-related variables. Results: Of the 21 722 respondents (86.2% male, 20.4% Black, 61.8% White non-Hispanic), 253 made an SA in the first 48 months of service (male [75.4%]; Black [22.7%], White non-Hispanic [59.9%], or other race or ethnicity [17.4%]). Risk of SA peaked toward the end of the first year of service for both those who did and did not receive an MH-Dx during service. Of the 42.3% of individuals reporting at least 1 of the 4 baseline risk factors, 50.2% received an administrative MH-Dx during service vs 41.5% of those with none, and 1.6% had a documented SA vs 1.0% of those with none. Among individuals with no MH-Dx, medically documented SAs were associated with suicide ideation (odds ratio [OR], 2.2; 95% CI, 1.1-4.4), SA (OR, 11.3; 95% CI, 4.3-29.2), and NSSI (OR, 3.0; 95% CI, 1.3-6.8). For those who received an MH-Dx, medically documented SAs were associated with mental disorder (OR, 1.4; 95% CI, 1.0-1.9), SA (OR, 3.4; 95% CI, 2.1-5.6), and NSSI (OR, 1.8; 95% CI, 1.1-2.8). Interactions indicated the only explanatory variable that differed based on history of MH-Dx was preenlistment SA (χ21 = 4.7; P = .03), which had a larger OR among soldiers with no MH-Dx than among those with an MH-Dx. Conclusions and Relevance: In this study, the period of greatest SA risk and baseline risk factors for SA were similar in soldiers with and without an MH-Dx. This finding suggests that knowledge of the time course and preenlistment mental health factors can equally aid in identifying SA risk in soldiers who do and do not receive an MH-Dx.

New insights into the competition between antioxidant activities and pro-oxidant risks of rosmarinic acid.

Direct and indirect antioxidant activities of rosmarinic acid (RA) based on HOO˙/CH3OO˙ radical scavenging and Fe(iii)/Fe(ii) ion chelation were theoretically studied using density functional theory at the M05-2X/6-311++G(2df,2p) level of theory. First, four antioxidant mechanisms including hydrogen atom transfer (HAT), radical adduct formation (RAF), proton loss (PL) and single electron transfer (SET) were investigated in water and pentyl ethanoate (PEA) phases. Regarding the free radical scavenging mechanism, HAT plays a decisive role with overall rate coefficients of 1.84 × 103 M-1 s-1 (HOO˙) and 4.49 × 103 M-1 s-1 (CH3OO˙) in water. In contrast to PL, RAF and especially SET processes, the HAT reaction in PEA is slightly more favorable than that in water. Second, the [Fe(iii)(H2O)6]3+ and [Fe(ii)(H2O)6]2+ ion chelating processes in an aqueous phase are both favorable and spontaneous especially at the O5, site-1, and site-2 positions with large negative Δr G 0 values and great formation constant K f. Finally, the pro-oxidant risk of RA- was also considered via the Fe(iii)-to-Fe(ii) complex reduction process, which may initiate Fenton-like reactions forming reactive HO˙ radicals. As a result, RA- does not enhance the reduction process when ascorbate anions are present as reducing agents, whereas the pro-oxidant risk becomes remarkable when superoxide anions are found. The results encourage further attempts to verify the speculation using more powerful research implementations of the antioxidant activities of rosmarinic acid in relationship with its possible pro-oxidant risks.

On the free radical scavenging and metallic ion chelating activities of pyridoxal - Could the pro-oxidant risk be competitive?

Primary and secondary antioxidant activities of pyridoxal have been investigated by using density functional theory (DFT) at the M05-2X level combined with 6-311++G(d,p) basis set for non-metallic atoms and LanL2DZ for metallic ions. The former has been examined by its free radical scavenging activity towards HOO●, HO●, and NO2●via different mechanisms including formal hydrogen transfer (FHT), proton transfer (PT), single electron transfer (SET), and radical adduct formation (RAF). The latter has been accomplished through its transition metal-chelating ability with Fe(III)/Fe(II) and Cu(II)/Cu(I) ions. The results show that pyridoxal illustrates as an efficient radical scavenger, especially, for HO● and NO2● in water. The overall rate constants (koverall) for the reactions with HOO●, HO●, and NO2● radicals are 1.30 × 104, 5.76 × 109, and 1.43 × 109 M-1s-1, respectively. The SET from the anionic state is the most dominant for the HOO● and NO2● scavenging reactions, while both RAF and SET contribute largely to the reaction with highly reactive HO● radicals. Moreover, the anionic form of pyridoxal demonstrates a better role as a metal chelator than the neutral. However, the pro-oxidant risks of the formed complexes could be observed if there are superoxide radical anion (O2●-) and ascorbate (Asc-) in aqueous media.