Metal-Free One-Pot Domino Synthesis of Oxazolidinethione Derivatives of Quaternary Amino Acids from α-Amino Esters and Aldehydes Using CS2.

We present a streamlined, metal-free, one-pot domino approach to efficiently synthesize oxazolidinethione derivatives containing substituted quaternary amino acids. This method employs α-amino esters, aldehydes, and CS2 under mild conditions, constructing three new bonds (C-N, C-C, and C-O) to produce oxazolidinethione compounds featuring a quaternary center and a beta-hydroxy derivative in high yields. This scalable protocol enables the creation of libraries of biologically significant, intricate amino acid derivatives using amino esters and aldehydes.

Applications of data envelopment analysis in acute care hospitals: a systematic literature review, 1984-2022.

This study reviews scholarly publications on data envelopment analysis (DEA) studies on acute care hospital (ACH) efficiency published between 1984 and 2022 in scholarly peer-reviewed journals. We employ systematic literature review (SLR) method to identify and analyze pertinent past research using predetermined steps. The SLR offers a comprehensive resource that meticulously analyzes DEA methodology for practitioners and researchers focusing on ACH efficiency measurement. The articles reviewed in the SLR are analyzed and synthesized based on the nature of the DEA modelling process and the key findings from the DEA models. The key findings from the DEA models are presented under the following sections: effects of different ownership structures; impacts of specific healthcare reforms or other policy interventions; international and multi-state comparisons; effects of changes in competitive environment; impacts of new technology implementations; effects of hospital location; impacts of quality management interventions; impact of COVID-19 on hospital performance; impact of teaching status, and impact of merger. Furthermore, the nature of DEA modelling process focuses on use of sensitivity analysis; choice of inputs and outputs; comparison with Stochastic Frontier Analysis; use of congestion analysis; use of bootstrapping; imposition of weight restrictions; use of DEA window analysis; and exogenous factors. The findings demonstrate that, despite several innovative DEA extensions and hospital applications, over half of the research used the conventional DEA models. The findings also show that the most often used inputs in the DEA models were labor-oriented inputs and hospital beds, whereas the most frequently used outputs were outpatient visits, followed by surgeries, admissions, and inpatient days. Further research on the impact of healthcare reforms and health information technology (HIT) on hospital performance is required, given the number of reforms being implemented in many countries and the role HIT plays in enhancing care quality and lowering costs. We conclude by offering several new research directions for future studies.

Selective detection of azelnidipine in pharmaceuticals via carbon dot mediated spectrofluorimetric method: A green approach.

A spectrofluorimetric method using fluorescent carbon dots (CDs) was developed for the selective detection of azelnidipine (AZEL) pharmaceutical in the presence of other drugs. In this study, N-doped CDs (N-CDs) were synthesized through a single-step hydrothermal process, using citric acid and urea as precursor materials. The prepared N-CDs showed a highly intense blue fluorescence emission at 447 nm, with a photoluminescence quantum yield of ~21.15% and a fluorescence lifetime of 0.47 ns. The N-CDs showed selective fluorescence quenching in the presence of all three antihypertensive drugs, which was used as a successful detection platform for the analysis of AZEL. The photophysical properties, UV-vis light absorbance, fluorescence emission, and lifetime measurements support the interaction between N-CDs and AZEL, leading to fluorescence quenching of N-CDs as a result of ground-state complex formation followed by a static fluorescence quenching phenomenon. The detection platform showed linearity in the range 10-200 µg/ml (R2 = 0.9837). The developed method was effectively utilized for the quantitative analysis of AZEL in commercially available pharmaceutical tablets, yielding results that closely align with those obtained from the standard method (UV spectroscopy). With a score of 0.76 on the 'Analytical GREEnness (AGREE)' scale, the developed analytical method, incorporating 12 distinct green analytical chemistry components, stands out as an important technique for estimating AZEL.

2-Amino-5-methylene-pyrimidine-4,6-dione-based Janus G-C nucleobase as a versatile building block for self-assembly.

This communication reports a nature-inspired Janus G-C nucleobase featuring two recognition sites: DDA (G mimic) and DAA (C mimic), which is capable of forming a linear tape-like supramolecular polymer structure. As demonstrated herein, the amino group of this self-assembling system can be further modified to yield a highly stable quadruple H-bonding system as well as a masked self-assembling system cleavable upon exposure to light.

Non-enzymatic glucose detection with screen-printed chemiresistive sensor using green synthesised silver nanoparticle and multi-walled carbon nanotubes-zinc oxide nanofibers.

Non-enzymatic screen-printed chemiresistive interdigitated electrodes (SPCIE) were designed and fabricated using a low-cost screen-printing method for detection of the glucose. The interdigitated electrodes (IDE) pattern was printed using conductive graphene ink on the glossy surface of the photo paper. The proposed glossy photo paper-based SPCIE are functionalized with multi-walled carbon nanotubes-zinc oxide (MWCNTs-ZnO) nanofibers to create the chemiresistive matrix. Further, to bind these nanofibers with the graphene electrode surface, we have used the green synthesized silver nanoparticles (AgNPs) with banana flower stem fluid (BFSF) as a binder solution. AgNPs with BFSF form the conductive porous natural binder layer (CPNBL). It does not allow to increase the resistivity of the deposited material on graphene electrodes and also keeps the nanofibers intact with paper-based SPCIE. The synthesized material of MWCNT-ZnO nanofibers and green synthesized AgNPs with BFSF as a binder were characterized by Ultraviolet-visible spectroscopy (UV-vis), scanning electron microscope (SEM), x-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR). The amperometric measurements were performed on the proposed SPCIE sensor to detect the glucose sample directly. The innovative paper-based SPCIE glucose sensor exhibits a linear corelation between current measurements and glucose concentration in the range between 45.22µm and 20 mm, with a regression coefficient (R2) of 0.9902 and a lower limit of detection (LoD) of 45.22µm (n= 5). The sensitivity of the developed SPCIE sensor was 2178.57µAmM-1cm-2, and the sensor's response time determined was approximately equal to 18 s. The proposed sensor was also tested for real blood serum sample, and relative standard deviation (RSD) was found equal to 2.95%.

Molecular basis of conformational changes and mechanics of integrins.

Integrin, as a mechanotransducer, establishes the mechanical reciprocity between the extracellular matrix (ECM) and cells at integrin-mediated adhesion sites. This study used steered molecular dynamics (SMD) simulations to investigate the mechanical responses of integrin αvß3 with and without 10th type III fibronectin (FnIII10) binding for tensile, bending and torsional loading conditions. The ligand-binding integrin confirmed the integrin activation during equilibration and altered the integrin dynamics by changing the interface interaction between ß-tail, hybrid and epidermal growth factor domains during initial tensile loading. The tensile deformation in integrin molecules indicated that fibronectin ligand binding modulates its mechanical responses in the folded and unfolded conformation states. The bending deformation responses of extended integrin models reveal the change in behaviour of integrin molecules in the presence of Mn2+ ion and ligand based on the application of force in the folding and unfolding directions of integrin. Furthermore, these SMD simulation results were used to predict the mechanical properties of integrin underlying the mechanism of integrin-based adhesion. The evaluation of integrin mechanics provides new insights into understanding the mechanotransmission (force transmission) between cells and ECM and contributes to developing an accurate model for integrin-mediated adhesion. This article is part of a discussion meeting issue 'Supercomputing simulations of advanced materials'.

A Coarse-Grained Model for the Mechanical Behavior of Na-Montmorillonite Clay.

Sodium montmorillonite (Na-MMT) is one of the most commonly found swelling clay minerals with diverse engineering and technological applications. The nanomechanical properties of this mineral have been extensively investigated computationally utilizing molecular dynamics (MD) simulations to portray the molecular-level changes at different environmental conditions. As the environmentally found Na-MMT clays are generally sized within hundreds of nanometers, all-atomistic (AA) MD simulations of clays within such size range are particularly challenging due to computational inefficiency. Informed from atomistic modeling, a coarse-grained (CG) modeling technique can be employed to overcome the spatiotemporal limitation. The current study presents a modeling strategy to develop a computationally efficient model of Na-MMT clay with a typical size over ≃100 nm by shrinking the atomistic platelet thickness and reducing the number of center-layer atoms. Using the "strain-energy conservation" approach, the force field parameters for the CG model are obtained and the developed CG model can well preserve in-plane tension, shear, and bending behaviors of atomistic counterparts. Remarkably, the CG tactoid model of Na-MMT, a hierarchical multilayer structure, can reproduce the interlayer shear and adhesion as well as d-spacing among the clay sheets as of atomistic one to a good approximation while gaining significantly improved computational speed. Our study demonstrates the efficacy of the CG modeling framework, paving the way for the bottom-up multiscale prediction of mechanical behaviors of clay and related minerals.

Venous thromboembolism in COVID-19 patients and prediction model: a multicenter cohort study.

BACKGROUND: Patients with COVID-19 infection are commonly reported to have an increased risk of venous thrombosis. The choice of anti-thrombotic agents and doses are currently being studied in randomized controlled trials and retrospective studies. There exists a need for individualized risk stratification of venous thromboembolism (VTE) to assist clinicians in decision-making on anticoagulation. We sought to identify the risk factors of VTE in COVID-19 patients, which could help physicians in the prevention, early identification, and management of VTE in hospitalized COVID-19 patients and improve clinical outcomes in these patients. METHOD: This is a multicenter, retrospective database of four main health systems in Southeast Michigan, United States. We compiled comprehensive data for adult COVID-19 patients who were admitted between 1st March 2020 and 31st December 2020. Four models, including the random forest, multiple logistic regression, multilinear regression, and decision trees, were built on the primary outcome of in-hospital acute deep vein thrombosis (DVT) and pulmonary embolism (PE) and tested for performance. The study also reported hospital length of stay (LOS) and intensive care unit (ICU) LOS in the VTE and the non-VTE patients. Four models were assessed using the area under the receiver operating characteristic curve and confusion matrix. RESULTS: The cohort included 3531 admissions, 3526 had discharge diagnoses, and 6.68% of patients developed acute VTE (N = 236). VTE group had a longer hospital and ICU LOS than the non-VTE group (hospital LOS 12.2 days vs. 8.8 days, p < 0.001; ICU LOS 3.8 days vs. 1.9 days, p < 0.001). 9.8% of patients in the VTE group required more advanced oxygen support, compared to 2.7% of patients in the non-VTE group (p < 0.001). Among all four models, the random forest model had the best performance. The model suggested that blood pressure, electrolytes, renal function, hepatic enzymes, and inflammatory markers were predictors for in-hospital VTE in COVID-19 patients. CONCLUSIONS: Patients with COVID-19 have a high risk for VTE, and patients who developed VTE had a prolonged hospital and ICU stay. This random forest prediction model for VTE in COVID-19 patients identifies predictors which could aid physicians in making a clinical judgment on empirical dosages of anticoagulation.

Emergency departments: The gatekeepers of admissions in Pennsylvania's rural hospitals.

STUDY OBJECTIVE: To analyze trends in admission rates and the proportion of admissions via the ED at rural hospitals in Pennsylvania and to identify factors that may impact admission rates. METHODS: We use retrospective, longitudinal data on rural acute care hospitals in Pennsylvania for 2000-19 to investigate temporal patterns in admission rates and the proportion of admissions via the ED. Regression analysis is then used to identify factors that may impact admission rates. RESULTS: In general admission rates, which averaged 14.5%, experienced a gradual decline (Change: -16.9%; from 15.7% to 13%) between 2000 and 2019. The proportion of hospital admissions via the ED, which averaged 64.9%, increased steadily (21%; from 57% to 69%). Critical access hospitals experienced a sharp decline in admissions via the ED (-49.1%) and admission rates (-55.3%). The fixed-effects regression model revealed several hospital- and ED-level characteristics were significantly associated with admission rate. CONCLUSIONS: Emergency departments are the gatekeepers of admissions at rural acute care hospitals in Pennsylvania. Many hospitals in rural Pennsylvania, including CAHs, are admitting most of their patients through the ED, concomitant with a significant decline in admissions and admission rates. This highlights the need to strengthen primary care practices serving rural Pennsylvania as well as the need to improve rural emergency and trauma systems. In the short to medium term, policy makers should explore innovative ways to fund smaller hospitals, especially CAHs, to develop level IV trauma center capabilities.

Flexible and Transparent Circularly Polarized Patch Antenna for Reliable Unobtrusive Wearable Wireless Communications.

This paper presents a circularly polarized flexible and transparent circular patch antenna suitable for body-worn wireless-communications. Circular polarization is highly beneficial in wearable wireless communications, where antennas, as a key component of the RF front-end, operate in dynamic environments, such as the human body. The demonstrated antenna is realized with highly flexible, robust and transparent conductive-fabric-polymer composite. The performance of the explored flexible-transparent antenna is also compared with its non-transparent counterpart manufactured with non-transparent conductive fabric. This comparison further demonstrates the suitability of the proposed materials for the target unobtrusive wearable applications. Detailed numerical and experimental investigations are explored in this paper to verify the proposed design. Moreover, the compatibility of the antenna in wearable applications is evaluated by testing the performance on a forearm phantom and calculating the specific absorption rate (SAR).

Dissociation Mechanisms of G-actin Subunits Govern Deformation Response of Actin Filament.

Actin molecules are essential structural components of the cellular cytoskeleton. Here, we report a comprehensive analysis of F-actin's deformation behavior and highlight underlying mechanisms using steered molecular dynamics simulations (SMD). The investigation of F-actin was done under tension, compression, bending, and torsion. We report that the dissociation pattern of conformational locks at intrastrand and interstrand G-actin interfaces regulates the deformation response of F-actin. The conformational locks at the G-actin interfaces are portrayed by a spheroidal joint, interlocking serrated plates' analogy. Further, the SMD simulation approach was utilized to evaluate Young's modulus, flexural rigidity, persistent length, and torsional rigidity of F-actin, and the values obtained were found to be consistent with available experimental data. The evaluation of the mechanical properties of actin and the insight into the fundamental mechanisms contributing to its resilience described here are necessary for developing accurate models of eukaryotic cells and for assessing cellular viability and mobility.

Changes in Bacterial Diversity and Composition in Response to Co-inoculation of Arbuscular Mycorrhizae and Zinc-Solubilizing Bacteria in Turmeric Rhizosphere.

In the present study, the impact of co-inoculation of arbuscular mycorrhizal fungi (AM Rhizophagus sp., NCBI-MN710507) and Zinc solubilizing bacteria (ZSB2- Bacillus megaterium, NCBI-KY687496) on plant growth, soil dehydrogenase activity, soil respiration and the changes in bacterial diversity in rhizosphere of turmeric (Curcuma longa) were examined. Our results showed that higher plant height and dry biomass were observed in treatments co-inoculated with AM and ZSB2. Likewise, dehydrogenase activity and soil respiration were more significant in the co-inoculation treatment, indicating abundance of introduced as well as inherent microflora. Bacterial community analysis using 16S rRNA revealed changes in the structure and diversity of various taxa due to co-inoculation of AM and ZSB2. Alpha diversity indexes (Shannon and Chao1) and beta diversity indexes obtained through unweighted unifrac approach also showed variation among the treated samples. Chloroflexi was the dominant phylum followed by Proteobacteria, Actinobacteria and Acidobacteria which accounted for 80% of all treated samples. The composition of bacterial communities at genus level revealed that co-inoculation caused distinct bacterial profiles. The Linear discriminant analysis effect size revealed the dominance of ecologically significant genera such as Bradyrhizobium, Candidatus, Pedomicrbium, Thermoporothrix, Acinetobacter and Nitrospira in treatments co-inoculated with AM and ZSB2. On the whole, co-inoculated treatments revealed enhanced microbial activities and caused significant positive shifts in the bacterial diversity and abundance compared to treatments with sole application of ZSB2 or AM.

Binding of SARS-COV-2 (COVID-19) and SARS-COV to human ACE2: Identifying binding sites and consequences on ACE2 stiffness.

The SARS-CoV-2 coronavirus (COVID-19) that is causing the massive global pandemic exhibits similar human cell invasion mechanism as the coronavirus SARS-CoV, which had significantly lower fatalities. The cell membrane protein Angiotensin-converting enzyme 2 (ACE2) is the initiation point for both the coronavirus infections in humans. Here, we model the molecular interactions and mechanical properties of ACE2 with both SARS-CoV and COVID-19 spike protein receptor-binding domains (RBD). We report that the COVID-19 spike RBD interacts with ACE2 more strongly and at only two protein residues, as compared to multi-residue interaction of the SARS-CoV. Although both coronaviruses stiffen the ACE2, the impact of COVID-19 is six times larger, which points towards differences in the severity of the reported respiratory distress. The recognition of specific residues of ACE2 attachments to coronaviruses is important as the residues suggest potential sites of intervention to inhibit attachment and subsequent entry of the COVID-19 into human host cells.

A Smart Archive Box for Museum Artifact Monitoring Using Battery-Less Temperature and Humidity Sensing.

For the first time, this paper reports a smart museum archive box that features a fully integrated wireless powered temperature and humidity sensor. The smart archive box has been specifically developed for microclimate environmental monitoring of stored museum artifacts in cultural heritage applications. The developed sensor does not require a battery and is wirelessly powered using Near Field Communications (NFC). The proposed solution enables a convenient means for wireless sensing with the operator by simply placing a standard smartphone in close proximity to the cardboard archive box. Wireless sensing capability has the advantage of enabling long-term environmental monitoring of the contents of the archive box without having to move and open the box for reading or battery replacement. This contributes to a sustainable preventive conservation strategy and avoids the risk of exposing the contents to the external environment, which may result in degradation of the stored artifacts. In this work, a low-cost and fully integrated NFC sensor has been successfully developed and demonstrated. The developed sensor is capable of wirelessly measuring temperature and relative humidity with a mean error of 0.37 °C and ±0.35%, respectively. The design has also been optimized for low power operation with a measured peak DC power consumption of 900 µW while yielding a 4.5 cm wireless communication range. The power consumption of the NFC sensor is one of the lowest found in the literature. To the author's knowledge, the NFC sensor proposed in this paper is the first reporting of a smart archive box that is wirelessly powered and uniquely integrated within a cardboard archive box.

Differences in Interactions Within Viral Replication Complexes of SARS-CoV-2 (COVID-19) and SARS-CoV Coronaviruses Control RNA Replication Ability.

COVID-19 has become a global pandemic caused by the SARS-CoV-2 coronavirus. SARS-CoV-2 shares many similarities with SARS coronavirus (SARS-CoV). A viral replication complex containing non-structural proteins (nsps) is the toolbox for RNA replication and transcription of both coronaviruses. In both cases, the RNA-dependent RNA polymerase (RdRp) domain of the coronaviral replication complex dictates the primary polymerase activity by cooperating with cofactors. The higher transmissibility and mortality due to SARS-CoV-2 are related to its higher RNA replication activity compared to SARS-CoV. The discrepancy between the RNA replication efficiency of SARS-CoV and SARS-CoV-2 can be understood by exploring interactions within their viral replication complexes. Our modeling of molecular interactions within the viral replication complexes of SARS-CoV and SARS-CoV-2 using molecular dynamics simulations suggests that in contrast to SARS-CoVnsp12, SARS-CoV2nsp12 prefers helices as the dominant interacting secondary motifs. The relative differences in nonbonded interactions between nsps could suggest viral RNA replication ability in coronaviruses. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s11837-021-04662-6.

Compression of Na-Montmorillonite Swelling Clay Interlayer Is Influenced by Fluid Polarity: A Steered Molecular Dynamics Study.

The compressive responses of an interlayer of the dry sodium-montmorillonite (Na-MMT) swelling clay as well as the clay intercalated with organic fluids of a wide range of dielectric constants from 110 (formamide) to 20 (acetone) are quantitatively evaluated using steered molecular dynamics simulations. Representative dry clay and clay with fluid (clay-fluid) molecular models are constructed, and the stress-strain relationships upon compression of these models are studied using constant force steered molecular dynamics (SMD) simulations. Our results show that the polarity of the fluids and the amount of the fluid molecules in the clay interlayer play a significant role in the interlayer spacing, interlayer volume, interlayer strain, interlayer modulus, nonbonded interactions, and conformation of the fluid molecules upon externally applied stresses. The clay interlayer responses upon compression are essential for the development of multiscale modeling of swelling clays and prediction of the reliable compressive behavior, which are critical for the accurate analysis and economical design of the infrastructures in swelling clay areas and the densification of clays for ceramics manufacturing.

Clinical Outcomes of Weight-Based Norepinephrine Dosing in Underweight and Morbidly Obese Patients: A Propensity-Matched Analysis.

BACKGROUND: Weight-based dosing strategy for norepinephrine in septic shock patients with extremes of body mass index has been lesser studied. METHODS: This historical study of adult septic shock patients was conducted from January 1, 2010, to December 31, 2015, at all intensive care units (ICUs) in Mayo Clinic, Rochester. Patients with documented body mass index were classified into underweight (body mass index <18.5 kg/m2), normal weight (18.5-24.9 kg/m2), and morbidly obese (≥40 kg/m2) patients. Patients with repeat ICU admissions, ICU stay <1 day, and body mass index 25 to 39.9 kg/m2 were excluded. The primary outcome was in-hospital mortality, and secondary outcomes included cumulative norepinephrine exposure acute kidney injury, cardiac arrhythmias, and 1-year mortality. Two-tailed P < .05 was considered statistically significant. RESULTS: From 2010 to 2015, 2016 patients met inclusion-145, 1406, and 466 patients, respectively, in underweight, normal weight, and morbidly obese cohorts. Underweight patients used the highest peak dose and absolute exposure was greatest for morbidly obese patients. In-hospital mortality decreased with increasing log10 body mass index: 41.4% (underweight), 28.4% (normal weight), and 24.7% (morbidly obese), respectively (P < .001); however, this relationship was not noted at 1 year. Unadjusted log10 norepinephrine cumulative exposure (mg) was associated with higher in-hospital mortality, acute kidney injury, cardiac arrhythmias, and 1-year mortality. After adjustment for demographics, body mass index, comorbidity, and illness severity, log10 norepinephrine exposure was an independent predictor of in-hospital mortality (odds ratio 2.4 [95% confidence interval, 2.0-2.8]; P < .001) and 1-year mortality (odds ratio 1.7 [95% confidence interval, 1.5-2.0]; P < .001). In a propensity-matched analysis of 1140 patients, log10 norepinephrine was an independent predictor of in-hospital mortality (odds ratio 2.2 [95% confidence interval, 1.8-2.6]; P < .001). CONCLUSIONS: Morbidly obese patients had lower in-hospital mortality but had higher 1-year mortality compared to normal weight and underweight patients. Cumulative norepinephrine exposure was highest in morbidly obese patients. Total norepinephrine exposure was an independent mortality predictor in septic shock.

Diagnostic Yield of Rescreening Adults for Pulmonary Arteriovenous Malformations.

PURPOSE: To determine the yield of rescreening adult hereditary hemorrhagic telangiectasia (HHT) patients with initial negative screening CT for pulmonary arteriovenous malformations (PAVMs). MATERIALS AND METHODS: Patients with a definite diagnosis of HHT were identified in the University of Toronto, Université de Montréal, and Mayo Clinic HHT databases. Inclusion criteria were: (i) definite diagnosis of HHT; (ii) initial negative PAVM screening based on bubble echocardiography and/or chest CT; and (iii) minimum 2-year imaging follow-up. A positive rescreen was defined as a newly detected PAVM on follow-up CT. Frequency of new PAVMs was calculated at 3 ± 1 years, 5 ± 1 years, 7-9 years, and ≥10 years. The primary endpoint was the rate of new PAVMs at 5 ± 1 years. RESULTS: One hundred seventy-two patients (mean age, 49.6 ± 16.7 years; 59% female) were followed for a median of 7 years. Nine patients (5.2%) had newly detected PAVMs. At the 3-, 5-, 7-, and ≥10-year time points, the cumulative rate of newly detected PAVMs was 1.8% (3/166), 5.0% (7/140), 8.8% (8/91), and 13.8% (9/65), respectively. Median feeding artery diameter was 1.3 mm. One patient had a feeding artery larger than 3 mm discovered after 6 years and was treated with embolization. The overall rate of newly detected PAVMs was 0.7%/patient-year. CONCLUSIONS: There is a definite but low rate of newly detected PAVMs in HHT patients with initial negative screening studies. No new treatable PAVMs were identified at the 5-year mark, although 1 treatable case was identified after 6 years. These findings suggest that a longer screening interval may be warranted.

Comparative Study of Antioxidant Potential of Selected Dietary Vitamins; Computational Insights.

Density functional theory (DFT) was used to explore the antioxidant properties of some naturally occurring dietary vitamins, and the reaction enthalpies related to various mechanisms of primary antioxidant action, i.e., hydrogen atom transfer, single electron transfer-proton transfer, and sequential proton loss-electron transfer were discussed in detail. B3LYP, M05-2X, and M06-2X functionals were utilized in this work. For aqueous phase studies, the integral equation formalism polarized continuum model (IEF-PCM) was employed. From the outcomes, hydrogen atom transfer (HAT) was the most probable mechanism for the antioxidant action of this class of compounds. Comparison of found results with experimental data (available in literature), vitamin C possesses the lowest enthalpy values for both proton affinity (PA) and bond dissociation energy (BDE)in the aqueous phase, suggesting it as the most promising candidate as an antioxidant. Accordingly, these computational insights encourage the design of structurally novel, simple vitamins which will be more economical and beneficial in the pharmaceutical industry.

Iron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process.

Earth abundant, first row transition metals offer a cheap and sustainable alternative to the rare and precious metals. However, utilization of first row metals in catalysis requires harsh reaction conditions, suffers from limited activity, and fails to tolerate functional groups. Reported here is a highly efficient iron catalyzed hydroformylation of alkenes under mild conditions. This protocol operates at 10-30 bar syngas pressure below 100 °C, utilizes readily available ligands, and applies to an array of olefins. Thus, the iron precursor [HFe(CO)4]-[Ph3PNPPh3]+ (1) in the presence of triphenyl phosphine catalyzes the hydroformylation of 1-hexene (S2), 1-octene (S1), 1-decene (S3), 1-dodecene (S4), 1-octadecene (S5), trimethoxy(vinyl)silane (S6), trimethyl(vinyl)silane (S7), cardanol (S8), 2,3-dihydrofuran (S9), allyl malonic acid (S10), styrene (S11), 4-methylstyrene (S12), 4- iBu-styrene (S13), 4- tBu-styrene (S14), 4-methoxy styrene (S15), 4-acetoxy styrene (S16), 4-bromo styrene (S17), 4-chloro styrene (S18), 4-vinylbenzonitrile (S19), 4-vinylbenzoic acid (S20), and allyl benzene (S21) to corresponding aldehydes in good to excellent yields. Both electron donating and electron withdrawing substituents could be tolerated and excellent conversions were obtained for S11-S20. Remarkably, the addition of 1 mol % acetic acid promotes the reaction to completion within 16-24 h. Detailed mechanistic investigations revealed in situ formation of an iron-dihydride complex [H2Fe(CO)2(PPh3)2] (A) as an active catalytic species. This finding was further supported by cyclic voltammetry investigations and intermediacy of an Fe(0)-Fe(II) species was established. Combined experimental and computational investigations support the existence of an iron-dihydride as the catalyst resting state, which then follows a Fe(II) based catalytic cycle to produce aldehyde.