Hexane extract of Persea schiedeana Ness as green corrosion inhibitor for the brass immersed in 0.5 M HCl.

The hexane extract of Persea schiedeana Ness (PSN) was analyzed as corrosion inhibitor for the brass surface immersed in 0.5 M HCl. Fourier-transform infrared spectroscopy and a gas chromatographic (GC) and mass spectrometric (MS) were used to identify the PSN extract's functional groups and compound constituents. The functional groups identified were CH 3 and CH 2 functional alkyl groups, C=O stretching vibration of aldehydes, ketones, and carbonyl groups. The GC/MS determined the presence of fatty acids in the PSN extract, where palmitic acid, oleic acid, and ethyl oleate were the major constituents. Electrochemical characterizations were conducted to observe the effect of PSN as corrosion inhibitor on the brass surface. The Rp and Rn calculated from EIS and ENA give the same behavior. Based on the OCP behavior, it was determined that the PSN works as a mix inhibitor, affecting both anodic and cathodic reactions. The corrosion current density (Icorr) suggests that the extract of PSN reduces the corrosion rate of the brass with efficiencies above 90% for all concentrations. The efficiency obtained for each PSN concentration was attributed to forming a corrosion scale of CuO and Cu 2 O , which reacted with the carboxyl group to form copper carboxylates on the metal surface.

Organometallic Intermediates in the Synthesis of Photoluminescent Zirconium and Hafnium Complexes with Pyridine Dipyrrolide Ligands.

The two commercially available zirconium complexes tetrakis(dimethylamido)zirconium, Zr(NMe2)4, and tetrabenzylzirconium, ZrBn4, were investigated for their utility as starting materials in the synthesis of bis(pyridine dipyrrolide)zirconium photosensitizers, Zr(PDP)2. Reaction with one equivalent of the ligand precursor 2,6-bis(5-methyl-3-phenyl-1H-pyrrol-2-yl)pyridine, H2MePDPPh, resulted in the isolation and structural characterization of the complexes (MePDPPh)Zr(NMe2)2thf and (MePDPPh)ZrBn2, which could be converted to the desired photosensitizer Zr(MePDPPh)2 upon addition of a second equivalent of H2MePDPPh. Using the more sterically encumbered ligand precursor 2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine, H2MesPDPPh, only ZrBn4 yielded the desired bis-ligand complex Zr(MesPDPPh)2. Careful monitoring of the reaction at different temperatures revealed the importance of the organometallic intermediate (cyclo-MesPDPPh)ZrBn, which was characterized by X-ray diffraction analysis and 1H NMR spectroscopy and shown to contain a cyclometalated MesPDPPh unit. Taking inspiration from the results for zirconium, syntheses for two hafnium photosensitizers, Hf(MePDPPh)2 and Hf(MesPDPPh)2, were established and shown to proceed through similar intermediates starting from tetrabenzylhafnium, HfBn4. Initial studies of the photophysical properties of the photoluminescent hafnium complexes indicate similar optical properties compared to their zirconium analogues.

QSTR Modeling to Find Relevant DFT Descriptors Related to the Toxicity of Carbamates.

Compounds containing carbamate moieties and their derivatives can generate serious public health threats and environmental problems due their high potential toxicity. In this study, a quantitative structure-toxicity relationship (QSTR) model has been developed by using one hundred seventy-eight carbamate derivatives whose toxicities in rats (oral administration) have been evaluated. The QSRT model was rigorously validated by using either tested or untested compounds falling within the applicability domain of the model. A structure-based evaluation by docking from a series of carbamates with acetylcholinesterase (AChE) was carried out. The toxicity of carbamates was predicted using physicochemical, structural, and quantum molecular descriptors employing a DFT approach. A statistical treatment was developed; the QSRT model showed a determination coefficient (R2) and a leave-one-out coefficient (Q2LOO) of 0.6584 and 0.6289, respectively.

New QSPR model for prediction of corrosion inhibition using conceptual density functional theory.

The relationship between structure and corrosion inhibition of a series of twenty-eight quinoline and pyridine derivatives has been established through the investigation of quantum descriptors calculated with PBE/6-311 + + G** method. A quantitative structure-property relationship (QSPR) model was obtained by examining these descriptors using a genetic algorithm approximation method based on a multiple linear regression analysis. The results indicate that the efficiency of corrosion inhibitors is strongly associated with hardness (η), minimal electrostatic potential (ESPmin), and volume (V) descriptors. Furthermore, the validity of the proposed model is corroborated by an adsorption study on an iron surface Fe(110).

Predicting Total Knee Arthroplasty Outpatient Discharge: Surgeons versus Insurance Companies.

BACKGROUND: Insurance companies are increasingly making unilateral determinations of admission status for primary total knee arthroplasty (TKA). These determinations may differ from those based on surgeon-derived criteria for outpatient knee replacement. The goal of this study is to determine if insurance company determinations of outpatient status are as reliable as surgeon-derived criteria in predicting outpatient discharge after TKA. METHODS: We retrospectively reviewed 709 patients who were preoperatively authorized for outpatient TKA. Patients were stratified into 2 groups: "outpatient per surgeon" (appropriate for outpatient surgery per institutional protocols) or "outpatient per insurance" (appropriate for inpatient surgery per institutional protocols but denied inpatient status by insurance). The primary endpoint of this study was the conversion rate of outpatient to inpatient stay. Univariate logistic regression was performed to compare the odds of conversion to inpatient stay between outpatient per surgeon and outpatient per insurance procedures and other covariates. RESULTS: The cohort included 434 outpatient per insurance (61.2%) and 275 outpatient per surgeon (38.8%) patients. Surgeons accurately predicted outpatients' discharge 92.0% of the time, while insurance companies did so 81.3% of time (P < .001). Outpatient per insurance procedures (odds ratio [OR] 2.20, P = .003) and body mass index >35 kg/m2 (OR 1.82, P = .026) had higher odds of being converted to inpatient. Males had higher odds (OR 1.52, P < .001) of being discharged as outpatient. CONCLUSION: Determining inpatient versus outpatient status is a complex decision involving both clinical and social factors. Surgeons accurately predicted outpatient discharge 92% of the time. Moreover, outpatient per insurance procedures were twice as likely to be converted to inpatient status. Therefore, insurance companies should leave deciding admission status up to both the patient and surgeon.

Nematicidal activity of furanoeremophilenes against Meloidogyne incognita and Nacobbus aberrans.

BACKGROUND: While searching for novel small molecules for new organic pesticide agents against plant-parasitic nematodes, we found that the hexane extract from the roots of Senecio sinuatos and its main secondary metabolite, 3ß-angeloyloxy-6ß-hydroxyfuranoeremophil-1(10)-ene (1), possess nematicidal activity against the second stage juvenile (J2) of Meloidogyne incognita and Nacobbus aberrans. Both species reduce yield of various vegetable crops. These results encouraged us to synthesize esters 3-9 formed by diol 2, obtained by alkaline hydrolysis of 1 and acetic anhydride, benzoic acid, 2-nitrobenzoic acid, 2-bromobenzoic acid, 4-nitrobenzoic acid, 4-bromobenzoic acid, and 4-methoxybenzoic acid, respectively. The nematicidal activity of these esters was evaluated and compared with that of the free benzoic acids. RESULTS: Natural product 1 and derivatives 2-9 were obtained and characterized by their physical and spectroscopic properties, including one-dimensional (1D) and two-dimensional (2D) nuclear magnetic resonance (NMR) experiments; X-ray diffraction analysis established their absolute configuration. The nematicidal activity of compounds 1-9 was assessed in vitro against M. incognita and N. aberrans J2 and was compared to activity shown by benzoic acid, 2-nitrobenzoic acid, 2-bromobenzoic acid, 4-nitrobenzoic acid, 4-bromobenzoic acid, and 4-methoxybenzoic acid. The esters suppressed nematodes more than free benzoic acid. Nacobbus aberrans J2 were suppressed, with compounds 5, 6, and 8 being the most active. CONCLUSION: Esters formed by 3ß,6ß-dihydroxyfuranoeremophil-1(10)-ene and ortho- or para-substituted benzoic acids containing electron acceptor groups had nematicidal activity against N. aberrans. These compound can potentially serve as a model for the development of new organic nematicidal agents. © 2022 Society of Chemical Industry.

Bridging the Gaps between Circulating Tumor Cells and DNA Methylation in Prostate Cancer.

Prostate cancer is the second most common male malignancy, with a highly variable clinical presentation and outcome. Therefore, diagnosis, prognostication, and management remain a challenge, as available clinical, imaging, and pathological parameters provide limited risk assessment. Thus, many biomarkers are under study to fill this critical gap, some of them based on epigenetic aberrations that might be detected in liquid biopsies. Herein, we provide a critical review of published data on the usefulness of DNA methylation and circulating tumor cells in diagnosis and treatment decisions in cases of prostate cancer, underlining key aspects and discussing the importance of these advances to the improvement of the management of prostate cancer patients. Using minimally invasive blood tests, the detection of highly specific biomarkers might be crucial for making therapeutic decisions, determining response to specific treatments, and allowing early diagnosis.

A new computational model for the prediction of toxicity of phosphonate derivatives using QSPR.

Structural and electronic properties of a series of 25 phosphonate derivatives were analyzed applying density functional theory, with the exchange-correlation functional PBEPBE in combination with the 6-311++G** basis set for all atoms. The chemical reactivity of these derivatives has been interpreted using quantum descriptors such as frontier molecular orbitals (HOMO, LUMO), Hirshfeld charges, molecular electrostatic potential, and the dual descriptor [[Formula: see text]]. These descriptors are directly related to experimental median lethal dose ([Formula: see text], expressed as its decimal logarithm [[Formula: see text]([Formula: see text]] through a multiple linear regression equation. The proposed model predicts the toxicity of phosphonates in function of the volume (V), the load of the most electronegative atom of the molecule (q), and the eigenvalue of the molecular orbital HOMO ([Formula: see text]. The obtained values in the internal validation of the model are: [Formula: see text]%, [Formula: see text]%, [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text]%. The toxicity of nine phosphonate derivatives used as test molecules was adequately predicted by the model. The theoretical results indicate that the oxygen atom of the O=P group plays an important role in the interaction mechanism between the phosphonate and the acetylcholinesterase enzyme, inhibiting the removal of the proton of the ser-200 residue by the his-440 residue.

From metallic gold to [Au(NHC)2]+ complexes: an easy, one-pot method.

A simple and direct method is described to prepare cationic bis(NHC)-Au(i) complexes containing N-alkyl or N-aryl NHC ligands to generate relevant gold complexes using metallic gold as the starting material.

Revisional Surgery Following Laparoscopic Gastric Plication.

BACKGROUND: The laparoscopic gastric plication (LGP) is a relative new bariatric procedure that has gained popularity over the last few years, but no real consensus exists and the evidence is unclear, especially in its real efficacy, safety, and durability. METHODS: Retrospective study analyzing the records patients submitted to LGP between 2009 and 2010. The primary objective was to describe the characteristics and outcomes of patients submitted to revisional surgery. Baseline data and evolution were obtained and analyzed. Surgical analysis included revision cause, perioperative outcome, type of surgery, complications, and weight loss after 18 months. A comparison between gastric bypass and sleeve gastrectomy was performed. RESULTS: One hundred LGP were performed. After a mean time of 13.5 months, 42 patients presented an overall excess weight loss (EWL) <50 % and 38 had severe symptoms. Thirty patients accepted revisional surgery with BMI before conversion of 38.6 ± 4.2 kg/m2. There were 17 laparoscopic sleeve gastrectomy (LSG) and 13 laparoscopic gastric bypass (LGBP) with comparable preoperative characteristics. The LSG group had lower pneumoperitoneum time and less hospital stay. At 18 months, the LGBP group had lower BMI (24.1 ± 1.1 vs. 25.8 ± 1.3 kg/m2 for the LSG; p = 0.006) and higher %EWL (75.7 ± 16.1 vs. 61.4 ± 14.5 % for the LSG; p = 0.008). CONCLUSION: In our series, LGP presented a high failure rate and an increased number of symptomatic patients. Revisional surgery proved to be safe and effective. Revision to LSG was faster and had less hospital stay. Revision to LGBP showed better %EWL at 18 months.

Reduced density gradient as a novel approach for estimating QSAR descriptors, and its application to 1, 4-dihydropyridine derivatives with potential antihypertensive effects.

The relationship between the chemical structure and biological activity (log IC50) of 40 derivatives of 1,4-dihydropyridines (DHPs) was studied using density functional theory (DFT) and multiple linear regression analysis methods. With the aim of improving the quantitative structure-activity relationship (QSAR) model, the reduced density gradient s( r) of the optimized equilibrium geometries was used as a descriptor to include weak non-covalent interactions. The QSAR model highlights the correlation between the log IC50 with highest molecular orbital energy (E HOMO), molecular volume (V), partition coefficient (log P), non-covalent interactions NCI(H4-G) and the dual descriptor [Δf(r)]. The model yielded values of R 2=79.57 and Q 2=69.67 that were validated with the next four internal analytical validations DK=0.076, DQ=-0.006, R P =0.056, and R N=0.000, and the external validation Q 2boot=64.26. The QSAR model found can be used to estimate biological activity with high reliability in new compounds based on a DHP series. Graphical abstract The good correlation between the log IC50 with the NCI (H4-G) estimated by the reduced density gradient approach of the DHP derivatives.

Activation of aldehydes by exocyclic iridium(i)-η4:π2-diene complexes derived from 1,3-oxazolidin-2-ones.

The Ir(i) complexes [TpMe2Ir(η4-1,4-diene)] 2b and 2c react thermally with a variety of aromatic aldehydes, 3a-e, to generate the metallabicyclic compounds 4e-k and the Fischer-type carbenes 5a-b in moderate yields. These reactions are proposed to take place with the initial formation of η1-aldehyde adducts as key intermediates. The formation of the metallabicyclic compounds 4e-k involves a formal decarboxylation process at the exo-2-oxazolidinone diene and an ortho metallation of the aromatic ring. The generation of the Fischer-type carbenes 5a-b is the result of a series of metal-based rearranged intermediates with no decarboxylation observed. Treatment of the η4-diene complex 2b with a variety of Lewis bases induces a change in the binding mode of the diene ligand from η4:π2 to η2:σ2 to form the Ir(iii) derivatives 6b-d of composition TpMe2Ir-(η4:π2-1,4-diene)(L) (L = CO, MeCN, and C5H5N). A study of reactions of complex 2b with either mono- or poly-deuterated aldehydes was performed to understand the mechanisms of such processes. The results of these studies were used to determine plausible formation mechanisms of the metallabicyclic compounds 4e-4k and Fischer-type carbenes 5a-b compound series. These mechanisms were corroborated by density functional theory (DFT) calculations of the free energy profiles.

'The past is the future of the present': Learning from long-time series of marine monitoring.

Using a long-term (1995-2014) monitoring network, from 51 sampling stations in estuaries and coasts of the Basque Country (Bay of Biscay), the objective of this investigation was to assess the responsiveness of 83 variables in water (18), sediments (27), biota (26), phytoplankton (2), macroinvertebrates (5) and fishes (5) to different human pressures and management actions. We used a total of 3247 series of data to analyse trends of improvement and worsening in quality. In a high percentage of the cases, the management actions taken have resulted in positive effects in the environment, as shown by the trend analysis in this investigation. Overall, much more trends of improvement than of worsening have been observed; this is true for almost all the media and biological components studied, with the exception of phytoplankton; and it applies as well to almost all the stations and water bodies, with the exception of those corresponding to areas with water treatment pending of accomplishment. In estuaries with decreasing human pressures during the period, the percentage of series showing quality improvement was higher (approx. 30%) than those showing worsening of quality (12%). Moreover, in those water bodies showing an increase of pressure, variables which can be considered indicators of anthropogenic effects showed negative trends (quality worsening). On the other hand, some of the variables analysed were more affected by natural variability than by changes in pressures. That was the case of silicate, nitrate and suspended solids, which followed trends correlated to salinity, which, in turn, was related to the rainfall regime during the study period.

Density Functional Theory and Electrochemical Studies: Structure-Efficiency Relationship on Corrosion Inhibition.

The relationship between structure and corrosion inhibition of a series of 30 imidazol, benzimidazol, and pyridine derivatives has been established through the investigation of quantum descriptors calculated with PBE/6-311++G**. A quantitative structure-property relationship model was obtained by examination of these descriptors using a genetic functional approximation method based on a multiple linear regression analysis. Our results indicate that the efficiency of corrosion inhibitors is strongly associated with aromaticity, electron donor ability, and molecular volume descriptors. In order to calibrate and validate the proposed model, we performed electrochemical impedance spectroscopy (EIS) studies on imidazole, 2-methylimidazole, benzimidazole, 2-chloromethylbenzimidazole, pyridine, and 2-aminopyridine compounds. The experimental values for efficiency of corrosion inhibition are in good agreement with the estimated values obtained by our model, thus confirming that our approach represents a promising and suitable tool to predict the inhibition of corrosion attributes of nitrogen containing heterocyclic compounds. The adsorption behavior of imidazole or benzimidazole heterocyclic molecules on the Fe(110) surface was also studied to elucidate the inhibition mechanism; the aromaticity played an important role in the adsorbate-surface complex.

Synthesis of Ir(III) complexes with Tp(Me2) and acac ligands and their reactivity with electrophiles.

The reaction of the bis(ethylene) complex [Tp(Me2)Ir(C2H4)2] () (Tp(Me2) = hydrotris(3,5-dimethylpyrazolyl)borate) with an excess of 2,4-pentanedione (acetylacetone, Hacac) at 70 °C produced a mixture of the Ir(iii) complex [Tp(Me2)Ir(acac)(C2H5)] () as a major product (67% yield) and two other side complexes [Tp(Me2)Ir(acac)(H)] () and [Tp(Me2)Ir(C9H14O2)] () in 20 and 13% yields, respectively. According to the proposed reaction mechanism and DFT calculations, complexes and are generated from an 18e(-) intermediate [Tp(Me2)Ir(C2H4)(acac)(C2H3)] () which undergoes either hydrogen insertion or ß-hydride elimination followed by the subsequent loss of a molecule of ethylene. The lowest yielding complex which features a 2-iridafuran is presumably generated from an unusual thermal coupling between one vinylic and one acac moiety. The availability of the acidic α-proton of the acac ligand was tested by the treatment of complex with Br2 and Cu(NO3)2 rendering the substitution complexes [Tp(3-Br,Me2)Ir(3-Br-acac)Br] () and [Tp(Me2)Ir(3-NO2-acac)(C2H5)] () in good yields. The series of heteroleptic iridium(iii) compounds display air and moisture stability and have been characterized by NMR, IR, and elemental analyses, and, in the case of , and , by single-crystal X-ray diffraction analyses.

Is there a possibility of ranking benthic quality assessment indices to select the most responsive to different human pressures?

Although a plethora of benthic indices exist, there is no agreement on what index or indices should be used by environmental managers to establish benthic quality. The objective of this investigation was to rank 35 benthic quality assessment indices used in different countries to evaluate the impact produced by 15 different human pressures (including multipressure, aquaculture, sewage discharges, eutrophication, physical alteration, chemical pollution, climate change, etc.). The ranking was determined by taking into account the coverage area of biogeographical provinces, number of citations testing a pressure and number of citations with significant correlation with pressure. We analysed 363 references, of which 169 showed quantitative data. Over a potential total score of 100, the highest values were obtained by the following indices: (i) AZTI's Marine Biotic Index (AMBI), which scored 77, tested by using 14 pressures in 14 provinces from the Arctic to tropical seas; (ii) multivariate AMBI (M-AMBI), which scored 74, tested with 12 pressures in 13 provinces; (iii) Bentix (BENTIX), which scored 68, tested with nine pressures in six provinces; (iv) Benthic Quality Index (BQI), which scored 66, tested with five pressures in seven provinces; and (v) Benthic Opportunistic Polychaetes Amphipods (BOPA) index, which scored 62, tested with eight pressures in six provinces.

Diastereoselective addition of diazomethane to zaluzanin A.

The diastereoselectivity of diazomethane addition to the conjugated double bond of alpha,beta-unsaturated sesquiterpene lactones was explored using zaluzanin A (1) as a model. Thus, the absolute configuration of 1 was assured by X-ray diffraction analysis including evaluation of Flack and Hooft parameters, and by vibrational circular dichroism spectroscopy of its diacetyl derivative 2, while the absolute configuration of the diazomethane addition product, zaluzanin A pyrazoline (3), was determined by evaluation of the 1H NMR chemical shift changes with respect to 1, and confirmed by X-ray diffraction analysis, again including evaluation of Flack and Hooft parameters.

Morbimortalidad por síndrome de broncoaspiración meconial en recién nacidos de un hospital público del estado Cojedes: Venezuela / Morbidity and mortality by meconium aspiration syndrome in newborns of Cojedes state public hospital: Venezuela

Normalmente el meconio es la primera excreción intestinal del recién nacido, está compuesto por células epiteliales, pelo fetal, moco y bilis. El estrés intrauterino puede causar evacuación in útero de meconio hacia el líquido amniótico el cual puede ser aspirado por el feto in útero o por el recién nacido durante el trabajo de parto. La aspiración del meconio puede causar obstrucción de la vía aérea y reacción inflamatoria intensa, lo que determinará dificultad respiratoria severa. La presencia de meconio en el líquido amniótico es un signo que advierte sufrimiento fetal y exige una supervisión cuidadosa del trabajo de parto con adecuada evaluación de la salud fetal. En atención a ello se planteo como objetivo del estudio, conocer la frecuencia del síndrome de broncoaspiración meconial en un hospital público, y establecer factores de riesgo asociados a su aparición. Se realizo una investigación de tipo descriptivo, transversal y de campo, en el servicio de neonatología de un hospital público del Estado Cojedes. Fue seleccionada una muestra no probabilística intencional, siendo evaluados 71 recién nacidos vivos que presentaron Síndrome de Dificultad Respiratoria. Los resultados reportaron que 13% de los sujetos presentaron el síndrome. La mortalidad fue de 44,4% causada por dificultad respiratoria. Los factores de riesgo predominantes fueron: expulsivo prolongado 44,4%, ruptura prematura de membrana 22,2% y traumatismo durante el parto 22,2%. Se concluye que la frecuencia y mortalidad elevada por esta condición, se encuentra asociado a factores de riesgo altamente prevenibles.

The violence constitutes one of the high-priority problems in America currently and together with the insecurity, they occupy the first place in the civic concern in most of the countries, Venezuela has been investing in security`s public politics, while the mortality for violent facts has had a tendency to increase in the last ten years. Exploring some answers was carried out a correlacional study with the purpose of looking for associations among the mortality for homicides, with socio-political variables that could be influencing in the behavior of the violent facts in the Aragua State. The results indicates the education investment influences the behavior of this mortality with 72,4%. Paradoxically, it was observed a coefficient of positive Pearson and a direct moderate (p = 0,05) correlation. 59,8% of the behavior of the mortality for the violent facts. This can be explained by the inefficacy of the developed security strategies and the current penal legislation. It concludes the behavior of the mortality for the violent facts of Aragua state. have been associated with the quality of the educational strategies and the police and repressive focus of the security politics carried out in region.

A macrocyclic dimeric diterpene with a C2 symmetry axis.

An unprecedented macrocyclic dimeric diterpene containing a C2 symmetry axis was isolated from Acacia schaffneri . This compound, named schaffnerine, was characterized as (5S,7S,8R,9R,10S,17S,5'S,7'S,8'R,9'R,10'S,17'S)-7,8:7,17':16,17:17,7':7',8':16',17'-hexaepoxy-7,8-seco-7',8'-seco-dicassa-13,13'-diene (1) from its spectroscopic data. Comparison of its experimental vibrational circular dichroism spectrum with that calculated using density functional theory, at the B3LYP/DGDZVP level, assigned its preferred conformation and absolute configuration. The latter was confirmed by evaluation of the Flack and Hooft parameters obtained after single-crystal X-ray diffraction analysis.