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2.
J Am Chem Soc ; 144(23): 10361-10367, 2022 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-35657101

RESUMO

The catalytic hydrofunctionalization of alkenes through radical-polar crossover metal hydrogen atom transfer (MHAT) offers a mild pathway for the introduction of functional groups in sterically congested environments. For M = Co, this reaction is often proposed to proceed through secondary alkylcobalt(IV) intermediates, which have not been characterized unambiguously. Here, we characterize a metastable (salen)Co(isopropyl) cation, which is capable of forming C-O bonds with alcohols as proposed in the catalytic reaction. Electron nuclear double resonance (ENDOR) spectroscopy of this formally cobalt(IV) species establishes the presence of the cobalt-carbon bond, and accompanying DFT calculations indicate that the unpaired electron is localized on the cobalt center. Both experimental and computational studies show that the cobalt(IV)-carbon bond is stronger than the analogous bond in its cobalt(III) analogue, which is opposite of the usual oxidation state trend of bond energies. This phenomenon is attributable to an inverted ligand field that gives the bond Coδ--Cδ+ character and explains its electrophilic reactivity at the alkyl group. The inverted Co-C bond polarity also stabilizes the formally cobalt(IV) alkyl complex so that it is accessible at unusually low potentials. Even another cobalt(III) complex, [(salen)CoIII]+, is capable of oxidizing (salen)CoIII(iPr) to the formally cobalt(IV) state. These results give insight into the electronic structure, energetics, and reactivity of a key reactive intermediate in oxidative MHAT catalysis.


Assuntos
Cobalto , Hidrogênio , Carbono , Catálise , Cobalto/química , Etilenodiaminas , Hidrogênio/química , Metais , Oxirredução , Estresse Oxidativo , Oxigênio/química
3.
Pattern Recognit ; 131: 108826, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-35698723

RESUMO

The devastating outbreak of Coronavirus Disease (COVID-19) cases in early 2020 led the world to face health crises. Subsequently, the exponential reproduction rate of COVID-19 disease can only be reduced by early diagnosis of COVID-19 infection cases correctly. The initial research findings reported that radiological examinations using CT and CXR modality have successfully reduced false negatives by RT-PCR test. This research study aims to develop an explainable diagnosis system for the detection and infection region quantification of COVID-19 disease. The existing research studies successfully explored deep learning approaches with higher performance measures but lacked generalization and interpretability for COVID-19 diagnosis. In this study, we address these issues by the Covid-MANet network, an automated end-to-end multi-task attention network that works for 5 classes in three stages for COVID-19 infection screening. The first stage of the Covid-MANet network localizes attention of the model to the relevant lungs region for disease recognition. The second stage of the Covid-MANet network differentiates COVID-19 cases from bacterial pneumonia, viral pneumonia, normal and tuberculosis cases, respectively. To improve the interpretation and explainability, three experiments have been conducted in exploration of the most coherent and appropriate classification approach. Moreover, the multi-scale attention model MA-DenseNet201 proposed for the classification of COVID-19 cases. The final stage of the Covid-MANet network quantifies the proportion of infection and severity of COVID-19 in the lungs. The COVID-19 cases are graded into more specific severity levels such as mild, moderate, severe, and critical as per the score assigned by the RALE scoring system. The MA-DenseNet201 classification model outperforms eight state-of-the-art CNN models, in terms of sensitivity and interpretation with lung localization network. The COVID-19 infection segmentation by UNet with DenseNet121 encoder achieves dice score of 86.15% outperforming UNet, UNet++, AttentionUNet, R2UNet, with VGG16, ResNet50 and DenseNet201 encoder. The proposed network not only classifies images based on the predicted label but also highlights the infection by segmentation/localization of model-focused regions to support explainable decisions. MA-DenseNet201 model with a segmentation-based cropping approach achieves maximum interpretation of 96% with COVID-19 sensitivity of 97.75%. Finally, based on class-varied sensitivity analysis Covid-MANet ensemble network of MA-DenseNet201, ResNet50 and MobileNet achieve 95.05% accuracy and 98.75% COVID-19 sensitivity. The proposed model is externally validated on an unseen dataset, yields 98.17% COVID-19 sensitivity.

4.
Chemosphere ; : 135464, 2022 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-35760140

RESUMO

Hydrotalcite-like anionic clays (HTs) also known as Layered double hydroxides (LDHs) have been developed as multifunctional materials in numerous applications related to catalysis, adsorption, and ion-exchange processes. These materials constitute an important class of ionic lamellar solid clays of Brucite-like structure which comprise of consecutive layers of divalent and trivalent metal cations with charge balancing anions and water molecules in interlayer space. These materials have received increasing attention in research due to their interesting properties namely layered structure, ease of preparation, flexible tunability, ability to intercalate different types of anions, electronic properties, high thermal stability, high biocompatibility, and easy biodegradation. Moreover, HTs/LDHs have unique tailorable and tuneable characteristics such as both acidic and basic sites, anion exchange capability, surface area, basal spacing, memory effect, and also exhibit high exchange capacities, which makes them versatile materials for a wide range of applications and extended their horizons to diverse areas of science and technology. This study enlightens the various rational researches related to the synthetic methods and features focusing on synthesis and/or fabrication with other hybrids and their applications. The diverse applications (namely catalyst, adsorbent to toxic chemicals, agrochemicals management, non-toxic flame retardants, and recycling of plastics) of these multifunctional materials related to a clean and sustainable environment were also summarized.

5.
J Am Soc Nephrol ; 33(7): 1229-1231, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35728882
6.
Urologia ; : 3915603221104047, 2022 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-35730727

RESUMO

INTRODUCTION: Idiopathic retroperitoneal fibrosis is a known cause of obstructive uropathy. Ureterolysis is done when medical management fails or the presentation is at an advanced stage. Conventionally ureterolysis without omental wrap has been considered incomplete. Our Institute has experience of laparoscopic or robotic ureterolysis with intraperitonealization of the ureter alone and no other adjunctive procedure. This study retrospectively assesses the result of the procedure with patients presenting with varying severity of disease. METHODS: From 2008, all patients who underwent laparoscopic or robotic ureterolysis were analyzed retrospectively for pre-operative management, operative findings, and post operative outcomes. RESULTS: We operated and released nine renal units in seven patients. Two of the nine cases were performed robotically completely and the rest was performed by laparoscopic approach. Median follow up was 60 months. All patients documented resolution of symptoms. The mean post-operative creatinine at 1 year was significantly decreased to 1.47 ± 0.49 mg/dl in comparison to preoperative creatinine (p < 0.05). The postoperative mean ESR decreased significantly from a preoperative value of 58.2 ± 19.41 mm to 15.8 ± 17.23. The nuclear scan revealed unobstructed drainage and radiological imaging revealed resolution of hydronephrosis and fibrosis in all. The mean GFR on the nuclear scan after 3 and 12 months of surgery was 36.3 ± 4.33 and 40 ± 3.77, respectively. Thus, there was significant increase noted in GFR at 3 and 12 months in comparison to preoperative GFR (p < 0.05). CONCLUSION: Laparoscopic/robotic ureterolysis with intraperitonealization alone is secure and durable procedure for idiopathic retroperitoneal fibrosis needing surgical release.

8.
Bioresour Technol ; 356: 127332, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35589042

RESUMO

This work studied the co-pyrolysis of wheat straw (WS) and polyethylene (PE) via thermogravimetric experiments from room temperature to 1000 °C at various heating rates (10, 20, and 30 °C/min). Thermal behavior revealed that the maximum decomposition of WS, PE, and their blend occurred in three temperature ranges, viz. 250 - 496, 200 - 486, and 200 - 501 °C. Kinetic parameters were determined using model-free isoconversional methods. Activation energy from KAS (163.56, 220.26 and 196.78 kJ/mol for WS, PE, and blend), FWO (165.97, 222.05, 198.86 kJ/mol for WS, PE, and blend), and Starink (163.45, 220.05, 196.46 kJ/mol for WS, PE, and blend) method was estimated. From among various solid-state kinetic models, first-order reaction kinetics and one and two-dimensional diffusion models dominated co-pyrolysis of WS and PE. Thermodynamic parameters confirmed the feasibility of co-pyrolysis of WS and PE while differential thermal analysis signified that endothermic and exothermic reactions occur simultaneously.


Assuntos
Pirólise , Triticum , Biomassa , Cinética , Plásticos , Polietileno , Termodinâmica , Termogravimetria
9.
J Multimorb Comorb ; 12: 26335565221098832, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35586031

RESUMO

Objectives: To estimate the prevalence of specific comorbid conditions (CCs) and multiple comorbid conditions (MCCs) among adult patients with hyperkalemia and examine the associations between MCCs and healthcare resource utilization (HRU) and costs. Methods: This retrospective observational cohort study was conducted using a large administrative claims database. We identified patients with hyperkalemia (ICD-10-CM: E87.5; or serum potassium >5.0 mEq/L; or NDC codes for either patiromer or sodium polystyrene sulfonate) during the study period (1/1/2016-6/30/2019). The earliest service/claim date with evidence of hyperkalemia was identified as index date. Qualified patients had ≥12 months of enrolment before and after index date, ≥18 years of age. Comorbid conditions were assessed using all data within 12 months prior to the index date. Healthcare resource utilization and costs were estimated using all data within 12 months after the index date. Association rule mining was applied to identify MCCs. Generalized linear models were used to examine the associations between MCCs and HRU and costs. Results: Of 22,154 patients with hyperkalemia, 94% had ≥3 CCs. The most common individual CCs were chronic kidney disease (CKD, 85%), hypertension (HTN, 83%), hyperlipidemia (HLD, 81%), and diabetes mellitus (DM, 47%). The most common dyad combination of CCs was CKD+HTN (71%). The most common triad combination was CKD+HTN+HLD (62%). The most common quartet combination was CKD+HTN+HLD+DM (36%). The increased number of CCs were significantly associated with increased ED visits, length of hospital stays, and total healthcare costs (all p-value < 0.0001). Conclusions: MCCs are very prevalent among patients with hyperkalemia and are strongly associated with HRU and costs.

10.
Plants (Basel) ; 11(9)2022 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-35567130

RESUMO

The influence of medicinal plants on humanity spans time immemorial. These plants are also used at present with local and tribal peoples for the cures of various illnesses. Nature has produced an immense number of medicinal plants, which directly or indirectly help to treat various ailments and have numerous applications in the fields of pharmaceuticals, agriculture, food flavors and preservatives, aromas, and cosmetics. Bergenia pacumbis (Buch.-Ham. ex D.Don) C.Y.Wu & J.T.Pan (synonym: Bergenia ligulate Engl.), is an important medicinal plant belonging to the Saxifragaceae family, and not to be confused with Bergenia ciliata (Haw.) Sternb., and is popularly known as Pashanbheda (meaning to dissolve the kidney stone). This plant is a rich source of secondary metabolites (SMs) such as coumarins, flavonoids, benzenoids, lactones, tannins, phenols, and sterols, which make this plant a highly valued medicinal herb with a broad spectrum of pharmacological activities such as anti-urolithic, antioxidant, anti-viral, free radical scavenging, antidiabetic, anti-hepatotoxic, diuretic, antipyretic, anti-oxaluria, anti-tumour, antibacterial, antifungal, anti-inflammatory, antimicrobial, and cardioprotective. This review summarizes traditional uses and offers up to date data for future research on B. pacumbis.

11.
Polymers (Basel) ; 14(9)2022 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-35566950

RESUMO

Recent research shows the growing interest in the development of composite edible films (EFs) by using multiple biopolymers for the substantial improvement in the shelf life and quality of food products, via preventing oxidation among other benefits. In the present work, EFs based on chitosan (CS) and porphyran (POR) loaded with ginger essential oil (GEO) have been developed to study the effect of GEO, glycerol (Gly), and POR on the film structure as well as physical and antioxidant properties. Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) results showed the level of crystallinity and electrostatic interactions between CS, POR, Gly, and GEO. It was found that electrostatic interactions between CS and POR and the incorporation of GEO substantially improved barrier, thermal, optical, and mechanical properties and reduced the moisture content, swelling index, and thickness values. The color values of the S5 film altered apparently with a shift towards yellowness. SEM micrographs of the composite CS-POR-GEO film (S5) showed improved morphological attributes such as more uniformity and homogeneous structure than other films (S1-S4). Results obtained from total phenolic content assay suggested the presence of high phenolic components (5.97 ± 0.01) mg of GAE/g in GEO. Further, findings obtained from antioxidant assays revealed that the addition of GEO and POR significantly increased the antioxidant effects of CS films. All these findings suggested that GEO loaded CS-POR based films showed better physical and chemical properties with a significant improvement in antioxidant potential and thus can be used as a potential packaging material in the food industry.

12.
Front Oncol ; 12: 855167, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35600406

RESUMO

The RE1 Silencing Transcription Factor (REST) is a major regulator of neurogenesis and brain development. Medulloblastoma (MB) is a pediatric brain cancer characterized by a blockade of neuronal specification. REST gene expression is aberrantly elevated in a subset of MBs that are driven by constitutive activation of sonic hedgehog (SHH) signaling in cerebellar granular progenitor cells (CGNPs), the cells of origin of this subgroup of tumors. To understand its transcriptional deregulation in MBs, we first studied control of Rest gene expression during neuronal differentiation of normal mouse CGNPs. Higher Rest expression was observed in proliferating CGNPs compared to differentiating neurons. Interestingly, two Rest isoforms were expressed in CGNPs, of which only one showed a significant reduction in expression during neurogenesis. In proliferating CGNPs, higher MLL4 and KDM7A activities opposed by the repressive polycomb repressive complex 2 (PRC2) and the G9A/G9A-like protein (GLP) complex function allowed Rest homeostasis. During differentiation, reduction in MLL4 enrichment on chromatin, in conjunction with an increase in PRC2/G9A/GLP/KDM7A activities promoted a decline in Rest expression. These findings suggest a lineage-context specific paradoxical role for KDM7A in the regulation of Rest expression in CGNPs. In human SHH-MBs (SHH-α and SHH-ß) where elevated REST gene expression is associated with poor prognosis, up- or downregulation of KDM7A caused a significant worsening in patient survival. Our studies are the first to implicate KDM7A in REST regulation and in MB biology.

14.
Ann Hematol ; 101(6): 1173-1179, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35396605

RESUMO

In developing countries, anti-D has been used in immune thrombocytopenia (ITP) as a cheaper alternative to human immunoglobulin. We aim to analyze the response and safety profile of anti-D in patients with severe ITP. A retrospective study was conducted at a tertiary care hospital in Northern India. Patients received a single intravenous infusion of 75 µg/kg anti-D. In total, 36 patients (20 females) were included in this study. The median duration from ITP diagnosis to anti-D therapy was 235 days (range 1-1613 days). Four (11.1%) patients received anti-D as an upfront treatment. The patients' platelet counts rose significantly by the end of day three and continued to be significantly high until day 30 of receiving anti-D (p ≤ 0.001). The overall response rate (ORR) by day seven was 88.89%. There was no effect of age, sex, duration of disease, prior therapy, and platelet count on the ORR. Patients were followed up for a median duration of 52 days (longest follow-up: 3080 days). Six (6/36, 16.67%) patients continued to be in remission till the last follow-up. The hemoglobin fall was statistically significant on day three and day seven (p < 0.001 and p = 0.001) and got normalized by day 30. We observed equally good ORR in mixed populations and different phases of ITP along with long-term sustained response. The study demonstrates a quick and high response rate along with good safety profile to anti-D in all forms of ITP.


Assuntos
Púrpura Trombocitopênica Idiopática , Trombocitopenia , Feminino , Humanos , Masculino , Púrpura Trombocitopênica Idiopática/diagnóstico , Estudos Retrospectivos , Imunoglobulina rho(D)/efeitos adversos , Trombocitopenia/induzido quimicamente , Resultado do Tratamento
15.
Biomed Chromatogr ; 36(7): e5372, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35304759

RESUMO

Pesticide residue in food commodities is a serious concern in relation to consumer safety and also the most significant barrier in the trade of food commodities. The dissipation pattern of four insecticides, namely novaluron, λ-cyhalothrin, imidacloprid, and fenazaquin, was evaluated on tomato fruits and cropped soil. The residues were extracted using the QuEChERS analytical method and quantized using a gas chromatograph with electron capture detector, gas chromatograph mass spectrometer, and high-performance liquid chromatography with photo diode array detector. The analytical method was validated using parameters like recovery, linearity, accuracy, matrix effect, and specificity, with limit of detection and limit of quantitation established to be 0.01 and 0.05 mg/kg, respectively, for all the pesticides. The average initial deposits (samples collected after 2 h of application) at the recommended dose of novaluron, λ-cyhalothrin, imidacloprid, and fenazaquin were 0.593, 0.293, 0.227, and 0.431 mg/kg on tomato fruits, respectively, and were below the limit of quantification in soil. The pre-harvest interval of 17, 8, 1, and 13 days was suggested for novaluron, λ-cyhalothrin, imidacloprid, and fenazaquin on tomato, respectively. Risk assessment studies revealed that all pesticides under study are safe and do not pose any threat to humans as theoretical maximum dietary intake is less than the maximum permissible intake and acceptable daily intake.


Assuntos
Inseticidas , Lycopersicon esculentum , Resíduos de Praguicidas , Monitoramento Ambiental , Meia-Vida , Humanos , Inseticidas/análise , Lycopersicon esculentum/química , Resíduos de Praguicidas/análise , Medição de Risco , Solo/química
16.
Indian J Cancer ; 59(Supplement): S11-S18, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-35343188

RESUMO

Background: Molecular tissue testing in non-small cell lung cancer (NSCLC) is done for the assessment of epidermal growth factor receptor (EGFR) mutation. EGFR mutation status is the basis for deciding the targeted treatment option for patients with metastatic NSCLC. The nonavailability of tissue samples and contraindications for biopsy pose a significant challenge. Hence, circulating tumor DNA (ctDNA) by liquid biopsy can be a viable alternative for NSCLC patients. Methods: This study was conducted at 15 sites across India. EGFR mutation testing from plasma was done as part of the study at the central laboratory by the next-generation sequencing (NGS) method, and EGFR mutation test results from tissue samples (done as part of routine practice) were recorded for all the patients. Results: Out of the total patients enrolled (N = 245), the majority (64.5%, n = 158) were men. The median age of patients was 58.0 (range: 26-84) years. The concordance between plasma and tissue testing was found to be 82.9% (95% confidence interval [CI]: 77.55, 87.45). The sensitivity and specificity of NGS were 68.4% (95% CI: 56.92, 78.37) and 90.1% [95% CI: 84.36, 94.21), respectively. Plasma testing detected 1.2% (n = 3) and tissue sample testing detected 2.4% (n = 6) positive status of exon 20 T790M EGFR mutation. Out of the total number of patients enrolled, 25 were tissue positive and plasma negative, while 16 were plasma positive and tissue negative. Conclusions: "> This real-world study in Indian patients suggests that plasma testing for EGFR mutation analysis is a viable diagnostic option in newly diagnosed advanced/metastatic NSCLC patients. The noninvasive plasma procedure in patients without available/evaluable tumor sample may enable more patients to receive appropriate targeted therapies by providing clinicians with valuable insights into the patient's tumor mutation status. ClinicalTrials.gov Identifier: NCT03562819.


Assuntos
Carcinoma Pulmonar de Células não Pequenas , DNA Tumoral Circulante , Neoplasias Pulmonares , Adulto , Idoso , Idoso de 80 Anos ou mais , Carcinoma Pulmonar de Células não Pequenas/diagnóstico , Carcinoma Pulmonar de Células não Pequenas/genética , DNA Tumoral Circulante/genética , Receptores ErbB/genética , Feminino , Humanos , Biópsia Líquida , Neoplasias Pulmonares/diagnóstico , Neoplasias Pulmonares/genética , Masculino , Pessoa de Meia-Idade , Mutação , Inibidores de Proteínas Quinases
17.
Qual Quant ; : 1-25, 2022 Mar 24.
Artigo em Inglês | MEDLINE | ID: mdl-35345629

RESUMO

The current research aims to explore and prioritize the key benefits that influence the acceptance of crowdfunding as a fund-raising tool, either directly or indirectly. The study utilized a multidisciplinary approach to find out the varied benefits of crowdfunding. The study also prioritized the benefits by applying the buckley fuzzy-AHP technique. The results indicate the various benefits of crowdfunding. The study's results suggest fund-raising (FR), venture viability (VV), cost structure (CS), customer relationships (CR), demand building (DB), general strategy (GS), market intelligence (MI), personal sphere (PS), business ecosystem (BE), team development (TD) and product lifecycle (PL) are the benefits associated with the crowdfunding process. The findings also suggest that the topmost benefit of crowdfunding is FR. But our study has not categorized the benefits according to different types of crowdfunding, and the study's findings cannot be generalized as the study was conducted in India. The study highlighted the critical financial and non-financial benefits of crowdfunding which can help the entrepreneurs to have more insightful knowledge of the potential benefits of crowdfunding. Studying the financial and non-financial benefits of crowdfunding can further help the entrepreneurs utilize crowdfunding platforms, depending on the need, to provide the right solution to their requirements. This research is the first study to apply the buckley fuzzy-AHP technique to prioritize the multidisciplinary benefits of crowdfunding, thereby widening the knowledge base of academicians and entrepreneurs.

18.
Dermatology ; : 1-7, 2022 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-35344957

RESUMO

BACKGROUND: Schools can play a major role in protecting students from skin cancer by instituting preventive policies and educational programs. METHODS: A high school-wide study was conducted to assess students' current understanding of skin cancer prevention, provide an up-to-date instruction lesson, and evaluate changes in students' knowledge and behaviors. RESULTS: Written surveys were distributed to 2,688 high school students with a return rate of 38.1% (n = 1,025). Surveys were administered prior to (survey 1), immediately after (survey 2), and 1 month after (survey 3) presenting a video lesson. Significant changes in knowledge gain (an increase from survey 1 to survey 2), knowledge decay (a decrease from survey 2 to survey 3), and knowledge persistence (an increase from survey 1 to survey 3) throughout all grade levels were found. Behavioral changes included an increase in students wearing sunscreen 5-7 days per week (p < 0.001) and students examining themselves for changing moles (p = 0.10). With this survey, the Health Education Framework for California Public Schools was revised to include updated recommendations regarding skin cancer prevention efforts in schools. CONCLUSIONS: A skin cancer video lesson given to high school students effectively increased students' knowledge and promoted healthy behaviors.

19.
BMJ Case Rep ; 15(3)2022 Mar 24.
Artigo em Inglês | MEDLINE | ID: mdl-35332000

RESUMO

A woman in her 70s who was being followed up for neovascular age-related macular degeneration (nAMD) in both eyes for 2 years with recalcitrant choroidal neovascularisation (CNV) and had an episode of acute endophthalmitis in one eye was identified. After treatment of postinjection culture-negative right eye (RE) endophthalmitis with intravitreal vancomycin and tazobactam, the patient had complete regression of treatment-resistant CNV in RE to date with postinfection follow-up of 2 years. In contrast, the fellow eye continued showing activity in the choroidal neovascular membrane that required antivascular endothelial growth factor injections on a pro re nata basis to date. Prolonged regression of nAMD for 3 years in the affected eye and continued activity in the fellow eye support the hypothesis that inflammation accompanying endophthalmitis or the drugs used for the treatment can have a role in the regression of nAMD.


Assuntos
Neovascularização de Coroide , Endoftalmite , Degeneração Macular , Pré-Escolar , Corioide/irrigação sanguínea , Neovascularização de Coroide/complicações , Neovascularização de Coroide/tratamento farmacológico , Endoftalmite/complicações , Endoftalmite/tratamento farmacológico , Feminino , Seguimentos , Humanos , Degeneração Macular/complicações , Degeneração Macular/tratamento farmacológico
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