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The synthesis of alkyl(aryl)-fluoroalkyl sulfanyl [R(Ar)-S-RF] and aryl-fluoroalkyl selenolyl (Ar-Se-RF) ethers through visible-light photocatalysis has been successfully carried out. This process involves disulfides, and diselenides [R(Ar)-X-X-R(Ar), where X = S or Se], and fluoroalkyl iodides (RF-I) in the presence of a base as an additive under photocatalysis. The photocatalyst Eosin Y and green light-emitting diodes are utilized for irradiation of R(Ar)-S-RF and Ar-Se-RF syntheses. Our method integrates low-energy visible-light photocatalysis, commercially available perfluoroalkylating reagents (RF-I), and easily obtainable disulfides and diselenides as starting materials. Mechanistic studies and a detailed synthetic procedure for (Ar)-S-RF on a large scale are presented.
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OBJECTIVES: To explore the cost conversations taking place when patients with atrial fibrillation and their clinicians decide on whether and how to use anticoagulation to prevent strokes. METHODS: Secondary qualitative thematic analysis of conversations from 476 clinical encounters in three sites of a multicenter randomized trial comparing usual care with and without a shared decision-making tool. RESULTS: We identified three themes with subthemes: (1) What was discussed: conversation content (2) How content was transmitted: communication patterns and (3) Implicit conversation drivers. Due to each patient's unique circumstances, bi-directional conversations focused on relationship- and solution-based content enabled better cost burden discovery. Conversation drivers included affordability, comorbidities, preferences, and uncertainty about future costs. CONCLUSIONS: Cost conversations were often initiated by clinicians, and if they did not invite a response, patients passively received information without understanding or weighing cost burden. When clinicians discussed cost information using relational or solution-focused content and bi-directional communication patients were more likely to engage in discussion including their unique situation. PRACTICE IMPLICATIONS: Solution-focused cost conversations can reduce financial treatment burden, but require estimates of out-of-pocket costs, insurance coverage, and long-term financial effects of various options. Conversation tools and information on financial resources are valuable to patients and clinicians.
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Primary thyroid lymphoma is a rare thyroid cancer, comprising Ë5% of thyroid neoplasms. Most cases are diffuse large B-cell lymphoma (DLBCL). Coexistence with papillary thyroid cancer (PTC) is extremely rare. This study presents a case of a 55-year-old woman with DLBCL and micropapillary thyroid cancer who underwent lobectomy, chemotherapy, and radiotherapy. Additionally, we performed a systematic review of 10 cases, including the reported case. The risk of bias in case reports varied. DLBCL diagnoses were mainly made after surgery, with total thyroidectomy being the most common surgical procedure. Chemotherapy was administered in most cases, and radiotherapy was used in some cases. Long-term outcomes indicated a low recurrence rate. While some debate the role of surgery in thyroid lymphoma, this study suggests that surgery should be considered in selected cases. Further research is needed to determine optimal treatment strategies for DLBCL with PTC.
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Blue LEDs-irradiation of a mixture of N,N,N',N'-tetramethylethylenediamine (TMEDA) and perfluoroalkyl iodides (RF-I) - Electron Donor Acceptor (EDA)-complex - in the presence of triphenylamines (TPAs) in an aqueous solvent mixture afforded mono-perfluoroalkylated triphenylamines (RF-TPA) in good yields. These RF-TPA were further subjected to acetone-sensitized [6π]-electrocyclization at 315â nm-irradiation affording exclusively perfluoroalkylated endo-carbazole derivatives (RF-CBz) in quantitative yields. Mechanistic studies and photophysical properties of products are studied.
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Radical reactions in water or aqueous media are important for organic synthesis, realizing high-yielding processes under non-toxic and environmentally friendly conditions. This overview includes (i) a general introduction to organic chemistry in water and aqueous media, (ii) synthetic approaches in, on, and with water as well as in heterogeneous phases, (iii) reactions of carbon-centered radicals with water (or deuterium oxide) activated through coordination with various Lewis acids, (iv) photocatalysis in water and aqueous media, and (v) synthetic applications bioinspired by naturally occurring processes. A wide range of chemical processes and synthetic strategies under different experimental conditions have been reviewed that lead to important functional group translocation and transformation reactions, leading to the preparation of complex molecules. These results reveal how water as a solvent/medium/reagent in radical chemistry has matured over the last two decades, with further discoveries anticipated in the near future.
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BACKGROUND: The global prevalence of thyroid cancer is on the rise. About one-third of newly diagnosed thyroid cancer cases comprise low-risk papillary thyroid cancer (1.5 cm or more minor). While surgical removal remains the prevailing approach for managing low-risk papillary thyroid cancer (LPTC) in patients, other options such as active surveillance (AS), radiofrequency ablation (RFA), microwave ablation (MWA), and laser ablation (LA) are also being considered as viable alternatives. This study evaluated and compared surgical thyroid resection (TSR) versus non-surgical (NS) methods for treating patients with LPTC. METHODS: The study encompassed an analysis of comparisons between surgical thyroid resection (TSR) and alternative approaches, including active surveillance (AS), radiofrequency ablation (RFA), microwave ablation (MWA), or laser ablation (LA). The focus was on patients with biopsy-confirmed low-risk papillary thyroid cancer (LPTC) of less than 1.5 cm without preoperative indications of local or distant metastasis. The primary outcomes assessed were recurrence rates, disease-specific mortality, and quality of life (QoL). Data were collected from prominent databases, including Cochrane Database, Embase, MEDLINE, and Scopus, from inception to June 3rd, 2020. The CLARITY tool was utilized to evaluate bias risk. The analysis involved odds ratios (OR) with 95% confidence intervals (CI) for dichotomous outcomes, as well as mean differences (MD) and standardized mean differences (SMD) for continuous outcomes. The study is registered on PROSPERO under the identifier CRD42021235657. RESULTS: The study incorporated 13 retrospective cohort studies involving 4034 patients. Surgical thyroid resection (TSR), active surveillance (AS), and minimally invasive techniques like radiofrequency ablation (RFA), microwave ablation (MWA), and laser ablation (LA) were performed in varying proportions of cases. The analysis indicated that specific disease mortality rates were comparable among AS, MWA, and TSR groups. The risk of recurrence, evaluated over different follow-up periods, showed no significant differences when comparing AS, RFA, MWA, or LA against TSR. Patients undergoing AS demonstrated better physical health-related quality of life (QoL) than those undergoing TSR. However, no substantial differences were observed in the overall mental health domain of QoL when comparing AS or RFA with TSR. The risk of bias was moderate in nine studies and high in four. CONCLUSION: Low-quality evidence indicates comparable recurrence and disease-specific mortality risks among patients with LPTC who underwent ablation techniques or active surveillance (AS) compared to surgery. Nevertheless, individuals who opted for AS exhibited enhanced physical quality of life (QoL). Subsequent investigations are warranted to validate these findings.
Subject(s)
Ablation Techniques , Catheter Ablation , Thyroid Neoplasms , Humans , Quality of Life , Catheter Ablation/methods , Thyroid Cancer, Papillary , Retrospective Studies , Watchful Waiting , Treatment OutcomeABSTRACT
Background: The frequency and factors associated with thyroid hormone replacement therapy among patients with subclinical hypothyroidism (SCH) remain uncertain. Methods: In this electronic health records-based observational cohort study, we included adults diagnosed with SCH from four academic centers (the United States and Mexico) from January 1, 2016, to December 31, 2018. We aimed to identify the determinants of thyroid hormone replacement therapy for SCH and the frequency of treated SCH. Results: A total of 796 patients (65.2% women) had SCH, and 165 (20.7%) were treated with thyroid hormone replacement therapy. The treated group was younger [51.0 (standard deviation {SD} 18.3) vs. 55.3 (SD 18.2) years, p = 0.008] and had a higher proportion of women (72.7% vs. 63.2%, p = 0.03) compared with the untreated group. Only 46.7% of patients in the treated group and 65.6% in the untreated group had confirmatory thyroid function tests (TFTs) before the decision to start thyroid hormone replacement therapy was made. There was no difference in the frequency of thyroid autoimmunity evaluation, but a positive thyroid autoimmunity test was more frequent in the treated group compared with the untreated group (48.2% vs. 20.3%, p < 0.001). In a multivariable logistic regression model, female sex (odds ratio [OR] = 1.71 [CI 1.13-2.59], p = 0.01) and index thyrotropin (TSH) level (OR = 1.97 [CI 1.56-2.49], p < 0.001 for every SD [2.75 mIU/L] change) were associated with higher odds of treatment. Conclusions: Among patients with SCH, female sex and index TSH level were associated with higher odds of treatment. Moreover, in our population, the decision to treat or not to treat SCH was often based on only one set of abnormal TFTs, and thyroid autoimmunity assessment was underused.
Subject(s)
Electronic Health Records , Hypothyroidism , Adult , Female , Humans , Male , Hypothyroidism/diagnosis , Thyrotropin/therapeutic use , Hormone Replacement Therapy , Thyroxine/therapeutic useABSTRACT
OBJECTIVE: The aim of this study was to determine inpatient health care utilization in an incident cohort of patients with systemic lupus erythematosus (SLE) compared with the general population. METHODS: This was a population-based cohort study in the upper Midwest, United States. We included patients fulfilling the European League Against Rheumatism/American College of Rheumatology SLE classification criteria between 1995 and 2018. They were 1:1 age-, sex-, county-matched with individuals without SLE. All hospital admissions and emergency department (ED) visits were electronically retrieved for 1995-2020. Rates for hospital admission, length of stay, readmission, ED visits, and discharge destination were compared between groups. RESULTS: Three hundred forty-one patients with SLE and 341 comparators without SLE were included (mean age, 48.6 years at diagnosis; 79.2% female). Rates of hospitalization for patients with SLE and comparators were 29.8 and 9.9 per 100 person-years, respectively. These differences were present across sexes and age groups. Hospitalization rates were higher in patients with SLE after diagnosis and remained higher than comparators for the first 15 years of the disease. Patients with SLE were more likely than comparators to visit the ED (hazard ratio, 2.71; 95% confidence interval, 2.05-3.59). Readmission rates (32% vs. 21%, p = 0.017) were higher in patients with SLE. Length of stay and discharge destination were similar between both groups. CONCLUSION: Patients with SLE were more likely to be hospitalized and to visit the ED than individuals without SLE, highlighting important inpatient care needs. Increased hospitalization rates were observed in both male and female patients and all age groups.
Subject(s)
Hospitalization , Lupus Erythematosus, Systemic , Humans , Male , Female , United States/epidemiology , Middle Aged , Cohort Studies , Retrospective Studies , Patient Acceptance of Health Care , Lupus Erythematosus, Systemic/diagnosis , Lupus Erythematosus, Systemic/epidemiology , Lupus Erythematosus, Systemic/therapyABSTRACT
OBJECTIVE: There is little information about the epidemiology and factors associated with opioid therapy in systemic lupus erythematosus (SLE). We aimed to assess the prevalence of opioid therapy and explore factors associated with long-term opioid therapy (LTOT) in patients with SLE. METHODS: Patients with SLE were matched with controls without SLE in a population-based cohort on January 1, 2015. We captured demographics, manifestations of SLE, comorbidities (ie, fibromyalgia, mood disorders, osteoarthritis, chronic low back pain [CLBP], chronic kidney disease (CKD), avascular necrosis, osteoporosis, fragility fractures, and cancer), and the Area Deprivation Index (ADI). Opioid prescription data were used to assess the prevalence of LTOT, defined as contiguous prescriptions (gaps of < 30 days between prescriptions) and receiving opioid therapy for ≥ 90 days or ≥ 10 prescriptions before the index date. RESULTS: A total of 465 patients with SLE and 465 controls without SLE were included. In total, 13% of patients with SLE and 3% of controls without SLE were receiving opioid therapy (P < 0.001), and 11% of patients with SLE were on LTOT vs 1% of controls without SLE. Among patients with SLE, acute pericarditis (odds ratio [OR] 3.92, 95% CI 1.78-8.66), fibromyalgia (OR 7.78, 95% CI 3.89-15.55), fragility fractures (OR 3.72, 95% CI 1.25-11.07), CLBP (OR 4.00, 95% CI 2.13-7.51), and mood disorders (OR 2.76, 95% CI 1.47-5.16) were associated with LTOT. We did not find an association between opioid therapy and ADI. CONCLUSION: Patients with SLE are more likely to receive LTOT than controls. Among patients with SLE, LTOT was associated with pericarditis and several comorbidities. However, LTOT was not associated with CKD despite the limited pain control options among these patients.
Subject(s)
Fibromyalgia , Fractures, Bone , Lupus Erythematosus, Systemic , Pericarditis , Humans , Analgesics, Opioid/therapeutic use , Retrospective Studies , Fibromyalgia/drug therapy , Fibromyalgia/epidemiology , Lupus Erythematosus, Systemic/complications , Lupus Erythematosus, Systemic/drug therapy , Lupus Erythematosus, Systemic/epidemiologyABSTRACT
Mitochondrial (mt) DNA and nuclear (n) DNA have known structures and roles in cells; however, they are rarely compared under specific conditions such as oxidative or degenerative environments that can create damage to the DNA base moieties. Six purine lesions were ascertained in the mtDNA of wild type (wt) CSA (CS3BE-wtCSA) and wtCSB (CS1AN-wtCSB) cells and defective counterparts CS3BE and CS1AN in comparison with the corresponding total (t) DNA (t = n + mt). In particular, the four 5',8-cyclopurine (cPu) and the two 8-oxo-purine (8-oxo-Pu) lesions were accurately quantified by LC-MS/MS analysis using isotopomeric internal standards after an enzymatic digestion procedure. The 8-oxo-Pu levels were found to be in the range of 25-50 lesions/107 nucleotides in both the mtDNA and tDNA. The four cPu were undetectable in the mtDNA both in defective cells and in the wt counterparts (CSA and CSB), contrary to their detection in tDNA, indicating a nonappearance of hydroxyl radical (HOâ¢) reactivity within the mtDNA. In order to assess the HO⢠reactivity towards purine nucleobases in the two genetic materials, we performed γ-radiolysis experiments coupled with the 8-oxo-Pu and cPu quantifications on isolated mtDNA and tDNA from wtCSB cells. In the latter experiments, all six purine lesions were detected in both of the DNA, showing a higher resistance to HO⢠attack in the case of mtDNA compared with tDNA, likely due to their different DNA helical topology influencing the relative abundance of the lesions.
Subject(s)
Cockayne Syndrome , Humans , DNA Damage , DNA, Mitochondrial/genetics , Chromatography, Liquid , Tandem Mass Spectrometry/methods , PurinesABSTRACT
Background: Rheumatoid arthritis has been associated with severe COVID-19, but few studies have investigated how phenotypes of rheumatoid arthritis affect these associations. We aimed to investigate the associations between rheumatoid arthritis and phenotypes of interstitial lung disease, serostatus, and bone erosions with COVID-19 severity. Methods: We did a retrospective, comparative, multicentre cohort study at two large health-care systems (Mayo Clinic [19 hospitals and affiliated outpatient centres] and Mass General Brigham [14 hospitals and affiliated outpatient centres]) in the USA. Consecutive patients with rheumatoid arthritis meeting the 2010 American College of Rheumatology/European League Against Rheumatism classification criteria and who had COVID-19 between March 1, 2020, and June 6, 2021, were matched 1:5 on age, sex, and calendar date with patients without rheumatoid arthritis (comparators). Data were received from electronic health records from Mayo Clinic and Mass General Brigham. We examined subgroups of patients with rheumatoid arthritis by phenotypic features: rheumatoid arthritis-associated interstitial lung disease, seropositivity (for anti-cyclic citrullinated peptide, rheumatoid factor, or both), and bone erosions. Severe COVID-19 was a composite of hospitalisation or death. We used Cox regression to estimate hazard ratios (HR) for severe COVID-19, comparing rheumatoid arthritis and subgroups to the comparator group. Findings: We identified 582 patients with rheumatoid arthritis and 2875 matched comparators, all of whom had COVID-19 within the study dates. The mean age of those with rheumatoid arthritis was 62 [SD 14] years, 421 (72%) of 582 were women and 161 (28%) were men, 457 (79%) were White, 65 (11%) were Hispanic or Latino, and 41 (7%) were Black. Among patients with rheumatoid arthritis, 50 (9%) of 582 had interstitial lung disease, 388 (68%) of 568 were seropositive, and 159 (27%) of 582 had bone erosions. Severe COVID-19 occurred in 126 (22%) of 582 patients with rheumatoid arthritis versus 363 (13%) 2875 in the comparator group. Patients with rheumatoid arthritis had an HR of 1·75 (95% CI 1·45-2·10) for severe COVID-19 versus the comparator group. Patients with rheumatoid arthritis-associated interstitial lung disease had an HR of 2·50 (1·66-3·77) versus the comparator group for severe COVID-19. The risk for severe COVID-19 was also higher in patients with rheumatoid arthritis who were seropositive (HR 1·97 [95% CI 1·58-2·46]) or had erosive disease (1·93 [1·41-2·63]) than for those in the comparator group. Interpretation: Patients with rheumatoid arthritis have an increased risk of severe COVID-19 across phenotypic subgroups, especially among patients with interstitial lung disease. These findings suggest that rheumatoid arthritis with interstitial lung disease, or its treatment, might be a substantial contributor to severe COVID-19 outcomes for patients with rheumatoid arthritis. Funding: None.
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Direct fluoroalkoxylation reactions of (hetero)arenes, carbon-carbon multiple bonds, and substitution reactions at Csp3 carbon centers by CF3 O, CHF2 O, and (CF3 )2 CFO groups are discussed. Emphasis on thermal radical, electron transfer, photocatalytic, electrochemical and redox-neutral radical methods are placed to accomplish fluoroalkoxylation reactions. All these methods employ either radical fluoroalkoxylating reagents or some nucleophilic trifluoromethoxylating sources of CF3 O. A summary of all these methods is provided in Tableâ 2.
Subject(s)
Alkenes , Carbon , Oxidation-Reduction , Indicators and Reagents , Carbon/chemistry , Physical PhenomenaABSTRACT
PURPOSE: Access to health care is a long-standing concern for rural patients; however, administrative measures fail to capture the subjective patient experience of accessing health care. The purpose of this review was to synthesize the qualitative literature on patient and caregiver experiences of accessing health care services for chronic disease management among US residents of rural areas. METHODS: We searched Embase, MEDLINE, PsycInfo, CINAHL, and Scopus to identify qualitative studies published during 2010-2019. A thematic synthesis approach was used to analyze findings from included studies. RESULTS: A total of 62 studies involving 1,354 unique participants were included. The largest share of studies (24.2%) was focused on the experience of patients with cancer, followed by behavioral health (16.1%), HIV and AIDS (14.5%), and diabetes (12.9%). We identified 4 primary analytic themes of barriers and facilitators associated with the experience of accessing health care services for chronic disease management in rural areas: (1) navigating the rural environment, (2) navigating the health care system, (3) financing chronic disease management, and (4) rural life (ie, common elements of a distinct "rural" way of thinking and behaving). CONCLUSIONS: In this comprehensive review, we found that important cultural, structural, and individual factors influenced the rural patient's experience of health care access and use, including barriers and facilitators posed by geographic and built environments, and distinct rural mores. Our findings can inform policies and programs that both facilitate structural aspects of access and include culturally appropriate interventions.VISUAL ABSTRACT.
Subject(s)
Health Services Accessibility , Rural Population , Chronic Disease , Humans , Patient Outcome Assessment , Qualitative ResearchABSTRACT
The introduction of robotics in living donor liver transplantation has been revolutionary. We aimed to examine the safety of robotic living donor right hepatectomy (RLDRH) compared to open (ODRH) and laparoscopic (LADRH) approaches. A systematic review was carried out in Medline and six additional databases following PRISMA guidelines. Data on morbidity, postoperative liver function, and pain in donors and recipients were extracted from studies comparing RLDRH, ODRH, and LADRH published up to September 2020; PROSPERO (CRD42020214313). Dichotomous variables were pooled as risk ratios and continuous variables as weighted mean differences. Four studies with a total of 517 patients were included. In living donors, the postoperative total bilirubin level (MD: −0.7 95%CI −1.0, −0.4), length of hospital stay (MD: −0.8 95%CI −1.4, −0.3), Clavien−Dindo complications I−II (RR: 0.5 95%CI 0.2, 0.9), and pain score at day > 3 (MD: −0.6 95%CI −1.6, 0.4) were lower following RLDRH compared to ODRH. Furthermore, the pain score at day > 3 (MD: −0.4 95%CI −0.8, −0.09) was lower after RLDRH when compared to LADRH. In recipients, the postoperative AST level was lower (MD: −0.5 95%CI −0.9, −0.1) following RLDRH compared to ODRH. Moreover, the length of stay (MD: −6.4 95%CI −11.3, −1.5) was lower after RLDRH when compared to LADRH. In summary, we identified low- to unclear-quality evidence that RLDRH seems to be safe and feasible for adult living donor liver transplantation compared to the conventional approaches. No postoperative deaths were reported.
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The Rose Bengal-photocatalyzed perfluorohexylation of olefins, alkynes, and electron-rich aromatic compounds in water was achieved employing perfluorohexyl iodide as fluoroalkyl source and TMEDA as sacrificial donor under green LED irradiation. Alkenes and alkynes rendered products derived from the atom transfer radical addition (ATRA) pathway, and in the case of alkynes, exclusively as E-stereoisomers. These are the first examples of photocatalyzed ATRA reactions carried out excursively in water alone. The reactions of aromatic compounds under the current protocol in water present the advantage of employing a perfluoroalkyl iodide (C6F13-I) as source of perfluorohexyl radicals. Examples of photocatalytic late-stage incorporations of fluoroalkyl moieties into two commercial drugs of widespread use are reported.
Subject(s)
Rose Bengal , Water , Alkenes/chemistry , Alkynes/chemistry , Iodides , Molecular StructureABSTRACT
Consensus-based recommendations guide standards of care for clinical practice. Pharmaceutical industry involvement in producing such recommendations might undermine their objectivity. We did a systematic review of rheumatology consensus-based recommendations that were published in English from 2000 to 2020. We compared those that were endorsed by major professional societies to those that were sponsored by industry using the validated Appraisal of Guidelines for Research & Evaluation (AGREE) II instrument. Of 234 consensus-based recommendation projects, 51 (22%) were endorsed by major societies and 74 (32%) were sponsored by the pharmaceutical industry. Among industry-sponsored projects, the sponsor was involved in the consensus-based process in 21 (28%), provided a medical writer in 12 (16%), offered honoraria for participation in five (7%), and was allowed to approve the final draft of one project. When compared with projects endorsed by major societies, industry-sponsored projects were less likely to have a high quality assessment on the AGREE II instrument. These results suggest that industry sponsorship of consensus-based recommendations is common in projects that do not receive endorsement by major societies. Such projects are often of lower quality than guidelines endorsed by major professional societies. Medical journals should consider steps to encourage greater rigour of development and to limit undue influence by industry sponsors.
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The conversion of ribonucleosides to 2'-deoxyribonucleosides is catalyzed by ribonucleoside reductase enzymes in nature. One of the key steps in this complex radical mechanism is the reduction of the 3'-ketodeoxynucleotide by a pair of cysteine residues, providing the electrons via a disulfide radical anion (RSSRâ¢-) in the active site of the enzyme. In the present study, the bioinspired conversion of ketones to corresponding alcohols was achieved by the intermediacy of disulfide radical anion of cysteine (CysSSCys)â¢- in water. High concentration of cysteine and pH 10.6 are necessary for high-yielding reactions. The photoinitiated radical chain reaction includes the one-electron reduction of carbonyl moiety by disulfide radical anion, protonation of the resulting ketyl radical anion by water, and H-atom abstraction from CysSH. The (CysSSCys)â¢- transient species generated by ionizing radiation in aqueous solutions allowed the measurement of kinetic data with ketones by pulse radiolysis. By measuring the rate of the decay of (CysSSCys)â¢- at λmax = 420 nm at various concentrations of ketones, we found the rate constants of three cyclic ketones to be in the range of 104-105 M-1s-1 at ~22 °C.
Subject(s)
Biomimetics , Disulfides , Ketones , Hydroxyl Radical/chemistry , Kinetics , WaterABSTRACT
The electron-rich nature of aminoaromatic compounds and the electrophilic character of fluoroalkyl RF radicals allow for a special match in substitution reactions. We herein present visible light photocatalyzed fluoroalkylation reactions of aniline derivatives, with a study of the reaction mechanisms. The examples evaluated make use of different photocatalysts, such as polypyridyl complexes of Ir or Ru transition metals, organic dyes such as Rose Bengal, phthalocyanine-metal organocatalysts, or visible-light activated complexes. Different visible light sources that span from the blue region of the electromagnetic spectrum to low power red light irradiation sources deliver the excited photocatalysts that ensue into the production of fluoroalkyl RF radicals. In turn, many sources of RF radicals can be employed, such as fluoroalkyl halides, Togni's reagents, Umemoto's reagent, etc. All these protocol variants demonstrate the expansion of the methodology and the versatility of photocatalytic techniques applied to a special family of organic compounds such as aminoaromatic substrates, which has been studied by different groups. Contributions from our own laboratory will be given.
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ABSTRACT Penalty kicks are often decisive in football matches. Therefore, any technique that yields an advantage either in scoring or saving them is of great importance. Here we show the influence of a training programme for goalkeepers on the probability of defending penalties in men's football. Virtual training was used through an app that shows the shooter at the moment of setting the support foot on the ground and requiring the answer of which side (right or left) the ball will be directed at. Complemented with physical training, four sub 21 professional goalkeepers from Santarém, Brazil, developed the ability to correctly choose the side (left or right) at which the ball will be aimed. Sets of 800 penalties were kicked before (acting as control group) and after the training programme and it was found that, after training, the chances of saving penalty kicks or, at least, choosing the correct side, increase dramatically. It is concluded that the training programme improved the goalkeeper's ability to choose the correct side. Other factors (laterality and height) were not found to be statistically significant.
RESUMO Os pênaltis são frequentemente decisivos em partidas de futebol. Portanto, qualquer técnica que produza uma vantagem tanto para marcar como para salvá-los é de grande importância. Aqui mostramos a influência de um programa de treinamento de goleiros na probabilidade de defesa de pênaltis no futebol masculino. O treinamento virtual foi utilizado por meio de um aplicativo que mostra o chutador no momento de colocar o pé de apoio no solo e exigir a resposta de qual lado (direito ou esquerdo) a bola será direcionada. Complementado com treinamento físico, quatro goleiros profissionais sub 21 de Santarém, Brasil, desenvolveram a habilidade de escolher corretamente o lado (esquerdo ou direito) para o qual a bola seria direcionada. Conjuntos de 800 pênaltis foram chutados antes (agindo como um grupo de controle) e depois do programa de treinamento e verificou-se que, após o treino, as chances de salvar pênaltis ou, pelo menos, de escolher o lado correto aumentam drasticamente. Conclui-se que o programa de treinamento melhorou a habilidade do goleiro em escolher o lado correto. Outros fatores (lateralidade e estatura) não mostraram ser estadísticamente significativos.
RESUMEN Los tiros penales suelen ser decisivos en los partidos de fútbol. Por lo tanto, cualquier técnica que proporcione una ventaja, ya sea para anotar o para atajarlos, es de gran importancia. Aquí mostramos la influencia de un programa de entrenamiento para goleros sobre la probabilidad de atajar los penaltis en el fútbol masculino. Se utilizó entrenamiento virtual a través de una aplicación que muestra al tirador en el momento de poner el pie de apoyo en el suelo y que requiere la respuesta de hacia qué lado (derecho o izquierdo) se dirigirá el balón. Complementado con entrenamiento físico, cuatro goleros profesionales sub 21 de Santarém, Brasil, desarrollaron la capacidad de elegir correctamente el lado (izquierdo o derecho) al que se dirigiría el balón. Se lanzaron series de 800 penales antes (actuando como un grupo de control) y después del programa de entrenamiento y se encontró que, después del entrenamiento, las posibilidades de atajarlos o, al menos, elegir el lado correcto, aumentan drásticamente. Se concluye que el programa de entrenamiento mejoró la capacidad del golero para elegir el lado correcto. Otros factores (lateralidad y estatura) no mostraron ser estadísticamente significativos.