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1.
BMJ Open ; 13(11): e062123, 2023 11 01.
Artículo en Inglés | MEDLINE | ID: mdl-37914308

RESUMEN

OBJECTIVES: Active case finding (ACF) is an important tuberculosis (TB) intervention in high-burden settings. However, empirical evidence garnered from field data has been equivocal about the long-term community-level impact, and more data at a finer geographic scale and data-informed methods to quantify their impact are necessary. METHODS: Using village development committee (VDC)-level data on TB notification and demography between 2016 and 2017 in four southern districts of Nepal, where ACF activities were implemented as a part of the IMPACT-TB study between 2017 and 2019, we developed VDC-level transmission models of TB and ACF. Using these models and ACF yield data collected in the study, we estimated the potential epidemiological impact of IMPACT-TB ACF and compared its efficiency across VDCs in each district. RESULTS: Cases were found in the majority of VDCs during IMPACT-TB ACF, but the number of cases detected within VDCs correlated weakly with historic case notification rates. We projected that this ACF intervention would reduce the TB incidence rate by 14% (12-16) in Chitwan, 8.6% (7.3-9.7) in Dhanusha, 8.3% (7.3-9.2) in Mahottari and 3% (2.5-3.2) in Makwanpur. Over the next 10 years, we projected that this intervention would avert 987 (746-1282), 422 (304-571), 598 (450-782) and 197 (172-240) cases in Chitwan, Dhanusha, Mahottari and Makwanpur, respectively. There was substantial variation in the efficiency of ACF across VDCs: there was up to twofold difference in the number of cases averted in the 10 years per case detected. CONCLUSION: ACF data confirm that TB is widely prevalent, including in VDCs with relatively low reporting rates. Although ACF is a highly efficient component of TB control, its impact can vary substantially at local levels and must be combined with other interventions to alter TB epidemiology significantly.


Asunto(s)
Tamizaje Masivo , Tuberculosis , Humanos , Nepal/epidemiología , Tamizaje Masivo/métodos , Tuberculosis/epidemiología , Incidencia
2.
Health Policy Plan ; 38(7): 830-839, 2023 Aug 02.
Artículo en Inglés | MEDLINE | ID: mdl-37300553

RESUMEN

The World Health Organization has supported the development of national tuberculosis (TB) patient cost surveys to quantify the socio-economic impact of TB in high-burden countries. However, methodological differences in the study design (e.g. cross-sectional vs longitudinal) can generate different estimates making the design and impact evaluation of socio-economic protection strategies difficult. The objective of the study was to compare the socio-economic impacts of TB estimated by applying cross-sectional or longitudinal data collections in Nepal. We analysed the data from a longitudinal costing survey (patients interviewed at three time points) conducted between April 2018 and October 2019. We calculated both mean and median costs from patients interviewed during the intensive (cross-sectional 1) and continuation (cross-sectional 2) phases of treatment. We then compared costs, the prevalence of catastrophic costs and the socio-economic impact of TB generated by each approach. There were significant differences in the costs and social impacts calculated by each approach. The median total cost (intensive plus continuation phases) was significantly higher for the longitudinal compared with cross-sectional 2 (US$119.42 vs 91.63, P < 0.001). The prevalence of food insecurity, social exclusion and patients feeling poorer or much poorer were all significantly higher by applying a longitudinal approach. In conclusion, the longitudinal design captured important aspects of costs and socio-economic impacts, which were missed by applying a cross-sectional approach. If a cross-sectional approach is applied due to resource constraints, our data suggest that the start of the continuation phase is the optimal timing for a single interview. Further research to optimize methodologies to report patient-incurred expenditure during TB diagnosis and treatment is needed.


Asunto(s)
Tuberculosis , Humanos , Nepal/epidemiología , Tuberculosis/epidemiología , Gastos en Salud , Encuestas y Cuestionarios , Aislamiento Social
3.
Trop Med Infect Dis ; 8(7)2023 Jul 17.
Artículo en Inglés | MEDLINE | ID: mdl-37505665

RESUMEN

This study compares the yield and additionality of community-based active tuberculosis (TB) active case-finding strategies using either smear microscopy or GeneXpert as the TB diagnostic test. Active case-finding strategies screened social contacts of index cases and high-risk groups in four districts of Nepal in July 2017-2019. Two districts (Chitwan and Dhanusha) applied GeneXpert testing and two districts (Makwanpur and Mahotarri) used smear microscopy. Two control districts implemented standard national TB program activities. Districts implementing GeneXpert testing screened 23,657 people for TB, tested 17,114 and diagnosed 764 TB cases, producing a yield of 4.5%. Districts implementing smear microscopy screened 19,961 people for TB, tested 13,285 and diagnosed 437 cases, producing a yield of 3.3%. The screening numbers required were 31 for GeneXpert and 45.7 for smear districts. The test numbers required were 22.4 and 30.4 for GeneXpert and smear. Using the TB REACH additionality method, social contact tracing for TB through GeneXpert testing contributed to a 20% (3958/3322) increase in district-level TB notifications, smear microscopy 12.4% (3146/2798), and -0.5% (2553/2566) for control districts. Therefore, social contact tracing of TB index cases using GeneXpert testing should be implemented throughout Nepal within the TB FREE initiative to close the notification gap and accelerate progress toward END TB strategy targets.

4.
J Am Chem Soc ; 134(50): 20250-3, 2012 Dec 19.
Artículo en Inglés | MEDLINE | ID: mdl-23198971

RESUMEN

This paper describes the unique catalytic activity of bimetallic Au/Pd alloy nanoclusters (NCs) for Ullmann coupling of chloroarenes in aqueous media at low temperature. The corresponding reaction cannot be achieved by monometallic Au and Pd NCs as well as their physical mixtures. On the basis of quantum chemical calculation, it was found that the crucial step to govern the unusual catalytic activity of Au/Pd is the dissociative chemisorption of ArCl, which is unlikely in the monometallic Au and Pd NCs.

5.
Glob Health Action ; 15(1): 2128283, 2022 12 31.
Artículo en Inglés | MEDLINE | ID: mdl-36239949

RESUMEN

BACKGROUND: The WHO recommends oral calcium supplementation (1.5-2.0 g) in pregnant women to reduce the risk of pre-eclampsia living in areas with low dietary calcium intake. Although maternal mortality is high in Nepal and eclampsia causes at least 20% of maternal deaths, implementing WHO recommendations would be a major undertaking. OBJECTIVE: This review aimed to assess whether the current evidence supports the blanket supplementation of calcium to prevent pre-eclampsia among pregnant women in Nepal. METHODS: We used a structured approach to appraise the evidence for calcium supplementation in Nepal. We identified what may influence the impact of calcium supplementation in Nepal and conducted a situation analysis in the country covering maternal mortality, pre-eclampsia occurrence, and existing government policy provisions for supplementation. We also consulted with experts and government officials to explore their perspectives and experience on supplementation. We then used AMSTAR (A MeaSurement Tool to Assess Systematic Reviews) to appraise the Cochrane Systematic Review of calcium supplementation. Finally, we used these data in a GRADE (Grading of Recommendations Assessment, Development and Evaluation)-Evidence to Decision framework to reach a policy recommendation. RESULTS: Our assessment of the Cochrane Review showed that the recommendation made by the WHO is based on weak evidence and trial findings that are not consistent between studies. The Cochrane Review found low certainty of the evidence for benefit (reduction in pre-eclampsia and maternal mortality). Conversely, there is a high certainty of the evidence of undesirable effects (HELLP [haemolysis, elevated liver enzymes and low platelets] syndrome) although this is uncommon. The likely absolute reduction in maternal deaths projected to Nepal was estimated to be low, while the implementation costs were high. Stakeholders also raised several concerns regarding feasibility, acceptability, appropriate dosing, and risk communication. CONCLUSIONS: This review concludes that the blanket supplementation of calcium cannot be recommended in Nepal. A better approach may be to identify high-risk pregnant women and manage their antenatal visits and delivery to prevent mortality from pre-eclampsia.


Asunto(s)
Muerte Materna , Preeclampsia , Calcio , Calcio de la Dieta , Suplementos Dietéticos , Femenino , Humanos , Nepal , Políticas , Preeclampsia/prevención & control , Embarazo , Mujeres Embarazadas
6.
ACS Omega ; 7(28): 24184-24189, 2022 Jul 19.
Artículo en Inglés | MEDLINE | ID: mdl-35874269

RESUMEN

In this study, a phenylboronic ester-activated aryl iodide-selective Buchwald-Hartwig-type amination was developed. When the reaction of aryl iodides and aryl/aliphatic amines using Ni(acac)2 is carried out in the presence of phenylboronic ester, the Buchwald-Hartwig-type amination proceeds smoothly to afford the corresponding amines in high yields. This reaction does not proceed in the absence of phenylboronic ester. A wide variety of aryl iodides can be applied in the presence of aryl chlorides and bromides, which remain intact during the reaction. The mechanistic studies of this reaction suggest that the phenylboronic ester acts as an activator for the amines to form the ″ate complex″. Chemical kinetics studies show that the reaction of aryl iodides, base, and Ni(acac)2 follows first-order kinetics, while that of amines and phenylboronic ester follows zero-order kinetics. The bioactivity screening of the corresponding products showed that some amination products exhibit antifungal activity.

7.
Wellcome Open Res ; 7: 141, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-36874579

RESUMEN

BACKGROUND: The World Health Organization's End TB (tuberculosis) Strategy advocates social and economic support for TB-affected households but evidence from low-income settings is scarce. We will evaluate the feasibility and acceptability of a locally-appropriate socioeconomic support intervention for TB-affected households in Nepal. METHODS: We will conduct a pilot randomised-controlled trial with mixed-methods process evaluation in four TB-endemic, impoverished districts of Nepal: Pyuthan, Chitwan, Mahottari, and Morang. We will recruit 128 people with TB notified to the Nepal National TB Program (NTP) and 40 multisectoral stakeholders including NTP staff, civil-society members, policy-makers, and ASCOT (Addressing the Social Determinants and Consequences of Tuberculosis) team members. People with TB will be randomised 1:1:1:1 to four study arms (n=32 each): control; social support; economic support; and combined social and economic (socioeconomic) support. Social support will be TB education and peer-led mutual-support TB Clubs providing TB education and stigma-reduction counselling. Economic support will be monthly unconditional cash transfers during TB treatment with expectations (not conditions) of meeting NTP goals. At 0, 2, and 6 months following TB treatment initiation, participants will be asked to complete a survey detailing the social determinants and consequences of TB and their feedback on ASCOT. Complementary process evaluation will use focus group discussions (FGD), key informant interviews (KII), and a workshop with multi-sectoral stakeholders to consider the challenges to ASCOT's implementation and scale-up. A sample of ~100 people with TB is recommended to estimate TB-related costs. Information power is estimated to be reached with approximately 25 FGD and 15 KII participants. CONCLUSIONS: The ASCOT pilot trial will both generate robust evidence on a locally-appropriate, socioeconomic support intervention for TB-affected households in Nepal and inform a large-scale future ASCOT trial, which will evaluate the intervention's impact on catastrophic costs mitigation and TB outcomes. The trial is registered with the ISRCTN ( ISRCTN17025974).

8.
ACS Omega ; 6(41): 27578-27586, 2021 Oct 19.
Artículo en Inglés | MEDLINE | ID: mdl-34693179

RESUMEN

To improve product yields in synthetic reactions, it is important to use appropriate catalysts. In this study, we used machine learning to design catalysts for a reaction system in which both Buchwald-Hartwig-type and Suzuki-Miyaura-type cross-coupling reactions proceed simultaneously. First, using an existing dataset, yield prediction models were constructed with machine learning between experimental conditions, including the substrate and catalyst and the yields of the two products. Seven methods for calculating both the substrate and catalyst descriptors were proposed, and the predictive ability of the yield prediction models was discussed in terms of the descriptors and machine learning methods. Then, the constructed models were used to predict the compound yields for new combinations of substrates and catalysts, and the predictions were experimentally validated with high reproducibility, confirming that machine learning can predict yields from experimental conditions with high accuracy. In addition, to design catalysts that will improve the yields in our dataset, we added datasets collected from scientific papers and designed catalyst ligands. The proposed catalyst candidates were tested in actual synthetic experiments, and the experimental results exceeded the existing yields.

9.
Trop Med Infect Dis ; 6(2)2021 Apr 14.
Artículo en Inglés | MEDLINE | ID: mdl-33919938

RESUMEN

This study compared the yield of tuberculosis (TB) active case finding (ACF) interventions applied under TB REACH funding. Between June 2017 to November 2018, Birat Nepal Medical Trust identified presumptive cases using simple verbal screening from three interventions: door-to-door screening of social contacts of known index cases, TB camps in remote areas, and screening for hospital out-patient department (OPD) attendees. Symptomatic individuals were then tested using smear microscopy or GeneXpert MTB/RIF as first diagnostic test. Yield rates were compared for each intervention and diagnostic method. We evaluated additional cases notified from ACF interventions by comparing case notifications of the intervention and control districts using standard TB REACH methodology. The project identified 1092 TB cases. The highest yield was obtained from OPD screening at hospitals (n = 566/1092; 52%). The proportion of positive tests using GeneXpert (5.5%, n = 859/15,637) was significantly higher than from microscopy testing 2% (n = 120/6309). (OR = 1.4; 95%CI = 1.12-1.72; p = 0.0026). The project achieved 29% additionality in case notifications in the intervention districts demonstrating that GeneXpert achieved substantially higher case-finding yields. Therefore, to increase national case notification for TB, Nepal should integrate OPD screening using GeneXpert testing in every district hospital and scale up of community-based ACF of TB patient contacts nationally.

10.
BMJ Open ; 11(10): e049900, 2021 10 01.
Artículo en Inglés | MEDLINE | ID: mdl-34598986

RESUMEN

OBJECTIVE: Psychosocial and economic (socioeconomic) barriers, including poverty, stigma and catastrophic costs, impede access to tuberculosis (TB) services in low-income countries. We aimed to characterise the socioeconomic barriers and facilitators of accessing TB services in Nepal to inform the design of a locally appropriate socioeconomic support intervention for TB-affected households. DESIGN: From August 2018 to July 2019, we conducted an exploratory qualitative study consisting of semistructured focus group discussions (FGDs) with purposively selected multisectoral stakeholders. The data were managed in NVivo V.12, coded by consensus and analysed thematically. SETTING: The study was conducted in four districts, Makwanpur, Chitwan, Dhanusha and Mahottari, which have a high prevalence of poverty and TB. PARTICIPANTS: Seven FGDs were conducted with 54 in-country stakeholders, grouped by stakeholders, including people with TB (n=21), community stakeholders (n=13) and multidisciplinary TB healthcare professionals (n=20) from the National TB Programme. RESULTS: The perceived socioeconomic barriers to accessing TB services were: inadequate TB knowledge and advocacy; high food and transportation costs; income loss and stigma. The perceived facilitators to accessing TB care and services were: enhanced championing and awareness-raising about TB and TB services; social protection including health insurance; cash, vouchers and/or nutritional allowance to cover food and travel costs; and psychosocial support and counselling integrated with existing adherence counselling from the National TB Programme. CONCLUSION: These results suggest that support interventions that integrate TB education, psychosocial counselling and expand on existing cash transfer schemes would be locally appropriate and could address the socioeconomic barriers to accessing and engaging with TB services faced by TB-affected households in Nepal. The findings have been used to inform the design of a socioeconomic support intervention for TB-affected households. The acceptability, feasibility and impact of this intervention on TB-related costs, stigma and TB treatment outcomes, is now being evaluated in a pilot implementation study in Nepal.


Asunto(s)
Tuberculosis , Humanos , Renta , Nepal , Pobreza , Investigación Cualitativa , Tuberculosis/terapia
11.
Health Policy Plan ; 36(5): 594-605, 2021 Jun 03.
Artículo en Inglés | MEDLINE | ID: mdl-33341891

RESUMEN

The aim of this study was to compare costs and socio-economic impact of tuberculosis (TB) for patients diagnosed through active (ACF) and passive case finding (PCF) in Nepal. A longitudinal costing survey was conducted in four districts of Nepal from April 2018 to October 2019. Costs were collected using the WHO TB Patient Costs Survey at three time points: intensive phase of treatment, continuation phase of treatment and at treatment completion. Direct and indirect costs and socio-economic impact (poverty headcount, employment status and coping strategies) were evaluated throughout the treatment. Prevalence of catastrophic costs was estimated using the WHO threshold. Logistic regression and generalized estimating equation were used to evaluate risk of incurring high costs, catastrophic costs and socio-economic impact of TB over time. A total of 111 ACF and 110 PCF patients were included. ACF patients were more likely to have no education (75% vs 57%, P = 0.006) and informal employment (42% vs 24%, P = 0.005) Compared with the PCF group, ACF patients incurred lower costs during the pretreatment period (mean total cost: US$55 vs US$87, P < 0.001) and during the pretreatment plus treatment periods (mean total direct costs: US$72 vs US$101, P < 0.001). Socio-economic impact was severe for both groups throughout the whole treatment, with 32% of households incurring catastrophic costs. Catastrophic costs were associated with 'no education' status [odds ratio = 2.53(95% confidence interval = 1.16-5.50)]. There is a severe and sustained socio-economic impact of TB on affected households in Nepal. The community-based ACF approach mitigated costs and reached the most vulnerable patients. Alongside ACF, social protection policies must be extended to achieve the zero catastrophic costs milestone of the End TB strategy.


Asunto(s)
Tuberculosis , Composición Familiar , Humanos , Nepal , Pobreza , Prevalencia
12.
J Phys Chem Lett ; 11(4): 1199-1203, 2020 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-31967476

RESUMEN

The photoluminescence properties of aryl iodides chemisorbed on gold nanoparticles were examined. Chemisorption of a series of aryl iodides onto poly(N-vinylpyrrolidone)-protected Au nanoparticles (Au:PVP) in solution resulted in highly enhanced luminescence. Kinetic studies revealed that the photoluminescence is derived from the excimer formation of aryl iodides on Au:PVP, and the process is significantly faster than intersystem crossing by the heavy atom.

13.
Org Lett ; 22(12): 4797-4801, 2020 Jun 19.
Artículo en Inglés | MEDLINE | ID: mdl-32484355

RESUMEN

Herein, we report the development of aryl halide-dependent chemoselective reactions, viz., the Buchwald-Hartwig type coupling reaction of an aryl iodide with an arylboronic acid and an aryl amine in the presence of a heterogeneous and reusable nickel catalyst and the Suzuki-Miyaura type coupling of an aryl chloride under similar conditions. Control experiments revealed that the presence of stoichiometric amounts of the phenylboronic acid/ester and aryl amine are essential for both reactions. NMR and XAFS studies suggested the formation of a boron-amine "ate" complex.

14.
Wellcome Open Res ; 5: 19, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-32964135

RESUMEN

Background: WHO's 2015 End TB Strategy advocates social and economic (socioeconomic) support for TB-affected households to improve TB control. However, evidence concerning socioeconomic support for TB-affected households remains limited, especially in low-income countries. Protocol: This mixed-methods study in Nepal will: evaluate the socioeconomic impact of accessing TB diagnosis and care (Project 1); and create a shortlist of feasible, locally-appropriate interventions to mitigate this impact (Project 2). The study will be conducted in the Chitwan, Mahottari, Makawanpur, and Dhanusha districts of Nepal, which have frequent TB and poverty. The study population will include: approximately 200 people with TB (Cases) starting TB treatment with Nepal's National TB Program and 100 randomly-selected people without TB (Controls) in the same sites (Project 1); and approximately 40 key in-country stakeholders from Nepal including people with TB, community leaders, and TB healthcare professionals (Project 2). During Project 1, visits will be made to people with TB's households during months 3 and 6 of TB treatment, and a single visit made to Control households. During visits, participants will be asked about: TB-related costs (if receiving treatment), food insecurity, stigma; TB-related knowledge; household poverty level; social capital; and quality of life. During Project 2, stakeholders will be invited to participate in: a survey and focus group discussion (FGD) to characterise socioeconomic impact, barriers and facilitators to accessing and engaging with TB care in Nepal; and a one-day workshop to review FGD findings and suggest interventions to mitigate the barriers identified. Ethics and dissemination: The study has received ethical approval. Results will be disseminated through scientific meetings, open access publications, and a national workshop in Nepal.  Conclusions: This research will strengthen understanding of the socioeconomic impact of TB in Nepal and generate a shortlist of feasible and locally-appropriate socioeconomic interventions for TB-affected households for trial evaluation.

15.
Trop Med Infect Dis ; 5(2)2020 Jun 10.
Artículo en Inglés | MEDLINE | ID: mdl-32532101

RESUMEN

Tuberculosis (TB), the leading single infectious diseases killer globally, is driven by poverty. Conversely, having TB worsens impoverishment. During TB illness, lost income and out-of-pocket costs can become "catastrophic", leading patients to abandon treatment, develop drug-resistance, and die. WHO's 2015 End TB Strategy recommends eliminating catastrophic costs and providing socioeconomic support for TB-affected people. However, there is negligible evidence to guide the design and implementation of such socioeconomic support, especially in low-income, TB-endemic countries. A national, multi-sectoral workshop was held in Kathmandu, Nepal, on the 11th and 12th September 2019, to develop a shortlist of feasible, locally appropriate socioeconomic support interventions for TB-affected households in Nepal, a low-income country with significant TB burden. The workshop brought together key stakeholders in Nepal including from the Ministry of Health and Population, Department of Health Services, Provincial Health Directorate, Health Offices, National TB Program (NTP); and TB/Leprosy Officers, healthcare workers, community health volunteers, TB-affected people, and external development partners (EDP). During the workshop, participants reviewed current Nepal NTP data and strategy, discussed the preliminary results of a mixed-methods study of the socioeconomic determinants and consequences of TB in Nepal, described existing and potential socioeconomic interventions for TB-affected households in Nepal, and selected the most promising interventions for future randomized controlled trial evaluations in Nepal. This report describes the activities, outcomes, and recommendations from the workshop.

16.
Infect Dis Poverty ; 8(1): 99, 2019 Dec 03.
Artículo en Inglés | MEDLINE | ID: mdl-31791412

RESUMEN

BACKGROUND: The World Health Organization (WHO) End TB Strategy has established a milestone to reduce the number of tuberculosis (TB)- affected households facing catastrophic costs to zero by 2020. The role of active case finding (ACF) in reducing patient costs has not been determined globally. This study therefore aimed to compare costs incurred by TB patients diagnosed through ACF and passive case finding (PCF), and to determine the prevalence and intensity of patient-incurred catastrophic costs in Nepal. METHODS: The study was conducted in two districts of Nepal: Bardiya and Pyuthan (Province No. 5) between June and August 2018. One hundred patients were included in this study in a 1:1 ratio (PCF: ACF, 25 consecutive ACF and 25 consecutive PCF patients in each district). The WHO TB patient costing tool was applied to collect information from patients or a member of their family regarding indirect and direct medical and non-medical costs. Catastrophic costs were calculated based on the proportion of patients with total costs exceeding 20% of their annual household income. The intensity of catastrophic costs was calculated using the positive overshoot method. The chi-square and Wilcoxon-Mann-Whitney tests were used to compare proportions and costs. Meanwhile, the Mantel Haenszel test was performed to assess the association between catastrophic costs and type of diagnosis. RESULTS: Ninety-nine patients were interviewed (50 ACF and 49 PCF). Patients diagnosed through ACF incurred lower costs during the pre-treatment period (direct medical: USD 14 vs USD 32, P = 0.001; direct non-medical: USD 3 vs USD 10, P = 0.004; indirect, time loss: USD 4 vs USD 13, P <  0.001). The cost of the pre-treatment and intensive phases combined was also lower for direct medical (USD 15 vs USD 34, P = 0.002) and non-medical (USD 30 vs USD 54, P = 0.022) costs among ACF patients. The prevalence of catastrophic direct costs was lower for ACF patients for all thresholds. A lower intensity of catastrophic costs was also documented for ACF patients, although the difference was not statistically significant. CONCLUSIONS: ACF can reduce patient-incurred costs substantially, contributing to the End TB Strategy target. Other synergistic policies, such as social protection, will also need to be implemented to reduce catastrophic costs to zero among TB-affected households.


Asunto(s)
Trazado de Contacto/estadística & datos numéricos , Costo de Enfermedad , Costos de la Atención en Salud , Tuberculosis Pulmonar/economía , Adolescente , Adulto , Anciano , Anciano de 80 o más Años , Trazado de Contacto/métodos , Femenino , Humanos , Masculino , Persona de Mediana Edad , Nepal , Adulto Joven
17.
Chem Asian J ; 10(12): 2669-76, 2015 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-26353972

RESUMEN

New catalytic activity of gold/palladium alloy nanoclusters (NCs) for carbon-halogen bond activation is demonstrated. In the case of an aryl chloride, the inclusion of gold in a bimetallic catalyst is indispensable to achieve the coupling reactions. Gold has the unique effect of stabilizing palladium, such that Pd(2+) leached from clusters by means of spillover of chloride during oxidative addition. The thus-formed spillover intermediate further reacts heterogeneously in both Ullmann and Suzuki-type coupling reactions through a new type of mechanism. In the case of an aryl bromide, Ullmann coupling occurs through the spillover of bromide, similar to that of aryl chloride. However, a significant fraction of palladium also leached, which diminished the Ullmann coupling activity of the aryl bromide and, as a result, the order of reactivity was ArCl>ArBr. With regard to the activation of the C-Br bond towards a Suzuki-type reaction, the inclusion of a higher gold content in gold/palladium clusters stabilized palladium to prevent the leaching of Pd(2+) from the clusters by means of spillover of bromide. The spillover intermediate reacts heterogeneously with PhB(OH)2, palladium-rich gold/palladium, or pure palladium clusters; the oxidative addition of ArBr favors the extraction of palladium from the clusters, yielding Pd(2+) intermediates. The extracted intermediates react homogenously (Pd(2+/)Pd(0) catalysis) with PhB(OH)2, which results in the higher selectivity of the cross-coupling product. An initial step to observe such unprecedented halide dependency, together with the dynamic behavior of palladium on the surface of gold is the oxidative addition of Ar-X. A detailed insight into the first oxidative addition process was also examined by quantum chemical calculations.

18.
Chem Commun (Camb) ; 51(64): 12724-7, 2015 Aug 18.
Artículo en Inglés | MEDLINE | ID: mdl-26152331

RESUMEN

The stabilization effect of Au towards Pd changed the reactivity of Pd in Au/Pd bimetallic nanoclusters, altering the reaction mechanism from homogeneous to heterogeneous in dechlorination reaction of aryl chlorides. This phenomenon was illustrated by the observed enhancement of the rate of reaction by in situ generated Au-rich bimetallic Au/Pd nanoclusters.


Asunto(s)
Cloruros/química , Oro/química , Halogenación , Nanopartículas del Metal/química , Paladio/química , Catálisis , Modelos Moleculares , Conformación Molecular
19.
Chem Commun (Camb) ; 49(25): 2542-4, 2013 Mar 28.
Artículo en Inglés | MEDLINE | ID: mdl-23423533

RESUMEN

The strong inhibitor effect of aryl iodides on the quasi-homogenous gold-catalyzed oxidation reaction was described. Aryl iodides were adsorbed on the exposed surface of Au clusters, which affected the accessibility of the nanoclusters to the reacting species and acted as strong inhibitors in catalysis.

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