Conspectus A comprehensive understanding of chemical bonding and reactions at the surface of nanomaterials is of great importance in the rational design of their functional properties and ...applications. With the rapid development in cluster science, it has become clear that atomically precise metal clusters represent ideal models for resolving various important and/or unsolved issues related to surface science. This Account highlights our recent efforts on the fabrication of ligand-stabilized coinage nanoclusters with atomic precision from the viewpoint of surface coordination chemistry in particular. The successful synthesis of a large variety of metal clusters in our group has greatly benefitted from the development of an effective amine-assisted NaBH4 reduction method. First discussed in this Account is how the introduction of amines in the synthetic protocol enhances the long-term stability and high-yield production of Ag/Cu-based metals in air. Such a method allows the utilization of different organic ligands as surface stabilizing agents to manipulate both the core and surface structures of metal nanoclusters, helping to understand the role of surface ligands in determining the structures of metal nanoclusters. The coordination chemistry of ligands used in the synthesis of metal nanoclusters is crucial in determining their overall shape, metal arrangement, surface ligand binding structure, chirality and also metal exposure. Detailed discussions are given in the following four different systems: (1) The co-use of phosphines and thiolates with rich coordination structures (2 to 4-coordinated) helps to control the formation of a sequence of Ag nanoclusters with a near-perfectly cubic shape; (2) The metal arrangements and surface structures of AuCu clusters highly depend on metal precursors and counter cations used in the synthesis; (3) Metal clusters with intrinsic chirality are readily prepared by introducing chiral ligands or counterions, making it possible to obtain optically active enantiomers and understand the origin of chirality of metal nanoclusters; (4) The variation of metal exposure of the inner metal core of metal nanocluster can be controlled by the surface ligand coordination structure. Such capabilities to manipulate the surface structure of metal nanoclusters allow the creation of model systems for investigating the structure–reactivity relationship of metal nanomaterials. Several important examples are then discussed to highlight the importance of ligand coordination chemistry in tuning the surface reactivity and catalysis of metal nanoclusters. For example, bulky thiolates on Ag are demonstrated to be more labile than small thiolates for making metal nanoclusters with both enhanced ligand exchange capability and catalysis. Alkynyl ligands can be thermally released from metal nanoclusters more easily than thiolates and halides while maintaining the overall structure, thereby serving as ideal systems for understanding the promoting effect of surface stabilizers on catalysis. Finally, we provide a perspective on the principles of surface coordination chemistry of metal nanoclusters and their potential applications with regards to catalysis of protected metal clusters.
Some studies, mainly from high-income countries (HICs), report that women receive less care (investigations and treatments) for cardiovascular disease than do men and might have a higher risk of ...death. However, very few studies systematically report risk factors, use of primary or secondary prevention medications, incidence of cardiovascular disease, or death in populations drawn from the community. Given that most cardiovascular disease occurs in low-income and middle-income countries (LMICs), there is a need for comprehensive information comparing treatments and outcomes between women and men in HICs, middle-income countries, and low-income countries from community-based population studies.
In the Prospective Urban Rural Epidemiological study (PURE), individuals aged 35–70 years from urban and rural communities in 27 countries were considered for inclusion. We recorded information on participants' sociodemographic characteristics, risk factors, medication use, cardiac investigations, and interventions. 168 490 participants who enrolled in the first two of the three phases of PURE were followed up prospectively for incident cardiovascular disease and death.
From Jan 6, 2005 to May 6, 2019, 202 072 individuals were recruited to the study. The mean age of women included in the study was 50·8 (SD 9·9) years compared with 51·7 (10) years for men. Participants were followed up for a median of 9·5 (IQR 8·5–10·9) years. Women had a lower cardiovascular disease risk factor burden using two different risk scores (INTERHEART and Framingham). Primary prevention strategies, such as adoption of several healthy lifestyle behaviours and use of proven medicines, were more frequent in women than men. Incidence of cardiovascular disease (4·1 95% CI 4·0–4·2 for women vs 6·4 6·2–6·6 for men per 1000 person-years; adjusted hazard ratio aHR 0·75 95% CI 0·72–0·79) and all-cause death (4·5 95% CI 4·4–4·7 for women vs 7·4 7·2–7·7 for men per 1000 person-years; aHR 0·62 95% CI 0·60–0·65) were also lower in women. By contrast, secondary prevention treatments, cardiac investigations, and coronary revascularisation were less frequent in women than men with coronary artery disease in all groups of countries. Despite this, women had lower risk of recurrent cardiovascular disease events (20·0 95% CI 18·2–21·7 versus 27·7 95% CI 25·6–29·8 per 1000 person-years in men, adjusted hazard ratio 0·73 95% CI 0·64-0·83) and women had lower 30-day mortality after a new cardiovascular disease event compared with men (22% in women versus 28% in men; p<0·0001). Differences between women and men in treatments and outcomes were more marked in LMICs with little differences in HICs in those with or without previous cardiovascular disease.
Treatments for cardiovascular disease are more common in women than men in primary prevention, but the reverse is seen in secondary prevention. However, consistently better outcomes are observed in women than in men, both in those with and without previous cardiovascular disease. Improving cardiovascular disease prevention and treatment, especially in LMICs, should be vigorously pursued in both women and men.
Full funding sources are listed at the end of the paper (see Acknowledgments).
Summary Background Reduced muscular strength, as measured by grip strength, has been associated with an increased risk of all-cause and cardiovascular mortality. Grip strength is appealing as a ...simple, quick, and inexpensive means of stratifying an individual's risk of cardiovascular death. However, the prognostic value of grip strength with respect to the number and range of populations and confounders is unknown. The aim of this study was to assess the independent prognostic importance of grip strength measurement in socioculturally and economically diverse countries. Methods The Prospective Urban-Rural Epidemiology (PURE) study is a large, longitudinal population study done in 17 countries of varying incomes and sociocultural settings. We enrolled an unbiased sample of households, which were eligible if at least one household member was aged 35–70 years and if household members intended to stay at that address for another 4 years. Participants were assessed for grip strength, measured using a Jamar dynamometer. During a median follow-up of 4·0 years (IQR 2·9–5·1), we assessed all-cause mortality, cardiovascular mortality, non-cardiovascular mortality, myocardial infarction, stroke, diabetes, cancer, pneumonia, hospital admission for pneumonia or chronic obstructive pulmonary disease (COPD), hospital admission for any respiratory disease (including COPD, asthma, tuberculosis, and pneumonia), injury due to fall, and fracture. Study outcomes were adjudicated using source documents by a local investigator, and a subset were adjudicated centrally. Findings Between January, 2003, and December, 2009, a total of 142 861 participants were enrolled in the PURE study, of whom 139 691 with known vital status were included in the analysis. During a median follow-up of 4·0 years (IQR 2·9–5·1), 3379 (2%) of 139 691 participants died. After adjustment, the association between grip strength and each outcome, with the exceptions of cancer and hospital admission due to respiratory illness, was similar across country-income strata. Grip strength was inversely associated with all-cause mortality (hazard ratio per 5 kg reduction in grip strength 1·16, 95% CI 1·13–1·20; p<0·0001), cardiovascular mortality (1·17, 1·11–1·24; p<0·0001), non-cardiovascular mortality (1·17, 1·12–1·21; p<0·0001), myocardial infarction (1·07, 1·02–1·11; p=0·002), and stroke (1·09, 1·05–1·15; p<0·0001). Grip strength was a stronger predictor of all-cause and cardiovascular mortality than systolic blood pressure. We found no significant association between grip strength and incident diabetes, risk of hospital admission for pneumonia or COPD, injury from fall, or fracture. In high-income countries, the risk of cancer and grip strength were positively associated (0·916, 0·880–0·953; p<0·0001), but this association was not found in middle-income and low-income countries. Interpretation This study suggests that measurement of grip strength is a simple, inexpensive risk-stratifying method for all-cause death, cardiovascular death, and cardiovascular disease. Further research is needed to identify determinants of muscular strength and to test whether improvement in strength reduces mortality and cardiovascular disease. Funding Full funding sources listed at end of paper (see Acknowledgments).
Global estimates of the effect of common modifiable risk factors on cardiovascular disease and mortality are largely based on data from separate studies, using different methodologies. The ...Prospective Urban Rural Epidemiology (PURE) study overcomes these limitations by using similar methods to prospectively measure the effect of modifiable risk factors on cardiovascular disease and mortality across 21 countries (spanning five continents) grouped by different economic levels.
In this multinational, prospective cohort study, we examined associations for 14 potentially modifiable risk factors with mortality and cardiovascular disease in 155 722 participants without a prior history of cardiovascular disease from 21 high-income, middle-income, or low-income countries (HICs, MICs, or LICs). The primary outcomes for this paper were composites of cardiovascular disease events (defined as cardiovascular death, myocardial infarction, stroke, and heart failure) and mortality. We describe the prevalence, hazard ratios (HRs), and population-attributable fractions (PAFs) for cardiovascular disease and mortality associated with a cluster of behavioural factors (ie, tobacco use, alcohol, diet, physical activity, and sodium intake), metabolic factors (ie, lipids, blood pressure, diabetes, obesity), socioeconomic and psychosocial factors (ie, education, symptoms of depression), grip strength, and household and ambient pollution. Associations between risk factors and the outcomes were established using multivariable Cox frailty models and using PAFs for the entire cohort, and also by countries grouped by income level. Associations are presented as HRs and PAFs with 95% CIs.
Between Jan 6, 2005, and Dec 4, 2016, 155 722 participants were enrolled and followed up for measurement of risk factors. 17 249 (11·1%) participants were from HICs, 102 680 (65·9%) were from MICs, and 35 793 (23·0%) from LICs. Approximately 70% of cardiovascular disease cases and deaths in the overall study population were attributed to modifiable risk factors. Metabolic factors were the predominant risk factors for cardiovascular disease (41·2% of the PAF), with hypertension being the largest (22·3% of the PAF). As a cluster, behavioural risk factors contributed most to deaths (26·3% of the PAF), although the single largest risk factor was a low education level (12·5% of the PAF). Ambient air pollution was associated with 13·9% of the PAF for cardiovascular disease, although different statistical methods were used for this analysis. In MICs and LICs, household air pollution, poor diet, low education, and low grip strength had stronger effects on cardiovascular disease or mortality than in HICs.
Most cardiovascular disease cases and deaths can be attributed to a small number of common, modifiable risk factors. While some factors have extensive global effects (eg, hypertension and education), others (eg, household air pollution and poor diet) vary by a country's economic level. Health policies should focus on risk factors that have the greatest effects on averting cardiovascular disease and death globally, with additional emphasis on risk factors of greatest importance in specific groups of countries.
Full funding sources are listed at the end of the paper (see Acknowledgments).
To our knowledge, no previous study has prospectively documented the incidence of common diseases and related mortality in high-income countries (HICs), middle-income countries (MICs), and low-income ...countries (LICs) with standardised approaches. Such information is key to developing global and context-specific health strategies. In our analysis of the Prospective Urban Rural Epidemiology (PURE) study, we aimed to evaluate differences in the incidence of common diseases, related hospital admissions, and related mortality in a large contemporary cohort of adults from 21 HICs, MICs, and LICs across five continents by use of standardised approaches.
The PURE study is a prospective, population-based cohort study of individuals aged 35–70 years who have been enrolled from 21 countries across five continents. The key outcomes were the incidence of fatal and non-fatal cardiovascular diseases, cancers, injuries, respiratory diseases, and hospital admissions, and we calculated the age-standardised and sex-standardised incidence of these events per 1000 person-years.
This analysis assesses the incidence of events in 162 534 participants who were enrolled in the first two phases of the PURE core study, between Jan 6, 2005, and Dec 4, 2016, and who were assessed for a median of 9·5 years (IQR 8·5–10·9). During follow-up, 11 307 (7·0%) participants died, 9329 (5·7%) participants had cardiovascular disease, 5151 (3·2%) participants had a cancer, 4386 (2·7%) participants had injuries requiring hospital admission, 2911 (1·8%) participants had pneumonia, and 1830 (1·1%) participants had chronic obstructive pulmonary disease (COPD). Cardiovascular disease occurred more often in LICs (7·1 cases per 1000 person-years) and in MICs (6·8 cases per 1000 person-years) than in HICs (4·3 cases per 1000 person-years). However, incident cancers, injuries, COPD, and pneumonia were most common in HICs and least common in LICs. Overall mortality rates in LICs (13·3 deaths per 1000 person-years) were double those in MICs (6·9 deaths per 1000 person-years) and four times higher than in HICs (3·4 deaths per 1000 person-years). This pattern of the highest mortality in LICs and the lowest in HICs was observed for all causes of death except cancer, where mortality was similar across country income levels. Cardiovascular disease was the most common cause of deaths overall (40%) but accounted for only 23% of deaths in HICs (vs 41% in MICs and 43% in LICs), despite more cardiovascular disease risk factors (as judged by INTERHEART risk scores) in HICs and the fewest such risk factors in LICs. The ratio of deaths from cardiovascular disease to those from cancer was 0·4 in HICs, 1·3 in MICs, and 3·0 in LICs, and four upper-MICs (Argentina, Chile, Turkey, and Poland) showed ratios similar to the HICs. Rates of first hospital admission and cardiovascular disease medication use were lowest in LICs and highest in HICs.
Among adults aged 35–70 years, cardiovascular disease is the major cause of mortality globally. However, in HICs and some upper-MICs, deaths from cancer are now more common than those from cardiovascular disease, indicating a transition in the predominant causes of deaths in middle-age. As cardiovascular disease decreases in many countries, mortality from cancer will probably become the leading cause of death. The high mortality in poorer countries is not related to risk factors, but it might be related to poorer access to health care.
Full funding sources are listed at the end of the paper (see Acknowledgments).
Metal nanoclusters whose surface ligands are removable while keeping their metal framework structures intact are an ideal system for investigating the influence of surface ligands on catalysis of ...metal nanoparticles. We report in this work an intermetallic nanocluster containing 62 metal atoms, Au34Ag28(PhCC)34, and its use as a model catalyst to explore the importance of surface ligands in promoting catalysis. As revealed by single-crystal diffraction, the 62 metal atoms in the cluster are arranged as a four-concentric-shell Ag@Au17@Ag27@Au17 structure. All phenylalkynyl (PA) ligands are linearly coordinated to the surface Au atoms with staple “PhCC–Au–CCPh” motif. Compared with reported thiolated metal nanoclusters, the surface PA ligands on Au34Ag28(PhCC)34 are readily removed at relatively low temperatures, while the metal core remains intact. The clusters before and after removal of surface ligands are used as catalysts for the hydrolytic oxidation of organosilanes to silanols. It is, for the first time, demonstrated that the organic-capped metal nanoclusters work as active catalysts much better than those with surface ligands partially or completely removed.
Copper–hydrides are known catalysts for several technologically important reactions such as hydrogenation of CO, hydroamination of alkenes and alkynes, and chemoselective hydrogenation of unsaturated ...ketones to unsaturated alcohols. Stabilizing copper-based particles by ligand chemistry to nanometer scale is an appealing route to make active catalysts with optimized material economy; however, it has been long believed that the ligand–metal interface, particularly if sulfur-containing thiols are used as stabilizing agent, may poison the catalyst. We report here a discovery of an ambient-stable thiolate-protected copper–hydride nanocluster Cu25H10(SPhCl2)183– that readily catalyzes hydrogenation of ketones to alcohols in mild conditions. A full experimental and theoretical characterization of its atomic and electronic structure shows that the 10 hydrides are instrumental for the stability of the nanocluster and are in an active role being continuously consumed and replenished in the hydrogenation reaction. Density functional theory computations suggest, backed up by the experimental evidence, that the hydrogenation takes place only around a single site of the 10 hydride locations, rendering the Cu25H10(SPhCl2)183– one of the first nanocatalysts whose structure and catalytic functions are characterized fully to atomic precision. Understanding of a working catalyst at the atomistic level helps to optimize its properties and provides fundamental insights into the controversial issue of how a stable, ligand-passivated, metal-containing nanocluster can be at the same time an active catalyst.
Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters ...that are surface‐active for liquid‐phase catalysis without any pre‐treatment. Now, an N‐heterocyclic carbene‐stabilized Au25 nanocluster with high thermal and air stabilities is presented as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as Au25(iPr2‐bimy)10Br72+ (iPr2‐bimy=1,3‐diisopropylbenzimidazolin‐2‐ylidene) (1), was synthesized by direct reduction of AuSMe2Cl and iPr2‐bimyAuBr with NaBH4 in one pot. X‐ray crystallization analysis revealed that the cluster comprises two centered Au13 icosahedra sharing a vertex. Cluster 1 is highly stable and can survive in solution at 80 °C for 12 h, which is superior to Au25 nanoclusters passivated with phosphines or thiols. DFT computations reveal the origins of both electronic and thermal stability of 1 and point to the probable catalytic sites. This work provides new insights into the bonding capability of N‐heterocyclic carbene to Au in a cluster, and offers an opportunity to probe the catalytic mechanism at the atomic level.
An atomically precise N‐heterocyclic carbene‐stabilized Au25 nanocluster is successfully synthesized in a one‐pot reaction. It exhibits much higher thermal stability in the solution form compared to Au25 protected by thiol or phosphine ligands. The cluster displays excellent catalytic activity in the cycloisomerization of alkynyl amine as a homogeneous catalyst.
This is the first book to comprehensively cover chromatic polynomials of graphs. It includes most of the known results and unsolved problems in the area of chromatic polynomials. Dividing the book ...into three main parts, the authors take readers from the rudiments of chromatic polynomials to more complex topics: the chromatic equivalence classes of graphs and the zeros and inequalities of chromatic polynomials. The early material is well suited to a graduate level course while the latter parts will be an invaluable resource for postgraduate students and researchers in combinatorics and graph theory.
A general strategy, using mixed ligands, is utilized to synthesize atomically precise, intrinsically chiral nanocluster Ag78(DPPP)6(SR)42 (Ag78) where DPPP is the achiral ...1,3-bis(diphenyphosphino)propane and SR = SPhCF3. Ag78 crystallizes as racemates in a centric space group. Using chiral diphosphines BDPP = 2,4-bis(diphenylphosphino)pentane, the enantiomeric pair Ag78(R/S-BDPP)6(SR)42 can be prepared with 100% optical purity. The chiral diphosphines gives rise to, separately, two asymmetric surface coordination motifs composed of tetrahedral R3PAg(SR)3 moieties. The flexible nature of C–C–C angles between the two phosphorus atoms restricts the relative orientation of the tetrahedral R3PAg(SR)3 moieties, thereby resulting in the enantiomeric selection of the intrinsic chiral metal core. This proof-of-concept strategy raises the prospect of enantioselectively synthesizing optically pure, atomically precise chiral noble metal nanoclusters for specific applications.
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