34 research outputs found
Recommended from our members
Healable polymeric materials: a tutorial review
Given the extensive use of polymers in the modern age with applications ranging from aerospace components to microcircuitry, the ability to regain the mechanical and physical characteristics of complex pristine materials after damage is an attractive proposition. This tutorial review focusses upon the key chemical concepts that have been successfully utilised in the design of healable polymeric materials
Global, regional, and national comparative risk assessment of 79 behavioural, environmental and occupational, and metabolic risks or clusters of risks, 1990-2015: a systematic analysis for the Global Burden of Disease Study 2015
Forouzanfar MH, Afshin A, Alexander LT, et al. Global, regional, and national comparative risk assessment of 79 behavioural, environmental and occupational, and metabolic risks or clusters of risks, 1990-2015: a systematic analysis for the Global Burden of Disease Study 2015. LANCET. 2016;388(10053):1659-1724.Background The Global Burden of Diseases, Injuries, and Risk Factors Study 2015 provides an up-to-date synthesis of the evidence for risk factor exposure and the attributable burden of disease. By providing national and subnational assessments spanning the past 25 years, this study can inform debates on the importance of addressing risks in context. Methods We used the comparative risk assessment framework developed for previous iterations of the Global Burden of Disease Study to estimate attributable deaths, disability-adjusted life-years (DALYs), and trends in exposure by age group, sex, year, and geography for 79 behavioural, environmental and occupational, and metabolic risks or clusters of risks from 1990 to 2015. This study included 388 risk-outcome pairs that met World Cancer Research Fund-defined criteria for convincing or probable evidence. We extracted relative risk and exposure estimates from randomised controlled trials, cohorts, pooled cohorts, household surveys, census data, satellite data, and other sources. We used statistical models to pool data, adjust for bias, and incorporate covariates. We developed a metric that allows comparisons of exposure across risk factors-the summary exposure value. Using the counterfactual scenario of theoretical minimum risk level, we estimated the portion of deaths and DALYs that could be attributed to a given risk. We decomposed trends in attributable burden into contributions from population growth, population age structure, risk exposure, and risk-deleted cause-specific DALY rates. We characterised risk exposure in relation to a Socio-demographic Index (SDI). Findings Between 1990 and 2015, global exposure to unsafe sanitation, household air pollution, childhood underweight, childhood stunting, and smoking each decreased by more than 25%. Global exposure for several occupational risks, high body-mass index (BMI), and drug use increased by more than 25% over the same period. All risks jointly evaluated in 2015 accounted for 57.8% (95% CI 56.6-58.8) of global deaths and 41.2% (39.8-42.8) of DALYs. In 2015, the ten largest contributors to global DALYs among Level 3 risks were high systolic blood pressure (211.8 million [192.7 million to 231.1 million] global DALYs), smoking (148.6 million [134.2 million to 163.1 million]), high fasting plasma glucose (143.1 million [125.1 million to 163.5 million]), high BMI (120.1 million [83.8 million to 158.4 million]), childhood undernutrition (113.3 million [103.9 million to 123.4 million]), ambient particulate matter (103.1 million [90.8 million to 115.1 million]), high total cholesterol (88.7 million [74.6 million to 105.7 million]), household air pollution (85.6 million [66.7 million to 106.1 million]), alcohol use (85.0 million [77.2 million to 93.0 million]), and diets high in sodium (83.0 million [49.3 million to 127.5 million]). From 1990 to 2015, attributable DALYs declined for micronutrient deficiencies, childhood undernutrition, unsafe sanitation and water, and household air pollution; reductions in risk-deleted DALY rates rather than reductions in exposure drove these declines. Rising exposure contributed to notable increases in attributable DALYs from high BMI, high fasting plasma glucose, occupational carcinogens, and drug use. Environmental risks and childhood undernutrition declined steadily with SDI; low physical activity, high BMI, and high fasting plasma glucose increased with SDI. In 119 countries, metabolic risks, such as high BMI and fasting plasma glucose, contributed the most attributable DALYs in 2015. Regionally, smoking still ranked among the leading five risk factors for attributable DALYs in 109 countries; childhood underweight and unsafe sex remained primary drivers of early death and disability in much of sub-Saharan Africa. Interpretation Declines in some key environmental risks have contributed to declines in critical infectious diseases. Some risks appear to be invariant to SDI. Increasing risks, including high BMI, high fasting plasma glucose, drug use, and some occupational exposures, contribute to rising burden from some conditions, but also provide opportunities for intervention. Some highly preventable risks, such as smoking, remain major causes of attributable DALYs, even as exposure is declining. Public policy makers need to pay attention to the risks that are increasingly major contributors to global burden. Copyright (C) The Author(s). Published by Elsevier Ltd
Recommended from our members
Self-assembled healable materials through a combination of pi-pi stacking and hydrogen bonding
The discovery of polymers with stimuli responsive physical properties is a rapidly expanding area of research. At the forefront of the field are self-healing polymers, which, when fractured can regain the mechanical properties of the material either autonomically, or in response to a stimulus. It has long been known that it is possible to promote healing in conventional thermoplastics by heating the fracture zone above the Tg of the polymer under pressure. This process requires reptation and subsequent re-entanglement of macromolecules across the fracture void, which serves to bridge, and ‘heal’ the crack. The timescale for this mechanism is highly dependent on the molecular weight of the polymer being studied. This process is in contrast to that required to affect healing in supramolecular polymers such as the plasticised, hydrogen bonded elastomer reported by Leibler et al. The disparity in bond energies between the non-covalent and covalent bonds within supramolecular polymers results in fractures propagating through scission of the comparatively weak supramolecular interactions, rather than through breaking the stronger, covalent bonds. Thus, during the healing process the macromolecules surrounding the fracture site only need sufficient energy to re-engage their supramolecular interactions in order to regenerate the strength of the pristine material.
Herein we describe the design, synthesis and optimization of a new class of supramolecular polymer blends that harness the reversible nature of pi-pi stacking and hydrogen bonding interactions to produce self-supporting films with facile healable characteristics
Recommended from our members
Bis(hydroxy-isoindolinone)s: synthesis, stereochemistry, polymer chemistry, and supramolecular assembly
Pseudoacid chlorides of 2,5-bis(4-fluorobenzoyl) terephthalic acid and 4,6-bis(4-fluorobenzoyl) isophthalic acid condense with primary amines to afford diastereomeric bis(hydroxyindolinone)s in good isolated yields and with diamines to give high molecular weight poly(hydroxyindolinone)s. Bis-N-pyrenemethyl bis(hydroxyindolinone)s assemble, even in dipolar solvents such as DMSO, with macrocyclic diimide-sulfones to give [3]pseudorotaxanes stabilized by electronically complementary aromatic π−π-stacking and shape-complementary van der Waals interactions
Recommended from our members
Mutual complexation between π−π stacked molecular tweezers
Aromatic and heterocyclic molecules which form electronically complementary π−π stacked complexes have recently found extensive application in functional materials, molecular machines, and stimuli-responsive supra- molecular polymers. Here we describe the design and synthesis of model compounds that self-assemble through complemen- tary stacking motifs, paralleling those postulated to exist in high-molecular weight, healable, supramolecular polymer systems. Complexation studies using 1H NMR and UV−vis spectroscopy indicated formation of a complementary complex between a π-electron rich dipyrenyl tweezer-motif and a tweezer-like, π-electron deficient bis-diimide. The binding stoichiometry in solution between the chain-folding diimide and the pyrenyl derivative was equimolar with respect to the two binding motifs, and the resulting association constant was measured at Ka = 1200 ± 90 M−1. Single crystal X-ray analysis of this “tweezer− tweezer” complex showed a low-energy conformation of the triethylenedioxy linker within the bis-diimide chain-fold. Interplanar separations of 3.4−3.5 Å were found within the π-stacks, and supporting hydrogen bonds between pyrenyl amide NH groups and diimide carbonyl oxygens were identified
Recommended from our members
Induced-fit binding of π-electron donor substrates to macrocyclic aromatic ether-imide-sulfones: a versatile approach to molecular assembly
Novel macrocyclic receptors which bind electron-donor aromatic substrates via π-stacking donor- acceptor interactions are obtained by cyclo-imidization of an amine-functionalized arylether-sulfone with pyromellitic- and 1,4,5,8-naphthalene-tetracarboxylic dianhydrides. These macrocycles complex with a wide variety of π-donor substrates including tetrathiafulvalene, naphthalene, anthracene, pyrene, perylene, and functional derivatives of these polycyclic hydrocarbons. The resulting supramolecular assemblies range from simple 1:1 complexes, to [2]- and [3]-pseudorotaxanes, and even (as a result of crystallographic disorder) an apparent polyrotaxane. Direct, five-component self-assembly of a metal-centred [3]pseudorotaxane is also observed, on complexation of a macrocyclic ether-imide with 8-hydroxyquinoline in the presence of palladium(II) ions. Binding studies in solution were carried out by 1H NMR and UV-visible spectroscopy, and the stoichiometries of binding were confirmed by Job plots based on charge-transfer absorption bands. The highest association constants are found for strong π-donor guests with large surface-areas, notably perylene and 1-hydroxypyrene, for which Ka values of 1.4 x 103 and 2.3 x 103 M-1 respectively are found. Single crystal X-ray analyses of the receptors and their derived complexes reveal large, induced-fit distortions of the macrocyclic frameworks as a result of complexation. These structures provide compelling evidence for the existence of strong, attractive forces between the electronically-complementary aromatic π-systems of host and guest
Recommended from our members
Mutual binding of polymer end-groups by complementary π–π-stacking: a molecular “Roman Handshake”
Self-complementary tweezer-molecules based on a naphthalenediimide core self-assemble into supramolecular dimers through mutual π–π-stacking and hydrogen bonding. The resulting motif is extremely stable in solution (Ka = 105 M−1), and its attachment to one terminal position of a poly(ethylene glycol) chain leads to a doubling of the polymer's apparent molecular weight
Recommended from our members
Mutual complexation between p-p stacked molecular tweezers
Aromatic and heterocyclic molecules which form electronically complementary p-p stacked complexes have recently found extensive application in functional materials, molecular machines, and stimuli-responsive supra- molecular polymers. Here we describe the design and synthesis of model compounds that self-assemble through complemen- tary stacking motifs, paralleling those postulated to exist in high-molecular weight, healable, supramolecular polymer systems. Complexation studies using 1H NMR and UV-vis spectroscopy indicated formation of a complementary complex between a p-electron rich dipyrenyl tweezer-motif and a tweezer-like, p-electron deficient bis-diimide. The binding stoichiometry in solution between the chain-folding diimide and the pyrenyl derivative was equimolar with respect to the two binding motifs, and the resulting association constant was measured at Ka = 1200 ± 90 M-1. Single crystal X-ray analysis of this “tweezer- tweezer” complex showed a low-energy conformation of the triethylenedioxy linker within the bis-diimide chain-fold. Interplanar separations of 3.4-3.5 Å were found within the p-stacks, and supporting hydrogen bonds between pyrenyl amide NH groups and diimide carbonyl oxygens were identified