Poly(lactic acid) (PLA) is a compostable bioplastic manufactured by the polymerization of lactic acid monomers derived from the fermentation of starch as a feedstock. Since its first ...commercialisation in the late 1990's, PLA production has grown annually and currently it estimated that worldwide production will reach at least 800,000 tons by 2020 with Japan and the USA the two major producers. PLA is used as a replacement to conventional petrochemical based plastics, principally as food packaging containers and films and more recently, in electronics and in the manufacture of synthetic fibres. Consequently, there has been a marked increase in PLA contamination in the environment as well as increasing amounts being diverted to commercial composting facilities. This review focuses on the development, production, stability and degradation of PLA in a range of differing environments and explores our current knowledge of the environmental and biological factors involved in PLA degradation.
Magnesium alloys that contain certain rare-earth (RE) additions are known to have improved formability and this can be partly attributed to the different texture they display after recrystallization. ...Previous experimental work has identified segregation of RE to grain boundaries and dislocations as being potentially important in producing this change in behavior. In the present paper, two classical models (Langmuir–McClean and Cahn–Lücke–Stüwe) are used to explore the likely effect of RE additions on grain boundary solute concentration and drag. It is demonstrated that a wide range of RE elements are predicted to segregate strongly to grain boundaries due to the large atomic size misfit with magnesium. The maximum level of segregation is produced for elements such as Y or Gd that combine a high misfit and high bulk solubility. Segregated Y is predicted to produce a solute drag pressure on migrating boundaries several orders of magnitude greater than that obtained by Al or Zn additions. It is demonstrated that while this drag is predicted to be insufficient to strongly retard static recrystallization under typical annealing conditions, it is expected to suppress dynamic recrystallization by any mechanism requiring boundary migration.
Poly(lactic) acid (PLA) is a compostable biopolymer and has been commercialised for the for the manufacture of short-shelf life products. As a result, increasing amounts of PLA are entering waste ...management systems and the environment; however, the degradation mechanism is unclear. While hydrolysis of the polymer occurs abiotically at elevated temperature in the presence of water, potential catalytic role for microbes in this process is yet to be established. In this study, we examined the degradation of PLA coupons from commercial packaging at a range of temperatures (25°, 37°, 45°, 50° and 55 °C) in soil and compost and compared with the degradation rates in sterile aqueous conditions by measuring loss of tensile strength and molecular weight (Mw). In addition, in order to assess the possible influence of abiotic soluble factors in compost and soil on degradation of PLA, degradation rates in microorganism-rich compost and soil were compared with sterile compost and soil extract at 50 °C. Temperature was determined to be the key parameter in PLA degradation and degradation rates in microorganism-rich compost and soil were faster than in sterile water at temperatures 45° and 50 °C determined by tensile strength and Mw loss. Furthermore, all tensile strength was lost faster after 30 and 36 days in microorganism-rich compost and soil, respectively, than in sterile compost and soil extract, 57 and 54 days, respectively at 50 °C. Significantly more Mw, 68% and 64%, was lost in compost and soil, respectively than in compost extract, Mw, 53%; and in soil extract, 57%. Therefore, degradation rates were faster in microorganism-rich compost and soil than in sterile compost and soil extract, which contained the abiotic soluble factors of compost and soil at 50 °C. These comparative studies support a direct role for microorganisms in PLA degradation at elevated temperatures in humid environments. No change in tensile strength or Mw was observed either 25° or 37 °C after 1 year suggesting that accumulation of PLA in the environment may cause future pollution issues.
Rapid innovations in cardiovascular magnetic resonance (CMR) now permit the routine acquisition of quantitative measures of myocardial and blood T1 which are key tissue characteristics. These ...capabilities introduce a new frontier in cardiology, enabling the practitioner/investigator to quantify biologically important myocardial properties that otherwise can be difficult to ascertain clinically. CMR may be able to track biologically important changes in the myocardium by: a) native T1 that reflects myocardial disease involving the myocyte and interstitium without use of gadolinium based contrast agents (GBCA), or b) the extracellular volume fraction (ECV)-a direct GBCA-based measurement of the size of the extracellular space, reflecting interstitial disease. The latter technique attempts to dichotomize the myocardium into its cellular and interstitial components with estimates expressed as volume fractions. This document provides recommendations for clinical and research T1 and ECV measurement, based on published evidence when available and expert consensus when not. We address site preparation, scan type, scan planning and acquisition, quality control, visualisation and analysis, technical development. We also address controversies in the field. While ECV and native T1 mapping appear destined to affect clinical decision making, they lack multi-centre application and face significant challenges, which demand a community-wide approach among stakeholders. At present, ECV and native T1 mapping appear sufficiently robust for many diseases; yet more research is required before a large-scale application for clinical decision-making can be recommended.
The influence of large (
>
1
μ
m
diameter) particles on the recrystallization behaviour of magnesium alloys deformed in plane strain compression has been studied. Deformation zones characterized by a ...misorientation gradient were observed surrounding large particles, which were similar to those seen in other alloys where particle-stimulated nucleation (PSN) of recrystallization occurs. During annealing, new grains formed by PSN, but only at a small fraction of the coarse particles. Recrystallization was instead dominated by growth of existing dynamically recrystallized grains and nucleation of new grains from the deformed grain mantle region.
•Biodegradation of four polymers (PCL, PHB, PLA and PBS) were compared.•Higher temperature was a key variable for faster biodegradation in compost.•Polycaprolactone (PCL) showed the fastest ...degradation rate under all conditions.•Aspergillus and Thermomyces fungal strains were the most abundant on all polymers.•Thermomyces lanuginosus was associated with rapid PCL degradation at 50 °C.
Plastics are an indispensable material but also a major environmental pollutant. In contrast, biodegradable polymers have the potential to be compostable. The biodegradation of four polymers as discs, polycaprolactone (PCL), polyhydroxybutyrate (PHB), polylactic acid (PLA) and poly(1,4 butylene) succinate (PBS) was compared in soil and compost over a period of more than 10 months at 25 °C, 37 °C and 50 °C. Degradation rates varied between the polymers and incubation temperatures but PCL showed the fastest degradation rate under all conditions and was completely degraded when buried in compost and incubated at 50 °C after 91 days. Furthermore, PCL strips showed a significant reduction in tensile strength in just 2 weeks when incubated in compost >45 °C. Various fungal strains growing on the polymer surfaces were identified by sequence analysis. Aspergillus fumigatus was most commonly found at 25 °C and 37 °C, while Thermomyces lanuginosus, which was abundant at 50 °C, was associated with PCL degradation.
Objectives This study sought to explore the potential role of noncontrast myocardial T1 mapping for detection of cardiac involvement in patients with primary amyloid light-chain (AL) amyloidosis. ...Background Cardiac involvement carries a poor prognosis in systemic AL amyloidosis. Late gadolinium enhancement (LGE) cardiac magnetic resonance (CMR) is useful for the detection of cardiac amyloid, but characteristic LGE patterns do not always occur or they appear late in the disease. Noncontrast characterization of amyloidotic myocardium with T1 mapping may improve disease detection. Furthermore, quantitative assessment of myocardial amyloid load would be of great value. Methods Fifty-three AL amyloidosis patients (14 with no cardiac involvement, 11 with possible involvement, and 28 with definite cardiac involvement based on standard biomarker and echocardiographic criteria) underwent CMR (1.5-T) including noncontrast T1 mapping (shortened modified look-locker inversion recovery ShMOLLI sequence) and LGE imaging. These were compared with 36 healthy volunteers and 17 patients with aortic stenosis and a comparable degree of left ventricular hypertrophy as the cardiac amyloid patients. Results Myocardial T1 was significantly elevated in cardiac AL amyloidosis patients (1,140 ± 61 ms) compared to normal subjects (958 ± 20 ms, p < 0.001) and patients with aortic stenosis (979 ± 51 ms, p < 0.001). Myocardial T1 was increased in AL amyloid even when cardiac involvement was uncertain (1,048 ± 48 ms) or thought absent (1,009 ± 31 ms). A noncontrast myocardial T1 cutoff of 1,020 ms yielded 92% accuracy for identifying amyloid patients with possible or definite cardiac involvement. In the AL amyloidosis cohort, there were significant correlations between myocardial T1 time and indices of systolic and diastolic dysfunction. Conclusions Noncontrast T1 mapping has high diagnostic accuracy for detecting cardiac AL amyloidosis, correlates well with markers of systolic and diastolic dysfunction, and is potentially more sensitive for detecting early disease than LGE imaging. Elevated myocardial T1 may represent a direct marker of cardiac amyloid load. Further studies are needed to assess the prognostic significance of T1 elevation.
Abstract Background Pheochromocytoma is associated with catecholamine-induced cardiac toxicity, but the extent and nature of cardiac involvement in clinical cohorts is not well-characterized. ...Objectives This study characterized the cardiac phenotype in patients with pheochromocytoma using cardiac magnetic resonance (CMR). Methods A total of 125 subjects were studied, including patients with newly diagnosed pheochromocytoma (n = 29), patients with previously surgically cured pheochromocytoma (n = 31), healthy control subjects (n = 51), and hypertensive control subjects (HTN) (n = 14), using CMR (1.5-T) cine, strain imaging by myocardial tagging, late gadolinium enhancement, and native T1 mapping (Shortened Modified Look-Locker Inversion recovery ShMOLLI). Results Patients who were newly diagnosed with pheochromocytoma, compared with healthy and HTN control subjects, had impaired left ventricular (LV) ejection fraction (<56% in 38% of patients), peak systolic circumferential strain (p < 0.05), and diastolic strain rate (p < 0.05). They had higher myocardial T1 (974 ± 25 ms, as compared with 954 ± 16 ms in healthy and 958 ± 23 ms in HTN subjects; p < 0.05), areas of myocarditis (median 22% LV with T1 >990 ms, as compared with 1% in healthy and 2% in HTN subjects; p < 0.05), and focal fibrosis (59% had nonischemic late gadolinium enhancement, as compared with 14% in HTN subjects). Post-operatively, impaired LV ejection fraction typically normalized, but systolic and diastolic strain impairment persisted. Focal fibrosis (median 5% LV) and T1 abnormalities (median 12% LV) remained, the latter of which may suggest some diffuse fibrosis. Previously cured patients demonstrated abnormal diastolic strain rate (p < 0.001), myocardial T1 (median 12% LV), and small areas of focal fibrosis (median 1% LV). LV mass index was increased in HTN compared with healthy control subjects (p < 0.05), but not in the 2 pheochromocytoma groups. Conclusions This first systematic CMR study characterizing the cardiac phenotype in pheochromocytoma showed that cardiac involvement was frequent and, for some variables, persisted after curative surgery. These effects surpass those of hypertensive heart disease alone, supporting a direct role of catecholamine toxicity that may produce subtle but long-lasting myocardial alterations.
Native T1 Mapping in Transthyretin Amyloidosis Fontana, Marianna, MD; Banypersad, Sanjay M., MB ChB; Treibel, Thomas A., MBBS ...
JACC. Cardiovascular imaging,
02/2014, Letnik:
7, Številka:
2
Journal Article
Recenzirano
Odprti dostop
Objectives The aims of the study were to explore the ability of native myocardial T1 mapping by cardiac magnetic resonance to: 1) detect cardiac involvement in patients with transthyretin amyloidosis ...(ATTR amyloidosis); 2) track the cardiac amyloid burden; and 3) detect early disease. Background ATTR amyloidosis is an underdiagnosed cause of heart failure, with no truly quantitative test. In cardiac immunoglobulin light-chain amyloidosis (AL amyloidosis), T1 has high diagnostic accuracy and tracks disease. Here, the diagnostic role of native T1 mapping in the other key type of cardiac amyloid, ATTR amyloidosis, is assessed. Methods A total of 3 groups were studied: ATTR amyloid patients (n = 85; 70 males, age 73 ± 10 years); healthy individuals with transthyretin mutations in whom standard cardiac investigations were normal (n = 8; 3 males, age 47 ± 6 years); and AL amyloid patients (n = 79; 55 males, age 62 ± 10 years). These were compared with 52 healthy volunteers and 46 patients with hypertrophic cardiomyopathy (HCM). All underwent T1 mapping (shortened modified look-locker inversion recovery); ATTR patients and mutation carriers also underwent cardiac 3,3-diphosphono-1,2-propanodicarboxylicacid (DPD) scintigraphy. Results T1 was elevated in ATTR patients compared with HCM and normal subjects (1,097 ± 43 ms vs. 1,026 ± 64 ms vs. 967 ± 34 ms, respectively; both p < 0.0001). In established cardiac ATTR amyloidosis, T1 elevation was not as high as in AL amyloidosis (AL 1,130 ± 68 ms; p = 0.01). Diagnostic performance was similar for AL and ATTR amyloid (vs. HCM: AL area under the curve 0.84 95% confidence interval: 0.76 to 0.92; ATTR area under the curve 0.85 95% confidence interval: 0.77 to 0.92; p < 0.0001). T1 tracked cardiac amyloid burden as determined semiquantitatively by DPD scintigraphy (p < 0.0001). T1 was not elevated in mutation carriers (952 ± 35 ms) but was in isolated DPD grade 1 (n = 9, 1,037 ± 60 ms; p = 0.001). Conclusions Native myocardial T1 mapping detects cardiac ATTR amyloid with similar diagnostic performance and disease tracking to AL amyloid, but with lower maximal T1 elevation, and appears to be an early disease marker.
The syntheses and the electrochemical spectroscopic properties of a suite of asymmetrical bistridentate cyclometalated Ru(II) complexes bearing terminal triphenylamine (TPA) substituents are ...reported. These complexes, which contain structural design elements common to both inorganic and organic dyes that exhibit superior power conversion efficiencies in the dye-sensitized solar cell (DSSC), are broadly formulated as RuII(L-2,5′-thiophene-TPA-R1)(L-R2)+ L = tridentate chelating ligand (e.g., 2,2′:6′,2′′-terpyridine (tpy); deprotonated forms of 1,3-di(pyridin-2-yl)benzene (Hdpb) or 6-phenyl-2,2′-bipyridine (Hpbpy)); R1 = −H, −Me, −OMe; R2 = −H, −CO2Me, −CO2H. The following structural attributes were systematically modified for the series: (i) electron-donating character of the terminal substituents (e.g., R1 = −H, −Me, −OMe) placed para to the amine of the “L-2,5′-thiophene-TPA-R1” ligand framework; (ii) electron-withdrawing character of the tridentate chelate distal to the TPA-substituted ligand (e.g., R2 = −H, −CO2Me, −CO2H); and (iii) position of the organometallic bond about the Ru(II) center. UV–vis spectra reveal intense and broad absorption bands arising from a collection of metal-to-ligand charge-transfer (MLCT) and TPA-based intraligand charge-transfer (ILCT) transitions that, in certain cases, extend beyond 800 nm. Electrochemical data indicate that the oxidative behavior of the TPA and metal chelate units can be independently modulated except in cases where the anionic phenyl ring is in direct conjugation with the TPA unit. In most cases, the anionic character of the cyclometalating ligands renders a metal-based oxidation event prior to the oxidation of the TPA unit. This situation can, however, be reversed with an appropriately positioned Ru–C bond and electron-rich R1 group. This finding is important in that this arrangement confines the highest occupied molecular orbital (HOMO) to the TPA unit rather than the metal, which is optimal for sensitizing TiO2; indeed, a remarkably high power conversion efficiency (η) in the DSSC (i.e., 8.02%) is measured for the TPA-substituted pbpy– chelate where R1 = −OMe. These results provide a comprehensive strategy for improving the performance of bistridentate Ru sensitizers devoid of NCS– groups for the DSSC.
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