Iridium-Functionalized Cellulose Microcrystals as a Novel Luminescent Biomaterial for Biocomposites

Microcrystalline cellulose (MCC) is an emerging material with outstanding properties in many scientific and industrial fields, in particular as an additive in composite materials. Its surface modification allows for the fine-tuning of its properties and the exploitation of these materials in a plethora of applications. In this paper, we present the covalent linkage of a luminescent Ir-complex onto the surface of MCC, representing the first incorporation of an organometallic luminescent probe in this biomaterial. This goal has been achieved with an easy and sustainable procedure, which employs a Bronsted-acid ionic liquid as a catalyst for the esterification reaction of -OH cellulose surface groups. The obtained luminescent cellulose microcrystals display high and stable emissions with the incorporation of only a small amount of iridium (III). Incorporation of MCC-Ir in dry and wet matrices, such as films and gels, has been also demonstrated, showing the maintenance of the luminescent properties even in possible final manufacturers

A synergic nanoantioxidant based on covalently modified halloysite-trolox nanotubes with intra-lumen loaded quercetin

We describe the preparation and properties of the first example of a synergic nanoantioxidant, obtained by different functionalizations of the external surface and the inner lumen of halloysite nanotubes (HNTs). Trolox, a mimic of natural α-tocopherol, was selectively grafted on the HNT external surface; while quercetin, a natural polyphenolic antioxidant, was loaded into the inner lumen to afford a bi-functional nanoantioxidant, HNT-Trolox/Que, which was investigated for its reactivity with transient peroxyl radicals and a persistent 1,1-diphenyl-2-picrylhydrazyl (DPPH•) radical in comparison with the corresponding mono-functional analogues HNT-Trolox and HNT/Que. Both HNT-Trolox and HNT/Que showed good antioxidant performance in the inhibited autoxidation of organic substrates; however HNT-Trolox/Que protection by reaction with peroxyl radicals was 35% higher in acetonitrile and 65% in chlorobenzene, as compared to the expected performance based on the sum of contributions of NHT-Trolox and NHT/Que. Similar enhancement was observed also in the trapping of DPPH• radicals. Synergism between the distinct antioxidant functions was based on the rapid reaction of externally exposed Trolox (rate constant with peroxyl radicals was 1.1 × 106 M-1 s-1 and 9 × 104 M-1 s-1 respectively in chlorobenzene and acetonitrile, at 30 °C), followed by its regeneration by quercetin released from the HNT lumen. The advantages of this novel nanoantioxidant are discussed

4-Phenyl-1,2,3-triazoles as Versatile Ligands for Cationic Cyclometalated Iridium(III) Complexes

Five cationic iridium(III) complexes (1-5) were synthesized exploiting two triazole-based cyclometalating ligands, namely, 1-methyl-4-phenyl-1H-1,2,3-triazole (A) and the corresponding mesoionic carbene 1,3-dimethyl-4-phenyl-1H-1,2,3-triazol-5-yliclene (B). From the combination of these two ligands and the ancillary one, i.e., 4,4'-di-tert-butyl-2,2'-bipyridine (for 1-3) or tert-butyl isocyanide (for 4 and 5), not only the typical bis-heteroleptic complexes but also the much less explored tris-heteroleptic analogues (2 and 5) could be synthesized. The redox and emission properties of all of the complexes are effectively fine-tuned by the different ligands: (i) cyclometalating ligand A induces a stronger highest occupied molecular orbital (HOMO) stabilization compared to B and leads to complexes with progressively narrower HOMO-lowest unoccupied molecular orbital (LUMO) and redox gaps, and lower emission energy; (ii) complexes 1-3, equipped with the bipyridine ancillary ligand, display fully reversible redox processes and emit from predominantly metal-to-ligand charge transfer (MLCT) states with high emission quantum yields, up to 60% in polymeric matrix; (iii) complexes 4 and 5, equipped with high-field isocyanide ligands, display irreversible redox processes and high-energy emission from strongly ligand-centered triplets with long emission lifetimes but relatively low quantum yields (below 6%, both in room-temperature solution and in solid state). This work demonstrates the versatility of phenyl-triazole derivatives as cyclometalating ligands with different chelation modes (i.e., C<^>N and C<^>C:) for the synthesis of photoactive iridium(III) complexes with highly tunable properties

Evaluating the impact of a maternal health voucher programme on service use before and after the introduction of free maternity services in Kenya: a quasi-experimental study.

INTRODUCTION: From 2006 to 2016, the Government of Kenya implemented a reproductive health voucher programme in select counties, providing poor women subsidised access to public and private sector care. In June 2013, the government introduced a policy calling for free maternity services to be provided in all public facilities. The concurrent implementation of these interventions presents an opportunity to provide new insights into how users adapt to a changing health financing and service provision landscape. METHODS: We used data from three cross-sectional surveys to assess changes over time in use of 4+ antenatal care visits, facility delivery, postnatal care and maternal healthcare across the continuum among a sample of predominantly poor women in six counties. We conducted a difference-in-differences analysis to estimate the impact of the voucher programme on these outcomes, and whether programme impact changed after free maternity services were introduced. RESULTS: Between the preintervention/roll-out phase and full implementation, the voucher programme was associated with a 5.5% greater absolute increase in use of facility delivery and substantial increases in use of the private sector for all services. After free maternity services were introduced, the voucher programme was associated with a 5.7% higher absolute increase in use of the recommended package of maternal health services; however, disparities in access to facility births between voucher and comparison counties declined. Increased use of private sector services by women in voucher counties accounts for their greater access to care across the continuum. CONCLUSIONS: Our findings show that the voucher programme is associated with a modest increase in women's use of the full continuum of maternal health services at the recommended timings after free maternity services were introduced. The greater use of private sector services in voucher counties also suggests that there is need to expand women's access to acceptable and affordable providers

Evaluating the impact of a maternal health voucher programme on service use before and after the introduction of free maternity services in Kenya: a quasi-experimental study

INTRODUCTION: From 2006 to 2016, the Government of Kenya implemented a reproductive health voucher programme in select counties, providing poor women subsidised access to public and private sector care. In June 2013, the government introduced a policy calling for free maternity services to be provided in all public facilities. The concurrent implementation of these interventions presents an opportunity to provide new insights into how users adapt to a changing health financing and service provision landscape. METHODS: We used data from three cross-sectional surveys to assess changes over time in use of 4+ antenatal care visits, facility delivery, postnatal care and maternal healthcare across the continuum among a sample of predominantly poor women in six counties. We conducted a difference-in-differences analysis to estimate the impact of the voucher programme on these outcomes, and whether programme impact changed after free maternity services were introduced. RESULTS: Between the preintervention/roll-out phase and full implementation, the voucher programme was associated with a 5.5% greater absolute increase in use of facility delivery and substantial increases in use of the private sector for all services. After free maternity services were introduced, the voucher programme was associated with a 5.7% higher absolute increase in use of the recommended package of maternal health services; however, disparities in access to facility births between voucher and comparison counties declined. Increased use of private sector services by women in voucher counties accounts for their greater access to care across the continuum. CONCLUSIONS: Our findings show that the voucher programme is associated with a modest increase in women’s use of the full continuum of maternal health services at the recommended timings after free maternity services were introduced. The greater use of private sector services in voucher counties also suggests that there is need to expand women’s access to acceptable and affordable providers

The protein "mycoarray": a novel serological assay for the laboratory diagnosis of primitive endemic mycoses

A protein microarray containing fungal antigens (the "mycoarray") has been set up to provide rapid and appropriate serodiagnosis of primitive endemic mycoses, an important cause of morbidity and mortality in an increasingly high number of patients. The mycoarray consists of three antigen extracts (histoplasmin, coccidioidin and Coccidioides "TP") and antibody dilution curves were spotted on microarray slides. The arrays were processed with coccidioidomycosis and histoplasmosis patients\ufffd sera or with control sera and the occurring immunocomplexes were detected by indirect immunofluorescence. In agreement with clinical and microbiological diagnosis, the results distinguished between histoplasmosis and coccidioidomycosis patients. In addition, the assay could clearly discriminate between IgM and IgG antibody reactivity. No reactivity was ever observed in the arrays processed with negative control sera. Therefore, this pilot study demonstrates that the "mycoarray" is sensitive and specific enough to discriminate between healthy individuals and patients with histoplasmosis or coccidioidomycosis. Because of miniaturization and multiparametricity, the new assay cuts costs and processing time. Thus, once clinically validated and implemented as a large-scale array, the "mycoarray" will be ready to be applied to the daily clinical practice

Health Impacts of Catastrophic Climate Change: Expert Workshop. Avoid Dangerous Climate Change (AVOID)

Climate change is likely to have serious and significant impacts on human population health. The mechanisms by which climate change may affect health are becoming better understood. Current quantitative methods of estimating future health impacts rely on disease-specific models that primarily describe relationships between mean values of weather variables and health outcomes and do not address the impacts of extreme events or weather disasters. Extreme events have the potential to disrupt community function, which is of concern for decision-makers. Estimating the magnitude and extent of impacts from low probability high impact events is challenging because there is often no analogue that can provide relevant evidence and that take into account the complexity of factors determining future vulnerability and health impacts (the social determinants of health)

Risk of SARS-CoV-2 infection, hospitalization, and death for COVID-19 in people with Parkinson disease or parkinsonism over a 15-month period: A cohort study

Background and purpose: The patterns of long-term risk of SARS-CoV-2 infection, hospitalization for COVID-19, and related death are uncertain in people with Parkinson disease (PD) or parkinsonism (PS). The aim of the study was to quantify these risks compared to a control population cohort, during the period March 2020–May 2021, in Bologna, Northern Italy. Methods: ParkLink Bologna cohort (759 PD, 192 PS) and controls (9226) anonymously matched (ratio = 1:10) for sex, age, district, and comorbidity were included. Data were analysed in the whole period and in the two different pandemic waves (March–May 2020 and October 2020–May 2021). Results: Adjusted hazard ratio of SARS-CoV-2 infection was 1.3 (95% confidence interval [CI] = 1.04–1.7) in PD and 1.9 (95% CI = 1.3–2.8) in PS compared to the controls. The trend was detected in both the pandemic waves. Adjusted hazard ratio of hospitalization for COVID-19 was 1.1 (95% CI = 0.8–1.7) in PD and 1.8 (95% CI = 0.97–3.1) in PS. A higher risk of hospital admission was detected in PS only in the first wave. The 30-day mortality risk after hospitalization was higher (p = 0.048) in PS (58%) than in PD (19%) and controls (26%). Conclusions: Compared with controls, after adjustment for key covariates, people with PD and PS showed a higher risk of SARS-CoV-2 infection throughout the first 15 months of the pandemic. COVID-19 hospitalization risk was increased only in people with PS and only during the first wave. This group of patients was burdened by a very high risk of death after infection and hospitalization