The synthesis of TBA‐DASA‐POM‐DASA, the first photoactive covalent hybrid polyoxometalate (POM) incorporating a donor–acceptor Stenhouse adduct (DASA) reverse photochrome, is presented. It has been ...evidenced that in solution the equilibrium between the colorless cyclopentenone and the highly colored triene conformers is strongly dependent not only on the nature of the solvent but also the countercations, allowing to tune its optical properties. This complex has been further associated to photochromic spironaphtoxazine cations, resulting in a material which can be activated by two distinct optical stimuli. Moreover, when combined with N‐methyldiethanolamine, TBA‐DASA‐POM‐DASA constitutes a performing photoinitiating system for polyethylene glycol diacrylate polymerization and under visible light irradiation, a promising result in a domain scarcely developed in POM chemistry.
POMs and DASA: the first compound associating in a single molecule a polyoxometalate and a reverse photochrome is reported. It can be activated via two orthogonal optical stimuli when ionically associated to an organic photochrome. Furthermore, its ability to act as a photoinitiator in free‐radical polymerization process under visible light is demonstrated.
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Australians from regional, rural, and remote areas face diverse and complex challenges in accessing and utilising mental health services. Previous research has pointed to a range of individual, ...community, structural, and systemic barriers at play, however, limited literature has synthesised the knowledge on this topic. Parallel to this, information on the facilitators to accessing and utilising mental health services for this group is not well documented. This protocol describes the methodology to undertake a scoping review, which aims to explore the barriers and facilitators associated with accessing and utilising mental health services in regional, rural, and remote Australia. In addition, the scoping review aims to geographically map the identified barriers and facilitators.
This protocol is guided by Arksey and O'Malley's methodological framework. A search strategy will be developed and implemented to identify relevant peer-reviewed and grey literature. Studies will be included if they report on the barriers and/or facilitators associated with accessing and/or utilising mental health services in regional, rural, and remote Australia. Two reviewers will independently screen the data at the title/abstract and full-text stage. One reviewer will extract the relevant data using a predetermined charting form and a second reviewer will validate the included data. A Geographical Information System program will be used to map the location of the studies; locations will be stratified according to the Modified Monash Model and relationships between barriers and facilitators will be analysed. Key findings will be presented in a narrative account and in text, tables, and maps.
This scoping review will provide a contemporary account on the barriers and facilitators to accessing and utilising mental health services for regional, rural, and remote Australians. It is anticipated that the results of this scoping review will have national policy relevance and may be useful to healthcare providers.
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Functional preferences in the use of right/left forelimbs are not exclusively present in humans but have been widely documented in a variety of vertebrate and invertebrate species. A matter of debate ...is whether non-human species exhibit a degree and consistency of functional forelimb asymmetries comparable to human handedness. The comparison is made difficult by the variability in hand use in humans and the few comparable studies conducted on other species. In spite of this, interesting continuities appear in functions such as feeding, object manipulation and communicative gestures. Studies on invertebrates show how widespread forelimb preferences are among animals, and the importance of experience for the development of forelimb asymmetries. Vertebrate species have been extensively investigated to clarify the origins of forelimb functional asymmetries: comparative evidence shows that selective pressures for different functions have likely driven the evolution of human handedness. Evidence of a complex genetic architecture of human handedness is in line with the idea of multiple evolutionary origins of this trait.
A near-infrared-absorbing heptamethine (HM+) incorporating three bulky benzocdindole heterocycles was designed to efficiently prevent self-aggregation of the dye, which results in a strong ...enhancement of its photoinitiating reactivity as compared to a parent bis-benzocdindole heptamethine (HMCl+) used as a reference system. In this context, we highlight an efficient free-radical NIR-polymerization up to a 100% acrylates C=C bonds conversion even under air conditions. Such an important initiating performance was obtained by incorporating our NIR-sensitizer into a three-component system leading to its self-regeneration. This original photoredox cycle was thoroughly investigated through the identification of each intermediary species using EPR spectroscopy.
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Ferroelectrics (FEs) are materials of paramount importance with a wide diversity of applications. Herein, we propose a postsynthetic methodology for the smart implementation of ferroelectricity in ...chiral metal−organic frameworks (MOFs): following a single-crystal to single-crystal cation metathesis, the Ca2+ counterions of a preformed chiral MOF of formula Ca6 II{CuII 24(S,S)-hismox12(OH2)3}·212H2O (1), where hismox is a chiral ligand derived from the natural amino acid l-histidine, are replaced by CH3NH3 +. The resulting compound, (CH3NH3)12{CuII 24(S,S)-hismox12(OH2)3}·178H2O (2), retains the polar space group of 1 and is ferroelectric below 260 K. These results open a new synthetic avenue to enlarge the limited number of FE MOFs.
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Photochemical processes offer the possibility of preparing functional hydrogels under green conditions that are compatible with both synthetic and natural polymers. In this study, chitosan-based ...poly(ethylene) glycol (PEG) were successfully synthesized under light irradiation in aqueous medium. Kinetic studies under irradiation showed that less than 2 min were necessary to obtain fully cross-linked networks. Thermomechanical analyses and swelling experiments indicated that introduction of chitosan overall weakens the hydrogel network but can create domains of higher thermal stability than the PEG-alone structure. The resulting chitosan-PEG hydrogels demonstrated a tremendous inhibition (100%) of bacterial growth (
Escherichia coli
and
Staphylococcus aureus
). After 6 months' ageing, one of the hydrogels preserved a high antifouling activity against
Escherichia coli
. This interesting result, which could be correlated with the network features, demonstrates the strong potential of these photochemical methods to obtain robust bio-functional materials.
The photo-induced synthesis of chitosan-PEG hydrogels with tremendous antibacterial and anti-adhesive properties even after 6 months' storage.
Bio‐sourced epoxy resins from resorcinol diglycidyl ether (RDGE) have been obtained by using cationic photopolymerization under UV‐light exposure. The photoinduced bulk resin samples were ...characterized by three‐point bending tests, dynamic mechanical analysis, as well as differential scanning calorimetry analysis, and thermogravimetric analysis. The influence of processing parameters, that is, reactant contents, UV irradiation time, and postcuring conditions on the thermomechanical behavior has been pointed out. For instance, the flexural modulus of the most performing materials reaches 4.1 GPa with the flexural strength and the glass‐transition temperature of around 105 MPa and 99°C, respectively. Interestingly, our optimized protocol has led to the synthesis of new bio‐based materials with more valuable thermal and mechanical properties than those of thermocured materials obtained from petroleum‐based commercial epoxy resins. Focus has been given on processing parameters to optimize the final properties of the material and to open an interesting alternative for sustainable building materials.
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A series of acetyl pyrenes and pyrenyl ynones with and without tert‐butyl groups showed distinct mechanofluorochromism (MFC). Four pairs of polymorphic solids were found out of six compounds and ...interestingly, each of them showed hypsochromic, bathochromic or off‐to‐on MFC. The MFC properties were rationalized by categorizing the packing schemes into herringbone, sandwich, beta and gamma motifs depending on the relative contributions of C⋅⋅⋅C (or π‐π) against C⋅⋅⋅H contacts. The bulky tert‐butyl and trimethylsilyl groups served not only to reduce the number of aggregation patterns but also to prohibit the complete back reactions in solid state. Our results suggest that the simple pyrene derivatives may be promising candidates for a novel group of mechanically‐sensitive materials.
Mechanically induced solid‐state fluorescence: Acetyl pyrenes and pyrenyl ynones with varied molecular arrangements show distinct emission property change upon mechanical stimuli, so‐called mechanofluorochromism. The direction of emission color change as well as the spontaneous solid‐state back reaction depend on the packing motifs and the steric hindrance of the side groups.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Aims
To describe the population distribution and socio‐economic position of residents across all states and territories of Australia, stratified using the 7 Modified Monash Model classifications. The ...numerical summary, and the methods described, can be applied by a variety of end users including workforce planners, researchers, policy‐makers and funding bodies for guiding future investment under different scenarios, and aid in evaluating geographically focused programs.
Context
The Commonwealth Department of Health is transitioning to the Modified Monash Model to objectively describe geographical access. This change applies to the Rural Health Multidisciplinary Training Program, one of the Australian Government's key policies to address the maldistribution of the rural health workforce. Unlike the previously applied Australian Statistical Geography Standard‐Remoteness Areas, a summary of the population in each Modified Monash Model classification is not available, nor is a socio‐economic overview of the communities within these areas.
Approach
Spatial analysis of Australian Bureau of Statistics data (Modified Monash Model, population data and the Index of Relative Socio‐economic Advantage and Disadvantage collected or derived from the 2016 census) at the Statistical Area 1—the smallest unit for the release of census data.
Conclusion
Linking the Modified Monash Model, a socio‐economic index and granular population data at the national level highlights the disadvantage of many residents in small rural towns (Modified Monash 5). The Modified Monash Model does not exhibit a continuum of the largest population residing in the most accessible classification and the smallest population residing in the least accessible classification that is seen in the Australian Statistical Geography Standard‐Remoteness Areas. Coupled with policy relevance, the advantage of using the Modified Monash Model as the basis for analysis is that it highlights areas that have both a critical mass of residents and differing levels of socio‐economic advantage and disadvantage. This will help end users to target funding to those regions where there is potential to improve access to services for the greatest number of rural residents.
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DOBA, FZAB, GIS, IJS, IZUM, KILJ, NLZOH, NUK, OILJ, PILJ, PNG, SAZU, SBCE, SBMB, SIK, UILJ, UKNU, UL, UM, UPUK, VSZLJ
This study highlights the outstanding photo-initiating properties of two new visible-light absorbing benzophenone porphyrin-based photosensitizers (
PBP
and
PBPZn
) for the free-radical (FRP), ...cationic (CP) photopolymerization and thiol-ene reactions under visible LEDs exposure (405, 505 and 530 nm) under air or in laminate, and at low intensities. As confirmed by electronic paramagnetic resonance spin trapping (EPR ST) and Laser Flash Photolysis studies, both porphyrins play a dual role as electron donor molecule when combined with iodonium salt (Iod) and participate in a H-abstraction reaction in association with
N
-methyldiethanol amine (MDEA) or thiol derivatives (cysteamine or
N
-acetylcysteine). For the first time, interesting kinetic profiles for the polymerization of a bio-based monomer (SOA) are observed under blue and green-light irradiation. Notably, the 4-methylphenyl-, aminoalkyl- and thiyl radicals which are generated from the photolysis of porphyrin/Iod, porphyrin/MDEA and porphyrin/cysteamine (or
N
-acetylcysteine) respectively, can initiate the radical polymerization of SOA and very high FCs are observed; up to 90% under LED@405 nm and >60% under LED@530 nm exposure. Finally,
PBPZn
-based materials demonstrated photoactivable properties for antibacterial applications. Under visible-light irradiation, these materials can produce biocide reactive oxygen species (ROS) leading to a tremendous inhibition of
S. aureus
proliferation.
This study highlights the outstanding photo-initiating properties of two new visible-light absorbing benzophenone porphyrin-based photosensitizers for the synthesis of photoactivable materials with antibacterial properties.
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