Directed Molecular Stacking for Engineered Fluorescent Three-Dimensional Reduced Graphene Oxide and Coronene Frameworks

[EN] Three‐dimensional fluorescent graphene frameworks with controlled porous morphologies are of significant importance for practical applications reliant on controlled structural and electronic properties, such as organic electronics and photochemistry. Here we report a synthetically accessible approach concerning directed aromatic stacking interactions to give rise to new fluorogenic 3D frameworks with tuneable porosities achieved through molecular variations. The binding interactions between the graphene‐like domains present in the in situ‐formed reduced graphene oxide (rGO) with functional porphyrin molecules lead to new hybrids via an unprecedented solvothermal reaction. Functional free‐base porphyrins featuring perfluorinated aryl groups or hexyl chains at their meso‐ and β‐positions were employed in turn to act as directing entities for the assembly of new graphene‐based and foam‐like frameworks and of their corresponding coronene‐based hybrids. Investigations in the dispersed phase and in thin‐film by XPS, SEM and FLIM shed light onto the nature of the aromatic stacking within functional rGO frameworks (denoted rGOFs) which was then modelled semi‐empirically and by DFT calculations. The pore sizes of the new emerging reduced graphene oxide hybrids are tuneable at the molecular level and mediated by the bonding forces with the functional porphyrins acting as the “molecular glue”. Single crystal X‐ray crystallography described the stacking of a perfluorinated porphyrin with coronene, which can be employed as a molecular model for understanding the local aromatic stacking order and charge transfer interactions within these rGOFs for the first time. This opens up a new route to controllable 3D framework morphologies and pore size from the Ångstrom to the micrometre scale. Theoretical modelling showed that the porosity of these materials is mainly due to the controlled inter‐planar distance between the rGO, coronene or graphene sheets. The host‐guest chemistry involves the porphyrins acting as guests held through π‐π stacking, as demonstrated by XPS. The objective of this study is also to shed light into the fundamental localised electronic and energy transfer properties in these new molecularly engineered porous and fluorogenic architectures, aiming in turn to understand how functional porphyrins may exert stacking control over the notoriously disordered local structure present in porous reduced graphene oxide fragments. By tuning the porosity and the distance between the graphene sheets using aromatic stacking with porphyrins, it is also possible to tune the electronic structure of the final nanohybrid material, as indicated by FLIM experiments on thin films. Such nanohybrids with highly controlled pores dimensions and morphologies open the way to new design and assembly of storage devices and applications incorporating π‐conjugated molecules and materials and their π‐stacks may be relevant towards selective separation membranes, water purification and biosensing applications.S.I.P. and S.W.B. thank The Royal Society and STFC for funding. B.Y.M. thanks the University of Bath for a studentship (ORS). D.G.C. thanks the Fundación General CSIC for funding (ComFuturo Program). Dr. Jose A. Ribeiro Martins, Professors Jeremy K. M. Sanders and Paul Raithby are acknowledged for training, helpful discussions and porphyrin supramolecular chemistry. The S.I.P. group thanks the EPSRC for funding to the Centre of Graphene Science (EP/K017160/1) and to the Centre for Doctoral Training in Sustainable Chemical Technologies (EP/L016354/1). The authors thank EPSRC National Service for Mass Spectrometry at Swansea and EPSRC National Service for Crystallography at Southampton for data collection. The authors also acknowledge the ERC for the Consolidator Grant O2SENSE (617107, 2014–2019)

Non-invasive sex determination of guinea fowl keets (numida meleagris) by polymerase chain reaction

Early sex determination of birds is crucial for controlled breeding for both production andconservation. Amidst the potential of the guinea fowl (Numida meleagris) industry for theeconomies of African countries and as a rich genetic resource to be conserved, inability toaccurately sex guinea fowl keets is a major constraint for breeding. In the present study sex of dayold guinea keets (n=132) and keets of 4 - 8 weeks (n=72) was determined by polymerase chain reaction (PCR) by amplifying a sequence homologous to Chicken EcoR1 fragment of 0.6 kb (EE0.6) using Universal Sex Primer 1(USP 1) and Universal Sex Primer 3 (USP 3) together with internal control primers using DNA extracted from feathers. Out of 72 keets, aged 4 - 8 weeks, 38 were identified as males and 34 were identified as females. Out of the 132, day-olds 69 and 63 were identified as female and male keets, respectively, were results from PCR were confirmed by the presence of respective gonads. The methods described can be used for accurate sex determination of guinea fowl keets from day-old with minimal stress and discomfort to the birds. The method can be used by researchers, breeders, conservationists directly or to develop farmer friendly methods in the future

Induction and processing of the radiation-induced gamma-H2AX signal and Its link to the underlying pattern of DSB: A combined experimental and modelling study

We present here an analysis of DSB induction and processing after irradiation with X-rays in an extended dose range based on the use of the γH2AX assay. The study was performed by quantitative flow cytometry measurements, since the use of foci counting would result in reasonable accuracy only in a limited dose range of a few Gy. The experimental data are complemented by a theoretical analysis based on the GLOBLE model. In fact, original aim of the study was to test GLOBLE predictions against new experimental data, in order to contribute to the validation of the model. Specifically, the γH2AX signal kinetics has been investigated up to 24 h after exposure to increasing photon doses between 2 and 500 Gy. The prolonged persistence of the signal at high doses strongly suggests dose dependence in DSB processing after low LET irradiation. Importantly, in the framework of our modelling analysis, this is related to a gradually increased fraction of DSB clustering at the micrometre scale. The parallel study of γH2AX dose response curves shows the onset of a pronounced saturation in two cell lines at a dose of about 20 Gy. This dose is much lower than expected according to model predictions based on the values usually adopted for the DSB induction yield (≈ 30 DSB/Gy) and for the γH2AX foci extension of approximately 2 Mbp around the DSB. We show and discuss how theoretical predictions and experimental findings can be in principle reconciled by combining an increased DSB induction yield with the assumption of a larger genomic extension for the single phosphorylated regions. As an alternative approach, we also considered in our model the possibility of a 3D spreading-mechanism of the H2AX phosphorylation around the induced DSB, and applied it to the analysis of both the aspects considered. Our results are found to be supportive for the basic assumptions on which GLOBLE is built. Apart from giving new insights into the H2AX phosphorylation process, experiments performed at high doses are of relevance in the context of radiation therapy, where hypo-fractionated schemes become increasingly popular

The need to address fragmentation and silos in mortality information systems: the case of Ghana and Peru

Objectives: We aimed to understand the information architecture and degree of integration of mortality surveillance systems in Ghana and Peru. Methods: We conducted a cross-sectional study using a combination of document review and unstructured interviews to describe and analyse the sub-systems collecting mortality data. Results: We identified 18 and 16 information subsystems with independent databases capturing death events in Peru and Ghana respectively. The mortality information architecture was highly fragmented with a multiplicity of unconnected data silos and with formal and informal data collection systems. Conclusion: Reliable and timely information about who dies where and from what underlying cause is essential to reporting progress on Sustainable Development Goals, ensuring policies are responding to population health dynamics, and understanding the impact of threats and events like the COVID-19 pandemic. Integrating systems hosted in different parts of government remains a challenge for countries and limits the ability of statistics systems to produce accurate and timely information. Our study exposes multiple opportunities to improve the design of mortality surveillance systems by integrating existing subsystems currently operating in silos

Intermolecular Interactions in Crystals Modulate Intramolecular Excited State Proton Transfer Reactions

Proton transfer is a fundamental process underlying chemical and biological phenomena, and its dynamics are significantly influenced by the surrounding environment. This paper studies the excited state intramolecular proton transfer (ESIPT) process, which is crucial to the photostability of hydroxyanthraquinone-based pigments through efficient energy dissipation, by investigating how crystalline packing influences photoinduced proton transfer dynamics in single crystals of dihydroxyanthraquinone (DHAQ) constitutional isomers. Comparing the proton transfer dynamics in crystalline and solution phases, we show substantial differences due to the crystalline environment, particularly in the 1,4- and 1,5-DHAQ isomers. These isomers show intermolecular hydrogen bonding within the crystal lattice, resulting in larger excitonic couplings, which significantly alters their reaction pathways compared to their behavior in solution. We show that 1,8-DHAQ, which does not form intermolecular hydrogen bonds in the crystal, shows minimal changes in dynamics between the phases. In contrast, in the case of 1,4-DHAQ, intermolecular interactions within the molecular crystal phase open up an ESIPT relaxation channel, which is not observed in the solution phase. These findings highlight the critical role of crystal packing in modulating proton transfer dynamics and offer insights into how molecular packing can be strategically manipulated to control and optimize reaction pathways in solid-state environments

The transmembrane domain of N-acetylglucosaminyltransferase I is the key determinant for its Golgi subcompartmentation

Golgi-resident type–II membrane proteins are asymmetrically distributed across the Golgi stack. The intrinsic features of the protein that determine its subcompartment-specific concentration are still largely unknown. Here, we used a series of chimeric proteins to investigate the contribution of the cytoplasmic, transmembrane and stem region of Nicotiana benthamiana N–acetylglucosaminyltransferase I (GnTI) for its cis/medial-Golgi localization and for protein–protein interaction in the Golgi. The individual GnTI protein domains were replaced with those from the well-known trans-Golgi enzyme α2,6–sialyltransferase (ST) and transiently expressed in Nicotiana benthamiana. Using co-localization analysis and N–glycan profiling, we show that the transmembrane domain of GnTI is the major determinant for its cis/medial-Golgi localization. By contrast, the stem region of GnTI contributes predominately to homomeric and heteromeric protein complex formation. Importantly, in transgenic Arabidopsis thaliana, a chimeric GnTI variant with altered sub-Golgi localization was not able to complement the GnTI-dependent glycosylation defect. Our results suggest that sequence-specific features in the transmembrane domain of GnTI account for its steady-state distribution in the cis/medial-Golgi in plants, which is a prerequisite for efficient N–glycan processing in vivo

Long-term effects of tongue piercing — a case control study

The aim of this study was to evaluate tooth and periodontal damage in subjects wearing a tongue piercing (TP) in comparison to matched control subjects without tongue piercing. Members of the German Federal Armed Forces who had TP (group TP) and a matched control group (group C) volunteered to take part in the study. The time in situ, localization and material of TP were documented. Dental examinations included DMF-T, oral hygiene, enamel fissures (EF), enamel cracks (EC) and recessions. Statistical analysis was determined by χ2 test and the t test. Both groups had 46 male subjects (mean age 22.1 years). The piercings had been in situ for 3.8 ± 3.1 years. Subjects in the TP group had a total of 1,260 teeth. Twenty-nine subjects had 115 teeth (9.1%) with EF (67% lingual). In group C (1,243 teeth), 30 subjects had 60 teeth with EF (4.8%, 78% vestibular) (p < 0.01). Thirty-eight subjects belonging to group TP had EC in 186 teeth (15%). In group C, 26 subjects with 56 teeth (4.5%) were affected by EC (p < 0.001). Twenty-seven subjects in group TP had 97 teeth (7.7%) with recessions. Lingual surfaces of anterior teeth in the lower jaw were affected most frequently (74%). In group C, 8 subjects had 19 teeth (1.5%) with recessions (65% vestibular). Differences between the two groups were statistically significant (p < 0.001). Tongue piercing is correlated with an increased occurrence of enamel fissures, enamel cracks and lingual recessions. Patients need better information on the potential complications associated with tongue piercing

An Expanded Multi-scale Monte Carlo Simulation Method for Personalized Radiobiological Effect Estimation in Radiotherapy: a feasibility study

A novel and versatile “bottom-up� approach is developed to estimate the radiobiological effect of clinic radiotherapy. The model consists of multi-scale Monte Carlo simulations from organ to cell levels. At cellular level, accumulated damages are computed using a spectrum-based accumulation algorithm and predefined cellular damage database. The damage repair mechanism is modeled by an expanded reaction-rate two-lesion kinetic model, which were calibrated through replicating a radiobiological experiment. Multi-scale modeling is then performed on a lung cancer patient under conventional fractionated irradiation. The cell killing effects of two representative voxels (isocenter and peripheral voxel of the tumor) are computed and compared. At microscopic level, the nucleus dose and damage yields vary among all nucleuses within the voxels. Slightly larger percentage of cDSB yield is observed for the peripheral voxel (55.0%) compared to the isocenter one (52.5%). For isocenter voxel, survival fraction increase monotonically at reduced oxygen environment. Under an extreme anoxic condition (0.001%), survival fraction is calculated to be 80% and the hypoxia reduction factor reaches a maximum value of 2.24. In conclusion, with biological-related variations, the proposed multi-scale approach is more versatile than the existing approaches for evaluating personalized radiobiological effects in radiotherapy

The architecture and effect of participation: a systematic review of community participation for communicable disease control and elimination. Implications for malaria elimination

Community engagement and participation has played a critical role in successful disease control and elimination campaigns in many countries. Despite this, its benefits for malaria control and elimination are yet to be fully realized. This may be due to a limited understanding of the influences on participation in developing countries as well as inadequate investment in infrastructure and resources to support sustainable community participation. This paper reports the findings of an atypical systematic review of 60 years of literature in order to arrive at a more comprehensive awareness of the constructs of participation for communicable disease control and elimination and provide guidance for the current malaria elimination campaign.Evidence derived from quantitative research was considered both independently and collectively with qualitative research papers and case reports. All papers included in the review were systematically coded using a pre-determined qualitative coding matrix that identified influences on community participation at the individual, household, community and government/civil society levels. Colour coding was also carried out to reflect the key primary health care period in which community participation programmes originated. These processes allowed exhaustive content analysis and synthesis of data in an attempt to realize conceptual development beyond that able to be achieved by individual empirical studies or case reports.Of the 60 papers meeting the selection criteria, only four studies attempted to determine the effect of community participation on disease transmission. Due to inherent differences in their design, interventions and outcome measures, results could not be compared. However, these studies showed statistically significant reductions in disease incidence or prevalence using various forms of community participation. The use of locally selected volunteers provided with adequate training, supervision and resources are common and important elements of the success of the interventions in these studies. In addition, qualitative synthesis of all 60 papers elucidates the complex architecture of community participation for communicable disease control and elimination which is presented herein.The current global malaria elimination campaign calls for a health systems strengthening approach to provide an enabling environment for programmes in developing countries. In order to realize the benefits of this approach it is vital to provide adequate investment in the 'people' component of health systems and understand the multi-level factors that influence their participation. The challenges of strengthening this component of health systems are discussed, as is the importance of ensuring that current global malaria elimination efforts do not derail renewed momentum towards the comprehensive primary health care approach. It is recommended that the application of the results of this systematic review be considered for other diseases of poverty in order to harmonize efforts at building 'competent communities' for communicable disease control and optimising health system effectiveness