The photophysical properties of chromophores assembled into metal-organic framework thin-films

Metallorganische Gerüste (MOFs) sind poröse Hybridmaterialien, die aus einem Metallzentrum bestehen, verbunden über Koordinationsbindungen mit einem organischen Linker. Nahezu unendliche Möglichkeiten der Metall-Linker-Kombination haben bisher zu einer großen Anzahl von MOF-Strukturen (>100.000) mit unterschiedlichen Strukturtopologien geführt. Die Eigenschaften von MOFs können durch eine durchdachte Auswahl der Metallzentren und organischen Linker abgestimmt werden, um MOFs spezifisch für bedarfsgerechte Anwendungen zu entwickeln. Bezugnehmend auf die weit fortgeschrittenen Anwendungen, ist die Herstellung von Festkörper-MOFs mittels der herkömmlichen Solvothermal-Methode nicht immer zielführend. Heterogene Morphologie, schwächere Anbindung an das Substrat und eine hohe Fehlstellendichte , wie in Festkörper-MOFs vorhanden, beeinflussen stark die Struktur-Eigenschafts Korrelation. Ein Ansatz zur Herstellung monolithischer kristalliner MOFs mit gut kontrollierten Dicke ist das Schicht-für-Schicht (LbL – layer-by-layer) -Verfahren über das Flüssigphasen-Epitaxie-Technik. In dieser Arbeit habe ich diese Technik verwendet, um hochkristalline, monolithische und orientierte SURMOF Strukturen aufzubauen. Eine hier verwendete Art von organischem Linker nennt sich photoaktive Verbindungen. Die räumliche Anordnung dieser photoaktiven Moleküle in der SURMOF-Plattform lieferte also hervorragende photophysikalische Eigenschaften. In der vorliegenden Arbeit habe ich ein Bianthrylchromophor untersucht, das mit metallkoordinierenden Gruppen ausgestattet ist, um einen photolumineszierenden oberflächenverankerten MOF -Dünnfilm (SURMOF) auf Zn-bianthrylbasis zu konstruieren. Die Zn-bianthryl-SURMOF haben eine gestapelte 2D-Schichtstruktur, die bei Anregung mit ultraviolettem (UV) Licht eine Cyan-Lumineszenz zeigt. In Reaktion auf die verlängerte UV-Bestrahlung in der Umgebungsbedingungen, zeigte der SURMOF auf Zn-bianthrylbasis jedoch eine deutliche Änderung der optischen Eigenschaften des Grund- und des angeregten Zustands, ohne seine Kristallstruktur zu verlieren. Eine detaillierte spektroskopische Untersuchung unter Verwendung von UV-Vis, FTIR, Raman, EPR und NEXAFS zeigte die Bildung der stabilen oxidierten Produkte von Bianthryl (Endoperoxid-Bianthryl) im SURMOF. Die vorliegende Studie identifiziert die Schlüsselfaktoren des Bianthryloxidationsprozesses, die einen selbstsensibilisierten photochemischen Weg beinhalten. Auch redoxaktive metallorganische Gerüste (MOFs) auf Viologenbasis haben in den letzten Jahren unter dem Gesichtspunkt intelligenter optisch aktiver Materialien großes Interesse gefunden. Hier wird ein Dicarboxylat-funktionalisiertes Viologen, 1,1‵-Bis (4- (carbonsäure) phenyl) - [4,4‵-bipyridin] -1,1‵-diiumdichlorid (viologen), als Linker zum Aufbau von SURMOF-Dünnfilmen unter Verwendung eines Schicht-für-Schicht-Flüssigphasen-Epitaxie-Verfahrens hergestellt. Diese Technik erzeugt ein hochkristallines, orientiertes SURMOF-2 auf Viologenbasis. Der orientierte, monolithische, kristalline SURMOF-Dünnfilm zeigt im Vergleich zu den zuvor beschriebenen Pulver-MOFs auf Viologenbasis eine schnell reversible Photochromie. Die Photochromie im SURMOF wird mittels UV-Vis, EPR und XPS untersucht

Prediction of the optimum asphalt content using artificial neural networks

The performance of the asphalt mix is significantly influenced by the optimum asphalt content (OAC). The asphalt content is responsible for coating the aggregate surface and filling the voids between the aggregate particles. Thus, the aggregate gradation has a significant influence on the required asphalt content. The Marshall design process is the most common method used for estimating the OAC, and this process is called the asphalt mix design. However, this method is time consuming, labor intensive, and its results are subjected to variations. Thus, this paper employs the artificial neural network (ANN) to estimate the OAC from the aggregate gradation for the two most common gradations used in asphalt mixes in Egypt (3D, 4C). Results show that the proposed ANN can predict the OAC with a coefficient of correlation of 0.98 and an average error of 0.026%. As a result, a new approach for the Marshall test can be adopted using results of the proposed ANN, and only three specimens, instead of fifteen, are prepared and tested for estimating the remaining parameters. This approach saves the time, effort, and resources required for estimating the OAC. Additionally, the ANN was validated with previously developed models, and the ANN shows promising results

Erectogenic Effects of Clerodendron capitatum

Clerodendron capitatum (Willd) (family: verbenaceae) is locally named as Gung and used traditionally to treat erectile dysfunction. Therefore, the current study was designed to investigate the erectogenic properties of C. capitatum. The relaxation effect of this plant was tested on phenylephrine precontracted rabbit corpus cavernosum smooth muscle (CCSM). The effects of C. capitatum were also examined on isolated Guinea pig atria alone, in the presence of calcium chloride (Ca2+ channel blocker), atropine (cholinergic blocker), and glibenclamide (ATP-sensitive K+ channel blocker). These effects were confirmed on isolated rabbit aortic strips. The extract, when tested colorimetrically for its inhibitory activities on phosphordiesterase-5 (PDE-5) in vitro towards p-nitrophenyl phenyl phosphate (PNPPP), was observed to induce significant dose-dependent inhibition of PDE-5, with an ID50 of 0.161 mg/ml (<.05). In conclusion, our results suggest that C. capitatum possesses a relaxant effect on CCSM, which is attributable to the inhibition of PDE-5, but not mediated by the release calcium, activation of adrenergic or cholinergic receptors, or the activation of potassium channels

Airway Management in Aviation, Space, and Microgravity

Although medical services in aviation have evolved over years based on our understanding of physiology, advancement in monitoring technology but airway management was only recently studied with a focus on space environment. The barometric pressure of ambient air declines as altitude increases, while the volume of air in a confined space will increase according to Boyle law, and therefore oxygen concentration remains at a constant 21%. Altitude sensitive equipment includes endotracheal and tracheostomy cuffs, pneumatic anti shock garments, air splints, colostomy bags, Foley catheters, orogastric and nasogastric tubes, ventilators, invasive monitors, and intra-aortic balloon pumps. The microgravity reduces the body compensation capacity for hemorrhage, while the redistribution of the blood can affect intubation by causing facial edema. Another change is the decreased gastric emptying during aviation. Acute respiratory failure, hypoxemia or inadequate ventilation and protection of the airway in a patient with impaired consciousness are common indications for advanced airway management in aviation. Airway management requires adequate training to maintain excellent medical care during aviation. Tracheal intubation using laryngoscopy would be difficult in microgravity, since the force exerted by the laryngoscope causes the head and neck move out of the field of vision by lever effect exerted on the head and generated through the laryngoscope blade by hand generating a lack of stability, resulting in the difficulty to insert the tracheal tube. While on the ground with the help of gravity, an adequate positioning of the patient is facilitated to achieve alignment of the laryngeal, pharyngeal and oral axes, which is known as sniffing position that allows visualization of the vocal cords and supraglottic structures allowing the introduction of an endotracheal tube

Expression patterns in reductive iron assimilation and functional consequences during phagocytosis of lichtheimia corymbifera , an emerging cause of mucormycosis

Iron is an essential micronutrient for most organisms and fungi are no exception. Iron uptake by fungi is facilitated by receptor-mediated internalization of siderophores, heme and reductive iron assimilation (RIA). The RIA employs three protein groups: (i) the ferric reductases (Fre5 proteins), (ii) the multicopper ferroxidases (Fet3) and (iii) the high-affinity iron permeases (Ftr1). Phenotyping under different iron concentrations revealed detrimental effects on spore swelling and hyphal formation under iron depletion, but yeast-like morphology under iron excess. Since access to iron is limited during pathogenesis, pathogens are placed under stress due to nutrient limitations. To combat this, gene duplication and differential gene expression of key iron uptake genes are utilized to acquire iron against the deleterious effects of iron depletion. In the genome of the human pathogenic fungus L. corymbifera, three, four and three copies were identified for FRE5, FTR1 and FET3 genes, respectively. As in other fungi, FET3 and FTR1 are syntenic and co-expressed in L. corymbifera. Expression of FRE5, FTR1 and FET3 genes is highly up-regulated during iron limitation (Fe-), but lower during iron excess (Fe+). Fe- dependent upregulation of gene expression takes place in LcFRE5 II and III, LcFTR1 I and II, as well as LcFET3 I and II suggesting a functional role in pathogenesis. The syntenic LcFTR1 I–LcFET3 I gene pair is co-expressed during germination, whereas LcFTR1 IILcFET3 II is co-expressed during hyphal proliferation. LcFTR1 I, II and IV were overexpressed in Saccharomyces cerevisiae to represent high and moderate expression of intracellular transport of Fe3+, respectively. Challenge of macrophages with the yeast mutants revealed no obvious role for LcFTR1 I, but possible functions of LcFTR1 II and IVs in recognition by macrophages. RIA expression pattern was used for a new model of interaction between L. corymbifera and macrophages

Phytochemical profiling of Costus (Saussurea lappa Clarke) root essential oil, and its antimicrobial and toxicological effects

Purpose: To carry out gas chromatography-mass spectrometry (GC-MS) analysis of the phytochemical content of the root essential oil of Saussurea lappa Clarke Asteraceae (Costus, SLEO), and to evaluate its physicochemical, antimicrobial and cytoxic properties. Methods: The oil was extracted from the plant’s roots by steam distillation using a Clevenger system. Various physicochemical parameters for the oil including refractive index, color, acid value, saponification number, ester and peroxide values were measured. Flavonoid content was assessed using thin layer chromatography (TLC). Thermoscientific trace ultra gas chromatograph equipped with a Thermoscientific capillary TR-5MS column was utilized to determine the volatile components of SLEO. Antimicrobial activity of SLEO was performed against various Gram (+ve) and Gram (-ve) microorganisms, viz, Bacillus subtilis, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and Candida albicans, while cytotoxic effect was monitored using Artemia salina (brine shrimp) lethality assay. Results: Essential oil yield was good (3 %). Concentration-dependent antimicrobial effects were observed on all test microorganisms and no marked difference in lethality levels was observed among the tested SLEO concentrations on brine shrimp (p &lt; 0.05). The main component of SLEO was costunolide or eudesma-5,11(13)-dien-8,12-olide (52.01 %). Conclusion: The results indicate the promising therapeutic properties of S. lappa. However, further phytochemical and biological investigations are required to establish the mechanism of action and toxicological the extract

Performance enhancement of energy saving and machining characteristic in electrical discharge machining on magnesium alloy: A review

Magnesium alloys have been widely used in biodegradable applications due to it tends to corrode inside the human body and combined with its initial mechanical property. Current research revealed that the structural stability of the implant is disturbed and lost rapidly due to the increased rate of degradation of magnesium inside the human body. Because of that, non-traditional machining method such as electrical discharge machining (EDM) die sinking process is implemented to create an intricate form with a high tolerance of magnesium alloy. The advantages of EDM are that it allows a versatile adaption of implant behaviour in machining complex 3D structures along with high corrosion resistant properties of electrochemical surface treatment. Various material types with different parameters are investigated to determine the influence of input process parameters on the energy saving, and machining characteristics included surface roughness, material removal rate, and tool wear rate. In addition to improving the machining performance especially in energy-saving, input on the machining parameter needs to be considered due to interaction with added conductive particles which would affect the size of discharge energy. The objective of this paper is to summarize the findings in research of EDM’s energy-saving and machining characteristics on magnesium alloy and to explore challenging issues that need to be resolved for future references and recommendations

The impact of episporic modification of Lichtheimia corymbifera on virulence and interaction with phagocytes

Fungal infections caused by the ancient lineage Mucorales are emerging and increasingly reported in humans. Comprehensive surveys on promising attributes from a multitude of possible virulence factors are limited and so far, focused on Mucor and Rhizopus. This study addresses a systematic approach to monitor phagocytosis after physical and enzymatic modification of the outer spore wall of Lichtheimia corymbifera, one of the major causative agents of mucormycosis. Episporic modifications were performed and their consequences on phagocytosis, intracellular survival and virulence by murine alveolar macrophages and in an invertebrate infection model were elucidated. While depletion of lipids did not affect the phagocytosis of both strains, delipidation led to attenuation of LCA strain but appears to be dispensable for infection with LCV strain in the settings used in this study. Combined glucano-proteolytic treatment was necessary to achieve a significant decrease of virulence of the LCV strain in Galleria mellonella during maintenance of the full potential for spore germination as shown by a novel automated germination assay. Proteolytic and glucanolytic treatments largely increased phagocytosis compared to alive resting and swollen spores. Whilst resting spores barely (1-2%) fuse to lysosomes after invagination in to phagosomes, spore trypsinization led to a 10-fold increase of phagolysosomal fusion as measured by intracellular acidification. This is the first report of a polyphasic measurement of the consequences of episporic modification of a mucormycotic pathogen in spore germination, spore surface ultrastructure, phagocytosis, stimulation of Toll-like receptors (TLRs), phagolysosomal fusion and intracellular acidification, apoptosis, generation of reactive oxygen species (ROS) and virulence

Pathological, microscopic, and molecular diagnosis of paratuberculosis/John’s disease in naturally infected dromedary camel (Camelus dromedarius)

Background and Aim: Paratuberculosis (PTB) or John’s disease is a chronic disease of ruminants impeding the reproduction and productivity of the livestock sector worldwide. Since there is a lack of pathological studies explaining the nature and development of the disease in camels, this study aimed to highlight the anatomopathological changes of PTB in camels, which may help in verifying and validating some diagnostic tests used to detect the etiology of the disease in camel tissues. Materials and Methods: In August 2017, at Alselaa border’s Veterinary Clinic of Al Dhafra Region, Western Abu Dhabi, UAE, one imported culled she-camel of 2 years old was subjected to clinical, microscopic, and anatomopathological investigations along with real-time quantitative polymerase chain reaction (q-PCR) to confirm the infection and correlate between clinical signs and pathological lesions of the PTB in dromedary camels. Results: Clinically, typical clinical signs compliant with the pathognomonic gross and histologic lesions of PTB were seen in naturally infected dromedary camel. As presumptive diagnosis microscopically, acid-fast coccobacillus bacterium clumps were demonstrated in direct fecal smears as well as in scraped mucosal and crushed mesenteric lymph node films, and in histopathological sections prepared from a necropsied animal and stained by Ziehl-Neelsen stain. Free and intracellular acid-fast clump phagosomes were further confirmed as Mycobacterium avium subsp. paratuberculosis by q-PCR. Conclusion: Clinical signs and pathological lesions of paratuberculosis in a dromedary camel were found to be similar to those of the other susceptible hosts

Global burden of 288 causes of death and life expectancy decomposition in 204 countries and territories and 811 subnational locations, 1990–2021:a systematic analysis for the Global Burden of Disease Study 2021

BackgroundRegular, detailed reporting on population health by underlying cause of death is fundamental for public health decision making. Cause-specific estimates of mortality and the subsequent effects on life expectancy worldwide are valuable metrics to gauge progress in reducing mortality rates. These estimates are particularly important following large-scale mortality spikes, such as the COVID-19 pandemic. When systematically analysed, mortality rates and life expectancy allow comparisons of the consequences of causes of death globally and over time, providing a nuanced understanding of the effect of these causes on global populations.MethodsThe Global Burden of Diseases, Injuries, and Risk Factors Study (GBD) 2021 cause-of-death analysis estimated mortality and years of life lost (YLLs) from 288 causes of death by age-sex-location-year in 204 countries and territories and 811 subnational locations for each year from 1990 until 2021. The analysis used 56 604 data sources, including data from vital registration and verbal autopsy as well as surveys, censuses, surveillance systems, and cancer registries, among others. As with previous GBD rounds, cause-specific death rates for most causes were estimated using the Cause of Death Ensemble model—a modelling tool developed for GBD to assess the out-of-sample predictive validity of different statistical models and covariate permutations and combine those results to produce cause-specific mortality estimates—with alternative strategies adapted to model causes with insufficient data, substantial changes in reporting over the study period, or unusual epidemiology. YLLs were computed as the product of the number of deaths for each cause-age-sex-location-year and the standard life expectancy at each age. As part of the modelling process, uncertainty intervals (UIs) were generated using the 2·5th and 97·5th percentiles from a 1000-draw distribution for each metric. We decomposed life expectancy by cause of death, location, and year to show cause-specific effects on life expectancy from 1990 to 2021. We also used the coefficient of variation and the fraction of population affected by 90% of deaths to highlight concentrations of mortality. Findings are reported in counts and age-standardised rates. Methodological improvements for cause-of-death estimates in GBD 2021 include the expansion of under-5-years age group to include four new age groups, enhanced methods to account for stochastic variation of sparse data, and the inclusion of COVID-19 and other pandemic-related mortality—which includes excess mortality associated with the pandemic, excluding COVID-19, lower respiratory infections, measles, malaria, and pertussis. For this analysis, 199 new country-years of vital registration cause-of-death data, 5 country-years of surveillance data, 21 country-years of verbal autopsy data, and 94 country-years of other data types were added to those used in previous GBD rounds.FindingsThe leading causes of age-standardised deaths globally were the same in 2019 as they were in 1990; in descending order, these were, ischaemic heart disease, stroke, chronic obstructive pulmonary disease, and lower respiratory infections. In 2021, however, COVID-19 replaced stroke as the second-leading age-standardised cause of death, with 94·0 deaths (95% UI 89·2–100·0) per 100 000 population. The COVID-19 pandemic shifted the rankings of the leading five causes, lowering stroke to the third-leading and chronic obstructive pulmonary disease to the fourth-leading position. In 2021, the highest age-standardised death rates from COVID-19 occurred in sub-Saharan Africa (271·0 deaths [250·1–290·7] per 100 000 population) and Latin America and the Caribbean (195·4 deaths [182·1–211·4] per 100 000 population). The lowest age-standardised death rates from COVID-19 were in the high-income super-region (48·1 deaths [47·4–48·8] per 100 000 population) and southeast Asia, east Asia, and Oceania (23·2 deaths [16·3–37·2] per 100 000 population). Globally, life expectancy steadily improved between 1990 and 2019 for 18 of the 22 investigated causes. Decomposition of global and regional life expectancy showed the positive effect that reductions in deaths from enteric infections, lower respiratory infections, stroke, and neonatal deaths, among others have contributed to improved survival over the study period. However, a net reduction of 1·6 years occurred in global life expectancy between 2019 and 2021, primarily due to increased death rates from COVID-19 and other pandemic-related mortality. Life expectancy was highly variable between super-regions over the study period, with southeast Asia, east Asia, and Oceania gaining 8·3 years (6·7–9·9) overall, while having the smallest reduction in life expectancy due to COVID-19 (0·4 years). The largest reduction in life expectancy due to COVID-19 occurred in Latin America and the Caribbean (3·6 years). Additionally, 53 of the 288 causes of death were highly concentrated in locations with less than 50% of the global population as of 2021, and these causes of death became progressively more concentrated since 1990, when only 44 causes showed this pattern. The concentration phenomenon is discussed heuristically with respect to enteric and lower respiratory infections, malaria, HIV/AIDS, neonatal disorders, tuberculosis, and measles.InterpretationLong-standing gains in life expectancy and reductions in many of the leading causes of death have been disrupted by the COVID-19 pandemic, the adverse effects of which were spread unevenly among populations. Despite the pandemic, there has been continued progress in combatting several notable causes of death, leading to improved global life expectancy over the study period. Each of the seven GBD super-regions showed an overall improvement from 1990 and 2021, obscuring the negative effect in the years of the pandemic. Additionally, our findings regarding regional variation in causes of death driving increases in life expectancy hold clear policy utility. Analyses of shifting mortality trends reveal that several causes, once widespread globally, are now increasingly concentrated geographically. These changes in mortality concentration, alongside further investigation of changing risks, interventions, and relevant policy, present an important opportunity to deepen our understanding of mortality-reduction strategies. Examining patterns in mortality concentration might reveal areas where successful public health interventions have been implemented. Translating these successes to locations where certain causes of death remain entrenched can inform policies that work to improve life expectancy for people everywhere.FundingBill &amp; Melinda Gates Foundation.<br/