The role of cats in human DNA transfer.

Domestic animals, such as cats and dogs, are present in the majority of Australian households. Recently, questions regarding the possibility that domestic animals can serve as silent witnesses, from whom evidence can be collected, or act as vectors of contamination and transfer, have started to be raised. Yet, little is known regarding the transfer and prevalence of human DNA to and from cats. This study investigated if cats are reservoirs and vectors for human DNA transfer. Twenty cats from 15 households were sampled from 4 different areas (head (fur), back (fur), left (skin) and right (fur)) to obtain information on the background DNA that may be found on an animal. Further, transfer of human DNA to and from an animal, after a short patting contact, was tested. Human DNA was found to be prevalent on all cats. Of the areas sampled, most DNA was collected from the top of the fur from the back followed by the head and right/fur. No or very low quantities of human DNA was recovered from the left (skin) area. Most of the human DNA originated from the owners, but DNA from others was also often present (47 % of samples). Further, the transfer tests demonstrated that human DNA transferred readily to (detected in 45 % of samples) and from (detected in 80 % of samples) cats during patting. These results show that animals can act as reservoirs of human DNA and vectors for human DNA transfer that may need to be considered during evaluative DNA reporting. Furthermore, if an interaction between an animal and a perpetrator is suspected, consideration should be given to collecting DNA evidence from suspected contact areas on an animal.

Cuprophilic Interactions in Polymeric [Cu10O2(Mes)6]n.

The properties of cuprophilic compounds and the underlying fundamental principles responsible for the Cu(I)···Cu(I) interactions have been the subject of intense research as their diverse structural and physical attributes are being explored. In this light, we performed a new study of the compound [Cu10O2(Mes)6] reported by Haakansson et al. using state of the art experimental and theoretical analysis techniques. Doing this, we found the compound to be a polymer in the solid state, best written as [Cu10O2(Mes)6]n, with unsupported Cu(I)···Cu(I) contacts linking the monomers (2.776 Å). The monomeric unit also exhibits various cuprophilic contacts bridged by mesityl and/or oxo ligands. The compound was analyzed in its solid state, revealing luminescent properties resulting from two distinct fluorescent emissions, as well as in solution, in which its polymeric structure reversibly decomposes. A quantum theory of atoms in molecules (QTAIM) analysis based on density functional theory (DFT) calculations allows to characterize the various Cu(I)···Cu(I) contacts, in which only a few, and not necessarily the shortest, are associated with a bond critical point. Additionally, an energy decomposition analysis of the bonding between monomers indicates that it is dominated by dispersion forces in which the ligands play a dominant role, resulting in bonding energies significantly larger than found in previous DFT investigations based on less bulky models.

Copper Imidazolin-imine Coordination Compounds as Precursors for a Cu/Al Complex.

The reactions of [(CF3SO3Cu)2(C6H6)] with the sterically hindered imidazolin-2-imine ligands DippImTMS (1,3-Bis(2,6-diisopropylphenyl)-2-(trimethylsilylimino)imidazoline) or DippImH (1,3-bis(2,6-diisopropylphenyl) imidazolin-2-imine) lead to the formation of the linear copper(I) complexes [Cu(DippImTMS)(OTf)] (1) and [Cu(DippImH)2][OTf] (2), respectively. The triflate counteranion in 2 can be easily exchanged to the weakly coordinating [BArF] giving [Cu(DippImH)2][BArF] (3) (BArF = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate). Substitution of the N-heterocyclic imine (NHI) ligand in 3 by AlCp* (Cp* = pentamethylcyclopentadienyl) gives the tetrahedral [Cu(AlCp*)4][BArF] (5). The reaction between lithiated imidazolin-2-iminate DippImLi and CuCl results in the triangular cluster [Cu3(DippIm)2Cl] (4). All products have been fully characterized by 1H- and 13C NMR, mass spectrometry, as well as SC-XRD.

Nitrogen nutrition effects on δ13C of plant respired CO2 are mostly caused by concurrent changes in organic acid utilisation and remobilisation.

Nitrogen (N) nutrition impacts on primary carbon metabolism and can lead to changes in δ13C of respired CO2. However, uncertainty remains as to whether (1) the effect of N nutrition is observed in all species, (2) N source also impacts on respired CO2 in roots and (3) a metabolic model can be constructed to predict δ13C of respired CO2 under different N sources. Here, we carried out isotopic measurements of respired CO2 and various metabolites using two species (spinach, French bean) grown under different NH4 +:NO3 - ratios. Both species showed a similar pattern, with a progressive 13C-depletion in leaf-respired CO2 as the ammonium proportion increased, while δ13C in root-respired CO2 showed little change. Supervised multivariate analysis showed that δ13C of respired CO2 was mostly determined by organic acid (malate, citrate) metabolism, in both leaves and roots. We then took advantage of nonstationary, two-pool modelling that explained 73% of variance in δ13C in respired CO2. It demonstrates the critical role of the balance between the utilisation of respiratory intermediates and the remobilisation of stored organic acids, regardless of anaplerotic bicarbonate fixation by phosphoenolpyruvate carboxylase and the organ considered.

Average treatment effect on the treated, under lack of positivity.

 The use of propensity score methods has become ubiquitous in causal inference. At the heart of these methods is the positivity assumption. Violation of the positivity assumption leads to the presence of extreme propensity scoreweights when estimating average causal effects, which affects statistical inference. To circumvent this issue, trimming or truncating methods have been widely used. Unfortunately, these methods require that we pre-specify a threshold. There are anumber of alternative methods to deal with the lack of positivity when we estimate the average treatment effect (ATE). However, no other methods exist beyond trimming and truncation to deal with the same issue when the goal is to estimate theaverage treatment effect on the treated (ATT). In this article, we propose a propensity score weight-based alternative for the ATT, called overlap weighted average treatment effect on the treated. The appeal of our proposed method lies in its abilityto obtain similar or even better results than trimming and truncation while relaxing the constraint to choose an a priori threshold (or related measures). The performance of the proposed method is illustrated via a series of Monte Carlo simulationsand a data analysis on racial disparities in health care expenditures.

Do fungi look like macroparasites? Quantifying the patterns and mechanisms of aggregation for host-fungal parasite relationships.

Most hosts contain few parasites, whereas few hosts contain many. This pattern, known as aggregation, is well-documented in macroparasites where parasite intensity distribution among hosts affects host-parasite dynamics. Infection intensity also drives fungal disease dynamics, but we lack a basic understanding of host-fungal aggregation patterns, how they compare to macroparasites, and if they reflect biological processes. To address these gaps, we characterized aggregation of the fungal pathogen Batrachochytrium dendrobatidis (Bd) in amphibian hosts. Utilizing the slope of Taylor's Power Law, we found Bd intensity distributions were more aggregated than macroparasites, conforming closely to lognormal distributions. We observed that Bd aggregation patterns are strongly correlated with known biological processes operating in amphibian populations, such as epizoological phase-invasion, post-invasion, and enzootic-and intensity-dependent disease mortality. Using intensity-dependent mathematical models, we found evidence of evolution of host resistance based on aggregation shifts in systems persisting with Bd following disease-induced declines. Our results show that Bd aggregation is highly conserved across disparate systems and is distinct from aggregation patterns in macroparasites, and contains signatures of potential biological processes of amphibian-Bd systems. Our work lays a foundation to unite host-fungal dynamics under a common theoretical framework and inform future modeling approaches that may elucidate host-fungus interactions.

Transfer and persistence of intruder DNA within an office after reuse by owner.

The heightened sensitivity of DNA typing techniques, paired with the extensive use of trace DNA in forensic investigations, has resulted in an increased need to understand how and when DNA is deposited on surfaces of interest. This study focussed on the transfer, persistence, and prevalence of trace DNA in a single occupation of an office space by an intruder, when all contacts made during occupation and for the two hours prior and post occupation were known. The extent to which DNA could be recovered from contacted/not contacted surfaces was investigated. This study investigates the impacts of these movements and use of an office space when the duration of occupancy, surface contact histories and shedder status of participants are known. Contacts were documented and surfaces in the office space were targeted for sampling. Categories were set for target sampling that included different types of contact. Direct and indirect DNA transfer was detected in 55 % and 6 % of samples, respectively. Contactless DNA transfer was detected in 0.5 % of samples. The owner was observed as the sole/major/majority contributor in 77 % of the samples and as minor contributor in 10 % of samples. The intruder was observed as the sole/major/majority contributor in 14 % of samples and as the minor contributor in 16 %. An increased number of contacts increased the relative DNA contribution of the individual making the contact, however, not all observed direct contacts resulted in detectable DNA transfer. The outcome of this study will aid in better sample targeting strategies and contribute to the pool of data assisting in the development of activity level assessments.

Where did it go? A study of DNA transfer in a social setting.

The sensitivity of DNA analysis has progressed to the point that trace levels of DNA, originating from only a few cells, can generate informative profiles. This means that virtually any item or surface can be sampled with a reasonable chance of obtaining a DNA profile. As the presence of DNA does not suggest how it was deposited, questions are often raised as to how the DNA came to be at a particular location and the activity that led to its deposition. Therefore, understanding different modes of DNA deposition, reflective of realistic forensic casework situations, is critical for proper evaluation of DNA results in court. This study aimed to follow the movements of DNA to and from individuals and common household surfaces in a residential premises, while socially interacting. This took place over an hour and involved four participants, with known shedder status, designated as visitors (a male and a female) and hosts (a male and a female), who engaged in the activity of playing a board game while being served food. During the study, the participants were instructed to use the toilet on a single occasion to assess the transfer of DNA to new and unused underwear that was provided. All contacts made by the participants in the dining room and kitchen were video recorded to follow the movements of DNA. Samples were collected based on the history of contact, which included hands, fingernails and penile swabs. Direct contacts resulted in detectable transfer (LR > 1) in 87 % (87/100) of the non-intimate samples and clothing. For surfaces touched by multiple participants, DNA from the person who made the last contact was not always detectable. The duration and number of contacts did not significantly affect the detection of the person contacting the item. On the other hand, presence of background DNA and participant's shedder status appear to play an important role. Further, unknown contributors were detected in the majority of samples. Finally, indirect transfer was observed on a number of occasions including co-habiting partners of guests who were not present at the study location. The results of this study may assist with decision making for exhibit selection or targeting areas for sampling within the home environment. Our findings can also be used in conjunction with previous literature to develop activity-level evaluations in such situations where the source of the DNA is conceded, but the mode of deposition is disputed.

Impact of Organic Anions on Metal Hydroxide Oxygen Evolution Catalysts.

Structural metamorphosis of metal-organic frameworks (MOFs) eliciting highly active metal-hydroxide catalysts has come to the fore lately, with much promise. However, the role of organic ligands leaching into electrolytes during alkaline hydrolysis remains unclear. Here, we elucidate the influence of organic carboxylate anions on a family of Ni or NiFe-based hydroxide type catalysts during the oxygen evolution reaction. After excluding interfering variables, i.e., electrolyte purity, Ohmic loss, and electrolyte pH, the experimental results indicate that adding organic anions to the electrolyte profoundly impacts the redox potential of the Ni species versus with only a negligible effect on the oxygen evolution activities. In-depth studies demonstrate plausible reasons behind those observations and allude to far-reaching implications in controlling electrocatalysis in MOFs, mainly where compositional modularity entails fine-tuning organic anions.

Ex vivo susceptibilities to ganaplacide and diversity in potential resistance mediators in Ugandan Plasmodium falciparum isolates.

Novel antimalarials are urgently needed to combat rising resistance to available drugs. The imidazolopiperazine ganaplacide is a promising drug candidate, but decreased susceptibility of laboratory strains has been linked to polymorphisms in the Plasmodium falciparum cyclic amine resistance locus (PfCARL), acetyl-CoA transporter (PfACT), and UDP-galactose transporter (PfUGT). To characterize parasites causing disease in Africa, we assessed ex vivo drug susceptibilities to ganaplacide in 750 P. falciparum isolates collected in Uganda from 2017 to 2023. Drug susceptibilities were assessed using a 72-hour SYBR Green growth inhibition assay. The median IC50 for ganaplacide was 13.8 nM, but some isolates had up to 31-fold higher IC50s (31/750 with IC50 > 100 nM). To assess genotype-phenotype associations, we sequenced genes potentially mediating altered ganaplacide susceptibility in the isolates using molecular inversion probe and dideoxy sequencing methods. PfCARL was highly polymorphic, with eight mutations present in >5% of isolates. None of these eight mutations had previously been selected in laboratory strains with in vitro drug pressure and none were found to be significantly associated with decreased ganaplacide susceptibility. Mutations in PfACT and PfUGT were found in ≤5% of isolates, except for two frequent (>20%) mutations in PfACT; one mutation in PfACT (I140V) was associated with a modest decrease in susceptibility. Overall, Ugandan P. falciparum isolates were mostly highly susceptible to ganaplacide. Known resistance mediators were polymorphic, but mutations previously selected with in vitro drug pressure were not seen, and mutations identified in the Ugandan isolates were generally not associated with decreased ganaplacide susceptibility.

Laser-patterned epoxy-based 3D microelectrode arrays for extracellular recording.

Microelectrode arrays are commonly used to study the electrophysiological behavior of cells. Recently, there has been a growing interest in fabricating three-dimensional microelectrode arrays. Here, we present a novel process for the fast fabrication of epoxy-based 3D microelectrode array platforms with the assistance of laser-patterning technology. To this end, we photopatterned 3D pillars as scaffolds using epoxy-based dry films. Electrodes and conductor traces were fabricated by laser patterning of sputtered platinum films on top of the 3D structures, followed by deposition of parylene-C for insulation. Microelectrodes at the tip of the 3D structures were exposed using a vertical laser ablation process. The final electrodes demonstrated a low impedance of ∼10 kΩ at 1 kHz in electrochemical impedance spectroscopy measurements under physiological conditions. We investigated the maximum compression force of the 3D structures, which could withstand approximately 0.6 N per pillar. The 3D microelectrode arrays were used to record extracellular signals from HL-1 cells in culture as a proof of principle. Our results show regular firing of action potentials recorded at the tip of the 3D structures, demonstrating the possibility of recording cell signals in non-planar environments.

The detection of blood, semen and saliva through fabrics: A pilot study.

This study aimed to identify if biological material could be detected on the opposite side to deposition on fabric by commonly used presumptive and/or secondary tests. Additionally, this study aimed to ascertain if there is a difference in the DNA quantity and quality from samples obtained from both sides of the same substrate: cotton, polyester, denim, or combined viscose and polyester swatches. Blood, semen, or saliva (25 µL) was deposited on one side of 5 replicates of each fabric type and left for 24 h. Blood swatches were tested using Hemastix® and the ABACard® HemaTrace® immunoassay, semen swatches were tested using acid phosphatase (AP) reagent, the ABACard® p30® immunoassay and hematoxylin and eosin staining, and saliva swatches were tested using Phadebas® paper and the RSID-Saliva™ immunoassay. Both sides of each swatch were separately wet/dry swabbed and subjected to DNA analysis. Blood was able to be detected on the underside of all fabrics using both tests. Semen was able to be detected on the underside of swatches using the presumptive AP test but not p30®, and sperm was rarely observed. Saliva was able to be detected by RSID-Saliva™ but not Phadebas® paper when the underside of swatches were tested. Across all biological materials, DNA was able to be recovered from the top side of all 60 swatches. For the underside, DNA was able to be recovered from 54 swatches. Of the 6 swatches that DNA was unable to be recovered from, one sample was from semen and the rest were from saliva. This study has demonstrated that DNA and components of interest in forensically relevant biological material can be recovered from the opposite side to where it was originally deposited, and that observing biological material and/or DNA on one side of fabric does not definitively indicate direct deposition on that side.

Biochemical and biophysical drivers of the hydrogen isotopic composition of carbohydrates and acetogenic lipids.

The hydrogen isotopic composition (δ2H) of plant compounds is increasingly used as a hydroclimatic proxy; however, the interpretation of δ2H values is hampered by potential coeffecting biochemical and biophysical processes. Here, we studied δ2H values of water and carbohydrates in leaves and roots, and of leaf n-alkanes, in two distinct tobacco (Nicotiana sylvestris) experiments. Large differences in plant performance and biochemistry resulted from (a) soil fertilization with varying nitrogen (N) species ratios and (b) knockout-induced starch deficiency. We observed a strong 2H-enrichment in sugars and starch with a decreasing performance induced by increasing NO3-/NH4+ ratios and starch deficiency, as well as from leaves to roots. However, δ2H values of cellulose and n-alkanes were less affected. We show that relative concentrations of sugars and starch, interlinked with leaf gas exchange, shape δ2H values of carbohydrates. We thus provide insights into drivers of hydrogen isotopic composition of plant compounds and into the mechanistic modeling of plant cellulose δ2H values.

The marriage between stable isotope ecology and plant metabolomics - new perspectives for metabolic flux analysis and the interpretation of ecological archives.

Even though they share many thematical overlaps, plant metabolomics and stable isotope ecology have been rather separate fields mainly due to different mass spectrometry demands. New high-resolution bioanalytical mass spectrometers are now not only offering high-throughput metabolite identification but are also suitable for compound- and intramolecular position-specific isotope analysis in the natural isotope abundance range. In plant metabolomics, label-free metabolic pathway and metabolic flux analysis might become possible when applying this new technology. This is because changes in the commitment of substrates to particular metabolic pathways and the activation or deactivation of others alter enzyme-specific isotope effects. This leads to differences in intramolecular and compound-specific isotope compositions. In plant isotope ecology, position-specific isotope analysis in plant archives informed by metabolic pathway analysis could be used to reconstruct and separate environmental impacts on complex metabolic processes. A technology-driven linkage between the two disciplines could allow to extract information on environment-metabolism interaction from plant archives such as tree rings but also within ecosystems. This would contribute to a holistic understanding of how plants react to environmental drivers, thus also providing helpful information on the trajectories of the vegetation under the conditions to come.

Assessing eDNA capture method from aquatic environment to optimise recovery of human mt-eDNA.

Previous studies have shown that environmental DNA (eDNA) from human sources can be recovered from natural bodies of water, and the generation of DNA profiles from such environmental samples may assist in forensic investigations. However, fundamental knowledge gaps exist around the factors influencing the probability of detecting human eDNA and the design of optimal sampling protocols. One of these is understanding the particle sizes eDNA signals are most strongly associated with and the most appropriate filter size needed for efficiently capturing eDNA particles. This study assessed the amount of mitochondrial eDNA associated with different particle sizes from human blood and skin cells recovered from freshwater samples. Samples (300 mL) were taken from experimental 10 L tanks of freshwater spiked with 50 µL of human blood or skin cells deposited by vigorously rubbing hands together for two minutes in freshwater. Subsamples were collected by passing 250 mL of experimental water sample through six different filter pore sizes (from 0.1 to 8 µm). This process was repeated at four time intervals after spiking over 72 hours to assess if the particle size of the amount of eDNA recovered changes as the eDNA degrades. Using a human-specific quantitative polymerase chain reaction (qPCR) assay targeting the HV1 mitochondrial gene region, the total amount of mitochondrial eDNA associated with different particle size fractions was determined. In the case of human blood, at 0 h, the 0.45 µm filter pore size captured the greatest amount of mitochondrial eDNA, capturing 42 % of the eDNA detected. The pattern then changed after 48 h, with the 5 µm filter pore size capturing the greatest amount of eDNA (67 %), and 81 % of eDNA at 72 h. Notably, a ten-fold dilution proved to be a valuable strategy for enhancing eDNA recovery from the 8 µm filter at all time points, primarily due to the PCR inhibition observed in hemoglobin. For human skin cells, the greatest amounts of eDNA were recovered from the 8 µm filter pore size and were consistent through time (capturing 37 %, 56 %, and 88 % of eDNA at 0 hours, 48 hours, and 72 hours respectively). There is a clear variation in the amount of eDNA recovered between different cell types, and in some forensic scenarios, there is likely to be a mix of cell types present. These results suggest it would be best to use a 5 µm filter pore size to capture human blood and an 8 µm filter pore size to capture human skin cells to maximize DNA recovery from freshwater samples. Depending on the cell type contributing to the eDNA, a combination of different filter pore sizes may be employed to optimize the recovery of human DNA from water samples. This study provides the groundwork for optimizing a strategy for the efficient recovery of human eDNA from aquatic environments, paving the way for its broader application in forensic and environmental sciences.

Causal inference in the absence of positivity: The role of overlap weights.

How to analyze data when there is violation of the positivity assumption? Several possible solutions exist in the literature. In this paper, we consider propensity score (PS) methods that are commonly used in observational studies to assess causal treatment effects in the context where the positivity assumption is violated. We focus on and examine four specific alternative solutions to the inverse probability weighting (IPW) trimming and truncation: matching weight (MW), Shannon's entropy weight (EW), overlap weight (OW), and beta weight (BW) estimators. We first specify their target population, the population of patients for whom clinical equipoise, that is, where we have sufficient PS overlap. Then, we establish the nexus among the different corresponding weights (and estimators); this allows us to highlight the shared properties and theoretical implications of these estimators. Finally, we introduce their augmented estimators that take advantage of estimating both the propensity score and outcome regression models to enhance the treatment effect estimators in terms of bias and efficiency. We also elucidate the role of the OW estimator as the flagship of all these methods that target the overlap population. Our analytic results demonstrate that OW, MW, and EW are preferable to IPW and some cases of BW when there is a moderate or extreme (stochastic or structural) violation of the positivity assumption. We then evaluate, compare, and confirm the finite-sample performance of the aforementioned estimators via Monte Carlo simulations. Finally, we illustrate these methods using two real-world data examples marked by violations of the positivity assumption.

Postoperative Access and Compliance Following Medial Patellofemoral Ligament Reconstruction in Hispanic Adolescents Mirrors the Non-Hispanic Adolescent Population.

BACKGROUND: Disparity in surgical care of patellar instability patients has not been fully investigated in the adolescent Hispanic population. This demographic has been shown to have differences in their care, including a lower rate of surgical treatment for patellar instability. Socioeconomic factors have been cited as a factor that influences patient outcomes and its relationship with ethnicity in context of patellar instability has not been evaluated. METHODS: Review performed of patients <19 years of age who underwent MPFL reconstruction between September 2008 and December 2015. Demographics, patient median household income data, and clinical variables were collected. Generalized linear mixed model (GLMM) with subject as random effects factor was utilized to evaluate differences between ethnicity groups due to nonindependence of data. It was then expanded to incorporate interactions between ethnicity and income. RESULTS: Ninety-five patellar dislocation events met criteria in 85 adolescents (mean age: 15.5 y). Thirty-four (40%) adolescents identified as Hispanic. In univariate analysis no differences were found between Hispanic and non-Hispanic patients. The multivariate GLMM demonstrated a significant interaction between ethnicity and income. The Hispanic group in the >100% State median income category had the highest rate of postoperative clinic appointments attended ( P =0.019). The Hispanic group in the <100% State median income category had the lowest rate of physical therapy appointments attended ( P =0.044). No differences were observed for duration of follow-up ( P =0.57) or final Kujala score ( P =0.75). CONCLUSIONS: Hispanic ethnicity alone is not associated with inferior postoperative management after MPFL reconstruction in adolescents. However, when socioeconomic status is considered, Hispanic patients of lower-income backgrounds are found to have lower compliance with postoperative rehab recommendations. LEVEL OF EVIDENCE: Level III.

Testing the Simplified Molecular Dynamics Approach to Improve the Reproduction of ECD Spectra and Monitor Aggregation.

A simplified molecular-dynamics-based electronic circular dichroism (ECD) approach was tested on three condensed derivatives with limited conformational flexibility and an isochroman-2H-chromene hybrid, the ECD spectra of which could not be precisely reproduced by the conventional ECD calculation protocol. Application of explicit solvent molecules at the molecular mechanics (MD) level in the dynamics simulations and subsequent TDDFT-ECD calculation for the unoptimized MD structures was able to improve the agreements between experimental and computed spectra. Since enhancements were achieved even for molecules with limited conformational flexibility, deformations caused by the solvent molecules and multitudes of conformers produced with unoptimized geometries seem to be key factors for better agreement. The MD approach could confirm that aggregation of the phenanthrene natural product luzulin A had a significant contribution to a specific wavelength range of the experimental ECD. The MD approach has proved that dimer formation occurred in solution and this was responsible for the anomalous ECD spectrum. The scope and limitations of the method have also been discussed.

Zr-based metalloporphyrin MOF probe for electrochemical detection of parathion-methyl.

An electrochemical (EC) sensor based on metalloporphyrin metal-organic framework (MOF) for the detection of parathion-methyl (PM) has been developed. The prepared MOF-525(Fe) exhibits great signal enhancement toward the electrochemical detection of PM owing to its unique structural properties and electrochemical activities. Under optimal experimental conditions, the as-prepared MOF-525(Fe) based EC sensor exhibited excellent PM sensing performance with a wide linear detection range (0.1 µM-100 µM) and low limit of detection (LOD, 1.4 nM). Compared to its corresponding Fe metalloporphyrin (linker), MOF-525(Fe) exhibited a superior sensitivity (28.31 µA cm-2·µM-1), which is 3.7 times higher than the sensitivity of FeTCPP linker (7.56 µA cm-2·µM-1) towards PM. The improved performance is associated with the high specific surface area and the large pore channels of MOF-525(Fe) facilitating a better interaction between PM and the Fe metalloporphyrin active sites, especially in the lower concentration range. Moreover, a possible affinity of the PM molecules toward Zr6 clusters may also contribute to the selective enrichment of PM on MOF-525(Fe). This EC sensor further demonstrated high selectivity in the presence of interfering molecules. The recovery results further confirm accurate PM sensing in actual samples, which suggests promising applications for the rapid detection of environmental organophosphates by metalloporphyrin MOFs.

Effect of molecular permanent dipole moment on guest aggregation and exciton quenching in phosphorescent organic light emitting diodes.

This study explores the effect of molecular permanent dipole moment (PDM) on aggregation of guest molecules in phosphorescent host-guest organic light-emitting diodes (OLEDs). Through a combination of photoluminescence measurements, high-angle annular dark-field scanning transmission electron microscopy analysis, and an Ising model based physical vapor-deposition simulation, we show that higher PDM of tris[2-phenylpyridinato-C2,N]iridium(III) guest can actually lead to a reduced aggregation relative to tris[bis[2-(2-pyridinyl-N)phenyl-C] (acetylacetonato)iridium(III) when doped into a non-polar host 1,3,5-tris(carbazol-9-yl)benzene. This study further explores the effect of host polarity by using a polar host 3',5'-di(carbazol-9-yl)-[1,1'-biphenyl]-3,5-dicarbonitrile, and it is shown that the polar host leads to reduced guest aggregation. This study provides a comprehensive understanding of the impact of molecular PDM on OLED material efficiency and stability, providing insights for optimizing phosphorescent OLED materials.