Central Site Research Articles

Tasmanian devil (Sarcophilus harrisii) gene flow and source-sink dynamics

Increased access to genetic data has substantially improved how we manage threatened species. The Tasmanian devil (Sarcophilus harrisii) is listed as endangered due to the ongoing threat of a highly contagious cancer, devil facial tumour disease (DFTD), causing more than 80% population reductions. To assist future management interventions (e.g. releases into wild sites) we expanded upon previous studies of gene flow for the devil by assessing more recent and broad-scale patterns. We use genome-wide single nucleotide polymorphisms generated via DArTSeq across 21 devil sites to delineate source-sink dynamics across the species’ range. Our findings revealed gene flow is stronger on the northeast and central regions of Tasmania, with high rates of bidirectional gene flow among central sites. The northwest exhibits weaker connectivity relative to other regions of Tasmania, while gene flow appears to be non-existent between the southwest and other areas. Northeast coastal sites tend to serve as ‘sources’ for inland central sites, whereas gene flow appears restricted to the coastline in the northwest. These results are consistent with genetic structure of devil sites and spatial spread of DFTD, which has yet to arrive in the southwest region of Tasmania. Southwest isolation is probably due to mountain ranges and lack of roadways. Interestingly, some waterbodies did not appear to restrict devil movement among sites. Conversely, areas of high elevation act as apparent barriers, as evidenced by limited gene flow observed between eastern and western sites. Integrating source-sink dynamics into conservation management planning will be crucial in developing effective strategies to safeguard the Tasmanian devil and other threatened species facing similar threats (i.e. disease, habitat loss).

Survival analysis after stereotactic ablative radiotherapy for early stage non-small cell lung cancer: a single-institution cohort study

BackgroundStereotactic ablative radiotherapy (SABR) is the standard treatment for medically inoperable early-stage non-small cell lung cancer (ES-NSCLC), but which patients benefit from stereotactic radiotherapy is unclear. The aim of this study was to analyze prognostic factors for early mortality.MethodsFrom August 2010 to 2022, 617 patients with medically inoperable, peripheral or central ES-NSCLC were treated with SABR at our institution. We retrospectively evaluated the data from 172 consecutive patients treated from 2018 to 2020 to analyze the prognostic factors associated with overall survival (OS). The biological effective dose was > 100 Gy10 in all patients, and 60 Gy was applied in 3–5 fractions for a gross tumor volume (GTV) + 3 mm margin when the tumor diameter was < 1 cm; 30–33 Gy was delivered in one fraction. Real-time tumor tracking or an internal target volume approach was applied in 96% and 4% of cases, respectively. In uni- and multivariate analysis, a Cox model was used for the following variables: ventilation parameter FEV1, histology, age, T stage, central vs. peripheral site, gender, pretreatment PET, biologically effective dose (BED), and age-adjusted Charlson comorbidity index (AACCI).ResultsThe median OS was 35.3 months. In univariate analysis, no correlation was found between OS and ventilation parameters, histology, PET, or centrality. Tumor diameter, biological effective dose, gender, and AACCI met the criteria for inclusion in the multivariate analysis. The multivariate model showed that males (HR 1.51, 95% CI 1.01–2.28; p = 0.05) and AACCI > 5 (HR 1.56, 95% CI 1.06–2.31; p = 0.026) were significant negative prognostic factors of OS. However, the analysis of OS showed that the significant effect of AACCI > 5 was achieved only after 3 years (3-year OS 37% vs. 56%, p = 0.021), whereas the OS in one year was similar (1-year OS 83% vs. 86%, p = 0.58).ConclusionSABR of ES-NSCLC with precise image guidance is feasible for all medically inoperable patients with reasonable performance status. Early deaths were rare in our real-life cohort, and OS is clearly higher than would have been expected after best supportive care.

763 Is Central Venous Catheter the Main Culprit for Clinically Significant Venous Thromboembolism in Burn Patients

Abstract Introduction Venous thromboembolism (VTE) is a significant clinical problem for burn patients. The incidence of VTE has been reported as 0.25% to 47.1%. Known risk factors include large burn size, increasing age, male gender, active smoker or alcohol use, blood transfusion and surgeries. Central venous line (CVL) use is also a known risk factor for VTE. With all the known factors, we retrospectively analyzed our patients with VTE. Methods Retrospective chart review was performed on a single institution burn center in the calendar year of 2022. Pediatric patients were excluded. Following data were collected: age, burn size, mechanism, length of hospital stays, VTE diagnosis, VTE chemoprophylaxis, and central venous line days. VTE diagnosis was made using CT venogram or ultrasound. This project was a quality improvement initiative. Results There were 420 patients in the study period. Of all the admitted patients, there were 6 patients diagnosed with 7 VTE. One patient had 2 separate diagnoses of VTE at 2 distinct period and anatomical site. The incidence of VTE is 1.7%. Upon further chart review, all the VTE were at the site of central venous catheters. All the patients were on VTE chemoprophylaxis. The correlation between burn size, age, length of hospital stay and VTE was not significant. Conclusions Risk of VTE is high in burn patients due to the correlation with the Virchow’s Triad. All the patients admitted to the burn unit are placed on chemoprophylaxis unless contraindicated. The 7 patients diagnosed with VTE were on chemoprophylaxis. All the VTE were at the site of central venous catheter insertion sites, which is a known complication of catheters. The incident of 1.7% is on par with VTE incidents of burn patients, but much less than VTE caused by central venous catheters in non-burn patients. Large multicenter data collection is needed to validate this finding. Applicability of Research to Practice Directly appliable

Transfer of ANS-Like Drugs from Micellar Drug Delivery Systems to Albumin Is Highly Favorable and Protected from Competition with Surfactant by "Reserved" Binding Sites.

Micellar drug delivery systems (MDDS) for the intravenous administration of poorly soluble drugs have great advantages over alternative formulations in terms of the safety of their excipients, storage stability, and straightforward production. A classic example is mixed micelles of glycocholate (GC) and lecithin, both endogenous substances in human blood. What limits the use of MDDS is the complexity of the transitions after injection. In particular, as the MDDS disintegrate partially or completely after injection, the drug has to be transferred safely to endogenous carriers in the blood, such as human serum albumin (HSA). If this transfer is compromised, the drug might precipitate─a process that needs to be excluded under all circumstances. The key question of this paper is whether the high local concentration of GC at the moment and site of MDDS dissolution might transiently saturate HSA binding sites and, hence, endanger quick drug transfer. To address this question, we have used a new approach, which is time-resolved fluorescence spectroscopy of the single tryptophan in HSA, Trp-214, to characterize the competitive binding of GC and the drug substitute anilinonaphthalenesulfonate (ANS) to HSA. Time-resolved fluorescence of Trp-214 showed important advantages over established methods for tackling this problem. ANS has been the standard "model drug" to study albumin binding for decades, given its structural similarity to the class of naphthalene-containing acidic drugs and the fact that it is displaced from HSA by numerous drugs (which presumably bind to the same sites). Our complex global fit uses the critical approximation that the average lifetimes behave similarly to a single lifetime, but the resulting errors are found to be moderate and the results provide a convincing explanation of the, at first glance, counterintuitive behavior. Accordingly, and largely in line with the literature, we observed two types of sites binding ANS at HSA: 3 type A, rather peripheral, and 2 type B, likely more central sites. The latter quench Trp-214 by Förster Resonance Energy Transfer (FRET) with a rate constant of ≈0.4 ns-1 per ANS. Adding millimolar concentrations of GC displaces ANS from the A sites but not from B sites. At incomplete ANS saturation, this causes a GC-induced translocation of ANS from A to the more FRET-active B sites. This leads to the apparent paradox that the partial displacement of ANS from HSA increases its quenching effect on Trp-214. The most important conclusion is that (ANS-like) drugs cannot be displaced from the type-B sites, and consequently, drug transfer to these sites is not impaired by competitive binding of GC in the vicinity of a dissolving micelle. The second conclusion is that for unbound GC above the CMC (9 mM), ANS equilibrates between HSA and GC micelles but with a strong preference for free sites on HSA. That means that even persisting micelles would lose their cargo readily once exposed to HSA. For all MDDS sharing this property, targeted drug delivery approaches involving them as the nanocarrier would be pointless.

Posting vulnerability on LinkedIn

Digital spaces such as LinkedIn, the world’s largest professional digital network, constitute central sites for self-promotion, where job seekers and the employed present their polished “best” professional selves. However, in recent years, LinkedIn members are increasingly publishing accounts that highlight their vulnerabilities and struggles. This article examines the emergence of vulnerability on LinkedIn by analyzing how vulnerability is articulated in a sample of 40 posts (2021–2023). It identifies three genres: (1) Triumph over tragedy: vulnerability as a vector for self-growth and resilience; (2) Snap: vulnerability as a breaking point; and (3) Subversive commentary on self-promotion. On one hand, posting vulnerability on LinkedIn is a strategic form of digital self-branding, which monetizes vulnerability and depoliticizes its meanings. At the same time, vulnerability posts have the potential to form a basis for resistance to digital and work cultures’ glorification of overwork, individualized resilience and self-sufficiency, and the constant pressure to self-promote.

Radon concentration in seawater as a geochemical indicator of submarine fault activity in the Yatsushiro Sea, Japan

This study examined the relationship between radon (222Rn) concentrations in seawater and crustal activity in the Yatsushiro Sea by investigating the submarine fault zone situated at the southern end of the Futagawa–Hinagu fault zone, activated by the 2016 Kumamoto earthquake (M7.3). We conducted an analysis of 222Rn concentration in samples of bottom water just above the seafloor and pore water in sediments, utilizing multiple and piston cores from the Hakuho Maru Expedition KH18-3. The findings revealed significantly elevated 222Rn concentrations in the central sites of the Yatsushiro Sea, coinciding with a high-stress field exhibiting dense active faults. Seismicity analysis revealed heightened moment release and a low b-value post the 2016 Kumamoto earthquake, indicative of increased seismic activity and the potential for substantial earthquakes in the Yatsushiro Sea vicinity. Our results indicate that heightened concentrations of 222Rn in seawater can serve as an effective tracer for identifying and estimating submarine fault activities. Moreover, our research highlights the utility of 222Rn concentrations in detecting active submarine faults and assessing their activity. It contributes to a comprehensive understanding of the potential for significant earthquakes in the Yatsushiro Sea in the future.

The Supportive Oncology Collaborative: Expanding upon Collaborative Care to Increase Supportive Care Access in Underserved Populations.

Background: Access to supportive services in community-based oncology is challenging but essential, particularly for underserved populations. Methods: We developed the Supportive Oncology Collaborative (SOC), built upon the tenets of Collaborative Care, an existing model used to increase access to behavioral health in community settings. Using a population-health-based approach with screening, a registry, and shared care, we added palliative care specialists to a team of social workers and a consulting psychiatrist. We provided integrated psychosocial and palliative care at community-based sites of a large comprehensive cancer center. Results: We implemented the model in 2020 at a community site with a racially and ethnically diverse patient population. Encounters grew from 527 in our first year to 2,130 in 2022. Using screening tools, we identify the highest-risk patients for discussion in team meetings. Discussion: We are expanding the SOC across the Dana-Farber Cancer Institute regional campuses and believe it can increase access to integrated psychosocial and palliative care in cancer centers across the country.

A Community Needs Assessment and Implementation Planning for a Community Exercise Program for Survivors of Stroke: Protocol for a Pilot Hybrid Type I Clinical Effectiveness and Implementation Study.

Physical activity and exercise are important aspects of maintaining health. People with mobility impairments, including survivors of stroke, are less likely to exercise and at greater risk of developing or worsening chronic health conditions. Increasing accessible, desired options for exercise may address the gap in available physical activity programs, provide an opportunity for continued services after rehabilitation, and cultivate social connections for people after stroke and others with mobility impairments. Existing evidence-based community programs for people after stroke target cardiovascular endurance, mobility, walking ability, balance, and education. While much is known about the effectiveness of these programs, it is important to understand the local environment as implementation and sustainment strategies are context-specific. This study protocol aims to evaluate community needs and resources for exercise for adults living with mobility impairments with initial emphasis on survivors of stroke in Richland County, South Carolina. Results will inform a hybrid type I effectiveness and implementation pilot of an evidence-based group exercise program for survivors of stroke. The exploration and preparation phases of the EPIS (Exploration, Preparation, Implementation, and Sustainment) implementation model guide the study. A community needs assessment will evaluate the needs and desires of survivors of stroke through qualitative semistructured interviews with survivors of stroke, rehabilitation professionals, and fitness trainers serving people with mobility impairments. Additional data will be collected from survivors of stroke through a survey. Fitness center sites will be assessed through interviews and the Accessibility Instrument Measuring Fitness and Recreation Environments inventory. Qualitative data will be evaluated using content analysis and supported by mean survey results. Data will be categorized by the community (outer context), potential participants (outer context), and fitness center (inner context) and evaluate needs, resources, barriers, and facilitators. Results will inform evidence-based exercise program selection, adaptations, and specific local implementation strategies to influence success. Pilot outcome measures for participants (clinical effectiveness), process, and program delivery levels will be identified. An implementation logic model for interventions will be created to reflect the design elements for the pilot and their complex interactions. The study was reviewed by the institutional review board and exempt approved on December 19, 2023. The study data collection began in January 2024 and is projected to be completed in June 2024. A total of 17 participants have been interviewed as of manuscript submission. Results are expected to be published in early 2025. Performing a needs assessment before implementing it in the community allows for early identification of complex relationships and preplanning to address problems that cannot be anticipated in controlled effectiveness research. Evaluation and preparation prior to implementation of a community exercise program enhance the potential to be successful, valued, and sustained in the community. DERR1-10.2196/55432.

Strict Liability in the Principles of European Tort Law: The Black Hole and Central Building Site

Abstract The rule on strict liability is regarded by many specialists as the central building site of the Principles of European Tort Law (PETL). The following contribution first gives a brief overview of the current state of the law in Europe regarding this area, which is of enormous importance in European practice. It then presents rationales for the introduction of strict liability with a precise proposal for a rule restating the current state of the law from a European-wide perspective, while, at the same time, allowing the courts sufficient flexibility in reaching a decision in individual cases.

Geometric and electronic engineering of cobalt, manganese oxide sites in porous nitrogen-doped carbon for boosted oxygen reduction activity in microbial fuel cell

The development microbial fuel cell relies heavily on cathodic catalysts to provide excellent activity and fast electron rotor transfer rates. However, the design of such electrocatalysts is extremely challenging. Here, a strategy is proposed to regulate the electrocatalyst comprised of cobalt and manganese oxides embedded the porous nitrogen-doped carbon (Co3O4-MnO2/NC) with dominant crystal surface by geometric and electronic engineering. Experimental results and theoretical calculations show that the coordination of bimetallic oxides with N atoms induces an asymmetric distribution of charge of central metal sites, which promotes the adsorption/desorption of oxygen intermediates. This electrocatalyst exhibits excellent oxygen reduction reaction (ORR) activity, long-term stability and antitoxic tolerance. Importantly, microbial fuel cell equipped with Co3O4-MnO2/NC generates excellent performance in power density, chemical oxygen demand (COD) removal rate and coulomb efficiency. This work demonstrates the importance of geometric and electronic engineering design of bimetallic oxide to expose more dominant crystal faces to improve electrocatalytic activity in electrochemical energy conversion systems.

Photocatalyzed Oxidative Tandem Reaction Mediated by Bipyridinium for Multifunctional Derivatization of Alcohols.

The multifunctional derivatization of alcohols has been achieved by the bipyridinium-based conjugated small molecule photocatalysts with redox center and Lewis acid site. Besides exhibiting high activity in the selective generation of aldehydes/ketones, acids from alcohols through solvent modulation, this system renders the first selective synthesis of esters via an attractive cross-coupling pattern, whose reaction route is significantly different from the traditional condensation of alcohols and acids or esterification from hemiacetals. Following the oxidization of alcohol to aldehyde via bipyridinium-mediated electron and energy transfer, the Lewis acid site of bipyridinium then activates the aldehyde and methanol to obtain the acetal, which further reacts with methanol to generate ester. This method not only demonstrates a clear advantage of bipyridinium in diverse catalytic activities, but also paves the way for designing efficient multifunctional small molecule photocatalysts. This metal- and additive-free photocatalytic esterification reaction marks a significant advancement towards a more environmentally friendly, cost-effective and green sustainable approach, attributed to the utilization of renewable substrate alcohol and the abundant, low-cost air as the oxidant. The mildness of this esterification reaction condition provides a more suitable alternative for large-scale industrial production of esters.

New insights from seasonal and weekly evolutions of aerosol absorption properties and their association with PM2.5 and NO2 concentrations at a central Mediterranean site

Aerosol absorption parameters were investigated in this study using the measurements performed by an aethalometer during a monitoring campaign from December 2021 to July 2022 in a suburban area in south-eastern Italy. The aerosol absorption coefficient was compared to both PM2.5 and NO2 concentrations from two nearby stations (a rural and an urban site). Different seasonal evolutions were identified for these extensive parameters, even if they also showed a common feature because all these parameters presented a higher variability in winter due to the highly variable meteorological conditions during that season. Intensive parameters like the aerosol absorption Ångström exponent and the PM2.5/PM10 ratio were also investigated showing the effects of wood burning from domestic heating and of vehicular traffic, especially both in the urban and in the suburban site. Then, the weekly evolution of both selected extensive and intensive parameters was also analyzed to identify potential impacts due to the weekly cycle of human activities. Most of the selected parameters presented a significant increase starting from Tuesday to Friday and then they generally decreased during the weekends due to the relevant reduction of the human activities. The selection of different types of monitoring sites (urban, suburban, and rural) and temporal scales (seasonal and weekly) has been proved for a proper characterization of the aerosol absorption properties at the monitored area due to its geographical location at the center of the Mediterranean area.

Hydrological regimes and evaporative flux partitioning at the climatic ends of high mountain Asia

Abstract High elevation headwater catchments are complex hydrological systems that seasonally buffer water and release it in the form of snow and ice melt, modulating downstream runoff regimes and water availability. In High Mountain Asia (HMA), where a wide range of climates from semi-arid to monsoonal exist, the importance of the cryospheric contributions to the water budget varies with the amount and seasonal distribution of precipitation. Losses due to evapotranspiration and sublimation are to date largely unquantified components of the water budget in such catchments, although they can be comparable in magnitude to glacier melt contributions to streamflow. Here, we simulate the hydrology of three high elevation headwater catchments in distinct climates in HMA over 10 years using an ecohydrological model geared towards high-mountain areas including snow and glaciers, forced with reanalysis data. Our results show that evapotranspiration and sublimation together are most important at the semi-arid site, Kyzylsu, on the northernmost slopes of the Pamir mountain range. Here, the evaporative loss amounts to 28% of the water throughput, which we define as the total water added to, or removed from the water balance within a year. In comparison, evaporative losses are 19% at the Central Himalayan site Langtang and 13% at the wettest site, 24 K, on the Southeastern Tibetan Plateau. At the three sites, respectively, sublimation removes 15%, 13% and 6% of snowfall, while evapotranspiration removes the equivalent of 76%, 28% and 19% of rainfall. In absolute terms, and across a comparable elevation range, the highest ET flux is 413 mm yr−1 at 24 K, while the highest sublimation flux is 91 mm yr−1 at Kyzylsu. During warm and dry years, glacier melt was found to only partially compensate for the annual supply deficit.

Short‐term effects of double‐layer ploughing reduced tillage on soil structure and crop yield

AbstractSoil tillage is widely acknowledged to affect soil characteristics and agricultural productivity. This research investigates the short‐term effects of various tillage methods on soil physical properties and crop yields at a Central German field site with a dry climate (mean temperature 9.5°C; annual precipitation 470 mm). Three tillage approaches were evaluated: conventional plough tillage (25 cm depth), cultivator tillage (18 cm depth), and double‐layer plough tillage (15 and 30 cm depth). We assessed soil physical properties through standard laboratory analyses, compression tests, soil pore structure via X‐ray computed tomography (X‐ray CT) and crop yields over 3 years. The results indicate that cultivator tillage approach increased soil bulk density relative to conventional tillage, especially in the second year, though this effect diminished over time. Double‐layer plough tillage emerged as a viable short‐term alternative to conventional tillage, achieving comparable soil bulk density. Saturated hydraulic conductivity values were generally higher for soils under conventional tillage or double‐layer plough tillage than for cultivator tillage, highlighting their soil loosening effect. Classical soil analysis methods combined with X‐ray computed tomography provided valuable insights into tillage induced changes to soil structure. Cultivator tillage resulted in a distinct pore structure with reduced macroporosity and pore connectivity. Despite notable soil property variations, crop yields remained consistent across the tillage methods. Overall, double‐layer plough tillage presents a sustainable option, moderately improving soil physical properties while maintaining crop yields. This study highlights the need to assess the short‐term effects of tillage on soils and contributes to the broader dialogue on optimizing tillage strategies for effective soil management and crop production.

Volumetric Analysis of Peri-implant Tissue Change Over Time: Validating an Innovative 3D Method.

To validate an innovative 3D volumetric method of evaluating tissue changes proposed by Lee et al in 2020 by comparing the results of this method-in which the scanned peri-implant surfaces were transformed, visualized, and analyzed as 3D objects-to the results reported by an existing method based on calculation of the mean distance between measured surfaces. The null hypothesis was that there was no statistically significant difference between the two methods. Additionally, the present study evaluated peri-implant tissue changes 5 years after single implant placement in the esthetic zone. Both methods were applied to 11 oral implant site casts (6 maxillary central incisor sites, 5 maxillary lateral incisor sites) taken from 11 patients at crown placement and at follow-up examinations 5 years later. The methods are based on digital workflows in which the reference and 5-year casts are scanned and the resulting STL files are superimposed and analyzed for three regions of interest (mesial papilla, central area, and distal papilla). The volumetric changes reported by the Lee et al method and the mean distance method were calculated and compared using the Spearman rank correlation coefficient (P < .01) and the Wilcoxon signed-rank test (P < .05). The correlation between the two sets of measurements was very high (Spearman rank correlation coefficient = 0.885). The new volumetric method indicated a mean volume loss of 2.82 mm3 (SD: 5.06), while the method based on the measurement of mean distance showed a mean volume loss of 2.92 mm3 (SD: 4.43; Wilcoxon signed-rank test result: P = .77). No statistically significant difference was found. The two methods gave equivalent results, and the null hypothesis was accepted. The new volumetric method was validated and can be considered a trustworthy tool.

Collaborative inference for treatment effect with distributed data-sharing management in multicenter studies.

Data sharing barriers present paramount challenges arising from multicenter clinical studies where multiple data sources are stored and managed in a distributed fashion at different local study sites. Merging such data sources into a common data storage for a centralized statistical analysis requires a data use agreement, which is often time-consuming. Data merging may become more burdensome when propensity score modeling is involved in the analysis because combining many confounding variables, and systematic incorporation of this additional modeling in a meta-analysis has not been thoroughly investigated in the literature. Motivated from a multicenter clinical trial of basal insulin treatment for reducing the risk of post-transplantation diabetes mellitus, we propose a new inference framework that avoids the merging of subject-level raw data from multiple sites at a centralized facility but needs only the sharing of summary statistics. Unlike the architecture of federated learning, the proposed collaborative inference does not need a center site to combine local results and thus enjoys maximal protection of data privacy and minimal sensitivity to unbalanced data distributions across data sources. We show theoretically and numerically that the new distributed inference approach has little loss of statistical power compared to the centralized method that requires merging the entire data. We present large-sample properties and algorithms for the proposed method. We illustrate its performance by simulation experiments and the motivating example on the differential average treatment effect of basal insulin to lower risk of diabetes among kidney-transplant patients compared to the standard-of-care.

Incorporation of Cu and Mn ions into hydroxyapatite channels and deposition of complex metal oxide

The Cu-and Mn-incorporated apatite-type phosphate, Ca10(PO4)6CuxMny(O,OH)2, was successfully synthesized by heating the hydroxyapatite under N2 at 900 °C after Cu- and Mn-nitrate aqueous solution loading with x = 0–0.2 and y = 0–0.2 onto it. In Ca10(PO4)6Cu0·2Mn0·2(O,OH)2, Cu occupies the apatite channel center site, and the Mn site shifts from the center. The deposition of Cu and Mn species was found to occur upon heating Cu0·2Mn0.2-Ca-HAp at 600–800 °C in air, accommodating the spinel-type complex metal oxide, (Cu, Mn)3O4 formation from the apatite channel. In addition, the CuO deposition from the Ca10(PO4)6Cu0·2(O,OH)2 apatite was observed for samples heated at 600–800 °C, whereas Mn3O4 was observed for the Ca10(PO4)6Mn0·2(O,OH)2 sample heated at 800 °C. These results suggest that the presence of Cu in the apatite channel facilitates the deposition of Mn species.

Practical and efficient oxygenation of benzylic C-H bonds with dioxygen catalyzed by two-dimensional porous organic frameworks possessing porphyrin cobalt(II) units

Metalloporphyrin T(4-Br)PPCo was used in the construction of two-dimensional porous organic framework materials (2D POFs) in order to achieve the direct benzyl C-H bonds oxygenation. In order to prevent the disordered diffusion of free radicals in 2D POFs, a restricted reaction channel was constructed, and heterogeneous catalysis was applied to decrease the deep oxygenation of partial oxygenation products due to central metal sites. All 2D POFs were characterized as amorphous microporous materials containing highly and uniformly dispersed Co2+. It was used to partially oxygenate C-H bonds at benzyl position employing dioxygen in solvent-free condition, and the conversion and selectivity were improved at the same time, especially when residual -B(OH)2 and -Br were capped. Compared with T(4-Br)PPCo, the substrate conversion increased from 39 % to 66 %, and the selectivity for 4-nitroacetophenone increased from 66 % to 91 %. The reaction mechanism, apparent kinetics and substrate compatibility were also studied. In this work, it provided a guiding reference for the effective C-H bonds oxygenation and other free radical based chemical reactions. The use of POFs in catalytic chemistry was further broadened, and a successful method for improving the catalytic characteristics of POFs by capping the remaining active groups was suggested.

Indoor and ambient black carbon and fine particulate matter associations with blood biomarkers in COPD patients

BackgroundSystemic inflammation contributes to cardiovascular risk and chronic obstructive pulmonary disease (COPD) pathophysiology. Associations between systemic inflammation and exposure to ambient fine particulate matter (PM ≤ 2.5 μm diameter; PM2.5), and black carbon (BC), a PM2.5 component attributable to traffic and other sources of combustion, infiltrating indoors are not well described. MethodsBetween 2012 and 2017, COPD patients completed in-home air sampling over one-week intervals, up to four times (seasonally), followed by measurement of plasma biomarkers of systemic inflammation, C-reactive protein (CRP) and interleukin-6 (IL-6), and endothelial activation, soluble vascular adhesion molecule-1 (sVCAM-1). Ambient PM2.5, BC and sulfur were measured at a central site. The ratio of indoor/ambient sulfur in PM2.5, a surrogate for fine particle infiltration, was used to estimate indoor BC and PM2.5 of ambient origin. Linear mixed effects regression with a random intercept for each participant was used to assess associations between indoor and indoor of ambient origin PM2.5 and BC with each biomarker. Results144 participants resulting in 482 observations were included in the analysis. There were significant positive associations between indoor BC and indoor BC of ambient origin with CRP [%-increase per interquartile range (IQR);95 % CI (13.2 %;5.2–21.8 and 11.4 %;1.7–22.1, respectively)]. Associations with indoor PM2.5 and indoor PM2.5 of ambient origin were weaker. There were no associations with IL-6 or sVCAM-1. ConclusionsIn homes of patients with COPD without major sources of combustion, indoor BC is mainly attributable to the infiltration of ambient sources of combustion indoors. Indoor BC of ambient origin is associated with increases in systemic inflammation in patients with COPD, even when staying indoors.

MoRF_ESM: Prediction of MoRFs in disordered proteins based on a deep transformer protein language model.

Molecular recognition features (MoRFs) are particular functional segments of disordered proteins, which play crucial roles in regulating the phase transition of membrane-less organelles and frequently serve as central sites in cellular interaction networks. As the association between disordered proteins and severe diseases continues to be discovered, identifying MoRFs has gained growing significance. Due to the limited number of experimentally validated MoRFs, the performance of existing MoRF's prediction algorithms is not good enough and still needs to be improved. In this research, we present a model named MoRF_ESM, which utilizes deep-learning protein representations to predict MoRFs in disordered proteins. This approach employs a pretrained ESM-2 protein language model to generate embedding representations of residues in the form of attention map matrices. These representations are combined with a self-learned TextCNN model for feature extraction and prediction. In addition, an averaging step was incorporated at the end of the MoRF_ESM model to refine the output and generate final prediction results. In comparison to other impressive methods on benchmark datasets, the MoRF_ESM approach demonstrates state-of-the-art performance, achieving [Formula: see text] higher AUC than other methods when tested on TEST1 and achieving [Formula: see text] higher AUC than other methods when tested on TEST2. These results imply that the combination of ESM-2 and TextCNN can effectively extract deep evolutionary features related to protein structure and function, along with capturing shallow pattern features located in protein sequences, and is well qualified for the prediction task of MoRFs. Given that ESM-2 is a highly versatile protein language model, the methodology proposed in this study can be readily applied to other tasks involving the classification of protein sequences.