bluuebunny/crossref_metadata_2025 huggingface dataset:
Efficacy of constructed wetlands to mitigate non-point source pollution from irrigation tailwaters in the San Joaquin Valley, California, USA
Authors: O'Geen A.T. , Maynard J.J. , Dahlgren R.A.
Published: February 2007

The efficacy of using constructed wetlands (CWs) to sequester organic carbon and nutrients from irrigation tailwaters was studied in the San Joaquin Valley, California. Two CWs were monitored during the 2004 irrigation season, a new CW (W-1) and 10-year-old CW (W-2). Input/output waters from CW were collected weekly and analyzed for a variety of water quality contaminants. Organic carbon, nutrient and sediment retention efficiencies were evaluated from input/output concentrations. Characteristics of sediment were examined spatially at W-2. Results indicate that W-2 was more efficient at contaminant removal. Average particulate organic carbon retention, was 70±13% (mean±standard deviation) in W-2 and 48±32% in W-1. Chlorophyll-a, a measure of algal biomass, was higher at W-1, especially in input waters. Initially, output concentration of chlorophyll-a increased 15-fold in W-2, however over time, as emergent vegetation established, chlorophyll-a decreased to 35% of input levels. Average total N removal efficiency was 45±18% for W-2 compared to 22±32% in W-1. Total P removal efficiency was 72±14% at W-2 compared to 18±26% at W-1. CWs were most effective at removing total suspended solids, 84±15% and 97±2% for W-1 and W-2, respectively. Results demonstrate that CWs are effective at capturing POC, sediment and nutrients from irrigation tailwaters.
Instruments to reduce the leaching of heavy metals from building materials in the Netherlands
Authors: van Breemen A.J.H. , Vermij P.H.M.
Published: February 2007

In the Netherlands the leaching of heavy metals from metal building and constructing materials results in serious contamination problems in the water system. The most common sources of these heavy metals in construction materials are copper waterworks and roofs, zinc roofs, gutters and rain pipes, zinced steel, stainless steel, and lead sealing material. In urban waters the surface water and sediment standards are often exceeded. Although building and construction materials are certainly not the only source of heavy metals, they are an important part of the problem. This article focuses on six instruments that are in use in the Netherlands to try to reduce impact on the surface waters. In addition to this, national as well as international, a reconsideration of the risks and surface water standards for several heavy metals is considered. A balanced use of instruments can be considered as the application of a best practice.
A knowledge gap analysis on multi-scale predictive ability for agriculturally derived sediments under South African conditions
Authors: van Zyl A.J.
Published: February 2007

Agriculture has been implicated as a major source of sediments in South Africa. The aim of the knowledge gap analysis was to understand the production and delivery components of agriculturally derived sediments under South African conditions and to assess the predictive ability to address the fate of these sediments from field to catchment scales. An overview is given of important erosion processes and erosion modelling applied in South Africa at the field and catchment scale. A limitation of the sediment models is that gully erosion is not simulated; therefore, the models should be complemented with gully erosion predictions if gullies are an important sediment source. Field-scale models inadequately predict sediment production localised at hydrologically sensitive areas as a result of saturation excess flow and/or throughflow. The discussion on erosion modelling reveals that more complex models have had limited application in South Africa because they require large and detailed data sets, and may have parameters that are difficult to measure or to estimate. A modelling framework is discussed which allows linking of sediment models requiring readily available data, gully erosion models/maps and the use of other techniques to assess the fate of agriculturally derived sediments from field to catchment scale.
Analysis and modelling of land-based nutrient pollution by watershed models coupled with GIS: a case study from Turkey
Authors: Erturk A. , Gurel M. , Varol E. , Ekdal A. , Baloch M. , Dikerler T. , Seker D.Z. , Tanik A.
Published: February 2007

Diffuse pollution is usually temporally and spatially uncertain, and thus hard to analyze. In many cases, discretizing a diffuse source of pollution into individual point sources can ease diffuse pollution modelling and analysis, and therefore reduce high uncertainty especially in the spatial distribution of pollution loads. This is however a difficult task, since quite a number of sub-drainage areas, with complex structures and land-use properties, has to be delineated. Watershed models can be used to delineate the sub-drainage areas in a watershed with high accuracy and locate the related outlets which connect the sub-drainage areas to the main waterbody in a watershed. In this study, such an approach has been used on a case study to model the diffuse nutrient loads carried to streams that reach to a medium-sized lake in Turkey. The annual nutrient loads, which were calculated by using mathematical models, were then converted to a load-map with the help of a geographical information system.
The dynamic water–sediment system: results from an intensive pesticide monitoring campaign
Authors: Holvoet K. , Seuntjens P. , Mannaerts R. , De Schepper V. , Vanrolleghem P.A.
Published: February 2007

To gain insight into the dynamics of pesticides in the different compartments of a river system, an intensive monitoring campaign was set up. An extensive dataset is useful when planning to model the fate of pesticides in river systems. In this study we focus on the Nil, a small, hilly basin situated in the central part of Belgium. Two automatic samplers were placed in the river basin, i.e., one at the mouth and one upstream, taking composite samples of water and suspended solids. Undisturbed sediment samples were taken by means of a macro-core and immediately frozen with CO2-ice. The samples were sliced and analysed for pesticides in pore water and on sediment. The results of the study revealed the dynamics of the different compartments of a river system. The water compartment showed hourly variations in pesticide peak concentrations, regularly exceeding the standards. The amount of pesticides transported by suspended solids increased after a rainfall event. The concentration of pesticides in pore water, measured on a monthly basis, followed the trends of the water compartment remarkably well, but in a significantly lower concentration. These observations may be explained by combined diffusion, biodegradation and chemical reactions occurring in the water column and the sediment. Further insight into the importance of each of these processes can be gained by dynamic modelling, an approach that is currently being followed.
Arteriovenous Access for Hemodialysis
Authors: Lok Charmaine E. , Huber Thomas S. , Orchanian-Cheff Ani , Rajan Dheeraj K.
Published: March 2024

Importance

Hemodialysis requires reliable vascular access to the patient’s blood circulation, such as an arteriovenous access in the form of an autogenous arteriovenous fistula or nonautogenous arteriovenous graft. This Review addresses key issues associated with the construction and maintenance of hemodialysis arteriovenous access.

Observations

All patients with kidney failure should have an individualized strategy (known as Patient Life-Plan, Access Needs, or PLAN) for kidney replacement therapy and dialysis access, including contingency plans for access failure. Patients should be referred for hemodialysis access when their estimated glomerular filtration rate progressively decreases to 15 to 20 mL/min, or when their peritoneal dialysis, kidney transplant, or current vascular access is failing. Patients with chronic kidney disease should limit or avoid vascular procedures that may complicate future arteriovenous access, such as antecubital venipuncture or peripheral insertion of central catheters. Autogenous arteriovenous fistulas require 3 to 6 months to mature, whereas standard arteriovenous grafts can be used 2 to 4 weeks after being established, and “early-cannulation” grafts can be used within 24 to 72 hours of creation. The prime pathologic lesion of flow-related complications of arteriovenous access is intimal hyperplasia within the arteriovenous access that can lead to stenosis, maturation failure (33%-62% at 6 months), or poor patency (60%-63% at 2 years) and suboptimal dialysis. Nonflow complications such as access-related hand ischemia (“steal syndrome”; 1%-8% of patients) and arteriovenous access infection require timely identification and treatment. An arteriovenous access at high risk of hemorrhaging is a surgical emergency.

Conclusions and Relevance

The selection, creation, and maintenance of arteriovenous access for hemodialysis vascular access is critical for patients with kidney failure. Generalist clinicians play an important role in protecting current and future arteriovenous access; identifying arteriovenous access complications such as infection, steal syndrome, and high-output cardiac failure; and making timely referrals to facilitate arteriovenous access creation and treatment of arteriovenous access complications.
Science and Sex—A Bold Agenda for Women’s Health
Authors: Johnson Paula A.
Published: March 2024

This Viewpoint examines why investigators should address women’s health in all biomedical and health-related research.
Differences in Care Team Response to Patient Portal Messages by Patient Race and Ethnicity
Authors: Tang Mitchell , Mishuris Rebecca G. , Payvandi Lily , Stern Ariel D.
Published: March 2024

Importance

The COVID-19 pandemic was associated with substantial growth in patient portal messaging. Higher message volumes have largely persisted, reflecting a new normal. Prior work has documented lower message use by patients who belong to minoritized racial and ethnic groups, but research has not examined differences in care team response to messages. Both have substantial ramifications on resource allocation and care access under a new care paradigm with portal messaging as a central channel for patient–care team communication.

Objective

To examine differences in how care teams respond to patient portal messages sent by patients from different racial and ethnic groups.

Design, Setting, and Participants

In a cross-sectional design in a large safety-net health system, response outcomes from medical advice message threads sent from January 1, 2021, through November 24, 2021, from Asian, Black, Hispanic, and White patients were compared, controlling for patient and message thread characteristics. Asian, Black, Hispanic, and White patients with 1 or more adult primary care visits at Boston Medical Center in calendar year 2020 were included. Data analysis was conducted from June 23, 2022, through December 21, 2023.

Exposure

Patient race and ethnicity.

Main Outcomes and Measures

Rates at which medical advice request messages were responded to by care teams and the types of health care professionals that responded.

Results

A total of 39 043 patients were included in the sample: 2006 were Asian, 21 600 were Black, 7185 were Hispanic, and 8252 were White. A total of 22 744 (58.3%) patients were women and mean (SD) age was 50.4 (16.7) years. In 2021, these patients initiated 57 704 medical advice request message threads. When patients who belong to minoritized racial and ethnic groups sent these messages, the likelihood of receiving any care team response was similar, but the types of health care professionals that responded differed. Black patients were 3.95 percentage points (pp) less likely (95% CI, −5.34 to −2.57 pp; P < .001) to receive a response from an attending physician, and 3.01 pp more likely (95% CI, 1.76-4.27 pp; P < .001) to receive a response from a registered nurse, corresponding to a 17.4% lower attending response rate. Similar, but smaller, differences were observed for Asian and Hispanic patients.

Conclusions and Relevance

The findings of this study suggest lower prioritization of patients who belong to minoritized racial and ethnic groups during triaging. Understanding and addressing these disparities will be important for improving care equity and informing health care delivery support algorithms.
Regulating the Electronic Synergy of Asymmetric Atomic Fe Sites with Adjacent Defects for Boosting Activity and Durability toward Oxygen Reduction
Authors: Ji Siqi , Wang Yuhao , Liu Hongxue , Lu Xue , Guo Chunmin , Xin Shixuan , Horton Joseph Hugh , Zhan Fei , Wang Yu , Li Zhijun
Published: March 2024

The oxygen reduction reaction (ORR) plays a fundamental role in sustainable energy technologies. However, the creation of non‐precious metal electrocatalysts with high ORR activity and durability under all pH conditions is of great significance but remains challenging. Herein, the aim is to overcome this challenge by creating a Fe single atom catalyst on a 2D defect‐containing nitrogen‐doped carbon support (Fe1/DNC) via a microenvironment engineering strategy. Microkinetic modeling reveals that FeN4(OH) moieties are the real active sites under reaction conditions. Due to the synergistic promotion effect of denser accessible FeN4(OH) moieties and defect‐induced electronic properties, Fe1/DNC catalyst achieves extraordinary ORR activity under alkaline, acidic, and neutral conditions, with half‐wave potentials of 0.95, 0.82, and 0.70 V, respectively. Moreover, a negligible performance decay is observed with this Fe catalyst in stability and methanol tolerance tests. Zn‐air battery employing Fe1/DNC delivers remarkable peak power density and long‐term operational durability. Theoretical analysis provides compelling evidence that the defects adjacent to FeN4(OH) moieties can endow an inductive effect to reshape electronic properties to balance the OOH* formation and OH* reduction. This work offers insight into the regulation of asymmetric coordination structure and electronic properties of metal sites for boosting electrocatalytic activity and stability.
Pre‐Oxidating and Pre‐Carbonizing to Regulate the Composition and Structure of Coal Tar Pitch: The Fabrication of Porous Carbon for Supercapacitor Applications
Authors: Liu Qian , Wu Dongling , Wang Tao , Wang Caige , Jia Dianzeng
Published: March 2024

The capacitive properties of supercapacitors highly rely on the reasonable design of high‐performance electrode materials. Herein, a synergetic strategy of pre‐oxidation and pre‐carbonization is proposed to prepare coal tar pitch (CTP) based porous carbon. The formation mechanism of porous carbon is revealed. Pre‐oxidation increases the heteroatom content and promotes the decomposition of polycyclic aromatic hydrocarbons into small molecules, which is more conducive to improving the subsequent activation and enhancing the microporous specific surface area. Also, the autoclave pre‐carbonization promotes the polymerization of the precursors and increases the carbon yield. Benefiting from the synergistic effect of pre‐oxidation and pre‐carbonation, the obtained carbon exhibits a superior specific capacitance of 365 F g−1. Meanwhile, ZnCl2 is used as a hydrogen‐bonding acceptor to synthesize ZnCl2‐EG/PVA deep eutectic solvent (DES) gel, and it is applicable to acidic, neutral, and alkaline electrolytes. The capacitor assembled with the prepared porous carbon and DES gel electrolyte achieves a high energy density of 41.3 Wh kg−1 and works well in unconventional temperatures (−40–75 °C). This work confirms the effect of pre‐oxidation and pre‐carbonization on the fabrication of CTP‐based carbon material and expects to prepare porous carbon using other pre‐oxidation/carbonization agents.
Transparent Composite Ceramic@aluminum with Ultra‐High Thermal Conductivity for High‐Brightness Laser‐Driven Lighting
Authors: Xi Guoyu , Zhou Zhenzhen , Li Jiang , Zeng Lingwei , Lin Shisheng , Wang Pengfei , Lin Hang , Wang Yuansheng , Zhou Su , Huang Feng , Chen Guilin , Chen Daqin
Published: March 2024

Next‐generation high‐brightness lighting faces a big challenge in developing laser‐drivable color‐converting materials with effective thermal management. Herein, a new material architecture of Al2O3‐Y3Al5O12: Ce3+ (YAG: Ce) transparent composite ceramics coated with Al film (TCC@Al) is proposed. The as‐prepared material shows the highest thermal conductivity (29.3 W m−1 K−1) among YAG: Ce‐related transparent ceramics (TC) ever reported owing to the combination role of short‐range thermal conduction of Al2O3 microcrystals and long‐range thermal conduction of Al film. Temperature‐dependent photoluminescence (PL) spectra and femtosecond transient absorption (fs‐TA) spectra evidence the importance of thermal management, whereby the luminescent loss of TCC@Al is only 8.92% at 450 K and is far smaller than TC counterpart (15.86%). Importantly, no obvious luminescence saturation is detected upon 20 W mm−2 blue laser irradiation and the inhomogeneous angular color distribution is suppressed by the scatter of Al2O3 microcrystals, yielding uniform white light with ultra‐high luminous flux (LF) of 4294 lm@20 W mm−2 and luminous efficacy (LE) of 215 lm W−1. As a consequence, the present TCC@Al‐converted laser‐driven lighting prototype exhibits much better optical performance than the commercial TC‐based one.
Living Synthelectronics: A New Era for Bioelectronics Powered by Synthetic Biology
Authors: Sun Jing , Yang Ruofan , Li Qingsong , Zhu Runtao , Jiang Ying , Zang Lei , Zhang Zhibo , Tong Wei , Zhao Hang , Li Tengfei , Li Hanfei , Qi Dianpeng , Li Guanglin , Chen Xiaodong , Dai Zhuojun , Liu Zhiyuan
Published: March 2024

Bioelectronics, which converges biology and electronics, has attracted great attention due to their vital applications in human–machine interfaces. While traditional bioelectronic devices utilize nonliving organic and/or inorganic materials to achieve flexibility and stretchability, a biological mismatch is often encountered because human tissues are characterized not only by softness and stretchability but also by biodynamic and adaptive properties. Recently, a notable paradigm shift has emerged in bioelectronics, where living cells, and even viruses, modified via gene editing within synthetic biology, are used as core components in a new hybrid electronics paradigm. These devices are defined as “living synthelectronics,” and they offer enhanced potential for interfacing with human tissues at informational and substance exchange levels. In this Perspective, the recent advances in living synthelectronics are summarized. First, opportunities brought to electronics by synthetic biology are briefly introduced. Then, strategic approaches to designing and making electronic devices using living cells/viruses as the building blocks, sensing components, or power sources are reviewed. Finally, the challenges faced by living synthelectronics are raised. It is believed that this paradigm shift will significantly contribute to the real integration of bioelectronics with human tissues.
Polyelectrolyte Hydrogel‐Functionalized Photothermal Sponge Enables Simultaneously Continuous Solar Desalination and Electricity Generation Without Salt Accumulation
Authors: Li Lin , Xue Chaorui , Chang Qing , Ren Xiaohu , Li Ning , Yang Jinlong , Hu Shengliang , Xu Haolan
Published: March 2024

Technologies that can simultaneously generate electricity and desalinate seawater are highly attractive and required to meet the increasing global demand for power and clean water. Here, a bifunctional solar evaporator that features continuous electric generation in seawater without salt accumulation is developed by rational design of polyelectrolyte hydrogel‐functionalized photothermal sponge. This evaporator not only exhibits an unprecedentedly high water evaporation rate of 3.53 kg m−2 h−1along with 98.6% solar energy conversion efficiency but can also uninterruptedly deliver a voltage output of 0.972 V and a current density of 172.38 µA cm−2 in high‐concentration brine over a prolonged period under one sun irradiation. Many common electronic devices can be driven by simply connecting evaporator units in series or in parallel without any other auxiliaries. Different from the previously proposed power generation mechanism, this study reveals that the water‐enabled proton concentration fields in intermediate water region can also induce an additional ion electric field in free water region containing solute, to further enhance electricity output. Given the low‐cost materials, simple self‐regeneration design, scalable fabrication processes, and stable performance, this work offers a promising strategy for addressing the shortages of clean water and sustainable electricity.
Dispersion‐Engineered Super‐Gain Parametric Amplification in Nanoscale Optical Cavities
Authors: Aşırım Özüm Emre
Published: March 2024

The gain factor of the optical parametric amplification (OPA) process is known to be negligible in the small scale due to low‐interaction‐medium length. Hence, in the nanoscale, OPA is deemed as infeasible. Therefore, in small‐scale‐integrated optical devices, stimulated‐emission‐based amplifiers (lasers) are employed instead of OPAs. In contrast, the major advantage of OPAs over lasers is that unlike lasers which only provide amplification over a narrow spectral band, OPAs provide high‐gain amplification over a very large, user‐controlled spectral band. In this article, it is shown that OPA can yield wideband high‐gain amplification over a nanoscale beam propagation distance through dispersion engineering. This is achieved by a proper tuning of the pump (source) wave frequency, which can maximize the effective medium nonlinearity by a few orders of magnitude, while concurrently maximizing the intracavity energy density, thereby compensating for the small co‐propagation distance for the input (signal) and pump beams. In this study, it is shown that an input wave can be amplified by a factor in a nanoscale cavity via precise dispersion engineering. Both empirical and computational formulations are used for the investigation, which display a reasonable agreement.
Synthesis of 2‐Amino‐3‐arylindoles and their Fused Analogues via Intramolecular C‐Arylation
Authors: Žáková Kateřina , Králová Petra , Soural Miroslav
Published: March 2024

2‐Aminobenzyl cyanide was reacted with nitrobenzenesulfonyl chlorides and alkylated under Mitsunobu or Fukuyama conditions. The resulting intermediates were exposed to basic conditions, which triggered a Truce‐Smiles rearrangement, leading to intramolecular C‐arylation. This reaction was followed by spontaneous cycloaddition, which yielded 2‐aminoindole derivatives. The developed synthetic route represents a metal‐free approach for accessing 1‐substituted 2‐amino‐3‐arylindoles. Furthermore, pyrimido[1,2‐a]indoles and 7,8dihydrobenzo[6,7][1,3]diazepino[4,5‐b]indoles were synthesized through the use of functionalized alcohols.
Humic Acids: A Material from Renewable Sources with the Potential for Making Supercapacitors
Authors: Vitale Paula , Bavio Marcela Alejandra
Published: March 2024

This paper examines the electrochemical performance of humic acids extracted from natural water and fertile soil, like electrode materials for supercapacitors, as proposed and evaluated. Humic acids come from the decomposition of organic matter in the humus formation process, therefore they are considered renewable resources. The humic acids are characterized by Fourier transform infrared spectroscopy, UV–vis spectroscopy, optical microscopy, and scanning electron microscopy with energy‐dispersive X‐ray spectroscopy. Electrochemical techniques are used to evaluate the behavior of humic acids like electrode materials for supercapacitors. Cyclic voltamperometry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy are performed in H2SO4 0.5 mol L−1. The highest capacitance, energy, and power values are found with humic acids from the soil. Thus, the specific capacitance of 87.15 F g−1 at 0.040 A g−1, maximum power of 32680 W kg−1, and energy of 60.52 W h kg−1 are obtained. The humic acids from soil have good cycling stability and high energy efficiency, placing them as promising materials in energy storage.
GrafeoPlad Palladium: Insight on Structure and Activity of a New Catalyst Series of Broad Scope
Authors: Formenti Matteo , Casaletto Maria Pia , Barone Giampaolo , Pagliaro Mario , Della Pina Cristina , Butera Valeria , Ciriminna Rosaria
Published: March 2024

GrafeoPlad‐Pd, a new metal‐organic alloy comprised of Pd nanoparticles doped with 3D‐entrapped graphene oxide, has promising applicative potential in sustainable synthetic organic chemistry. Besides hydrogenation, the metal nanopowder comprising the material is also active and relatively stable in cross‐coupling reactions carried out consecutively. X‐ray photoelectron spectroscopy (XPS) surface investigation and density functional theory (DFT) calculations are applied to gain new insight into the structure and potential new catalytic activity of this new class of molecularly doped metals.
Redox Engineering of Fe‐Rich Disordered Rock‐Salt Li‐Ion Cathode Materials
Authors: Fong Richie , Mubarak Nauman , Park Sang‐Wook , Lazaris Gregory , Liu Yiwei , Malik Rahul , Seo Dong‐Hwa , Lee Jinhyuk
Published: March 2024

The pursuit of high‐performance and cost‐effective Li‐ion batteries emphasizes the need for cathode materials composed of abundant elements, such as Fe. Disordered rock‐salt (DRX) cathode materials, known for their high compositional flexibility, offer a unique opportunity in this regard. However, Fe‐rich DRX (Fe‐DRX) cathodes, potentially the most cost‐effective among all DRXs, have seen limited research interest due to their comparatively restrained performance. This limitation stems from the inaccessibility of the Fe3+/Fe4+ redox in the DRX structure, prompting the need for redox engineering to enable Fe‐DRXs with readily utilizable redox mechanisms. In this work, utilizing both experiments and theoretical study, reversible Fe2+/Fe3+ redox in an Fe2+‐based DRX cathode is demonstrated. This design minimizes the reliance on O redox, resulting in a high capacity (≈290 mAh g−1) and energy density (≈700 Wh kg−1), as opposed to an Fe3+‐based DRX operating on the limited Fe3+/Fe4+ redox and extensive O redox upon cycling. Overall, the study introduces a novel approach to redox engineering to develop low‐cost, high‐performing Fe‐rich cathode materials.
Ramadan fasting in the third trimester of pregnancy and postpartum colostrum cortisol concentrations in Morocco
Authors: Guilfoyle Meagan M.
Published: March 2024

Breast milk cortisol concentration varies among and within lactating women, but the causes and consequences of variation are not yet fully understood. This study investigated whether maternal fasting from food and water for over 16 h per day during the third trimester of pregnancy was associated with increased concentrations of cortisol in colostrum during the month of Ramadan in a Moroccan sample. Participants were women who gave birth at the public maternity hospital in Rabat, Morocco throughout the month of and month following Ramadan. Participants completed interviews (N = 92), underwent anthropometric assessment (N = 73), and colostrum samples (N = 63) were collected approximately 48–72 h postpartum. Cortisol analysis was completed on a subset of colostrum samples (N = 43). Women were categorized as fasting every day of Ramadan before giving birth (N = 52/92, 57%), fasting some days (N = 29/92, 32%), and not fasting (N = 11/92, 11%). For women who fasted, average fasting duration was 19.5 days (range: 1–29 days), and average time between the last day of fasting and birth was 8.8 days (range: 0–43 days). The number of days of fasting was positively associated with cortisol concentrations in colostrum (p < .009) in a multivariate analysis controlling for maternal anthropometry, hypertension and/or diabetes, and reasons for opting out of fasting. Each day of fasting was associated with a 4.05% increase in colostrum cortisol. Results are consistent with the hypothesis that maternal fasting during the third trimester of pregnancy increases breast milk cortisol and thus alters the hormonal milieu to which the infant is exposed.
Delineating cognitive resilience using fractal regulation: Cross‐sectional and longitudinal evidence from the Rush Memory and Aging Project
Authors: Li Peng , Gao Chenlu , Yu Lei , Gao Lei , Cai Ruixue , Bennett David A. , Schneider Julie A. , Buchman Aron S. , Hu Kun
Published: March 2024

INTRODUCTION

Degradation of fractal patterns in actigraphy independently predicts dementia risk. Such observations motivated the study to understand the role of fractal regulation in the context of neuropathologies.

METHODS

We examined associations of fractal regulation with neuropathologies and longitudinal cognitive changes in 533 older participants who were followed annually with actigraphy and cognitive assessments until death with brain autopsy performed. Two measures for fractal patterns were extracted from actigraphy, namely, α1 (representing the fractal regulation at time scales of <90 min) and α2 (for time scales 2 to 10 h).

RESULTS

We found that larger α1 was associated with lower burdens of Lewy body disease or cerebrovascular disease pathologies; both α1 and α2 were associated with cognitive decline. They explained an additional significant portion of the variance in the rate of cognitive decline above and beyond neuropathologies.

DISCUSSION

Fractal patterns may be used as a biomarker for cognitive resilience against dementia‐related neuropathologies.
Wrist‐worn actigraphy in agitated late‐stage dementia patients: A feasibility study on digital inclusion
Authors: Guu Ta‐Wei , Brem Anna‐Katharine , Albertyn Christopher P. , Kandangwa Pooja , Aarsland Dag , ffytche Dominic
Published: March 2024

BACKGROUND

Wrist‐worn actigraphy can be an objective tool to assess sleep and other behavioral and psychological symptoms in dementia (BPSD). We investigated the feasibility of using wearable actigraphy in agitated late‐stage dementia patients.

METHODS

Agitated, late‐stage Alzheimer's dementia care home residents in Greater London area (n = 29; 14 females, mean age ± SD: 80.8 ± 8.2; 93.1% White) were recruited to wear an actigraphy watch for 4 weeks. Wearing time was extracted to evaluate compliance, and factors influencing compliance were explored.

RESULTS

A high watch‐acceptance (96.6%) and compliance rate (88.0%) was noted. Non‐compliance was not associated with age or BPSD symptomatology. However, participants with “better” cognitive function (R = 0.42, p = 0.022) and during nightshift (F1.240, 33.475 = 8.075, p = 0.005) were less compliant. Female participants were also marginally less compliant (F1, 26 = 3.790, p = 0.062).

DISCUSSIONS

Wrist‐worn actigraphy appears acceptable and feasible in late‐stage agitated dementia patients. Accommodating the needs of both the patients and their carers may further improve compliance.
Stereodivergent, Kinetically Controlled Isomerization of Terminal Alkenes via Nickel Catalysis
Authors: Rubel Camille Z. , Ravn Anne K. , Ho Hang Chi , Yang Shenghua , Li Zi‐Qi , Engle Keary M. , Vantourout Julien C.
Published: March 2024

Because internal alkenes are more challenging synthetic targets than terminal alkenes, metal‐catalyzed olefin mono‐transposition (i.e., positional isomerization) approaches have emerged to afford valuable E‐ or Z‐ internal alkenes from their complementary terminal alkene feedstocks. However, the applicability of these methods has been hampered by lack of generality, commercial availability of precatalysts, and scalability. Here, we report a nickel‐catalyzed platform for the stereodivergent E/Z‐selective synthesis of internal alkenes at room temperature. Commercial reagents enable this one‐carbon transposition of terminal alkenes to valuable E‐ or Z‐internal alkenes via a Ni−H‐mediated insertion/elimination mechanism. Though the mechanistic regime is the same in both systems, the underlying pathways that lead to each of the active catalysts are distinct, with the Z‐selective catalyst forming from comproportionation of an oxidative addition complex followed by oxidative addition with substrate and the E‐selective catalyst forming from protonation of the metal by the trialkylphosphonium salt additive. In each case, ligand sterics and denticity control stereochemistry and prevent over‐isomerization.
Light‐Regulated Nucleation for Growing Highly Uniform Single‐Crystalline Microrods
Authors: Sun Lishan , Gong Yanjun , Che Yanxue , Ji Hongwei , Liu Bing , Che Yanke , Zhao Jincai
Published: March 2024

We report a light‐irradiation method to control the synchronous nucleation of a donor‐acceptor (D‐A) fluorophore for growing highly uniform single‐crystalline microrods, which is in sharp contrast to the prevailing methods of restricting spontaneous nucleation and additionally adding seeds. The D‐A fluorophore was observed to undergo photoinduced electron transfer to CrCl3, leading to the generation of HCl and the subsequent protonation of the D‐A fluorophore. By intensifying photoirradiation or prolonging its duration, the concentration of protonated D‐A fluorophores can be rapidly increased to a high supersaturation level. This results in the formation of a controlled number of nuclei in a synchronous manner, which in turn kickstart the epitaxial growth of protonated D‐A fluorophores towards uniform single‐crystalline microrods of controlled sizes. The light‐regulated synchronous nucleation and uniform growth of microrods are a unique phenomenon that can only be achieved by specific Lewis acids, making it a novel probing method for sensitively detecting strong Lewis acids such as chromium chloride.
Reticular Modulation of Piezofluorochromic Behaviors in Organic Molecular Cages by Replacing Non‐Luminous Components
Authors: Li Yang , Wang Kai , Feng Rui , Wang Jingtian , Xi Xiao‐Juan , Lang Feifan , Li Quanwen , Li Wei , Zou Bo , Pang Jiandong , Bu Xian‐He
Published: March 2024

Organic piezochromic materials that manifest pressure‐stimuli‐responses are important in various fields such as data storage and anticounterfeiting. The manipulation of piezofluorochromic behaviors for these materials is promising but remains a great challenge. Herein, a non‐luminous components regulated strategy is developed and organic molecular cages (OMCs), a burgeoning class of crystalline organic materials with structural dynamics, are first explored for the design of piezofluorochromic materials with tunable luminescence. A series of OMCs based on aggregation‐induced emission (AIE) chromophores, termed Cage 1–3, are synthesized and their piezofluorochromic behaviors are investigated by diamond anvil cell technique. Due to the sufficient voids between its flexible chromophores offered by the OMC structure, Cage 1 exhibits thermofluorochromic and piezofluorochromic properties. Moreover, the piezofluorochromic performance of this OMC could be further promoted by replacing its non‐luminous components with improved flexibilities, and a remarkable luminescence peak shift by 150 nm together with a response sensitivity of 13.8 nm GPa−1 was achieved upon hydrostatic compression. The cage structure plays a vital role in facilitating efficient and reversible piezofluorochromic behaviors. This study has shed light on the rational design and exploitation of OMCs as an exceptional platform to accomplish customizable piezofluorochromic behaviors and enlarge their potential applications in pressure‐based luminescence.
Dual Enhancement of Phosphorescence and Circularly Polarized Luminescence through Entropically Driven Self‐Assembly of a Platinum(II) Complex
Authors: Wang Yanqing , Li Na , Chu Liangwen , Hao Zelin , Chen Junyu , Huang Jiang , Yan Junlin , Bian Hongtao , Duan Pengfei , Liu Jing , Fang Yu
Published: March 2024

Addressing the dual enhancement of circular polarization (glum) and luminescence quantum yield (QY) in circularly polarized luminescence (CPL) systems poses a significant challenge. In this study, we present an innovative strategy utilizing the entropically driven self‐assembly of amphiphilic phosphorescent platinum(II) complexes (L−Pt) with tetraethylene glycol chains, resulting in unique temperature dependencies. The entropically driven self‐assembly of L−Pt leads to a synergistic improvement in phosphorescence emission efficiency (QY was amplified from 15 % at 25 °C to 53 % at 60 °C) and chirality, both in the ground state and the excited state (glum value has been magnified from 0.04×10−2 to 0.06) with increasing temperature. Notably, we observed reversible modulation of phosphorescence and chirality observed over at least 10 cycles through successive heating and cooling, highlighting the intelligent control of luminescence and chiroptical properties by regulating intermolecular interactions among neighboring L−Pt molecules. Importantly, the QY and glum of the L−Pt assembly in solid state were measured as 69 % and 0.16 respectively, representing relatively high values compared to most self‐assembled CPL systems. This study marks the pioneering demonstration of dual thermo‐enhancement of phosphorescence and CPL and provides valuable insights into the thermal effects on high‐temperature and switchable CPL materials.
Robust Covalent Organic Framework Photocatalysts for H2O2 Production: Linkage Position Matters
Authors: Yang Tao , Zhang De , Kong Aiguo , Zou Yingying , Yuan Ling , Liu Chao , Luo Sijia , Wei Guangfeng , Yu Chengzhong
Published: March 2024

Covalent organic frameworks (COFs) are promising photocatalysts for hydrogen peroxide (H2O2) synthesis. However, the nature of organic polymers makes the balance between high activity and stability challenging. We demonstrate that the linkage position matters in the design of robust COF photocatalysts with durable high activity without sacrificial reagents. COFs with ortho‐ and para‐linkages (o‐COFs and p‐COFs) were constructed by 1,3,5‐triformylphloroglucinol with benzene‐, pyridine‐, pyrazine‐orthodiamines and paradiamines. The pyrzaine‐containing o‐COFs with two pyridinic nitrogen atoms exhibited a H2O2 production rate of 4396 μmol g−1 h−1 together with long‐time continuous H2O2 photosynthesis performance in pure water (48 h), superior to the corresponding p‐COFs. A four‐step reaction mechanism is proposed by density function calculations. Moreover, the active sites and origin of stability enhancement for o‐COFs are clarified. This work provides a simple and effective molecular design strategy in the design of robust COF photocatalysts for artificial H2O2 photosynthesis.
Near‐Infrared Light Activated Formulation for the Spatially Controlled Release of CRISPR‐Cas9 Ribonucleoprotein for Brain Gene Editing
Authors: Simões Susana , Lino Miguel , Barrera Angela , Rebelo Catarina , Tomatis Francesca , Vilaça Andreia , Breunig Christopher , Neuner Andrea , Peça João , González Ricardo , Carvalho Alexandra , Stricker Stefan , Ferreira Lino
Published: March 2024

The CRISPR/Cas9 system has emerged as a promising platform for gene editing; however, the lack of an efficient and safe delivery system to introduce it into cells continues to hinder clinical translation. Here, we report a rationally designed gene‐editing nanoparticle (NP) formulation for brain applications: an sgRNA:Cas9 ribonucleoprotein complex is immobilized on the NP surface by oligonucleotides that are complementary to the sgRNA. Irradiation of the formulation with a near‐infrared (NIR) laser generates heat in the NP, leading to the release of the ribonucleoprotein complex. The gene‐editing potential of the formulation was demonstrated in vitro at the single‐cell level. The safety and gene editing of the formulation were also demonstrated in the brains of reporter mice, specifically in the subventricular zone after intracerebral administration and in the olfactory bulb after intranasal administration. The formulation presented here offers a new strategy for the spatially controlled delivery of the CRISPR system to the brain.
Entropy‐Driven Direct Air Electrofixation
Authors: Sun Yuntong , Li Ming , Duan Jingjing , Antonietti Markus , Chen Sheng
Published: March 2024

According to the principles of chemical thermodynamics, the catalytic activation of small molecules (like N2 in air and CO2 in flue gas) generally exhibits a negative activity dependence on O2 owning to the competitive oxygen reduction reaction (ORR). Nevertheless, some catalysts can show positive activity dependence for N2 electrofixation, an important route to produce ammonia under ambient condition. Here we report that the positive activity dependence on O2 of (Ni0.20Co0.20Fe0.20Mn0.19Mo0.21)3S4 catalyst arises from high‐entropy mechanism. Through experimental and theoretical studies, we demonstrate that under the reaction condition in the mixed N2/O2, the adsorption of O2 on high‐entropy catalyst contributes to activating N2 molecules characteristic of elongated N≡N bond lengths. As comparison to the low‐ and medium‐entropy counterparts, high entropy can play the second role of attenuating competitive ORR by displaying a negative exponential entropy‐ORR activity relationship. Accordingly, benefiting from the O2, the system for direct air electrofixation has demonstrated an ammonia yield rate of 47.70 μg h−1 cm−2, which is even 1.5 times of pure N2 feedstock (31.92 μg h−1 cm−2), overtaking all previous reports for this reaction. We expect the present finding providing an additional dimension to high entropy that leverages systems beyond the constraint of traditional rules.
Photocatalytic Functionalization of Dehydroalanine‐Derived Peptides in Batch and Flow
Authors: Kaplaneris Nikolaos , Akdeniz Merve , Fillols Méritxell , Arrighi Francesca , Raymenants Fabian , Sanil Gana , Gryko Daniel T. , Noël Timothy
Published: March 2024

Unnatural amino acids, and their synthesis by the late‐stage functionalization (LSF) of peptides, play a crucial role in areas such as drug design and discovery. Historically, the LSF of biomolecules has predominantly utilized traditional synthetic methodologies that exploit nucleophilic residues, such as cysteine, lysine or tyrosine. Herein, we present a photocatalytic hydroarylation process targeting the electrophilic residue dehydroalanine (Dha). This residue possesses an α,β‐unsaturated moiety and can be combined with various arylthianthrenium salts, both in batch and flow reactors. Notably, the flow setup proved instrumental for efficient scale‐up, paving the way for the synthesis of unnatural amino acids and peptides in substantial quantities. Our photocatalytic approach, being inherently mild, permits the diversification of peptides even when they contain sensitive functional groups. The readily available arylthianthrenium salts facilitate the seamless integration of Dha‐containing peptides with a wide range of arenes, drug blueprints, and natural products, culminating in the creation of unconventional phenylalanine derivatives. The synergistic effect of the high functional group tolerance and the modular characteristic of the aryl electrophile enables efficient peptide conjugation and ligation in both batch and flow conditions.
K2CO3 on porous supports for moisture‐swing CO2 capture from ambient air
Authors: Zheng Shiqiang , Cheng Xinyue , Zhou Wenjia , Wang Tong , Zhu Liangliang , Xiao Hang , Chen Xi
Published: March 2024

Direct air capture (DAC) of CO2 is an important technology to mitigate mobile carbon emissions, reduce atmospheric CO2 concentration, and cope with climate change. Moisture‐swing adsorption is regarded as one of the most promising technologies in DAC due to its low energy consumption and ease of operation. In this work, a cheap and easily available moisture‐swing adsorbent of potassium carbonate loaded on porous supports (i.e., activated carbon, magnesium oxide, and zeolite) was prepared for CO2 capture from ambient air. The composite adsorbent of potassium carbonate on activated carbon showed the best performance with a DAC capacity of 0.562 mmol/g at 25°C and 5% relative humidity. The effects of temperature, relative humidity, and CO2 concentration on the adsorption performance were investigated systematically, as well as the cyclic DAC performance. In 50 adsorption–desorption cycles, the adsorption capacity of the composite adsorbent decreased by ~40% due to potassium carbonate leaching loss during water evaporation but can be fully recovered simply by re‐impregnating with potassium carbonate again.
Sulfonamide‐incorporated bis(α‐aminophosphonates) as promising carbonic anhydrase inhibitors: Design, synthesis, biological evaluation, and X‐ray crystallographic studies
Authors: Sobati Marjan , Abdoli Morteza , Angeli Andrea , Bonardi Alessandro , Ferraroni Marta , Supuran Claudiu T. , Žalubovskis Raivis
Published: March 2024

A novel series of sulfonamide‐incorporated bis(α‐aminophosphonates) acting as effective carbonic anhydrase (CA, EC 4.2.1.1) inhibitors is reported. The synthesized bivalent ligands were tested against five human (h) isoforms, hCA I, hCA II, hCA VII, hCA IX, and hCA XIII. Such derivatives showed high activity and selectivity against the cancer‐related, membrane‐bound isoform hCA IX, and among them, compound 5h, tetraisopropyl (1,3‐phenylenebis{[(4‐sulfamoylphenyl)amino]methylene})bis(phosphonate) showed a KI of 15.1 nM, being highly selective against this isoform over all other investigated ones (hCA I/IX = 42; hCA II/IX = 6, hCA VII/IX = 3, hCA XIII/IX = 5). Therefore, compound 5h could be a potential lead for the development of selective anticancer agents. The newly developed sulfonamides were also found effective inhibitors against the cytosolic hCA XIII isoform. Compound 5i displayed the best inhibition against this isoform with a KI of 17.2 nM, equal to that of the well‐known inhibitor acetazolamide (AAZ), but significantly more selective over all other tested isoforms (hCA I/XIII = 239; hCA II/XIII = 23, hCA VII/XIII = 2, hCA IX/XIII = 3) compared to AAZ.
Revisiting Stereoselective Propene Polymerization Mechanisms: Insights through the Activation Strain Model
Authors: Romano Eugenio , Barone Vincenzo , Budzelaar Peter H. M. , De Rosa Claudio , Talarico Giovanni
Published: March 2024

The stereoelectronic factors responsible for stereoselectivity in propene polymerization with several metallocene and post–metallocene transition metal catalysts have been revisited using a combined approach of DFT calculations, the Activation Strain Model, Natural Energy Decomposition Analysis and a molecular descriptor (%VBur). There are in most cases two different paths leading to the formation of stereoerrors (SE), and the classical model does not suffice to fully understand stereoregulation. Improving stereoselectivity requires raising the energies of both SE insertion transition states. Our analyses show that the degrees of deformation of the active site (catalyst+chain) and the prochiral monomer differ for these two paths, and between different catalyst classes. Based on such analyses we discuss: a) the subtle differences in SE formation between stereoselective catalysts with different ligand frameworks; b) the reason for exceptional stereoselectivity reported for a special ansa–metallocene catalyst; c) the (double) stereocontrol origin for isoselective catalysts; d) the electronic contribution for isoselective catalysts generating SE by a modification of the ligand wrapping mode during the polymerization. Although this study will not immediately suggest new catalyst structures, we believe that understanding stereoregulation in great detail will increase our chances of success.