bluuebunny/crossref_metadata_2025 huggingface dataset:
Antibacterial Activity of Calycophyllum spruceanum Leaf Extract against Enterococcus faecalis Strains “In vitro” for Endodontic Purposes
Authors: Silva Brena Barros Mendonça da , Silva Bruna Barros Mendonça da , Souza Giovana Pereira de , Arruda Eder Ferreira de , Muniz Ana Bessa , Carvalho Clarice Maia , Rodrigues Rodrigo Asfury
Published: March 2023

Aims: The indiscriminate use of antimicrobials contributed to the selection of multiresistant bacterial strains, mainly Enterococcus faecalis, leading to the search for new strategies for these infections, requiring the identification of new bioactive compounds from medicinal plants, an example is C. spruceanum used in traditional communities in the Amazon.

In this sense, this study aimed to evaluate the antibacterial activity of C. spruceanum leaf extract against E. faecalis "in vitro" for endodontic purposes.

Place and Duration of Study: Sample: the study was carried out at the microbiology laboratory of the Federal University of Acre (UFAC), in the city of Rio Branco, state of Acre, Brazil, from July 2021 to January 2022.

Methodology: For this study, 50mg/mL of the crude extract of C. spruceanum leaf was diluted in Dimethylsulfoxide, as well as 50mg/mL of the extract with 1000mg of calcium hydroxide and 1000mg of calcium hydroxide in 1mL of distilled water. After preparing the extracts, 20µL were deposited in the wells made on Müeler-Hinton agar medium seeded with E. faecalis, incubated for 24 hours at 37°C. After this period, the positive activity of the extracts was obtained from the formation of the inhibition halo in millimeters.

Results: The best results were for extract associated with calcium hydroxide (20mm), followed by calcium hydroxide solution (17.67mm) and with lower activity, C. spruceanum extract (14.33mm). The best results of the Minimum Inhibitory Concentration with values ​​of 6.25 mg/mL for the extract combined with calcium hydroxide and Minimum Bactericidal Concentration that was 25mg/mL for the association of the extract with calcium hydroxide.

Conclusion: The C. spruceanum extract has antibacterial activity against E. faecalis and its association with calcium hydroxide potentiated its effect.
Duration of Antibiotics in Community Acquired Pneumonia, Physicians Fancy?
Authors: Jayakrishnan B. , Al-Rahbi Sulaiman , Al-Mubaihsi Saif , Balkhair Abdullah
Published: March 2023

In spite of guidelines on the use of antibiotics in Community acquired pneumonia (CAP), very often the antibiotics are prescribed for longer than necessary. Of the 37 in-patients with CAP over a 25-month period,12 had reasons for a longer antibiotic course. In the remaining 25, ten received antibiotics for ≤ 7 and 15 for more than 7 days. Respiratory rate (23.53± 4.32; p=0.039) and albumin levels (37.73±5.27; p=0.001) were higher in patients who received the longer course. Extent of opacities (p=0.690); single lobe 9 (60%). > 1 lobe unilateral 1 (100%) and bilateral 5 (55.6%) or the pattern; lobar 10(83.3%), segmental 1(20%) or interstitial 4 (50%); > 65 years 7 (53.8%); male 9 (60%), prior antibiotics 4 (57.1%), co-morbidities 11 (61.1%), Diabetes 8 (57.1%), aspiration risk 3 (42.9%) or higher CURB score 7(63.3%) did not influence the prescription. We find that physicians use their instinct rather than scientific backing in this decision. Often antibiotics are continued on discharge possibly due to a feeling of protection.
Former NIH Director Francis S. Collins on the New White House Plan to Eliminate Hepatitis C
Authors: Abbasi Jennifer
Published: March 2023

This Medical News article is an interview with Francis S. Collins, MD, PhD, former National Institutes of Health director, and JAMA Editor in Chief Kirsten Bibbins-Domingo, PhD, MD, MAS, about a historic Biden-Harris administration proposal to cure and prevent all hepatitis C infections in the US.
Comparison of Incremental Costs and Medicare Reimbursement for Simple vs Complex Cataract Surgery Using Time-Driven Activity-Based Costing
Authors: Portney David S. , Berkowitz Sean T. , Garner Desmond C. , Qalieh Adel , Tiwari Vikram , Friedman Scott , Patel Shriji , Parikh Ravi , Mian Shahzad I.
Published: March 2023

Importance

Cataract surgery is one of the most commonly performed surgeries across medicine and an integral part of ophthalmologic care. Complex cataract surgery requires more time and resources than simple cataract surgery, yet it remains unclear whether the incremental reimbursement for complex cataract surgery, compared with simple cataract surgery, offsets the increased costs.

Objective

To measure the difference in day-of-surgery costs and net earnings between simple and complex cataract surgery.

Design, Setting, and Participants

This study is an economic analysis at a single academic institution using time-driven activity-based costing methodology to determine the operative-day costs of simple and complex cataract surgery. Process flow mapping was used to define the operative episode limited to the day of surgery. Simple and complex cataract surgery cases (Current Procedural Terminology codes 66984 and 66982, respectively) at the University of Michigan Kellogg Eye Center from 2017 to 2021 were included in the analysis. Time estimates were obtained using an internal anesthesia record system. Financial estimates were obtained using a mix of internal sources and prior literature. Supply costs were obtained from the electronic health record.

Main Outcomes and Measures

Difference in day-of-surgery costs and net earnings.

Results

A total of 16 092 cataract surgeries were included, 13 904 simple and 2188 complex. Time-based day-of-surgery costs for simple and complex cataract surgery were $1486.24 and $2205.83, respectively, with a mean difference of $719.59 (95% CI, $684.09-$755.09; P < .001). Complex cataract surgery required $158.26 more for costs of supplies and materials (95% CI, $117.00-$199.60; P < .001). The total difference in day-of-surgery costs between complex and simple cataract surgery was $877.85. Incremental reimbursement for complex cataract surgery was $231.01; therefore, complex cataract surgery had a negative earnings difference of $646.84 compared with simple cataract surgery.

Conclusions and Relevance

This economic analysis suggests that the incremental reimbursement for complex cataract surgery undervalues the resource costs required for the procedure, failing to cover increased costs and accounting for less than 2 minutes of increased operating time. These findings may affect ophthalmologist practice patterns and access to care for certain patients, which may ultimately justify increasing cataract surgery reimbursement.
Comparative evaluation of PD‐L1 expression in cytology imprints, circulating tumour cells and tumour tissue in non‐small cell lung cancer patients
Authors: Abdo Mustafa , Belloum Yassine , Heigener David , Welker Lutz , von Weihe Sönke , Schmidt Milena , Heuer‐Olewinski Nadine , Watermann Iris , Szewczyk Marlen , Kropidlowski Jolanthe , Pereira‐Veiga Thais , Elmas Hatice , Perner Sven , Steurer Stefan , Wikman Harriet , Pantel Klaus , Reck Martin
Published: March 2023

Alternative sources of tumour information need to be explored in patients with non‐small cell lung cancer (NSCLC). Here, we compared programmed cell death ligand 1 (PD‐L1) expression on cytology imprints and circulating tumour cells (CTCs) with PD‐L1 tumour proportion score (TPS) from immunohistochemistry staining of tumour tissue from patients with NSCLC. We evaluated PD‐L1 expression using a PD‐L1 antibody (28‐8) in representative cytology imprints, and tissue samples from the same tumour. We report good agreement rates on PD‐L1 positivity (TPS ≥ 1%) and high PD‐L1 expression (TPS ≥ 50%). Considering high PD‐L1 expression, cytology imprints showed a PPV of 64% and a NPV of 85%. CTCs were detected in 40% of the patients and 80% of them were PD‐L1+. Seven patients with PD‐L1 expression of < 1% in tissue samples or cytology imprints had PD‐L1+ CTCs. The addition of PD‐L1 expression in CTCs to cytology imprints markedly improved the prediction capacity for PD‐L1 positivity. A combined analysis of cytological imprints and CTCs provides information on the tumoural PD‐L1 status in NSCLC patients, which might be used when no tumor tissue is available.
Exploring the effect of ADHD traits on the moment‐to‐moment interplay between provocation and aggression: Evidence from dynamic structural equation modeling
Authors: Brown Ruth H. , Speyer Lydia G. , Eisner Manuel P. , Ribeaud Denis , Murray Aja
Published: March 2023

The relation between attention deficit hyperactivity disorder (ADHD) symptoms and aggression is well documented; however, the processes that account for higher levels of aggression associated with ADHD in the course of daily life are little understood. The current study used ecological momentary assessment to explore how ADHD traits relate to individual differences in perceiving provocation from others and the resultant aggressive behaviors; and the strengths of the links between provocation and aggression in the flow of daily life. A dynamic structural equation model was fit using data from a subpopulation of young adults involved in the longitudinal z‐proso study (n = 259, median‐age 20). Data on provocation and aggression was collected at four quasi‐random time periods per day over a 14‐day period. Individuals with higher ADHD trait levels reported higher instances of provocation and aggression, with ADHD traits significantly moderating aggression inertia such that those with higher levels of ADHD traits showed greater persistence of aggressive behavior over time. However, ADHD trait levels did not significantly moderate any of the observed cross‐lagged effects. Our findings suggest that individuals with higher levels of ADHD traits are at greater risk of exposure to interpersonal interactions involving interpersonal provocation, show higher levels of aggressive behavior in daily life, and find it more difficult to reduce their aggression once triggered. These findings support the importance of targeting factors such as social skills and emotion regulation that may underpin the increased difficulties in interpersonal interactions often experienced by individuals with high levels of ADHD symptoms.
Toward Stable Cycling of a Cost‐Effective Cation‐Disordered Rocksalt Cathode via Fluorination
Authors: Qian Ji , Ha Yang , Koirala Krishna Prasad , Huang Di , Huang Zhi , Battaglia Vincent S. , Wang Chongmin , Yang Wanli , Tong Wei
Published: March 2023

The recently developed Li‐excess cation‐disordered rock salts (DRXs) exhibit an excellent chemical diversity for the development of alternative Co/Ni‐free high‐energy cathodes. Herein, the synthesis of a highly fluorinated DRX cathode, Li1.2Mn0.6Ti0.2O1.8F0.2, based on cost‐effective and earth‐abundant transition metals, via a solid‐state reaction, is reported. The fluorinated DRX cathode using ammonium fluoride precursor exhibits more uniform particle size and delivers a specific discharge capacity of 233 mAh g−1 and specific energy of 754 Wh kg−1, with 206 mAh g−1 retained after 200 cycles. The combined synchrotron X‐ray absorption spectroscopy and resonant inelastic X‐ray scattering spectroscopy analysis reveals that the remarkable cycling performance is attributed to the high fluorination and thus enhanced Mn content, enabling the utilization of more Mn redox than the oxide analog. This study demonstrates a great promise to develop next‐generation cost‐effective DRX cathodes with enhanced capacity retention for high‐energy Li‐ion batteries.
Tuned Intra‐ and Intermolecular Photoreactions of Tridentate Cyanostilbenes with Distinct Aggregated‐State Photomechanical and Dispersed‐State Photochromic Behaviors
Authors: Ding Yanglan , Guo Jing , He Xuan , Tao Wei , Shi Yadong , Xu Jiahui , Xu Lei , Tang Mingxing , Shen Dengke , Bi Hong , Wu Zong‐Quan , Yang Kun , Zeng Zebing , Wei Peifa
Published: March 2023

Developing a new strategy to realize on‐demand photoreactions with distinguishable signals is highly desirable. Herein, by simply tuning the molecular state, tuned photoreactions with different dynamic signals based on a series of tridentate cyanostilbene molecules (TCS1‐5) are realized. The results show that in the crystalline state, the ordered and densely molecular packing facilitates the successive intermolecular photocycloaddition between adjacent cyanostilbene molecules and causes accumulated stresses within the crystals, which further induces variable photo‐induced mechanical motions such as peeling, bending, twisting, and so on. In the monodispersed solution state, however, the larger distances between TCS1‐5 molecules afford a photo‐induced radical‐assisted intramolecular photocyclization process and give rise to multiple domino photochromic and photofluorochromic behaviors. Based on their distinct yet controllable thermostability and radical colors, photochromic films are fabricated from TCS1@PMMA and TCS1/TFA@PMMA for Morse code and rewritable photopatterning applications, showing excellent photochromism. By coating TCS3 on a piece of plastic bag, the macroscopic mechanical motion is achieved by amplifying the collective molecular motion from the nanoscale up to the macroscopic dimension. The molecular state‐based strategy reveals the regularity between photoreactions and molecular packing and further provides an opportunity to rapidly access controllable photoresponsive systems.
Pathophysiological Reconstruction of a Tissue‐Specific Multiple‐Organ On‐A‐Chip for Type 2 Diabetes Emulation using 3D Cell Printing
Authors: Kim Joeng Ju , Park Ju Young , Nguyen Vy Vuong‐Tuong , Bae Mihyeon , Kim Myungji , Jang Jinah , Won Jae Yon , Cho Dong‐Woo
Published: March 2023

Type 2 diabetes mellitus (T2D), a chronic complex disease with high prevalence, causes severe damage to various organs. T2D has many etiologies that have not been fully elucidated. Although various models have been created to understand T2D, reconstructing the tissue‐specific microenvironment and complications of T2D remain difficult. Therefore, a dynamic multiple‐organ on‐a‐chip that mimics T2D in a hyperglycemic environment and visceral adipose tissue (vAT) using 3D cell printing with decellularized extracellular matrix (dECM) bioinks is developed. This chip composed of separate compartments for the pancreas, adipose tissue, and liver, closely related to T2D, and a retinal compartment is added to confirm T2D complications. Furthermore, the pathological features of T2D are clearly revealed in the chip with vAT‐derived dECM bioink in a hyperglycemic environment. These pathological features caused cellular dysfunctions of the retinal compartment. Moreover, treated T2D medications on the chip showed clinically identical efficacy. The chip is suitable for recapitulating the key features of T2D and is a promising platform for drug testing and T2D complication research.
Solar‐Driven Interfacial Evaporation Accelerated Electrocatalytic Water Splitting on 2D Perovskite Oxide/MXene Heterostructure
Authors: Lu Yi , Zhang Hao , Wang Yida , Zhu Xiaorong , Xiao Weiping , Xu Haolan , Li Gaoran , Li Yafei , Fan Deqi , Zeng Haibo , Chen Zupeng , Yang Xiaofei
Published: March 2023

The rational design of economic and high‐performance electrocatalytic water‐splitting systems is of great significance for energy and environmental sustainability. Developing a sustainable energy conversion‐assisted electrocatalytic process provides a promising novel approach to effectively boost its performance. Herein, a self‐sustained water‐splitting system originated from the heterostructure of perovskite oxide with 2D Ti3C2Tx MXene on Ni foam (La1‐xSrxCoO3/Ti3C2Tx MXene/Ni) that shows high activity for solar‐powered water evaporation and simultaneous electrocatalytic water splitting is presented. The all‐in‐one interfacial electrocatalyst exhibits highly improved oxygen evolution reaction (OER) performance with a low overpotential of 279 mV at 10 mA cm−2 and a small Tafel slope of 74.3 mV dec−1, superior to previously reported perovskite oxide‐based electrocatalysts. Density functional theory calculations reveal that the integration of La0.9Sr0.1CoO3 with Ti3C2Tx MXene can lower the energy barrier for the electron transfer and decrease the OER overpotential, while COMSOL simulations unveil that interfacial solar evaporation could induce OH− enrichment near the catalyst surfaces and enhance the convection flow above the catalysts to remove the generated gas, remarkably accelerating the kinetics of electrocatalytic water splitting.
An Ultra‐Sensitive Fluorescent Probe Based on Hybridized Local and Charge‐Transfer Materials for Quantitative Detection of Propanol Isomers
Authors: Zhou Changjiang , Liu Haichao , Chen Jianai , Zhang Shitong , Dong Yujie , Yang Bing , Li Weijun
Published: March 2023

Isopropanol has been widely applied in various fields as an important chemical solvent, which is produced by direct hydration of propylene accompanied with the byproduct of n‐propanol. Herein, an ultra‐sensitive fluorescent probe of TPA‐9AC, based on a non‐equivalent hybridized local and charge‐transfer (HLCT) material, is designed and synthesized to quantitatively detect the percentage of n‐propanol in propanol isomers. Owing to the stronger electron acceptor ability of n‐propanol, the excited state of probe transfers from highly emissive HLCT state to non‐emissive charge‐transfer state, resulting in the substantial fluorescence quenching. The low limit of detection (LOD) is achieved as sensitive as 0.02% v/v of n‐propanol in isopropanol. This contribution demonstrates a new approach to distinguish propanol isomers and an effective strategy for designing real‐time fluorescent sensors with high performances.
Influence of Geometrical Parameters on the Optical Activity of Chiral Gold Nanorods
Authors: Obelleiro‐Liz Manuel , Martín Víctor F. , Solís Diego M. , Taboada José M. , Obelleiro Fernando , Liz‐Marzán Luis M.
Published: March 2023

Chiral metal nanoparticles (NPs) offer a powerful means of inducing and harnessing optical activity. However, due to the incomplete knowledge of the underlying growth mechanisms, there is still limited control over the achievable morphological detail and, consequently, over the resulting optical activity. Therefore, theoretical modeling is needed to guide experimental development toward optimizing the plasmonic chiroptical response. Toward filling this gap, herein an extensive parametric analysis is presented, via computer‐aided‐design (CAD) models and full‐wave electrodynamic simulations, which aims at systematically analyzing the influence of structural changes on the plasmonic circular dichroism (CD) spectra of rod‐shaped gold NPs comprising helical indentations on achiral nanorod cores. From this analysis, interesting patterns in the plasmon‐mediated resonant behavior are identified and cause–effect relationships are drawn that may serve as a go‐to recipe for the understanding and fabrication of these NPs and their applications, such as spectroscopic (bio)detection including CD spectral shifts and surface‐enhanced Raman optical activity.
Immunomodulatory Microparticles Epigenetically Modulate T Cells and Systemically Ameliorate Autoimmune Arthritis
Authors: McBride David A. , Kerr Matthew D. , Johnson Wade T. , Nguyen Anders , Zoccheddu Martina , Yao Mina , Prideaux Edward B. , Dorn Nicholas C. , Wang Wei , Svensson Mattias N.D. , Bottini Nunzio , Shah Nisarg J.
Published: March 2023

Disease modifying antirheumatic drugs (DMARDs) have improved the prognosis of autoimmune inflammatory arthritides but a large fraction of patients display partial or nonresponsiveness to front‐line DMARDs. Here, an immunoregulatory approach based on sustained joint‐localized release of all‐trans retinoic acid (ATRA), which modulates local immune activation and enhances disease‐protective T cells and leads to systemic disease control is reported. ATRA imprints a unique chromatin landscape in T cells, which is associated with an enhancement in the differentiation of naïve T cells into anti‐inflammatory regulatory T cells (Treg) and suppression of Treg destabilization. Sustained release poly‐(lactic‐co‐glycolic) acid (PLGA)‐based biodegradable microparticles encapsulating ATRA (PLGA‐ATRA MP) are retained in arthritic mouse joints after intra‐articular (IA) injection. IA PLGA‐ATRA MP enhance migratory Treg which in turn reduce inflammation and modify disease in injected and uninjected joints, a phenotype that is also reproduced by IA injection of Treg. PLGA‐ATRA MP reduce proteoglycan loss and bone erosions in the SKG and collagen‐induced arthritis mouse models of autoimmune arthritis. Strikingly, systemic disease modulation by PLGA‐ATRA MP is not associated with generalized immune suppression. PLGA‐ATRA MP have the potential to be developed as a disease modifying agent for autoimmune arthritis.
Perspective and Prospects for Ordered Functional Materials
Authors: Zhang Hai‐Tian , Zhang Tao , Zhang Xiangyi
Published: March 2023

Many functional materials are approaching their performance limits due to inherent trade‐offs between essential physical properties. Such trade‐offs can be overcome by engineering a material that has an ordered arrangement of structural units, including constituent components/phases, grains, and domains. By rationally manipulating the ordering with abundant structural units at multiple length scales, the structural ordering opens up unprecedented opportunities to create transformative functional materials, as amplified properties or disruptive functionalities can be realized. In this perspective article, a brief overview of recent advances in the emerging ordered functional materials across catalytic, thermoelectric, and magnetic materials regarding the fabrication, structure, and property is presented. Then the possibility of applying this structural ordering strategy to highly efficient neuromorphic computing devices and durable battery materials is discussed. Finally, remaining scientific challenges are highlighted, and the prospects for ordered functional materials are made. This perspective aims to draw the attention of the scientific community to the emerging ordered functional materials and trigger intense studies on this topic.
Engineering of Grain Boundaries in CeO2 Enabling Tailorable Resistive Switching Properties
Authors: Dou Hongyi , Hellenbrand Markus , Xiao Ming , Hu Zedong , Kunwar Sundar , Chen Aiping , MacManus‐Driscoll Judith L. , Jia Quanxi , Wang Haiyan
Published: March 2023

Defect engineering in valence change memories aimed at tuning the concentration and transport of oxygen vacancies are studied extensively, however mostly focusing on contribution from individual extended defects such as single dislocations and grain boundaries. In this work, the impact of engineering large numbers of grain boundaries on resistive switching mechanisms and performances is investigated. Three different grain morphologies, that is, “random network,” “columnar scaffold,” and “island‐like,” are realized in CeO2 thin films. The devices with the three grain morphologies demonstrate vastly different resistive switching behaviors. The best overall resistive switching performance is shown in the devices with “columnar scaffold” morphology, where the vertical grain boundaries extending through the film facilitate the generation of oxygen vacancies as well as their migration under external bias. The observation of both interfacial and filamentary switching modes only in the devices with a “columnar scaffold” morphology further confirms the contribution from grain boundaries. In contrast, the “random network” or “island‐like” structures result in excessive or insufficient oxygen vacancy concentration migration paths. The research provides design guidelines for grain boundary engineering of oxide‐based resistive switching materials to tune the resistive switching performances for memory and neuromorphic computing applications.
Manipulation of the Ferromagnetism in LaCoO3 Thin Films Through Cation‐Stoichiometric Engineering
Authors: Huang Tongtong , Lyu Yingjie , Huyan Huaixun , Ni Jinyang , Saremi Sahar , Wang Yujia , Yan Xingxu , Yi Di , He Qing , Martin Lane W. , Xiang Hongjun , Pan Xiaoqing , Yu Pu
Published: March 2023

Spin‐state transitions are an important research topic in complex oxides with the diverse magnetic states involved. In particular, the low‐spin to high‐spin transition in LaCoO3 thin films has drawn a wide range of attention due to the emergent ferromagnetic state. Although various mechanisms (e.g., structural distortion, oxygen‐vacancy formation, spin‐state ordering) have been proposed, an understanding of what really underlies the emergent ferromagnetism remains elusive. Here, the ferromagnetism in LaCoO3 thin films is systematically modulated by varying the oxygen pressure during thin‐film growth. Although the samples show dramatic different magnetization, their cobalt valence state and perovskite crystalline structure remain almost unchanged, ruling out the scenarios of both oxygen‐vacancy and spin‐ordering. This work provides compelling evidence that the tetragonal distortion due to the tensile strain significantly modifies the orbital occupancy, leading to a low‐spin to high‐spin transition with emergent ferromagnetism, while samples grown at reduced pressure demonstrate a pronounced lattice expansion due to cation‐off‐stoichiometry, which suppresses the tetragonal distortion and the consequent magnetization. This result not only provides important insight for the understanding of exotic ferromagnetism in LaCoO3 thin films, but also identifies a promising strategy to design electronic states in complex oxides through cation‐stoichiometry engineering.
Ultrahigh‐Rate and Ultralong‐Duration Sodium Storage Enabled by Sodiation‐Driven Reconfiguration
Authors: Dong Yulian , Xu Changfan , Li Yueliang , Zhang Chenglin , Zhao Huaping , Kaiser Ute , Lei Yong
Published: March 2023

Despite their variable valence and favorable sodiation/desodiation potential, vanadium sulfides (VSx) used as anode materials of sodium‐ion batteries (SIBs) have been held back by their capacity decline and low cycling capability, associated with the structure distortion volume expansion and pulverization. This study reports an accessible process to tackle these challenges via fabricating a 3D‐VSx anode for SIBs with ultrahigh‐rate and ultralong‐duration stable sodium storage. The sodiation‐driven reactivation of micro‐nano 3D‐VSx activates the reconfiguration effect, effectively maintaining structural integrity. Interestingly, the mechanical degradation of 3D‐VSx over the sodiation process can be controlled by fine‐tuning the operating voltage. The self‐reconfigured open nanostructures with large void space not only effectively withstand repetitive volume changes and mitigate the damaging mechanical stresses, but also in turn construct a self‐optimized shortened ion diffusion pathway. Moreover, the sodiation‐driven reconfiguration excites many active sites and optimizes a stable solid‐electrolyte interface, thereby delivering a reversible capacity of 961.4 mA h g−1 after 1500 cycles at a high rate of 2 A g−1. This work provides new insight into the rational design of electrodes toward long‐lived SIBs through sodiation‐driven reconfiguration.
Efficient scarless skin regeneration enabled by loading micronized amnion in a bioinspired adhesive wound dressing
Authors: Zhang Huicong , Song Mingyu , Hu Changhong , Zhang Zhiyi , Zhang Shuqi , Zhang Yan , Yang Yingming , Zhou Puxu , Zheng Liwen , Li Lan , Mao Mengjie , Zhang Yu Shrike , Ji Ping , Zhang Ximu
Published: March 2023

Complete skin reconstruction is a hierarchical, physiological assembly process involving healing of the epidermis, dermis, vasculature, nerves, and cutaneous appendages. To date, few works have reported complete skin regeneration, particularly lacking vascular structures and hair follicles after full skin defects. In this study, a hydrogel derived from the skin secretion of Andrias davidianus (SSAD) that features adhesiveness was used as a bioactive scaffold to load micronized amnion (MA). The SSAD hydrogel was found to promote the migration and proliferation of amnion stem cells and human keratinocytes, as well as inhibit their apoptosis in vitro. In a rat full‐skin defect model, the regeneration of skin appendages was observed at the wound area, achieving scarless healing. Transcriptome analyses further validated that SSAD could positively regulate cell migration, proliferation, and differentiation. These functions might be attributed to the abundant growth factors present in the SSAD. Synergized by the delivery of MA, SSAD loaded with the MA could achieve a significantly better skin regeneration effect than SSAD or MA used alone, providing a simple yet highly effective means to obtain complete, scarless skin regeneration, suggesting favorable potential for clinical translation.
High‐Throughput Screening of Electrocatalysts for Nitrogen Reduction Reactions Accelerated by Interpretable Intrinsic Descriptor
Authors: Lin Xiaoyun , Wang Yongtao , Chang Xin , Zhen Shiyu , Zhao Zhi‐Jian , Gong Jinlong
Published: March 2023

Developing easily accessible descriptors is crucial but challenging to rationally design single‐atom catalysts (SACs). This paper describes a simple and interpretable activity descriptor, which is easily obtained from the atomic databases. The defined descriptor proves to accelerate high‐throughput screening of more than 700 graphene‐based SACs without computations, universal for 3–5d transition metals and C/N/P/B/O‐based coordination environments. Meanwhile, the analytical formula of this descriptor reveals the structure–activity relationship at the molecular orbital level. Using electrochemical nitrogen reduction as an example, this descriptor's guidance role has been experimentally validated by 13 previous reports as well as our synthesized 4 SACs. Orderly combining machine learning with physical insights, this work provides a new generalized strategy for low‐cost high‐throughput screening while comprehensive understanding the structure‐mechanism‐activity relationship.
Enantioselective Rhodium‐Catalyzed Pauson–Khand Reactions of 1,6‐Chloroenynes with 1,1‐Disubstituted Olefins
Authors: Ylagan Ridge Michael P. , Lee Eric Jaewon , Negru Daniela E. , Ricci Paolo , Park Bohyun , Ryu Haram , Baik Mu‐Hyun , Evans P. Andrew
Published: March 2023

An enantioselective rhodium(I)‐catalyzed Pauson–Khand reaction (PKR) using 1,6‐chloroenynes that contain challenging 1,1‐disubstituted olefins is described. In contrast to the previous studies with these types of substrates, which are only suitable for a single type of tether and alkyne substituent, the new approach results in a more expansive substrate scope, including carbon and heteroatom tethers with polar and non‐polar substituents on the alkene. DFT calculations provide critical insight into the role of the halide, which pre‐polarizes the alkyne to lower the barrier for metallacycle formation and provides the proper steric profile to promote a favorable enantiodetermining interaction between substrate and chiral diphosphine ligand. Hence, the chloroalkyne enables the efficient and enantioselective PKR with 1,6‐enynes that contain challenging 1,1‐disubstituted olefins, thereby representing a new paradigm for enantioselective reactions involving 1,6‐enynes.
Nahinfrarot Fluoreszenz‐Lebensdauer Mikroskopie von Biomolekülen mit Kohlenstoffnanoröhren**
Authors: Sistemich Linda , Galonska Phillip , Stegemann Jan , Ackermann Julia , Kruss Sebastian
Published: March 2023

Einwandige Kohlenstoffnanoröhren (single‐walled carbon nanotubes, SWCNTs) sind vielseitig einsetzbare Bausteine für Biosensoren, die im nahen Infrarot (NIR) fluoreszieren. Ihre Oberfläche kann chemisch so modifiziert werden, dass sie auf Analyten mit einer Veränderung ihrer Fluoreszenz reagieren. Intensitätsbasierte Signale werden jedoch leicht durch äußere Faktoren wie Bewegungen der Probe beeinflusst. Hier zeigen wir Fluoreszenz‐Lebensdauer Mikroskopie (fluorescence lifetime imaging microscopy, FLIM) von SWCNT‐basierten Sensoren im NIR. Dafür wurde ein konfokales Laser‐Scanning‐Mikroskop (CLSM) für NIR‐Signale (>800 nm) angepasst und zeitkorrelierte Einzelphotonenzählung von (GT)10‐DNA‐funktionalisierten SWCNTs verwendet. (GT)10‐SWCNTs fungieren als Sensoren für den wichtigen Neurotransmitter Dopamin. Ihre Fluoreszenzlebensdauer (>900 nm) fällt biexponentiell ab, wobei die längere Lebensdauerkomponente (370 ps) mit steigender Dopaminkonzentration um bis zu 25 % ansteigt. Mit diesen Sensoren können Zellen beschichtet werden, um extrazelluläres Dopamin in 3D mittels FLIM zu messen. Wir demonstrieren damit das Potenzial der Fluoreszenzlebensdauer als Messgröße für SWCNT‐basierte NIR‐Sensoren.
Assembly of an A6L6 Anion Trigonal Antiprism and Binding of Glucopyranosides and Polyethylene Glycols (PEGs)
Authors: Li Boyang , Wei Tianfu , Zhao Xiaotong , Wang Yue , Xu Lizheng , Yang Xiao‐Juan , Wu Biao
Published: March 2023

Anion‐coordination‐driven assembly (ACDA) has proven to be a very effective strategy for the construction of polyhedral structures. Here we demonstrate that variation of the “angle” of the backbone of C3‐symmetric tris‐bis(urea) ligands, from triphenylamine to triphenylphosphine oxide, results in the change of the final construct from an A4L4 tetrahedron to a higher‐nuclearity, A6L6 trigonal antiprism (A=anion, herein PO43−; L=ligand). Most interestingly, this assembly features a huge hollow internal space that is divided into three compartments: one central cavity and two large outer pockets. This multi‐cavity character enables the binding of different guests, namely monosaccharides or polyethylene glycol molecules (PEG600, PEG1000 and PEG2000), respectively. The results prove that anion coordination by multiple hydrogen bonds may provide both sufficient strength and flexibility, thus making possible the formation of complicated structures with adaptive guest binding ability.
Dual‐Atomic‐Site Catalysts for Molecular Oxygen Activation in Heterogeneous Thermo‐/Electro‐catalysis
Authors: Wang Zhongsen , Cheng Ming , Liu Yi , Wu Zewei , Gu Huayu , Huang Yi , Zhang Lizhi , Liu Xiao
Published: March 2023

Efficient molecular oxygen activation (MOA) is the key to environmentally friendly catalytic oxidation reactions. In the last decade, single‐atomic‐site catalysts (SASCs) with nearly 100 % atomic utilization and unique electronic structure have been widely investigated for MOA. However, the single active site makes the activation effect unsatisfactory and difficult to deal with complex catalytic reactions. Recently, dual‐atomic‐site catalysts (DASCs) have provided a new idea for the effective activation of molecular oxygen (O2) due to more diverse active sites and synergetic interactions among adjacent atoms. In this review, we systematically summarized the recent research progress of DASCs for MOA in heterogeneous thermo‐ and electrocatalysis. Finally, we look forward to the challenges and application prospects in the construction of DASCs for MOA.
High‐Performance and Self‐Powered X‐Ray Detectors Made of Smooth Perovskite Microcrystalline Films with 100 μm Grains
Authors: Li Ning , Li Yuyang , Xie Shengdan , Wu Jinming , Liu Nianqiao , Yu Yuan , Lin Qinglian , Liu Yang , Yang Shuang , Lian Gang , Fang Yanjun , Yang Deren , Chen Zhaolai , Tao Xutang
Published: March 2023

Perovskite single crystals and polycrystalline films have complementary merits and deficiencies in X‐ray detection and imaging. Herein, we report preparation of dense and smooth perovskite microcrystalline films with both merits of single crystals and polycrystalline films through polycrystal‐induced growth and hot‐pressing treatment (HPT). Utilizing polycrystalline films as seeds, multi‐inch‐sized microcrystalline films can be in situ grown on diverse substrates with maximum grain size reaching 100 μm, which endows the microcrystalline films with comparable carrier mobility‐lifetime (μτ) product as single crystals. As a result, self‐powered X‐ray detectors with impressive sensitivity of 6.1×104 μC Gyair−1 cm−2 and low detection limit of 1.5 nGyair s−1 are achieved, leading to high‐contrast X‐ray imaging at an ultra‐low dose rate of 67 nGyair s−1. Combining with the fast response speed (186 μs), this work may contribute to the development of perovskite‐based low‐dose X‐ray imaging.
Post‐Nickelation of a Crystalline Trinuclear Copper Organic Framework for Synergistic Photocatalytic Carbon Dioxide Conversion
Authors: Wang Xinxin , Ding Xu , Jin Yucheng , Qi Dongdong , Wang Hailong , Han Yuesheng , Wang Tianyu , Jiang Jianzhuang
Published: March 2023

Rational regulation of electronic structures and functionalities of framework materials still remains challenging. Herein, reaction of 4,4′,4′′‐nitrilo‐tribenzhydrazide with tris(μ2‐4‐carboxaldehyde‐pyrazolato‐N,N′)‐tricopper (Cu3Py3) generates the crystalline copper organic framework USTB‐11(Cu). Post‐modification with divalent nickel ions affords the heterometallic framework USTB‐11(Cu,Ni). Powder X‐ray diffraction and theoretical simulations reveal their two‐dimensional hexagonal structure geometry. A series of advanced spectroscopic techniques disclose the mixed CuI/CuIIstate nature of Cu3Py3in USTB‐11(Cu,Ni) with a uniform bistable Cu34+(CuI2CuII) : Cu35+(CuICuII2) (ca. 1 : 3) oxidation state, resulting in a significantly improved formation efficiency of the charge‐separation state. This endows the Ni sites with enhanced activity and USTB‐11(Cu,Ni) with outstanding photocatalytic CO2to CO performance with a conversion rate of 22 130 μmol g−1 h−1and selectivity of 98 %.
A Near‐Infrared Light‐Activated Photocage Based on a Ruthenium Complex for Cancer Phototherapy
Authors: He Guangli , He Maomao , Wang Ran , Li Xuezhao , Hu Hanze , Wang Dongsheng , Wang Ziqian , Lu Yang , Xu Ning , Du Jianjun , Fan Jiangli , Peng Xiaojun , Sun Wen
Published: March 2023

Conventional photocages only respond to short wavelength light, which is a significant obstacle to developing efficient phototherapy in vivo. The development of photocages activated by near‐infrared (NIR) light at wavelengths from 700 to 950 nm is important for in vivo studies but remains challenging. Herein, we describe the synthesis of a photocage based on a ruthenium (Ru) complex with NIR light‐triggered photocleavage reaction. The commercial anticancer drug, tetrahydrocurcumin (THC), was coordinated to the RuII center to create the Ru‐based photocage that is readily responsive to NIR light at 760 nm. The photocage inherited the anticancer properties of THC. As a proof‐of‐concept, we further engineered a self‐assembled photocage‐based nanoparticle system with amphiphilic block copolymers. Upon exposure to NIR light at 760 nm, the Ru complex‐based photocages were released from the polymeric nanoparticles and efficiently inhibited tumor proliferation in vivo.
Near‐Infrared Fluorescence Lifetime Imaging of Biomolecules with Carbon Nanotubes**
Authors: Sistemich Linda , Galonska Phillip , Stegemann Jan , Ackermann Julia , Kruss Sebastian
Published: March 2023

Single‐walled carbon nanotubes (SWCNTs) are versatile near infrared (NIR) fluorescent building blocks for biosensors. Their surface is chemically tailored to respond to analytes by a change in fluorescence. However, intensity‐based signals are easily affected by external factors such as sample movements. Here, we demonstrate fluorescence lifetime imaging microscopy (FLIM) of SWCNT‐based sensors in the NIR. We tailor a confocal laser scanning microscope (CLSM) for NIR signals (>800 nm) and employ time correlated single photon counting of (GT)10‐DNA functionalized SWCNTs. They act as sensors for the important neurotransmitter dopamine. Their fluorescence lifetime (>900 nm) decays biexponentially and the longer lifetime component (370 ps) increases by up to 25 % with dopamine concentration. These sensors serve as paint to cover cells and report extracellular dopamine in 3D via FLIM. Therefore, we demonstrate the potential of fluorescence lifetime as a readout of SWCNT‐based NIR sensors.
Using critical fluid carbon dioxide to optimize the enzymatic transesterification of soybean oil and ethyl ferulate to feruloyl soy glycerides
Authors: Eller Fred J. , Compton David L.
Published: March 2023

Feruloyl Soy Glyceride (FSG) is an all‐natural replacement for petroleum‐based ultraviolet absorbing ingredients currently used in sunscreens. It is produced by the Novozym® 435‐catalyzed transesterification of ethyl ferulate (EF) with triglycerides. By‐product fatty acid ethyl esters (FAEEs) are more soluble in CO2than the EF and triglyceride starting materials. It was hypothesized that the preferential removal of the FAEEs over EF would drive the enzymatic reaction towards the desired FSG product. The effect of CO2pressure and temperature on the solubilities of components of the FSG reaction mixture was studied to select optimized conditions for the enzymatic reaction and purification. Pressure–temperature conditions were then selected to use in a recycling system. The enzymatic products were analyzed for CO2with and without recycling CO2. The solubilities of all components of the reaction mixture were proportional to CO2density but the relative solubilities of individual components were not equal at all pressures and temperatures. At 60°C, the ratio of ethyl linoleate to EF was only 1.1 at 6.9 MPa but 3.1 at 13.8 MPa. The CO2was recycled through the reactor at 13.8 MPa (removing more FAEE by‐products) and through the receiver at 6.0 MPa (removing less FAEEs). In the recycling treatment, the material left behind in the reactor had 99.6% FSG content. The use of the reduced pressure receiver in a recycling CO2system effectively increased the amount of EF incorporated onto the soybean oil increasing the yield of the FSG product.
Scale‐down of oxygen and glucose fluctuations in a tubular photobioreactor operated under oxygen‐balanced mixotrophy
Authors: Moñino Fernández Pedro , Vidal García Albert , Jansen Tanisha , Evers Wendy , Barbosa Maria , Janssen Marcel
Published: March 2023

Oxygen‐balanced mixotrophy (OBM) is a novel type of microalgal cultivation that improves autotrophic productivity while reducing aeration costs and achieving high biomass yields on substrate. The scale‐up of this process is not straightforward, as nonideal mixing in large photobioreactors might have unwanted effects in cell physiology. We simulated at lab scale dissolved oxygen and glucose fluctuations in a tubular photobioreactor operated under OBM where glucose is injected at the beginning of the tubular section. We ran repeated batch experiments with the strain Galdieria sulphuraria ACUF 064 under glucose pulse feeding of different lengths, representing different retention times: 112, 71, and 21 min. During the long and medium tube retention time simulations, dissolved oxygen was depleted 15–25 min after every glucose pulse. These periods of oxygen limitation resulted in the accumulation of coproporphyrin III in the supernatant, an indication of disruption in the chlorophyll synthesis pathway. Accordingly, the absorption cross‐section of the cultures decreased steeply, going from values of 150–180 m2 kg−1 at the end of the first batch down to 50–70 m2 kg−1 in the last batches of both conditions. In the short tube retention time simulation, dissolved oxygen always stayed above 10% air saturation and no pigment reduction nor coproporphyrin III accumulation were observed. Concerning glucose utilization efficiency, glucose pulse feeding caused a reduction of biomass yield on substrate in the range of 4%–22% compared to the maximum levels previously obtained with continuous glucose feeding (0.9 C‐g C‐g−1). The missing carbon was excreted to the supernatant as extracellular polymeric substances constituted by carbohydrates and proteins. Overall, the results point out the importance of studying large‐scale conditions in a controlled environment and the need for a highly controlled glucose feeding strategy in the scale‐up of mixotrophic cultivation.
Preparation of lignin nanoparticles via ultra‐fast microwave‐assisted fractionation of lignocellulose using ternary deep eutectic solvents
Authors: Yan Zhiyan , Wang Zhongren , Chen Yuehui , Liu Chenrui , Liu Yun , Li Ruijie , Si Mengying , Shi Yan
Published: March 2023

Lignin separation from natural lignocellulose for the preparation of lignin nanoparticles (LNPs) is often challenging owing to the recalcitrant and complex structure of lignocellulose. This paper reports a strategy for the rapid synthesis of LNPs via microwave‐assisted lignocellulose fractionation using ternary deep eutectic solvents (DESs). A novel ternary DES with strong hydrogen bonding was prepared using choline chloride, oxalic acid, and lactic acid in a 1:0.5:1 ratio. Efficient fractionation of rice straw (0.5 × 2.0 cm) (RS) was realized by the ternary DES under microwave irradiation (680 W) within only 4 min, and 63.4% of lignin could be separated from the RS to prepare LNPs with a high lignin purity (86.8%), an average particle size of 48–95 nm, and a narrow size distribution. The mechanism of lignin conversion was also investigated, which revealed that dissolved lignin aggregated into LNPs via π–π stacking interactions.
Bioguided Fractionation and Isolation of an Antiplasmodial Saponin from the Roots of Nauclea xanthoxylon (A.Chev.) Aubrév. (Rubiaceae)
Authors: Nkouayeb Nangmou Brice Maxime , Maza Djomkam Hermine Laure , Bellier Tabekoueng Georges , Tékapi Tsopgni Willifred Dongmo , Mbahbou Bitchagno Gabin Thierry , Mbock Michel Arnaud , Kamkumo Raceline Gounoue , Frese Marcel , Ndjakou Lenta Bruno , Ngouela Silvère Augustin , Sewald Nobert , Blaise Azebaze Anatole Guy
Published: March 2023

The root extract of Nauclea xanthoxylon (A.Chev.) Aubrév. displayed significant 50 % inhibition concentration (IC50s) of 0.57 and 1.26 μg/mL against chloroquine resistant and sensitive Plasmodium falciparum (Pf) Dd2 and 3D7 strains, respectively. Bio‐guided fractionation led to an ethyl acetate fraction with IC50s of 2.68 and 1.85 μg/mL and subsequently, to the new quinovic acid saponin named xanthoxyloside (1) with IC50s of 0.33 and 1.30 μM, respectively against the tested strains. Further compounds obtained from ethyl acetate and hexane fractions were the known clethric acid (2), ursolic acid (3), quafrinoic acid (4), quinovic acid (5), quinovic acid 3‐O‐β‐D‐fucopyranoside (6), oleanolic acid (7), oleanolic acid 3‐acetate (8), friedelin (9), β‐sitosterol (10a), stigmasterol (10b) and stigmasterol 3‐O‐β‐D‐glucopyranoside (11). Their structures were characterised with the aid of comprehensive spectroscopic methods (1 and 2D NMR, Mass). Bio‐assays were performed using nucleic acid gel stain (SYBR green I)‐based fluorescence assay with chloroquine as reference. Extracts and compounds exhibited good selectivity indices (SIs) of >10. Significant antiplasmodial activities measured for the crude extract, the ethyl acetate fraction and xanthoxyloside (1) from that fraction can justify the use of the root of N. xanthoxylon in ethnomedicine to treat malaria.
Bioinformatic Analysis of Immobilized Enzymes: Towards a Better Understanding of The Guiding Forces
Authors: Padrosa David Roura , Paradisi Francesca
Published: March 2023

Protein bioinformatics has been applied to a myriad of opportunities in biocatalysis from enzyme engineering to enzyme discovery, but its application in enzyme immobilization is still very limited. Enzyme immobilization brings clear advantages in terms of sustainability and cost‐efficiency but is still limited in its implementation. This, because it is a technique that remains tied to a quasi‐blind protocol of trial and error, and therefore, is regarded as a time‐intensive and costly approach. Here, we present the use of a set of bioinformatic tools to rationalize the results of protein immobilization that have been previously described. The study of proteins with these new tools allows the discovery of key driving forces in the process of immobilization that explain the obtained results, moving us a step closer to the final goal: predictive enzyme immobilization protocols.