bluuebunny/crossref_metadata_2025 huggingface dataset:
Anticancer Tetranuclear Cu(I) Complex Catalyzes a Click Reaction to Synthesize a Chemotherapeutic Agent in situ to Achieve Targeted Dual‐Agent Combination Therapy for Cancer
Authors: Man Xueyu , Li Wenjuan , Zhu Minghui , Li Shanhe , Xu Gang , Zhang Zhenlei , Liang Hong , Yang Feng
Published: September 2024

To develop next‐generation metal‐based drugs and dual‐drug combination therapy for cancer, we proposed to develop a copper (Cu) complex that exerts anticancer function by integrating chemotherapy, immunotherapy and catalyzes a click reaction for the in situ synthesis of a chemotherapeutic agent, thereby achieving targeted dual‐agent combination therapy. We designed and synthesized a tetranuclear Cu(I) complex (Cu4) with remarkable cytotoxicity and notable catalytic ability for the in situ synthesis of a chemotherapeutic agent via Cu(I)‐catalyzed azide‐alkyne 1,3‐cycloaddition (CuAAC). We also constructed an apoferritin (AFt)‐Cu4 nanoparticles (NPs) delivery system. Aft‐Cu4 NPs not only showed an enhanced performance of tumor growth inhibition, but also improved the targeting ability and reduced the systemic toxicity of Cu4 in vivo. Importantly, the anticancer effect was enhanced by combining the Aft‐Cu4 NPs with the resveratrol analogue obtained from the CuAAC reaction in situ. Finally, we revealed the anticancer mechanism of the Cu4/Aft‐Cu4 NPs, which involves both cuproptosis and cuproptosis‐induced systemic immune response.
Reaktivität in Molekularen Gefäßen: Beschleunigungsmodi und Arten der Erzielbaren Selektivität
Authors: Syntrivanis Leonidas‐Dimitrios , Tiefenbacher Konrad
Published: September 2024

Es gibt ein zunehmendes Interesse an der Entdeckung und Anwendung von molekularen Gefäßen ‐ supramolekularen Wirtsstrukturen, die organische Reaktionen katalysieren können. Molekulare Gefäße, die an Enzyme erinnern, weil sie einen Hohlraum besitzen, der einer aktiven Bindungstasche ähnelt, können komplexe katalytische Mechanismen aufweisen und in vielen Fällen eine Selektivität ermöglichen, die in regulärer Lösung nicht erreicht werden kann. In diesem Übersichtsartikel versuchen wir, die immer vielfältigeren Beispiele durch eine zweiteilige Struktur zu organisieren. Im ersten Teil geben wir einen Überblick über die verschiedenen Beschleunigungsmodi, die in molekularen Gefäßen wirken, während wir im zweiten Teil anhand ausgewählter Beispiele die verschiedenen Arten von Selektivität aufzeigen, die durch den Einsatz von molekularen Gefäßen erreicht werden können. Besonderes Augenmerk wird dabei auf Beispiele gelegt, die für aktuelle Herausforderungen in der synthetischen organischen Chemie relevant sind. Wir sind der Meinung, dass diese Struktur das Gebiet zugänglicher macht und so die Entwicklung neuer Anwendungen von molekularen Gefäßen anregen wird.
Nonconventional Fluorescent Non‐Isocyanate Polyurethane Foams for Multipurpose Sensing Applications
Authors: Mahapatra Manas , Bourguignon Maxime , Grignard Bruno , Vandevenne Marylène , Galleni Moreno , Detrembleur Christophe
Published: September 2024

Fluorescent foams with interconnected pores are attractive for the detection and quantification of various products. However, many fluorescent probes are suffering from aggregation‐caused fluorescence quenching in their solid/aggregated state, are costly, and/or not straightforward to incorporate in foams, limiting their utility for this application. Herein, non‐isocyanate polyurethane foams, prepared by the simple water‐induced self‐blowing process, present a nonconventional fluorescence behaviour, i.e. they are intrinsically fluorescent with a multicolor emission without requiring ex situ traditional fluorescent probes. These foams demonstrate utility for capturing‐sensing gaseous formaldehyde (an emblematic indoor air pollutant), as well as for detecting and quantifying various metal ions (Fe2+, Cu2+, Fe3+, Hg2+). They are also able to selectively sense tetracycline antibiotic in a ratiometric way with a high sensitivity. By exploiting the unique multicolor photoluminescent foam properties, a smartphone‐compatible device is used for the facile antibiotic quantification. This nonconventional fluorescence behaviour is discussed experimentally and theoretically, and is mainly based on clusteroluminescence originating from multiple hydrogen bonding and hetero‐atomic sub‐luminophores, thus from aggregation‐induced emission luminogens that are naturally present in the foams. This work illustrates that easily accessible non‐conventional fluorescent NIPU foams characterized by a modular emission wavelength have an enormous potential for multiple substrates detection and quantification.
Reactivity Inside Molecular Flasks: Acceleration Modes and Types of Selectivity Obtainable
Authors: Syntrivanis Leonidas‐Dimitrios , Tiefenbacher Konrad
Published: September 2024

There is increasing interest in the discovery and application of molecular flasks–supramolecular host structures capable of catalyzing organic reactions. Reminiscent of enzymes due to possessing a host cavity akin to an active site, molecular flasks can exhibit complex catalytic mechanisms and in many cases provide selectivity not achievable in bulk solvent. In this Review, we aim to organize the increasingly diverse examples through a two‐part structure. In part one, we provide an overview of the different acceleration modes that operate within molecular flasks, while in part two we showcase, through selected examples, the different types of selectivity that are obtainable through the use of molecular flasks. Particular attention is given to examples that are relevant to current challenges in synthetic organic chemistry. We believe that this structure makes the field more approachable and thus will stimulate the development of novel applications of molecular flasks.
Selectivity Modulation of Multistep Reduction Reactions by Gold Nanoclusters
Authors: Zhang Jing‐Zheng , Zhang Yi‐Bao , Chai Hui‐Li , Luo Hui‐Ling , Du Chen‐Xia , Huang Ren‐Wu , Zang Shuang‐Quan
Published: September 2024

The selective synthesis of valuable azo‐ and azoxyaromatic chemicals via transfer coupling of nitroaromatic compounds has been achieved by fine‐tuning the catalyst structure. Here, a direct method to modulate nitrobenzene reduction and selectively alter the product from azobenzene to azoxybenzene by employing the size effect of Au is reported. Au nanoclusters (NCs) with smaller sizes embedded in ZIF‐8 controllably converted nitrobenzene into azoxybenzene, while supported Au nanoparticles (NPs) selectively catalyzed nitrobenzene reduction to azobenzene. X‐ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform spectroscopy on CO adsorption (CO‐DRIFTS) of Au NC/ZIF‐8 revealed a higher valence state and a lower electron density of Au than that of Au NP/ZIF‐8, combined with the desorption of azoxybenzene from the Au NC and Au NP surface, suggesting that the Au NCs with lower electron density exhibit stronger adsorption. Density functional theory (DFT) calculations and charge density difference maps indicated that azoxybenzene bonded to Au NC/ZIF‐8 with greater adsorption energy, resulting in more electron transfer between azoxybenzene and the generated Au sites, which inhibited further reduction of azoxybenzene and resulted in high azoxybenzene selectivity. The application of the size effect of Au particles to regulate nitrobenzene transfer coupling provided new insights into the structure‐selectivity relationships.
Direct C3−H Alkylation and Alkenylation of Quinolines with Enones
Authors: Xu Liqing , Wang Xu , Yang Dezhi , Yang Xiaolong , Wang Dong
Published: September 2024

Conversion of quinoline C−H bonds into C−C bonds is essential for obtaining the enormous array of derivatives required for pharmaceutical and agrochemical development. Despite over a century of synthetic efforts, direct alkylation and alkenylation at C3−H positions in a wide array of quinoline precursors remain predominantly challenging and elusive. This report outlines the first successful quinoline C3−H alkylation and alkenylation reactions, exhibiting exceptional regio‐ and stereoselectivity, all achieved under redox‐neutral and transition‐metal‐free conditions. The method involves a three‐step, one‐pot or two‐pot sequence, including 1,4‐dearomative addition, functionalization at C3, and elimination or transalkylation to produce 3‐alkylated/alkenylated quinolines. The presence of a carbonyl group in these products allows for further synthetic manipulations, enabling the production of cyanides, amides, amines, and simple alkyl derivatives.
The need to identify anatomy‐related competencies in medical education
Authors: Syed Abd Halim Syarifah Aisyah , Yusoff Muhamad Saiful Bahri , Yaman Mohamad Nurman , Roslan Nurhanis Syazni , Tengku Muda Tg Fatimah Murniwati , Ramli Ramiza Ramza , Kadir Fairrul , Hadie Siti Nurma Hanim
Published: September 2024

A profound grasp of anatomy is indispensable for shaping competent and safe medical practitioners. This knowledge acquisition is pivotal in the early stages of medical education and remains crucial throughout clinical training. However, the evolving landscape of medical education has ushered in changes to the anatomy curriculum, marked by a reduction in contact hours and a streamlined content structure to accommodate novel subjects and teaching methodologies. This transformation has precipitated a quandary in defining the essential scope and depth of anatomical knowledge to be imparted. Traditionally, surgeons assumed the role of anatomy instructors until Flexner's recommendations catalyzed the integration of trained anatomists. Nevertheless, the varied backgrounds of anatomists and the heterogeneity in anatomy curricula across institutions have introduced potential disparities in the quality of graduates. Addressing these challenges mandates the identification of key anatomy competencies tailored for undergraduate medical students. The imperative lies in ensuring that these competencies span cognitive, psychomotor, and affective domains, offering not only comprehensiveness but also direct applicability to clinical practice. Hence, this viewpoint highlights the necessity of adopting a systematic approach that includes gathering input from various stakeholders in developing and implementing a universal anatomy core competency framework, ensuring graduates are equipped for the multifaceted demands of clinical practice. Overall, the manuscript provides a comprehensive overview of the challenges and opportunities in anatomy education, with a clear call to action for a transformative approach to meet the evolving needs of medical practice.
Catalyzing Knoevenagel Condensation and Radioiodine Sequestration with Tuned Porous Organic Polymers to Decipher the Role of Surface Area, Pore Volume, and Heteroatom
Authors: Chakraborty Argha , Sarkar Sayantan , Munjal Ritika , Majhi Jagannath , Bandyopadhyay Anasuya , Mukhopadhyay Suman
Published: September 2024

The impact of surface area, pore volume, and heteroatom type on the performance of porous organic polymers (POPs) in various applications remains unclear. To investigate this, three isoreticular POPs were employed having one common building block, resulting in varying surface areas, pore volumes, and heteroatom compositions. This study aimed to establish a correlation between the structural features of POPs (surface area, pore volume, and heteroatom type) with their adsorption capacity, and catalytic efficiency. To explore this relationship, the Knoevenagel condensation reaction was used as a model system, testing various substituted aldehydes to further validate our findings. Additionally, the capture of radioactive iodine vapor at 75 °C was simulated to examine the correlation with adsorption capacity, comparing the gravimetric iodine uptake capacity of each POP to gain insights into this relationship.
Synthesis of 5‐Seleno‐Substituted Spirocyclopenta[b]pyridine‐2,5‐dien‐4‐ones and Benzo[h]quinolines via Radical Cyclization of Arylethynylpyridines
Authors: Bartz Ricardo H. , Santos Rafaela R. S. A. , Hellwig Paola S. , Silva Márcio S. , Lenardão Eder J. , Jacob Raquel G. , Perin Gelson
Published: September 2024

A practical strategy for obtaining novel 5‐seleno‐substituted spirocyclopenta[b]pyridines‐2,5‐dien‐4‐ones and benzo[h]quinolines via radical cyclization is reported. The synthetic protocol explores the reaction between arylethynylpyridines and diorganyl diselenides in acetonitrile as solvent and Oxone® as oxidant at 82 °C. This easy‐to‐handle, eco‐friendly metal‐free approach was carried out under an open atmosphere, affording functionalized organoselenium compounds in good to excellent yields. Control experiments and scale‐up test were performed to demonstrate the efficiency of this methodology.
Fractional‐order fixed‐time sliding mode control of robotic manipulators with robust exact differentiator
Authors: Wang Xinsheng , Jiang Bin , Yao Tong , Zhang Huaqiang
Published: September 2024

This paper introduces a robust position tracking control structure of exoskeleton robots (ERs). An open environment and body flexibility are the main challenges in ER control system design. First, a fractional‐order nonsingular terminal sliding mode (FONTSM) controller is proposed for a robotic manipulator with uncertainty, where lumped unknown dynamics are computed by time‐delay estimation (TDE). Secondly, a robust exact differentiator (RED) is employed as the output feedback observer for the velocity sensorless robotic system. Thirdly, the stability of the FONTSM control system is demonstrated. It is proved that the system error can move to the specified value along the sliding mode surface at a fixed time and can reach the sliding mode surface after a finite time. Finally, simulations on a 2‐DOF robotic manipulator show the effectiveness of the fixed‐time control strategies. When a combined trigonometric function disturbance is applied, the joint angle error is reduced to 1% by the model‐free controller based on output feedback within approximately 1 s.
Challenges and Prospects of Electrolyte Design for Lithium‐Sulfurized Polyacrylonitrile Batteries
Authors: Ma Tao , Tao Zhanliang
Published: September 2024

Sulfurized polyacrylonitrile (SPAN) is regarded as a promising organic sulphur cathode material for lithium‐sulfur (Li−S) batteries. It undergoes a solid‐solid conversion without forming polysulfide intermediate phases, overcoming the poor electrochemical performance caused by the shuttle effect of elemental S cathodes. However, realizing this unique conversion mechanism requires employing appropriate electrolytes. Furthermore, the direct application of metallic Li as the anode unavoidable introduces a series of issues triggered by Li dendrites in Li‐SPAN batteries, such as low lifespan, short circuits, fire, etc. In this review, we endeavor to encapsulate recent advancements in electrolyte research, with a particular focus on the intrinsic relationship between the solvation structure of the electrolyte and the interfacial chemistry of the Li anode and SPAN electrode, aim to provide insights into the electrolytes design for high performance Li‐SPAN full batteries.
Development of an automated high‐content immunofluorescence assay of pSmads quantification: Proof‐of‐concept with drugs inhibiting the BMP/TGF‐β pathways
Authors: Khodr Valia , Clauzier Laura , Machillot Paul , Sales Adrià , Migliorini Elisa , Picart Catherine
Published: September 2024

Introduction

Bone morphogenetic proteins (BMPs) and transforming growth factors (TGF‐β) are members of the TGF‐β superfamily, known for their roles in several physiological and pathological processes. These factors are known to bind in vivo to BMP and TGF‐β receptors, respectively, which induces the phosphorylation of Smad (pSmad) transcription factors. This pathway is generally studied with Western blot and luciferase bioluminescence assay, which presents some limitations.

Purpose

In this work, we developed and optimized a high‐throughput assay to study pSmad pathways using immunofluorescence (IF) as an alternative to Western blot. We aimed to overcome the technical challenges usually faced in the classical IF assay in image acquisition, analysis, and quantification.

Methods

We used C2C12 cells as a cellular model. The cells were stimulated with BMP‐2 and TGF‐β1 that were delivered either in solution (soluble) or via a biomaterial presenting the growth factor (GF), that is in a “matrix‐bound” manner. Image acquisition parameters, analysis methods, and quantification of pSmads using IF were optimized for cells cultured on two types of supports: on bare glass and on a biomimetic coating made by self‐assembly of the biopolymers hyaluronic acid and poly(l‐lysine), which was crosslinked and then loaded with the GFs.

Results

We performed high‐content kinetic studies of pSmad expression for cells cultured in 96‐well microplates in response to soluble and matrix‐bound BMP‐2 and TGF‐β1. The detection limit of the IF‐based assay was found to be similar to Western blot. Additionally, we provide a proof‐of‐concept for drug testing using inhibitors of BMP and TGF‐β receptors, under conditions where specific signaling pathways are engaged via the ligand/receptor interactions. Altogether, our findings offer perspectives for future mechanistic studies on cell signaling and for studies at the single cell level using imaging methods.
Strategies to overcome mental health stigma: Insights and recommendations from young people with major depressive disorder (MDD)
Authors: Prizeman Katie , Weinstein Netta , McCabe Ciara
Published: September 2024

Background

Young people with depression are met with stigma related to their mental health, which exacerbates loneliness, social isolation, and depression symptoms. While disclosing depression could improve one's mental health, stigma can also make social interactions more challenging and reduce the likelihood of receiving treatment. This research explored young people's experiences with stigma and recommendations for addressing it.

Methods

Semi‐structured interviews conducted withN = 35 young people aged 18–25 years (Mage= 20.09) were analyzed with thematic analysis. Participants met the criteria for clinical depression using the Mood and Feelings Questionnaire (score >27) or had recently obtained a medical diagnosis (N = 18) of depression by a medical professional.

Results

Participants faced stigma when deciding to disclose their depression, which fed into a vicious cycle influencing feelings of loneliness, social isolation, and withdrawal. Their recommendations for others to avoid this cycle can be summarized under three main themes: (1) Social affirmation: identify allies and build meaningful connections; (2) Self‐affirmation: build a constructive relationship with the self; and (3) Societal affirmation: structural changes are needed.

Conclusions

The current research indicates that social, self‐, and societal affirmation are considered important for reducing the detrimental impacts of stigma. Policies and programs are needed that provide mental health support to young people, and public awareness campaigns that guide young people to appropriate resources (i.e., support and intervention) via governmental public health bodies.
Longitudinal DNA methylation in parent–infant pairs impacted by intergenerational social adversity: An RCT of the Michigan Model of Infant Mental Health Home Visiting
Authors: Petroff Rebekah L. , Jester Jennifer , Riggs Jessica , Alfafara Emily , Springer Katherine , Kerr Natalie , Issa Meriam , Hall Alanah , Rosenblum Katherine , Goodrich Jaclyn M. , Muzik Maria ,   the Michigan Collaborative for Infant Mental Health Research
Published: September 2024

Introduction

Early childhood development is a strong predictor of long‐term health outcomes, potentially mediated via epigenetics (DNA methylation). The aim of the current study was to examine how childhood experiences, punitive parenting, and an intergenerational psychotherapeutic intervention may impact DNA methylation in young children and their mothers.

Methods

Mothers and their infants/toddlers between 0 and 24 months were recruited at baseline (n = 146, 73 pairs) to participate in a randomized control trial evaluating the effectiveness of The Michigan Model of Infant Mental Health Home Visiting (IMH‐HV) parent–infant psychotherapy compared to treatment as usual. Baseline and 12‐month post‐enrollment data were collected in the family's home and included self‐report questionnaires, biological saliva samples, home environment observation, video‐taped parent–child interaction, and audio‐recorded interviews. Saliva DNA methylation was measured at the genes, nuclear receptor subfamily 3 group C member 1 (NR3C1), solute carrier family 6 member 4 (SLC6A4), brain‐derived neurotrophic factor (BDNF), and the genetic element, long interspersed nuclear element‐1 (LINE1).

Results

For mothers, baseline methylation of BDNF, SLC6A4, NR3C1, or LINE1 was largely not associated with baseline measures of their childhood adversity, adverse life experiences, demographic characteristics related to structurally driven inequities, or to IMH‐HV treatment effect. In infants, there were suggestions that methylation in SLC6A4 and LINE1 was associated with parenting attitudes. Infant BDNF methylation suggested an overall decrease in response to IMH‐HV psychotherapy over 12 months.

Conclusions

Overall, our findings suggest that the epigenome in infants and young children may be sensitive to both early life experiences and parent–infant psychotherapy.
Patuletin Ameliorates Inflammation and Letrozole–Induced Polycystic Ovarian Syndrome in Rats
Authors: Shah Syeda Farah , Noorali Samina , Faizi Shaheen , Jabeen Almas
Published: September 2024

Concerns about inflammation‐related issues affecting female reproductive health are growing. Chronic low‐grade inflammation in women with polycystic ovarian syndrome (PCOS) affects follicular growth, ovulation, and androgen production. The present investigation aimed to elucidate the efficacy of flavonoid patuletin in ameliorating the letrozole–induced PCOS and associated inflammation in rats. Female Wistar rats (32 days old) were divided into five groups (n = 12): Group I, control; Group II, vehicle control; Group III, letrozole oral (1 mg/kg) for 28 days; Group IV and Group V treatment groups, patuletin i.p. (25 mg/kg) and clomiphene citrate + metformin i.p. (50 mg/kg + 300 mg/kg), respectively. Leterozole–induced PCOS and ovarian inflammation were ameliorated by patuletin, as reflected in the improved histopathology, prevention of cyst formation, significant upregulation of growth factors such as growth differentiation factor 9 (GDF‐9) and bone morphogenetic protein‐15 (BMP‐15) expression, and a decrease in the pro‐inflammatory cytokines TNF‐α, IL‐6, and COX‐2. Additionally, the plasma levels of reproductive hormones were restored. Upregulation of FSH‐R, PR, and CYP19a1, along with downregulation of ERα, LHR, CYP17a1, CYP11a1 and HSDβ17a1, showed the regulation of gonadotropin receptors and steroid biosynthesis genes in ovarian tissues. Patuletin demonstrated a promising protective approach against the biological model of PCOS by increasing the inflammation in ovarian tissues with consequent regulation of growth factors, enzymes, and hormones, and might be used as adjuvant therapy in the treatment of problems related to female reproductive health.
Percutaneous closure of coronary fistulas in adults using microvascular plugs
Authors: Unzué Leire , Wasniewski Samantha , García Eulogio , Teijeiro‐Mestre Rodrigo
Published: September 2024

Percutaneous closure of coronary fistulas can be a challenge, given the tortuosity and the small caliber of the anomalous vessel. The microvascular plugs (MVP) are polytetrafluoroethylene‐coated nitinol devices designed to perform embolization of small peripheral vessels. Its reduced profile allows the release of the device through microcatheters, facilitating the intervention. We present three cases of coronary fistulas in adults, percutaneously closed through radial access using these devices.
Localized retroperitoneal mass suspected malignancy: A rare case of unicentric Castleman's disease
Authors: Alhariry Engy S. , Hasan Abdulkarim , Abdelghany Ashraf , Nafie Khalid
Published: September 2024

Key Clinical Message

Castleman's Disease should be considered in the differential diagnosis of retroperitoneal masses, especially in equivocal cases. Clinician should not presume all cases of retroperitoneal masses as a malignancy.

Castleman's Disease is a heterogeneous group of lymphoproliferative disorders, that can develop in lymph nodes or in extranodal sites. It has three distinct histological subtypes; hyaline vascular, plasma cell or mixed. It can be unicentric or multicentric, and sometimes oligocentric or regional. In this article, we report a case of a 30‐year‐old male who presented with a palpable left lumbar mass, clinically suspected as sarcoma vs GIST, which was surgically excised and pathologically examined revealing a rare condition of intra‐abdominal unicentric Castleman's Disease with good prognosis. Castleman's Disease should be considered in the differential diagnosis of retroperitoneal masses, especially in equivocal cases.
Mononuclear and Multinuclear O^N^O‐donor Zn(II) Complexes as Robust Catalysts for the Production and Depolymerization of Poly(Lactide)
Authors: Zikode Mnqobi , Fuchs Martin , Langletz Tim , Burkart Lisa , Herres‐Pawlis Sonja , Ojwach Stephen O.
Published: September 2024

Mononuclear and multinuclear O^N^O‐donor Zn(II) complexes are herein reported as catalysts in the ring‐opening polymerization (ROP) of rac‐lactide (rac‐LA) and depolymerization of poly(lactide) (PLA). Reactions of imino‐phenol proligand 2[((2‐hydroxyethyl)imino)methyl]phenol (L1H2) with ZnCl2 and ZnEt2 afforded the dinuclear and tetranuclear complexes [Zn2(L1H)2Cl2] (Zn1) and [Zn4(L1)4] (Zn2), respectively. Separately, treatments of proligands 2‐[1‐((2‐hydroxyethyl)imino)ethyl]phenol (L2H2) and [((2‐methoxyethyl)imino)methyl]phenol (L3H) with ZnCl2 gave the respective mononuclear complexes [Zn(L2H2)2Cl2] (Zn3) and [Zn(L3H)2Cl2] (Zn4), while the reactions of L3H with ZnEt2 afforded the bis(chelated) mononuclear complex [Zn(L3)2] (Zn5). The complexes were characterized using NMR and IR spectroscopy, elemental analyses and single crystal X‐ray crystallography. All the Zn(II) complexes showed high catalytic activities in the ROP of rac‐LA (kapp of up to 4.18 × 10−4 s−1) to give moderate molecular weight PLA (39,960 g mol−1) with relatively narrow dispersities (Đ = 1.4–2.1). The complexes produced mainly atactic PLAs with Pr values of 0.51–0.58. More significantly, complexes Zn1, Zn2, and Zn5 were also active in the depolymerization of commercial PLA in methanol (kapp of up to 2.67 × 10−4 s−1) to produce alkyl lactates. The ROP and depolymerization behavior were largely controlled by the structure and nuclearity of the complexes.
Biosynthesis of Nonribosomal Peptides Chitinimides Reveal a Special Type of Thioesterase Domains
Authors: Niu Weijing , Liu Jiaqi , Duan Yuwei , Zhong Lin , Pang Linlin , Zhong Guannan , Zhang Youming , Bian Xiaoying
Published: September 2024

Non‐ribosomal peptide synthetases (NRPSs) and their tailored enzymes have diverse biological functions. In this study, we investigated the biosynthesis and function of chitinimides, which belong to the non‐ribosomal peptide (NRP) subfamily featuring a pyrrolidine‐containing part (X part) connected to the polypeptide chain via an ester bond. A conserved gene cassette, chmHIJK, is responsible for oxyacylation of the pyrrolidine moiety in the X part. The thioesterase (TE) domain of ChmC (ChmC‐TE) catalyzes transesterification reactions with a free X part or methanol as a nucleophilic reagent to form different chitinimides. The crucial amino acid residues in the ChmC‐TE domains responsible for the specific recognition of the X part were identified, and they were conserved in all the biosynthetic pathways of this NRP subfamily to form a signature motif, YNHNR, suggesting a special type of TE domain in NRPSs. Chitinimides demonstrate the biological function of promoting the swarming ability of the native producer. This study provides deep insights into the biosynthesis of this special NRP subfamily, and shows that the special TE domain could be used to generate diverse NRPs by combinatorial biosynthesis.
Effectiveness of Imagery Rescripting for Trauma‐Affected Voice Hearers: An Open Trial
Authors: Strachan Laura , McEvoy Peter , Arntz Arnoud , Steel Craig , Paulik Georgie
Published: September 2024

Objective

People who hear voices (auditory verbal hallucinations) often have post‐traumatic stress disorder (PTSD) symptoms. Cognitive behavioural therapies (CBT) have yielded inconsistent findings when treating voices and PTSD symptoms in voice hearers. Preliminary evidence suggests imagery rescripting (ImRs) is associated with large reductions in voice hearing and PTSD symptoms. This study replicated past studies using a larger sample to examine the effectiveness of ImRs in reducing such symptoms.

Method

Participants (N = 49; 65.3% female; Mage = 35.86) were clients at an Australian transdiagnostic clinic for voice hearers. A one‐arm open trial design was used with three pre‐treatment baselines and a mid‐treatment, post‐treatment and 3‐month follow up assessments of PTSD symptoms (Posttraumatic Diagnostic Scale for DSM‐5), voices (Hamilton Program for Schizophrenia Voices Questionnaire) and emotional symptoms (Depression Anxiety and Stress Scales‐21). Five single‐item measures were administered weekly to explore the trajectories of change in trauma intrusions, voice‐related distress, voice frequency and positive and negative voice valance.

Results

ImRs was associated with very large reductions in PTSD symptoms and voices (both emotional and physical characteristics of voices) and emotional symptoms at post‐treatment and follow‐up (η2p = 0.24–0.44). There were medium‐large to large reductions in weekly symptoms of intrusions, voice‐related distress, voice frequency and negative voices (η2p = 0.12–0.16) and a non‐significant increase in positive voices (η2p = 0.05).

Conclusions

This study provides further evidence that ImRs is an effective treatment for voices and PTSD symptoms in voice hearers with a range of diagnoses. Randomised controlled trials are needed to compare the efficacy of ImRs to CBT protocols.
Design and Synthesis of Aggregation‐Caused Quenching Hydroxy‐Phenanthroimidazole Derivatives for Probing of Fe3+ Ions and as Potential Blue Light Emitters
Authors: Odedara Nisha , Borane Niteen , Boddula Rajamouli
Published: September 2024

Fluorescence aggregated molecules tend to employ versatile opportunities in metal ion probe sensors and fluorescent lighting. To achieve this dual challenging task, currently synthesized three phenanthroimidazole‐naphthalene‐based compounds Pq‐tBu‐OH, Pq‐mF‐OH, and Pq‐pF‐OH are derived based on substitution at N1 position for better photophysical and electrochemical properties. Compared experimental and theoretical calculations define the highest bandgap to be 2.75 eV of Pq‐pF‐OH, and the same molecule expressed a higher (348 °C) thermal decomposition. The calculated singlet and triplet energies found in the range of 3.24–3.67 and 2.70–2.72 eV indicate well energy transfer from S1→S0 (quantum yield of 23.36 %, lifetime is 4.05 ns). Among the numerous morphologies, the solid form exhibited improved intensive deep blue emission (x=0.159, y=0.051), and its InGaN LED results demonstrated a strong deep blue emission at 418 nm. Moreover, the fluorophores were experimentally visualizing the aggregation‐caused quenching (ACQ) which enables the probing of Fe3+ ion. However, for the first time, the ACQ‐assisted concept is applied through synthesized molecules for Fe3+ ion probing via fluorescence spectra, Job's plot calculation, and 1H NMR results. In addition, the probe works excellently at a detection limit of 10 μM and it could also act as a potential competitor for lighting applications.
In Vitro Effect of Anodization of Titanium Abutments on Color Parameters and Color Difference of Lithium Disilicate All‐Ceramic Crowns
Authors: Khorshidi Sotude , Zarbakhsh Arash , Lawaf Shirin , Golalipour Shaghayegh , Sayyari Maryam , Nahavandi Alireza Mahmoudi
Published: September 2024

Objective

This study assessed the effect of the anodization of titanium abutments on the color parameters and color difference of lithium disilicate (LDS) all‐ceramic crowns.

Materials and Methods

In this study, 19 straight abutments were divided into two groups: anodized (n = 9) and non‐anodized control (n = 9), with one hybrid zirconia abutment as a reference. Anodization was achieved by applying 63 V energy using seven 9 V flat batteries in series, with an electrolyte solution comprising 1 g trisodium phosphate in 250 mL distilled water for 5 s, resulting in a gold‐yellow color. Abutments were then scanned, and full‐contour monolithic IPS e.max maxillary central incisor crowns were fabricated with 2 mm thickness and glazed. Reflectance was measured using a spectroradiometer, and color coordinates (L*, a*, b*, h*, and C*) were calculated using CS‐10W software. Color differences of the crowns in both groups were quantified using the CIEDE2000 (ΔE00) color difference formula and analyzed by t‐test (α = 0.05) compared to the standard sample.

Results

The L*, a*, b*, and c* parameters in anodized abutments were significantly higher than those in non‐anodized abutments, while the h* parameter in anodized abutments was significantly lower than that in non‐anodized abutments (p < 0.001 for all). There was a significant difference in ΔE00 of the two groups (p = 0.043).

Conclusion

Anodization of titanium abutments improved the color parameters of LDS all‐ceramic crowns and significantly decreased their ΔE compared with non‐anodized abutments.
Effect of Needle Insertion Angle on Pain During Labial Infiltration Anesthesia of the Anterior Maxilla: A Randomized Clinical Trial
Authors: Moaddabi Amirhossein , Molania Tahereh , Arezoumandi Alireza , Ghaedsharaf Sahar , Cernera Mariangela , Nikbakht Roya , Soltani Parisa , Spagnuolo Gianrico , Shahnaseri Shirin
Published: September 2024

Objectives

This study aimed to assess the effect of needle insertion angle on pain during labial infiltration anesthesia in the anterior maxillary region.

Material and Methods

In this parallel‐design randomized clinical trial, participants were randomly assigned to four groups for labial infiltration anesthesia of the anterior maxilla. Local anesthesia was performed with needle orientation parallel to the longitudinal axis of the tooth using a conventional syringe (Syringe‐0), needle at α angle with a conventional syringe (Syringe‐α), computer‐controlled local anesthetic delivery (CCLAD) device parallel to the longitudinal axis of the tooth (CCLAD‐0), and CCLAD at α angle (CCLAD‐α). The heart rate (HR), blood pressure (BP), and respiratory rate (RR) of participants were measured before needle insertion, immediately after needle insertion, and immediately after the injection by a vital signs monitor. The level of pain experienced by participants was quantified using a numerical rating scale (NRS). Data were analyzed by repeated‐measures ANOVA and regression models (α = 0.05).

Results

Thirty‐six participants aged from 21 to 60 years, with a mean age of 35.36 years were recruited. The mean pain scores were 7.44, 4.67, 2.89, and 0.67 in groups Syringe‐0, Syringe‐α, CCLAD‐0, and CCLAD‐α, respectively (p < 0.001). Age and sex had no significant effect on pain scores (p = 0.914 and p = 0.702, respectively). The four groups had no significant difference in vital signs (p > 0.05).

Conclusions

Injection at an α angle and the application of CCLAD can be used in clinical practice to decrease the pain experienced by participants during labial infiltration anesthesia of the anterior maxilla.

Trial Registration

Iranian Registry of Clinical Trials: IRCT20230719058849N1.
Knowledge and Attitude of General Dentists, Senior Dental Students, and Orthodontic Residents Toward Obstructive Sleep Apnea
Authors: Shekarian Mina , Feizbakhsh Masood , Rafie Mehdi
Published: September 2024

Objective

The main objective of this study was to compare the knowledge and attitude of general dentists, senior dental students, and orthodontic residents toward obstructive sleep apnea (OSA).

Materials and Methods

A questionnaire was designed and administered among 73 senior dental students, 84 general dentists, and 50 orthodontic residents. The questionnaire asked for demographic information of the participants and assessed their knowledge and attitude toward OSA. The validity and reliability of the questionnaire were confirmed by experts. Data were analyzed by the Kruskal−Wallis and Bonferroni tests using SPSS (α = 0.05).

Results

The mean knowledge scores of general dentists and senior dental students were significantly lower than those of orthodontic residents (p < 0.001). However, there was no significant difference in the knowledge score of senior dental students and general dentists (p = 1). The mean knowledge score was significantly higher in dentists with 1–3 years of professional clinical experience (p = 0.02). The knowledge score was the highest in dentists working in private clinics followed by private offices and public clinics. The mean attitude score was the highest in orthodontic residents followed by general dentists and dental students. There was no significant difference in attitude based on the attended university, age, or time of graduation.

Conclusion

According to the results, general dentists had insufficient knowledge about OSA, which could result in under‐diagnosis or misdiagnosis of patients with OSA. This finding highlights the need for further education and training for dentists to properly identify and refer OSA patients to orthodontists or sleep specialists.
Paleopteran molecular clock: Time drift and recent acceleration
Authors: Osozawa Soichi , Nel André
Published: September 2024

Applying BEAST v1.10.4, we constructed a Bayesian Inference tree comprising 322 taxa, primarily representing Paleoptera (Odonata and Ephemeroptera; Pterygota), Zygentoma and Archaeognatha (Apterygota; paraphyly), and Neoptera (Plecoptera; Pterygota), based on a 2685 bp sequence dataset. Our analyses revealed that robust dating required the incorporation of both Quaternary and pre‐Quaternary dates. To achieve this, our dating incorporated a 1.55 Ma (Quaternary) geological event (the formation of the Ryukyu Islands) and a set of chronologically well‐founded fossil dates, spanning from up to 400 Ma (Devonian) for the stem Archaeognatha, 320 Ma (Carboniferous) for the crown of Paleoptera, 300 Ma (Carboniferous) for the crown Ephemeroptera, and 280 Ma (Permian) for the crown Odonata, down to 1.76 Ma (Quaternary) for Calopteryx japonica, encompassing a total of 22 calibration points (events: 6, fossils: 16; Quaternary: 7, pre‐Quaternary: 15). The resulting dated tree aligns with previous research, albeit with some dates being overestimated. This overestimation was mainly due to the lack of Quaternary calibration and the exclusive dependence on pre‐Quaternary calibration, though the application of maximum age constraints also played a role. Our minimum age dating demonstrates that the molecular clock did not uniformly progress, rendering rate dating an inapplicable approach. We observed that the base substitution rate is time‐dependent, with an exponential increase evident from around 20 Ma (Miocene) to the present time, exceeding an order of magnitude. The extensive radiation and speciation of Insecta and Paleoptera, potentially resulting from the severe climatic changes associated with the Quaternary, including the commencement of glacial and interglacial cycles, may have significantly contributed to this increase in base substitution rates. Additionally, we identified a potential peak in base substitution rates during the Carboniferous period, around 320 million years ago, possibly corresponding to the Late Paleozoic Ice Age.
Key benthic species are affected by predicted warming in winter but show resistance to ocean acidification
Authors: Schertenleib Katrin S. H. , Davey Tallulah , Taylor David , O'Connor Nessa E.
Published: September 2024

The effects of climate change on coastal biodiversity are a major concern because altered community compositions may change associated rates of ecosystem functioning and services. Whilst responses of single species or taxa have been studied extensively, it remains challenging to estimate responses to climate change across different levels of biological organisation. Studies that consider the effects of moderate realistic near‐future levels of ocean warming and acidification are needed to identify and quantify the gradual responses of species to change. Also, studies including different levels of biological complexity may reveal opportunities for amelioration or facilitation under changing environmental conditions. To test experimentally for independent and combined effects of predicted near‐future warming and acidification on key benthic species, we manipulated three levels of temperature (winter ambient, +0.8 and +2°C) and two levels of pCO2 (ambient at 450 ppm and elevated at 645 ppm) and quantified their effects on mussels and algae growing separately and together (to also test for inter‐specific interactions). Warming increased mussel clearance and mortality rates simultaneously, which meant that total biomass peaked at +0.8°C. Surprisingly, however, no effects of elevated pCO2 were identified on mussels or algae. Moreover, when kept together, mussels and algae had mutually positive effects on each other's performance (i.e. mussel survival and condition index, mussel and algal biomass and proxies for algal productivity including relative maximum electron transport rate [rETRmax], saturating light intensity [Ik] and maximum quantum yield [Fv/Fm]), independent of warming and acidification. Our results show that even moderate warming affected the functioning of key benthic species, and we identified a level of resistance to predicted ocean acidification. Importantly, we show that the presence of a second functional group enhanced the functioning of both groups (mussels and algae), independent of changing environmental conditions, which highlights the ecological and potential economic benefits of conserving biodiversity in marine ecosystems.
Toward improved human health: Ferroptosis‐related “Hyperfoods” as the nutritional supplement in COVID‐19
Authors: Zhao Yanan , Cao Hui , Ma Linyin , Wang Zixu , Guan Shuang , Teng Hui , Chen Lei
Published: September 2024

The outbreak of coronavirus disease 2019 (COVID‐19) stimulates a body of studies for better investigating the essential mechanisms and clinical characteristics of this disease. Notwithstanding, the underlying mechanisms of multiple organ failure (MOF) remain unclear. Understanding the mechanism of COVID‐19‐stimulated programmed cell death (RCD) may contribute to better strategies for these patients. Based on the exploration of COVID‐19‐related basic science reports and clinical research, we speculate that ferroptosis, a recently identified RCD, might be a substantial stimulator for MOF in COVID‐19, and it may act as a novel treatment target. However, the published investigations to determine how ferroptosis works in severe acute respiratory syndrome coronavirus 2 infection are still lacking. This review reveals new crucial missing links in our prevailing understanding of the mechanisms that ferroptosis‐triggered MOF in COVID‐19 patients. We also specifically summarize several literatures evidence about the functional food components as the nutritional supplement for COVID‐19 by its characteristics of ferroptosis inhibition. We hope this hypothesis may launch a new wave of studies to unveil the relationship between ferroptosis and COVID‐19 and explore more ferroptosis‐related functional food components in daily life for preventing the COVID‐19 and/or to improve the outcome during therapy.
Photocatalyst‐Free Chiral Phosphoric Acid‐Catalyzed Enantioselective Minisci‐Type Alkylation of N‐Heteroarenes
Authors: Jin Songyang , Li Yujun , Wang Rong , Zheng Ke
Published: September 2024

In this study, we present an efficient radical approach for the enantioselective Minisci‐type alkylation of N‐heteroarenes, using chiral phosphoric acid (CPA) as a catalyst under mild conditions, without the need for metals, photocatalysts, and other additives. Prochiral α‐aminoalkyl radicals generated from RAEs were successfully introduced to N‐heteroarene derivatives, including pyridine, quinoline, and isoquinoline, resulting in a range of valuable chiral alkylated N‐heteroarenes with secondary amines in high yields and good to excellent enantioselectivities (up to 98 % ee). The chiral phosphoric acid catalyst not only activates the substrate and induces asymmetry but also facilitates essential electron transfer processes.
Research Progress in Dielectric Properties of Inorganic Two‐Dimensional Nano‐Fillers Polyvinylidene Fluoride Nano‐Dielectric Materials
Authors: Qin Jinqi , Lu Hongwei , Yang Shijia , Su Weitao , Xing Yu
Published: September 2024

Two‐dimensional (2D) nanofillers can effectively improve the performance of nano‐dielectrics by having larger aspect ratios and larger electron‐scattering interfaces than one‐dimensional (1D) nanofillers and zero‐dimensional (0D) nanofillers; the formation of a large interfacial area in the polymer matrix effectively traps or scatters the mobile charges and increases the curvature of the propagation paths of the electric tree, thus effectively increasing the breakdown strength and the energy‐storage density of nanodielectrics. In this article, the intrinsic mechanism of 2D nanodielectrics is elaborated using percolation theory, microcapacitance theory, interfacial model, and ping‐pong racket model. Surface modification, oriented alignment, and multilayer structural design are reviewed to enhance the dielectric properties of nanodielectrics. Additionally, an outlook on the multiple challenges and potential opportunities in the process of preparing energy‐storage capacitors with excellent performance is provided.