bluuebunny/crossref_metadata_2025 huggingface dataset:
Diradical B/N‐Doped Polycyclic Hydrocarbons
Authors: Guo Jiaxiang , Li Zeyi , Tian Xinyu , Zhang Tianyu , Wang Yue , Dou Chuandong
Published: January 2023

Heterocyclic diradicaloids with atom‐precise control over open‐shell nature are promising materials for organic electronics and spintronics. Herein, we disclose quinoidal π‐extension of a B/N‐heterocycle for generating B/N‐type organic diradicaloids. Two quinoidal π‐extended B/N‐doped polycyclic hydrocarbons that feature fusion of the B/N‐heterocycle motif with the antiaromatic s‐indacene or dicyclopenta[b,g]naphthalene core were synthesized. This quinoidal π‐extension and B/N‐heterocycle leads to their open‐shell electronic nature, which stands in contrast to the multiple‐resonance effect of conventional B/N‐type emitters. These B/N‐type diradicaloids have modulated (anti)aromaticity and enhanced diradical characters comparing with the all‐carbon analogues, as well as intriguing properties, such as magnetic activities, narrow energy gaps and highly red‐shifted absorptions. This study thus opens the new space for both of B/N‐doped polycyclic π‐systems and heterocyclic diradicaloids.
Molecular Nickel Thiolate Complexes for Electrochemical Reduction of CO2 to C1–3 Hydrocarbons
Authors: Du Jiehao , Cheng Banggui , Yuan Huiqing , Tao Yuan , Chen Ya , Ming Mei , Han Zhiji , Eisenberg Richard
Published: January 2023

We report the unprecedented electrocatalytic activity of a series of molecular nickel thiolate complexes (1–5) in reducing CO2 to C1–3 hydrocarbons on carbon paper in pH‐neutral aqueous solutions. Ni(mpo)2 (3, mpo=2‐mercaptopyridyl‐N‐oxide), Ni(pyS)3− (4, pyS=2‐mercaptopyridine), and Ni(mp)2− (5, mp=2‐mercaptophenolate) were found to generate C3 products from CO2 for the first time in molecular complex. Compound 5 exhibits Faradaic efficiencies (FEs) of 10.6 %, 7.2 %, 8.2 % for C1, C2, C3 hydrocarbons respectively at −1.0 V versus the reversible hydrogen electrode. Addition of CO to the system significantly promotes the FEC1–C3 to 41.1 %, suggesting that a key Ni−CO intermediate is associated with catalysis. A variety of spectroscopies have been performed to show that the structures of nickel complexes remain intact during CO2 reduction.
A Carbon‐Negative Hydrogen Production Strategy: CO2Selective Capture with H2Production
Authors: Gao Mingyu , Fan Jiaxuan , Li Xintao , Wang Qian , Li Dianqing , Feng Junting , Duan Xue
Published: January 2023

We reported a strategy of carbon‐negative H2production in which CO2capture was coupled with H2evolution at ambient temperature and pressure. For this purpose, carbonate‐type CuxMgyFezlayered double hydroxide (LDH) was preciously constructed, and then a photocatalysis reaction of interlayer CO32−reduction with glycerol oxidation was performed as driving force to induce the electron storage on LDH layers. With the participation of pre‐stored electrons, CO2was captured to recover interlayer CO32−in presence of H2O, accompanied with equivalent H2production. During photocatalysis reaction, Cu0.6Mg1.4Fe1exhibited a decent CO evolution amount of 1.63 mmol g−1and dihydroxyacetone yield of 3.81 mmol g−1. In carbon‐negative H2production process, it showed an exciting CO2capture quantity of 1.61 mmol g−1and H2yield of 1.44 mmol g−1. Besides, this system possessed stable operation capability under simulated flu gas condition with negligible performance loss, exhibiting application prospect.
Improving the flame retardancy efficiency and mechanical properties of the intumescent flame retarded low‐density polyethylene by the dual actions of polyurea microencapsulation and aluminum hypophosphite
Authors: Jiang Licong , Gao Ming , Xiao Leqin , Wang Xinlong , Zhou Weiliang
Published: January 2023

The use of intumescent flame retardants to retard polyethylene usually had the disadvantages of low flame retardancy efficiency and poor compatibility between intumescent flame retardants and low‐density polyethylene (LDPE), which led to the reduction of mechanical properties of materials. In order to solve these issues, the microencapsulated ammonium polyphosphate (MAPP) and microencapsulated aluminum hypophosphite (MAHP) with polyurea were prepared through the interfacial polymerization of water‐in‐oil (W/O) microemulsions. The flame retarded polyethylene composites with MAPP and MAHP were manufactured. The LDPE composites with 17.3 wt% of MAPP and 3.9 wt% of MAHP possessed a LOI value of 27.3% and achieved the V‐0 standard. The PHRR and THR were remarkably decreased by 30.3% and 31.1% compared with that of the LDPE. Furthermore, the tensile strength of LDPE/MAPP‐MAHP was 19.1% higher than that of LDPE/APP‐AHP because of good dispersion and compatibility of MAPP and MAHP with LDPE. This work provides a new method to prepare flame‐retardant LDPE with high performance and the related mechanisms were discussed in detail.
Experimental and modeling studies of IPDI‐based polyurea elastomers – The role of hard segment fraction
Authors: Tzelepis Demetrios A. , Suzuki Jorge , Su Yi Feng , Wang Yiyu , Lim Yong Chae , Zayernouri Mohsen , Ginzburg Valeriy V.
Published: January 2023

Segmented polyureas (PUa) are industrially important class of polymers widely used in coatings, sealant, and adhesive applications. Here, we report synthesis, characterization, and modeling of Isophorone Diisocyanate‐Diethyl‐Toluene‐Diamine‐Polyether amine (IPDI‐DETDA‐PO PUa) with varied hard segment contents of 20, 30, and 40 weight percent. For each of the three materials, we study its structure and phase behavior using FTIR, DSC, and TEM, and clearly show the presence of microphase separation between the hard and soft nanodomains. We then measure the linear viscoelastic response of the PUa‐s using DMA (frequency sweeps at multiple temperatures). The DMA data are shown to obey the time‐temperature superposition. Finally, we develop a new micromechanical model describing the DMA results; the model describes a phase‐separated PUa as two “Fractional‐order Maxwell gels” branches, connected in parallel, with the first FMG branch representing the “percolated hard phase" and the second one modeling the “filled soft phase". In agreement with the earlier thermodynamic theories, the volume‐fraction of the percolated hard phase is related to the hard segment weight‐fraction (HSWF), defined as the combined mass of IPDI and DETDA normalized to the total mass of the polymer. The data and model are found to be in a good qualitative and quantitative agreement.
Amined polyallylamine particles synthesized by plasma
Authors: Flores‐Nava Fernando G. , Ramírez Rosario , Olayo González M. Guadalupe , Colín‐Orozco Elena , Palacios González J. Cuauhtémoc , Cruz Guillermo J.
Published: January 2023

This work presents the synthesis of polyallylamine (PAl) particles starting from allylamine using resistive‐inductive electrical glow discharges. PAl particles obtained directly from allylamine had not been reported before, only in combination with other components. PAl has a great number of applications as a biomaterial, due among other things to its great amine content. The particles were synthesized with a spherical profile with diameter in the 47–2900 nm range and were eroded with an Argon beam in a X‐ray photoelectron spectrometer to calculate the amine content inside. Primary (4%–10%), secondary (38%–49%), tertiary (7%–31%), and unsaturated (22%–41%) amines were found in the particles as a function of the power of synthesis. Analyzing from the surface to the interior of the particles, the results showed that secondary amines slightly reduce, and tertiary amines increase. The electric conductivity of the particles was calculated as a function of temperature in the 10−8–10−4 S/m interval with a semiconductor behavior increasing as the diameter reduces. The electrical properties are important in the application of these particles in the central nervous system.
Endocast, brain, and bones: Correspondences and spatial relationships in squamates
Authors: Allemand Rémi , Abdul‐Sater Jade , Macrì Simone , Di‐Poï Nicolas , Daghfous Gheylen , Silcox Mary T.
Published: January 2023

Vertebrate endocasts are widely used in the fields of paleoneurology and comparative neuroanatomy. The validity of endocranial studies is dependent upon the extent to which an endocast reflects brain morphology. Due to the variable neuroanatomical resolution of vertebrate endocasts, direct information about the brain morphology can be sometimes difficult to assess and needs to be investigated across lineages. Here, we employ X‐ray computed tomography (CT), including diffusible iodine‐based contrast‐enhanced CT, to qualitatively compare brains and endocasts in different species of squamates. The relative position of the squamate brain within the skull, as well as the variability that may exist in such spatial relationships, was examined to help clarify the neurological regions evidence on their endocasts. Our results indicate that squamate endocasts provide variable representation of the brain, depending on species and neuroanatomical regions. The olfactory bulbs and peduncles, cerebral hemispheres, as well as the medulla oblongata represent the most easily discernable brain regions from squamate endocasts. In contrast, the position of the optic lobes, the ventral diencephalon and the pituitary may be difficult to determine depending on species. Finally, squamate endocasts provide very limited or no information about the cerebellum. The spatial relationships revealed here between the brain and the surrounding bones may help to identify each of the endocranial region. However, as one‐to‐one correspondences between a bone and a specific region appear limited, the exact delimitation of these regions may remain challenging according to species. This study provides a basis for further examination and interpretation of squamate endocast disparity.
Pyrazole/pyrazoline as an excellent pharmacophore in the design of carbonic anhydrase inhibitors (2018–2022)
Authors: Dorbabu Atukuri
Published: January 2023

Carbonic anhydrase (CA) is a metalloenzyme that catalyzes the interconversion between carbon dioxide and water and dissociated ions of carbonic acid. In addition, CA performs various other functions in animals and plants, depending on the part of the living being. CAs have been found in almost all organisms. Besides, CAs are associated with several diseases, such as glaucoma, obesity, epilepsy, cancer, and so on. CAs are also involved in tumor cell growth and angiogenesis. Thus, inhibition of CA may be an attractive way of control of such diseases. Hence, CA inhibitors have been designed and developed to cure CA‐associated diseases. Some examples of approved CA inhibitors are dorzolamide, methazolamide, brinzolamide, and dichlorphenamide. Furthermore, various heterocyclic scaffolds were utilized for the design of CA inhibitors. Among those, pyrazole/pyrazoline derivatives have exhibited greater potency toward CA inhibition. Hence, research that took place in the field of drug design and discovery of CA inhibition has been systematically reviewed and collated. Alongside, the structure–activity relationship has been described, followed by a description of the most potent molecules and their structural features.
Ligand‐Dependant Selective Synthesis of Mono‐ and Dialkenylcarbazoles through Rhodium(III)‐Catalyzed C−H Alkenylation
Authors: Tanaka Rikuto , Ochiai Shiho , Sakai Asumi , Usuki Yoshinosuke , Kang Bubwoong , Shinada Tetsuro , Satoh Tetsuya
Published: January 2023

The C−H alkenylation of N‐acetylcarbazoles proceeds smoothly at the C1‐position in the presence of a cationic Cp*Rh(III) catalyst to produce 1‐alkenylcarbazoles. The use of a cationic CpERh(III) catalyst enables further alkenylation to give 1,8‐dialkenylcarbazoles. The direct alkenylation procedure in combination with the ready removal of the acetyl directing group provides a straightforward synthetic pathway to 1‐ and/or 8‐alkenyl‐N‐H‐carbazole derivatives. One of 1‐alkenyl‐N‐H‐carbazoles obtained by the present C−H alkenylation/deacetylation exhibits solvatochromism.
Swing option pricing consistent with futures smiles
Authors: Daluiso Roberto , Nastasi Emanuele , Pallavicini Andrea , Sartorelli Giulio
Published: January 2023

In commodity and energy markets swing options allow the buyer to hedge against futures price fluctuations and to select its preferred delivery strategy within daily or periodic constraints, possibly fixed by observing quoted futures contracts. In this paper we focus on the natural gas market and we present a dynamical model for commodity futures prices able to calibrate liquid market quotes and to imply the volatility smile for futures contracts with different delivery periods. We implement the numerical problem by means of a least‐square Monte Carlo simulation and we investigate alternative approaches based on reinforcement learning algorithms.
Application of preparative high‐speed countercurrent chromatography for the separation and purification of three flavonoids from Oroxylum indicum
Authors: Zhou Yan , Shan Hu , Lü Haitao
Published: January 2023

An efficient method was established by high‐speed countercurrent chromatography (HSCCC) for the separation and purification of three flavonoids from Oroxylum indicum. Optimized by single‐factor and orthogonal experiments, the optimal extraction conditions were an extraction temperature of 50°C, a solid‐to‐liquid ratio of 1:50 (g/ml), an ethanol concentration of 75% and an extraction time of 45 min. Using a two‐phase solvent system composed of chloroform–methanol–water (6:10:5, v/v/v), the preparative separation was successfully performed by HSCCC in head‐to‐tail elution mode. Totals of 12.63 mg of oroxin A at a purity of 97.61% with 96.46% recovery, 10.96 mg oroxin B at a purity of 98.32% with 98.81% recovery, and 9.34 mg baicalein at a purity of 98.64% with 97.87% recovery were obtained in one‐step separation from 200 mg crude extract. Their chemical structures were confirmed by melting points, HPLC, UV, FTIR, MS, 1H and 13C NMR data. Furthermore, they were efficient scavengers of 1,1‐diphenyl‐2‐picrylhydrazyl and hydroxyl free radicals in a concentration‐dependent manner.
The core of maintaining neuropathic pain: Crosstalk between glial cells and neurons (neural cell crosstalk at spinal cord)
Authors: Zhang Tianrui , Zhang Mingqian , Cui Shuang , Liang Wulin , Jia Zhanhong , Guo Fanfan , Ou Wenjing , Wu Yonghong , Zhang Shuofeng
Published: January 2023

Background

Neuropathic pain (NP) caused by the injury or dysfunction of the nervous system is a chronic pain state accompanied by hyperalgesia, and the available clinical treatment is relatively scarce. Hyperalgesia mediated by pro‐inflammatory factors and chemokines plays an important role in the occurrence and maintenance of NP.

Data treatment

Therefore, we conducted a systematic literature review of experimental NP (PubMed Medline), in order to find the mechanism of inducing central sensitization and explore the intervention methods of hyperalgesia caused by real or simulated injury.

Result

In this review, we sorted out the activation pathways of microglia, astrocytes and neurons, and the process of crosstalk among them. It was found that in NP, the microglia P2X4 receptor is the key target, which can activate the mitogen‐activated protein kinase pathway inward and then activate astrocytes and outwardly activate neuronal tropomyosin receptor kinase B receptor to activate neurons. At the same time, activated neurons continue to maintain the activation of astrocytes and microglia through chemokines on CXCL13/CXCR5 and CX3CL1/CX3CR1. This crosstalk process is the key to maintaining NP.

Conclusion

We summarize the further research on crosstalk among neurons, microglia, and astrocytes in the central nervous system, elaborate the ways and connections of relevant crosstalk, and find potential crosstalk targets, which provides a reference for drug development and preclinical research.
Abnormal gait and motor cortical processing in drug‐resistant juvenile myoclonic epilepsy
Authors: Maidan Inbal , Yam Mor , Glatt Sigal , Nosatzki Shai , Goldstein Lilach , Giladi Nir , Hausdorff Jeffrey M , Mirelman Anat , Fahoum Firas
Published: January 2023

Background

Juvenile myoclonic epilepsy (JME) is characterized by generalized seizures. Nearly 30% of JME patients are drug‐resistant (DR‐JME), indicating a widespread cortical dysfunction. Walking is an important function that necessitates orchestrated coordination of frontocentral cortical regions. However, gait alterations in JME have been scarcely investigated. Our aim was to assess changes in gait and motor‐evoked responses in DR‐JME patients.

Methods

Twenty‐nine subjects (11 JME drug‐responder, 8 DR‐JME, and 10 healthy controls) underwent a gait analyses during usual walking and dual‐task walking. Later, subjects underwent 64‐channel EEG recordings while performing a simple motor task. We calculated the motor‐evoked current source densities (CSD) at a priori chosen cortical regions. Gait and CSD measures were compared between groups and tasks using mixed model analysis.

Results

DR‐JME patients demonstrated an altered gait pattern that included slower gait speed (p = .018), reduced cadence (p = .003), and smaller arm‐swing amplitude (p = .011). The DR‐JME group showed higher motor‐evoked CSD in the postcentral gyri compared to responders (p = .049) and both JME groups showed higher CSD in the superior frontal gyri compared to healthy controls (p < .011). Moreover, higher CSD in the superior frontal gyri correlated with worse performance in dual‐task walking (r > |–0.494|, p < .008).

Conclusions

These alterations in gait and motor‐evoked responses in DRE‐JME patients reflect a more severe dysfunction of motor‐cognitive neural processing in frontocentral regions, leading to poorer gait performance. Further studies are needed to investigate the predictive value of altered gait and cortical motor processing as biomarkers for poor response to treatment in JME and other epilepsy syndromes.
How does anticipatory trauma reaction and climate‐friendly behaviour make an affect at the individual level? The role of social norms and self‐efficacy
Authors: Yadav Radha , Kumar Dharmendra , Kumar Anil , Luthra Sunil
Published: January 2023

Climate change is unavoidable and requires serious consideration at both the organizational and individual levels. Climate change mitigation, reduction in greenhouse gas emissions globally and climate financing for developing countries and so forth are key issues and challenges toward environmental sustainability. This paper aims to develop a framework for climate‐friendly behaviour (CFB) for environmental sustainability from an individual perspective. The present study recognizes the role of social norms and self‐efficacy in developing positive behaviour toward environmental sustainability. On the proposed integrated CFB framework of value‐belief‐norms (VBN) and self‐efficacy theory, this study is a unique conceptual‐empirical scholarly development, examining individual‐level contemplation toward climate‐supportive policy measures. This research evaluates the relationship between anticipatory trauma reaction (ATR) and CFB in the presence of perceived social efficacy (PSE) and perceived social norms (PSN) as moderators and mediators. We have used the survey method to examine a sample of 238 respondents and assess the structural equation modelling analysis and PLS predictions using SmartPLS software. The findings indicate that climate change‐related anxiety‐driven ATR facilitates CFB among individuals. Next, the study adds value to VBN theory as the results also suggest that PSN improve ATR's positive impact on CFB. This work further expands the horizon of self‐efficacy theory by arguing that PSE transmits the positive effect of ATR on CFB. The study delivers many worthy theoretical and practical contributions toward climate change policies and environmental sustainability implications.
Cessation of dangerousness status in Brasília, Brazil: An analysis of 144 reports from Federal District Medical Examiner's Office in the last 10 years
Authors: de Oliveira Gustavo Carvalho , Dumay Henrique Oliveira , da Silva Thayná Pereira , Fraga Marina Clara Oliveira , Valença Alexandre Martins
Published: January 2023

The aim of this study is to evaluate factors related to cessation of dangerousness of individuals under safety measures, through the study of psychiatric reports. This is a cross‐sectional study, conducted through a retrospective analysis of expert psychiatric dangerousness cessation reports issued by the Federal District Coroner's Office, Brasília, Brazil. By examining official files, information was extracted from the reports (socio‐demographic data, clinical characteristics, type of crime, historical characteristics and the search for items related to risk assessment present in instruments such as Historical, Clinical and Risk Management [HCR‐20], Psychopathy Checklist – Revised [PCL‐R], Two‐Tiered Violence Risk Scale [TTV], Short‐Term Assessment of Risk and Treatability [START] and others) and submitted to statistical analysis and then compared to other studies on the subject. The items most considered by the experts were those referring to PCL‐R, START and the “non static” part of HCR‐20 and TTV. For the non‐cessation of dangerousness, we've found: absence of remorse, fragile behavioral control, early behavioral problems, juvenile delinquency. For the cessation of dangerousness, we've found: presence of social skills, balanced emotional state, presence of social support, adherence to rules, good coping strategies, involvement with treatment and adherence. The systematization and standardization of forensic psychiatric reports needs to be established and the use of risk assessment instruments are essential to support better decisions by the experts.
Acyltransferase Domain Exchange between Two Independent Type I Polyketide Synthases in the Same Producer Strain of Macrolide Antibiotics
Authors: Kudo Fumitaka , Kishikawa Kosuke , Tsuboi Kazuma , Kido Takafusa , Usui Takeo , Hashimoto Junko , Shin‐ya Kazuo , Miyanaga Akimasa , Eguchi Tadashi
Published: January 2023

Streptomyces graminofaciens A‐8890 produces two macrolide antibiotics, FD‐891 and virustomycin A, both of which show significant biological activity. In this study, we identified the virustomycin A biosynthetic gene cluster, which encodes type I polyketide synthases (PKSs), ethylmalonyl‐CoA biosynthetic enzymes, methoxymalony‐acyl carrier protein biosynthetic enzymes, and post‐PKS modification enzymes. Next, we demonstrated that the acyltransferase domain can be exchanged between the Vsm PKSs and the PKSs involved in FD‐891 biosynthesis (Gfs PKSs), without any supply problems of the unique extender units. We exchanged the malonyltransferase domain in the loading module of Gfs PKS with the ethylmalonyltransferase domain and the methoxymalonyltransferase domain of Vsm PKSs. Consequently, the expected two‐carbon‐elongated analog 26‐ethyl‐FD‐891 was successfully produced with a titer comparable to FD‐891 production by the wild type; however, exchange with the methoxymalonyltransferase domain did not produce any FD‐891 analogs. Furthermore, 26‐ethyl‐FD‐891 showed potent cytotoxic activity against HeLa cells, like natural FD‐891.
Nutlin‐3a‐aa: Improving the Bioactivity of a p53/MDM2 Interaction Inhibitor by Introducing a Solvent‐Exposed Methylene Group
Authors: Nietzold Florian , Rubner Stefan , Labuzek Beata , Golik Przemysław , Surmiak Ewa , del Corte Xabier , Kitel Radoslaw , Protzel Christoph , Reppich‐Sacher Regina , Stichel Jan , Magiera‐Mularz Katarzyna , Holak Tad A. , Berg Thorsten
Published: January 2023

Nutlin‐3a is a reversible inhibitor of the p53/MDM2 interaction. We have synthesized the derivative Nutlin‐3a‐aa bearing an additional exocyclic methylene group in the piperazinone moiety. Nutlin‐3a‐aa is more active than Nutlin‐3a against purified wild‐type MDM2, and is more effective at increasing p53 levels and releasing transcription of p53 target genes from MDM2‐induced repression. X‐ray analysis of wild‐type MDM2‐bound Nutlin‐3a‐aa indicated that the orientation of its modified piperazinone ring was altered in comparison to the piperazinone ring of MDM2‐bound Nutlin‐3a, with the exocyclic methylene group of Nutlin‐3a‐aa pointing away from the protein surface. Our data point to the introduction of exocyclic methylene groups as a useful approach by which to tailor the conformation of bioactive molecules for improved biological activity.
Synthesis of Efficient and Stable Tetrabutylammonium Copper Halides with Dual Emissions for Warm White Light‐Emitting Diodes
Authors: Meng Wen , Wang Chuying , Li Yacong , Hu Guangcai , Sui Shiqi , Xu Guangyong , Peng Min , Deng Zhengtao
Published: January 2023

In order to achieve a high color‐rendering index (CRI) and low correlated color temperature (CCT) indoor lighting, single‐component phosphors with broad‐band dual emission are in high demand for white‐light‐emitting diodes (WLEDs). However, phosphors with such fluorescent properties are rare at present. Herein, we report a facile solid‐state chemical method for the synthesis of single‐component phosphor with broad‐band emission and a large Stokes shift that can meet the requirements of future white‐light sources. These new tetrabutylammonium copper halides phosphors have excellent warm white emission characteristics, and their luminescence peaks are located at 494 and 654 nm. The optimized photoluminescence (PL) quantum yield can reach 93.7 %. The typical CIE coordinate of the as‐fabricated WLED is at (0.3620, 0.3731) with a CRI of 89 and low CCT of 4516 K.
Transition‐Metal‐Free Intermolecular Hydrocarbonation of Styrenes Mediated by NaH/1,10‐Phenanthroline
Authors: Nozawa‐Kumada Kanako , Onuma So , Ono Kanako , Kumagai Tomohiro , Iwakawa Yuki , Sato Katsuhiko , Shigeno Masanori , Kondo Yoshinori
Published: January 2023

A transition‐metal‐free intermolecular coupling reaction of halocompounds with styrenes in the presence of NaH and 1,10‐phenanthroline was developed. This reaction afforded hydrocarbonated products with complete anti‐Markovnikov selectivity. The method allows the use of a wide range of halocompounds, including aryl and alkyl halides, and good functional group tolerance. Detailed mechanistic studies indicated that an anilide anion generated in situ by the NaH‐mediated reduction of 1,10‐phenanthroline works as an electron donor and a hydrogen source.
Ring‐Expanding Rearrangement of Benzo‐Fused Tris‐Cycloheptenylenes towards Nonplanar Polycyclic Aromatic Hydrocarbons
Authors: Ejlli Barbara , Rominger Frank , Freudenberg Jan , Bunz Uwe H. F. , Müllen Klaus
Published: January 2023

A strongly twisted benzo‐fused tris‐cycloheptenylene, containing three dibenzosuberenone units fused to a common benzene ring, was subjected to Ramirez olefination and subsequent palladium‐catalyzed Suzuki‐Miyaura cross‐coupling with 4‐substituted phenylboronic acids. The high steric demand within the overcrowded, benzene‐rich benzo‐fused tris‐cycloheptenylenes enforced an unprecedented 1,2‐rearrangement upon π‐extension during the Suzuki coupling reaction. According to crystal structure analysis, the resulting negatively curved polycyclic aromatic hydrocarbons consist of two heptagons and one octagon surrounding a central benzene ring as a result of strain release. In the solid state, the materials exhibit a blue to blue‐green fluorescence with increased quantum yields and a hypsochromic shift of the emission maxima compared to their respective solutions.
Asymmetric aza‐Friedel–Crafts Reaction of Cyclic Ketimines with 5‐Aminopyrazole Derivatives: Expedient Access to Pyrazole‐Based C2‐quaternary Indolin‐3‐Ones
Authors: Qiao Xiu‐Xiu , He Yonghui , Ma Tao , Zou Chang‐Peng , Wu Xi‐Xi , Li Ganpeng , Zhao Xiao‐Jing
Published: January 2023

A chiral phosphoric acid‐catalyzed enantioselective aza‐Friedel–Crafts reaction of 5‐aminopyrazole derivatives with cyclic ketimines attached to a neutral functional group is reported. This protocol allows the formation of pyrazole‐based C2‐quaternary indolin‐3‐ones with high enantioselectivities and regioselectivities. Moreover, gram‐scale synthesis of the 5‐aminopyrazole‐based C2‐quaternary indolin‐3‐ones was performed, with no decrease in the yield and enantioselectivity.
Advances in Polymethine Dyes for Near‐Infrared Organic Photodiodes†
Authors: He Jin , Xiao Qi , Shao Ming , Li Zhong'an
Published: January 2023

Comprehensive Summary

Near‐infrared organic photodiodes (NIR OPDs) have tremendous potential in industrial, military, and scientific applications, due to their unique features of lightweight, low toxicity, high structural flexibility, cooling‐system‐free, etc. However, the overall performance of currently available NIR OPDs still lags behind the commercial inorganic photodetectors, ascribed to the critical challenge of realizing organic semiconductors with sufficiently low optical bandgap and excellent optoelectronic properties simultaneously. Among various types of NIR‐absorbing organic semiconductors, polymethine dyes not only possess advantages of simple synthesis and structural diversity, but also show fascinating optical and aggregation features in the solid state, making them attractive material candidates for NIR OPDs. In this review, after a brief introduction of NIR OPDs and polymethine dyes, we comprehensively summarize the advances of polymethine dyes for broadband and narrowband NIR OPDs, and further introduce their applications in all‐organic optical upconversion devices and photoplethysmography sensors. In particular, the relationship between the chemical structure and the aggregation behaviors of polymethine dyes and the device performance is carefully discussed, providing some important molecular insights for developing high performance NIR OPDs.
Understanding the Target Search by Multiple Transcription Factors on Nucleosomal DNA
Authors: Kumar Mishra Sujeet , Bhattacherjee Arnab
Published: January 2023

The association of multiple Transcription Factors (TFs) in the cis‐regulatory region is imperative for developmental changes in eukaryotes. The underlying process is exceedingly complex, and it is not at all clear what orchestrates the overall search process by multiple TFs. In this study, by developing a theoretical model based on a discrete‐state stochastic approach, we investigated the target search mechanism of multiple TFs on nucleosomal DNA. Experimental kinetic rate constants of different TFs are taken as input to estimate the Mean‐First‐Passage time to recognize the binding motifs by two TFs on a dynamic nucleosome model. The theory systematically analyzes when the TFs search their binding motifs hierarchically and when simultaneously by proceeding via the formation of a protein‐protein complex. Our results, validated by extensive Monte Carlo simulations, elucidate the molecular basis of the complex target search phenomenon of multiple TFs on nucleosomal DNA.
Tailored Charge Transfer Kinetics in Precursors for Organic Radical Batteries: A Joint Synthetic‐Theoretical Approach
Authors: Zens Clara , Friebe Christian , Schubert Ulrich S. , Richter Martin , Kupfer Stephan
Published: January 2023

Invited for this month's cover is the group of Stephan Kupfer at the Friedrich Schiller University Jena. The image shows the charge transfer from TEMPO to thiophene in organic radical batteries. The Research Article itself is available at 10.1002/cssc.202201679.
The functional anatomy of the cornea of the Shorthead lamprey, Mordacia mordax (Mordaciidae, Agnatha): A comparison between downstream and upstream migrants
Authors: Collin Hermann Barry , Ratcliffe Julian , Collin Shaun P.
Published: January 2023

The Shorthead lamprey Mordacia mordax (Mordaciidae, Agnatha) represents one of the earliest stages of vertebrate evolution. This study investigates the ultrastructural anatomy of the cornea, iris and anterior chamber in the eyes of this species in both the downstream and upstream migrant phases of its protracted lifecycle to assess the morphological and quantitative changes associated with growth, corneal function and vision. Using light and both scanning and transmission electron microscopy, the cornea is found to be divided into dermal and scleral components separated by a mucoid layer. A range of distinguishing corneal features are compared in the two adult phases of the lifecycle, including epithelial microprojections, mucus‐secreting epithelial cells, the number, thickness, formation and level of branching and anastomosing of collagen lamellae, the type and distribution of vertical sutures, the structure of the mucoid layer and annular ligament and the number and distribution of a large number of basement membranes throughout the cornea. Significant differences are found between the two phases, which are thought to reflect adaptations to the variable environmental conditions encountered throughout this species' lifecycle. The study provides insights into the evolutionary pressures on extant representatives of the earliest stages in the evolution of the vertebrate eye.
National trends in physical activity among adolescents in South Korea before and during the COVID‐19 pandemic, 2009−2021
Authors: Kwon Rosie , Koo Min Ji , Lee Seung Won , Choi Yong Sung , Shin Youn Ho , Shin Jung U. , Koyanagi Ai , Jacob Louis , Smith Lee , Rhee Sang Youl , Kim Hyug‐Gi , Min Chanyang , Cho Seong Ho , Yeniova Abdullah Özgür , Kim So Young , Lee Jinseok , Yeo Seung Geun , Il Shin Jae , Yon Dong Keon
Published: January 2023

With the ongoing COVID‐19 pandemic, several previous studies from different countries showed that physical activity (PA) decreased during the COVID‐19 outbreak. However, few studies have examined the recent tendency of PA in the adolescent population. Thus, we aimed to investigate the long‐term trend of PA in Korean youth and the prevalence changes between before and during the COVID‐19 pandemic. Data from Korea Youth Risk Behavior Web‐Based Survey (KYRBS) was collected for consecutive years between 2009 and 2021. The period was separated into prepandemic (2009−2019), early‐pandemic (2020), and mid‐pandemic (2021). Self‐reported amount of PA was categorized into four groups (insufficient, aerobic, muscle strengthening, and both physical activities) according to World Health Organization (WHO) PA guidelines. A total of 840 488 adolescents aged 12−18 who fully responded to the survey were selected (response rate: 95.2%). The 13‐year trends in the proportion of adolescents who reported aerobic and muscle‐strengthening activities met or exceeded 2020 WHO exercise guidelines for adolescents plateaued (11.9% from 2009 to 2011, 14.2% from 2018 to 2019, 14.4% from 2020, and 14.0% from 2021); however, the slope decreased during the pandemic (βdiff, −0.076; 95% confidence interval [CI], −0.123 to −0.029). Proportion of sufficient aerobic exercise among adolescents sharply decreased midst the pandemic (28.0% from 2009 to 2011, 29.4% from 2018 to 2019, and 23.8% from 2020; βdiff, −0.266; 95% CI, −0.306 to −0.226) but increased again in 2021 (26.0% from mid‐COVID 19; 95% CI, 25.4−26.7). Similar patterns were observed in Metabolic Equivalent Task (MET) score (MET‐min/week; 804.1 from 2018 to 2019, 720.9 from 2020, and 779.6 from 2021). The mean difference in MET score between pre‐COVID and post‐COVID was −55.4 MET‐min/week (95% CI, −70.5 to −40.3). Through a nationwide representative study, there was no significant difference with regard to the number of Korean adolescents who achieved the PA guidelines (pre and postpandemic); however, the prevalence of recommended levels of PA needs to increase more based on the trend before the COVID‐19 outbreak. The findings of this study suggest reinforcement of the importance of public health policies for Korean youths to be more physically active, especially during and after the pandemic.
Memory impairment among recovered COVID‐19 patients: The prevalence and risk factors, a retrospective cohort study
Authors: Merza Muayad A. , Almufty Hind B. , Younis Heewa A. , Rasool Suzan O. , Mohammed Shinah A.
Published: January 2023

The aim of this study is to demonstrate the prevalence of the long‐term side effects of COVID‐19, namely memory impairment among recovered patients, and obtaining the associated factors that link with memory impairment. It is a cross‐sectional retrospective cohort study, that has been conducted from September to November 2022 in Iraq. People who were previously infected with COVID‐19 were included. The study was performed by asking people to complete a questionnaire platform by either online or face‐to‐face interview. The Memory Assessment Clinic‐Q (MAC‐Q) test was utilized, scores that are equal or higher than 25 are indicative of memory decline. Thousand two hundred and eighty‐seven participated in this study. However, only 1157 were included in the final analysis. Three hundred ninety‐nine (34.49%) have memory impairment after COVID‐19 recovery. Female gender, older age group, repeated exposure to COVID‐19 infections, severe diseases, and exposure to multiple SARS‐CoV‐2 variants were independent risk factors of memory deficit in post‐COVID‐19 survivors with a p‐value of 0.0001, 0.02, 0.0001, 0.001, 0.0001 respectively. It is crucial to pay particular attention to psychosocial rehabilitation of such risky groups. COVID‐19 vaccine administrations with booster shots are necessary steps to decrease the disease incidence and avoid subsequent post‐COVID‐19 symptoms.
Infection by SARS‐CoV‐2 with alternate frequencies of mRNA vaccine boosting
Authors: Townsend Jeffrey P. , Hassler Hayley B. , Dornburg Alex
Published: January 2023

One of the most consequential unknowns of the COVID‐19 pandemic is the frequency at which vaccine boosting provides sufficient protection from infection. We quantified the statistical likelihood of breakthrough infections over time following different boosting schedules with messenger RNA (mRNA)‐1273 (Moderna) and BNT162b2 (Pfizer‐BioNTech). We integrated anti‐Spike IgG antibody optical densities with profiles of the waning of antibodies and corresponding probabilities of infection associated with coronavirus endemic transmission. Projecting antibody levels over time given boosting every 6 months, 1, 1.5, 2, or 3 years yielded respective probabilities of fending off infection over a 6‐year span of >93%, 75%, 55%, 40%, and 24% (mRNA‐1273) and >89%, 69%, 49%, 36%, and 23% (BNT162b2). Delaying the administration of updated boosters has bleak repercussions. It increases the probability of individual infection by SARS‐CoV‐2, and correspondingly, ongoing disease spread, prevalence, morbidity, hospitalization, and mortality. Instituting regular, population‐wide booster vaccination updated to predominant variants has the potential to substantially forestall—and with global, widespread uptake, eliminate—COVID‐19.
Development and validation of a deep learning model to diagnose COVID‐19 using time‐series heart rate values before the onset of symptoms
Authors: Chung Heewon , Ko Hoon , Lee Hooseok , Yon Dong Keon , Lee Won Hee , Kim Tae‐Seong , Kim Kyung Won , Lee Jinseok
Published: January 2023

One of the effective ways to minimize the spread of COVID‐19 infection is to diagnose it as early as possible before the onset of symptoms. In addition, if the infection can be simply diagnosed using a smartwatch, the effectiveness of preventing the spread will be greatly increased. In this study, we aimed to develop a deep learning model to diagnose COVID‐19 before the onset of symptoms using heart rate (HR) data obtained from a smartwatch. In the deep learning model for the diagnosis, we proposed a transformer model that learns HR variability patterns in presymptom by tracking relationships in sequential HR data. In the cross‐validation (CV) results from the COVID‐19 unvaccinated patients, our proposed deep learning model exhibited high accuracy metrics: sensitivity of 84.38%, specificity of 85.25%, accuracy of 84.85%, balanced accuracy of 84.81%, and area under the receiver operating characteristics (AUROC) of 0.8778. Furthermore, we validated our model using external multiple datasets including healthy subjects, COVID‐19 patients, as well as vaccinated patients. In the external healthy subject group, our model also achieved high specificity of 77.80%. In the external COVID‐19 unvaccinated patient group, our model also provided similar accuracy metrics to those from the CV: balanced accuracy of 87.23% and AUROC of 0.8897. In the COVID‐19 vaccinated patients, the balanced accuracy and AUROC dropped by 66.67% and 0.8072, respectively. The first finding in this study is that our proposed deep learning model can simply and accurately diagnose COVID‐19 patients using HRs obtained from a smartwatch before the onset of symptoms. The second finding is that the model trained from unvaccinated patients may provide less accurate diagnosis performance compared with the vaccinated patients. The last finding is that the model trained in a certain period of time may provide degraded diagnosis performances as the virus continues to mutate.
The effect of synbiotic adjunct therapy on clinical and paraclinical outcomes in hospitalized COVID‐19 patients: A randomized placebo‐controlled trial
Authors: Vaezi Mahsa , Ravanshad Sahar , Akbari Rad Mina , Zarrinfar Hossein , Kabiri Mona
Published: January 2023

Therapeutic approaches with immune‐modulatory effects such as probiotics and prebiotics adjuvant therapy may be essential to combat against COVID‐19 pandemic. The present trial aimed to reveal the efficacy of synbiotic supplementation on clinical and paraclinical outcomes of hospitalized COVID‐19 patients. The current randomized placebo‐controlled trial enrolled 78 hospitalized patients with confirmed COVID‐19 infection. Participants were randomly allocated to intervention and control groups that received synbiotic or placebo capsules twice daily for 2 weeks, respectively. The synbiotic capsule contains multi‐strain probiotics such as Lactobacillus (L.) rhamnosus, L. helveticus, L. casei, Bifidobacterium (B.) lactis, L. acidophilus, B. breve, L. bulgaricus, B. longum, L. plantarum, B. bifidum, L. gasseri, and Streptococcus (S.) thermophilus (109 CFU), as well as fructooligosaccharides prebiotic agent. Besides COVID‐19 clinical features, levels of proinflammatory interleukin‐6 (IL‐6), C‐reactive protein (CRP), erythrocyte sedimentation rate (ESR), liver and renal function markers, as well as hematological parameters, were assessed during follow‐up. The serum level of IL‐6 was significantly decreased in the intervention group compared to the placebo after 2 weeks of intervention (p = 0.002). A significant difference was found regarding the count of white blood cells (WBC) within the synbiotic group from pre to post‐treatment (p = 0.004). The levels of ESR (p = 0.935) and CRP (p = 0.952) had a higher reduction trend in the synbiotic group relative to the placebo, with no significant between‐group differences. Other findings had no statistical differences between groups. Our results provide the support that synbiotic adjuvant therapy for 2 weeks can be effective to modulate inflammatory responses against COVID‐19 infection.
Neurocognitive impairment in multiple sclerosis and its association with thiol‐disulfide homeostasis and ischemia‐modified albumin
Authors: Can Demirdöğen Birsen , Kiliç Osman Oğuzhan , Yilmaz Ata Ayhan , Mungan Semra , Neşelioğlu Salim , Erel Özcan
Published: January 2023

This study aimed to assess the possible association between cognitive impairment and two important biochemical biomarkers of oxidative stress, thiol‐disulfide homeostasis (TDH), and ischemia‐modified albumin (IMA) in patients with multiple sclerosis (MS). This study included 85 patients with MS (38 treatment‐naïve relapsing–remitting MS (RRMS), 31 RRMS on fingolimod therapy, and 16 secondary progressive MS (SPMS)) and 33 healthy controls. Cognitive evaluation was carried out by applying the Brief International Cognitive Assessment for Multiple Sclerosis (BICAMS) test battery and the scores were adjusted for age and years of education. Plasma TDH was assessed using an automated method and plasma IMA levels were determined using the cobalt‐albumin binding assay. Plasma native thiol and total thiol levels were significantly decreased in patients with SPMS when compared with the naïve patients and healthy controls. Cognitive impairment was detected in 47.4% of naïve patients, 64.5% of patients on fingolimod therapy, and 80% of patients with SPMS. Naïve patients or patients on fingolimod therapy who were cognitively impaired had significantly decreased levels of native thiol and total thiol compared to the cognitively normal patients. Logistic regression analysis revealed total thiol and native thiol to be significantly associated with cognitive impairment in naïve patients and patients on fingolimod therapy. Significant correlations were determined between BICAMS scores, TDH, IMA, clinical indices of disease severity (EDSS and MSSS), and magnetic resonance imaging parameters. This study has shown for the first time that plasma TDH parameters are associated with cognitive impairment in MS.
Casual Observers' Perception on the Aesthetics of the Butterfly Graft
Authors: Mims Mark M. , Shockley William W. , Clark Joseph Madison
Published: January 2023

Objective

The butterfly graft is an effective technique for improving the internal nasal valve, however, there is hesitancy among surgeons due to possible aesthetic changes. This study aims to determine if average observers rated the post‐operative appearance of the butterfly graft negatively.

Methods

An online survey was distributed by social media to non‐medical observers in which they rated either the pre‐operative or post‐operative appearance of 22 patients' noses (11 butterfly graft, 11 spreader graft). A heat map was used to determine if the supratip region was rated as the least aesthetically appealing. Post‐operative ratings and heat maps of the butterfly graft patients were compared to pre‐operative ratings as well as ratings of the spreader graft group.

Results

226 observers responded. There was no difference in the pre‐operative and post‐operative rating of the butterfly graft group (58.27 vs. 58.00, p = 0.88) or the number of supratip regions selected as least attractive (165 vs. 169, p = 0.60). Similarly, there was no difference in post‐operative ratings between the butterfly graft group and spreader graft group (58.00 vs. 58.21, p = 0.63) or in selection of the supratip as the least attractive region (169 vs. 172, p = 0.74).

Conclusion

The butterfly graft did not negatively affect observers' opinion of patients' noses.

Level of Evidence

3 Laryngoscope, 133:2578–2583, 2023