bluuebunny/crossref_metadata_2025 huggingface dataset:
Structure Engineered High Piezo‐Photoelectronic Performance for Boosted Sono‐Photodynamic Therapy
Authors: Zhang Rui , Yang Dan , Zang Pengyu , He Fei , Gai Shili , Kuang Ye , Yang Guixin , Yang Piaoping
Published: November 2023

Sono‐photodynamic therapy is hindered by the limited tissue penetration depth of the external light source and the quick recombination of electron–hole owing to the random movement of charge carriers. In this study, orthorhombic ZnSnO3 quantum dots (QDs) with piezo‐photoelectronic effects are successfully encapsulated in hexagonal upconversion nanoparticles (UCNPs) using a one‐pot thermal decomposition method to form an all‐in‐one watermelon‐like structured sono‐photosensitizer (ZnSnO3@UCNPs). The excited near‐infrared light has high penetration depth, and the watermelon‐like structure allows for full contact between the UCNPs and ZnSnO3 QDs, achieving ultrahigh Förster resonance energy transfer efficiency of up to 80.30%. Upon ultrasonic and near‐infrared laser co‐activation, the high temperature and pressure generated lead to the deformation of the UCNPs, thereby driving the deformation of all ZnSnO3 QDs inside the UCNPs, forming many small internal electric fields similar to isotropic electric domains. This piezoelectric effect not only increases the internal electric field intensity of the entire material but also prevents random movement and rapid recombination of charge carriers, thereby achieving satisfactory piezocatalytic performance. By combining the photodynamic effect arising from the energy transfer from UCNPs to ZnSnO3, synergistic efficacy is realized. This study proposes a novel strategy for designing highly efficient sono‐photosensitizers through structural design.
Associations of the Mediterranean‐DASH Intervention for Neurodegenerative Delay diet with brain structural markers and their changes
Authors: Chen Hui , Dunk Michelle M. , Wang Binghan , Zhao Mengjia , Shen Jie , Zong Geng , Pan Yuesong , Tong Lusha , Xu Weili , Yuan Changzheng
Published: November 2023

INTRODUCTION

The associations of the Mediterranean‐DASH Intervention for Neurodegenerative Delay (MIND) diet with brain structural changes are unclear.

METHODS

Among 26,466 UK Biobank participants, a 15‐point MIND score was calculated from 24‐hour diet recalls from 2009 to 2012. We assessed its associations with 17 magnetic‐resonance‐derived brain volumetric markers and their longitudinal changes and explored whether genetic factors modify the associations.

RESULTS

Higher MIND adherence was associated with larger volumes of thalamus, putamen, pallidum, hippocampus, and accumbens (beta per 3‐unit increment ranging from 0.024 to 0.033) and lower white matter hyperintensities (P‐trends < 0.05), regardless of genetic predispositions of Alzheimer's disease. MIND score was not associated with their longitudinal changes (P > 0.05) over a median of 2.2 years among participants with repeated imaging assessments (N = 2963), but was associated with slower atrophy in putamen (beta: 0.026, P‐trend = 0.044) and pallidum (beta: 0.030, P‐trend = 0.033) among APOE ε4 non‐carriers (N = 654).

DISCUSSION

The MIND diet showed beneficial associations with certain brain imaging markers, and its associations with long‐term brain structural changes warrants future investigation.

Highlights

Adherence to the Mediterranean‐DASH Intervention for Neurodegenerative Delay (MIND) diet was significantly associated with higher volumes and larger gray matter volumes in certain brain regions in UK adults, and the associations were not modified by genetic factors.

No significant associations were observed between MIND diet and longitudinal changes in the investigated brain structural markers over a median of 2.2 years.

Higher MIND score was significantly associated with slower atrophy in the putamen and pallidum among APOE ε4 non‐carriers.
Vascular risk, gait, behavioral, and plasma indicators of VCID
Authors: Raghavan Sheelakumari , Przybelski Scott A. , Lesnick Timothy G. , Fought Angela J. , Reid Robert I. , Gebre Robel K. , Windham B. Gwen , Algeciras‐Schimnich Alicia , Machulda Mary M. , Vassilaki Maria , Knopman David S. , Jack Clifford R. , Petersen Ronald C. , Graff‐Radford Jonathan , Vemuri Prashanthi
Published: November 2023

INTRODUCTION

Cost‐effective screening tools for vascular contributions to cognitive impairment and dementia (VCID) has significant implications. We evaluated non‐imaging indicators of VCID using magnetic resonance imaging (MRI)‐measured white matter (WM) damage and hypothesized that these indicators differ based on age.

METHODS

In 745 participants from the Mayo Clinic Study of Aging (≥50 years of age) with serial WM assessments from diffusion MRI and fluid‐attenuated inversion recovery (FLAIR)‐MRI, we examined associations between baseline non‐imaging indicators (demographics, vascular risk factors [VRFs], gait, behavioral, plasma glial fibrillary acidic protein [GFAP], and plasma neurofilament light chain [NfL]) and WM damage across three age tertiles.

RESULTS

VRFs and gait were associated with diffusion changes even in low age strata. All measures (VRFs, gait, behavioral, plasma GFAP, plasma NfL) were associated with white matter hyperintensities (WMHs) but mainly in intermediate and high age strata.

DISCUSSION

Non‐imaging indicators of VCID were related to WM damage and may aid in screening participants and assessing outcomes for VCID.

Highlights

Non‐imaging indicators of VCID can aid in prediction of MRI‐measured WM damage but their importance differed by age.

Vascular risk and gait measures were associated with early VCID changes measured using diffusion MRI.

Plasma markers explained variability in WMH across age strata.

Most non‐imaging measures explained variability in WMH and vascular WM scores in intermediate and older age groups.

The framework developed here can be used to evaluate new non‐imaging VCID indicators proposed in the future.
Scalable Total Synthesis of Acremolactone B
Authors: Ba Mengyu , He Fengqi , Ren Lu , Whittingham William G. , Yang Peng , Li Ang
Published: November 2023

Acremolactone B is a pyridine‐containing azaphilone‐type polyketide. The first total synthesis of this molecule was achieved on a gram scale, based on an aza‐6π electrocyclization–aromatization strategy for construction of the tetra‐substituted pyridine ring. A bicyclic intermediate was expeditiously prepared by using [2+2] photocycloaddition and chemoselective Baeyer–Villiger oxidation, which was further elaborated to a densely substituted aza‐triene. An electrocyclization–aromatization cascade was utilized to forge the tetracyclic core of this natural product, and the side chain was introduced through diastereoselective acylation and reduction.
Unlocking a Dual‐Channel Pathway in CO2 Hydrogenation to Methanol over Single‐Site Zirconium on Amorphous Silica
Authors: Yang Meng , Yu Jiafeng , Zimina Anna , Sarma Bidyut Bikash , Grunwaldt Jan‐Dierk , Zada Habib , Wang Linkai , Sun Jian
Published: November 2023

Converting CO2 into methanol on a large scale is of great significance in the sustainable methanol economy. Zirconia species are considered to be an essential support in Cu‐based catalysts due to their excellent properties for CO2 adsorption and activation. However, the evolution of Zr species during the reaction and the effect of their structure on the reaction pathways remain unclear. Herein, single‐site Zr species in an amorphous SiO2 matrix are created by enhancing the Zr−Si interaction in Cu/ZrO2‐SiO2 catalysts. In situ X‐ray absorption spectroscopy (XAS) reveals that the coordination environment of single‐site Zr is sensitive to the atmosphere and reaction conditions. We demonstrate that the CO2 adsorption occurs preferably on the interface of Cu and single‐site Zr rather than on ZrO2 nanoparticles. Methanol synthesis in reverse water‐gas‐shift (RWGS)+CO‐hydro pathway is verified only over single‐dispersed Zr sites, whereas the ordinary formate pathway occurs on ZrO2 nanoparticles. Thus, it expands a non‐competitive parallel pathway as a supplement to the dominant formate pathway, resulting in the enhancement of Cu activity sixfold and twofold based on Cu/SiO2 and Cu/ZrO2 catalysts, respectively. The establishment of this dual‐channel pathway by single‐site Zr species in this work opens new horizons for understanding the role of atomically dispersed oxides in catalysis science.
Late‐Stage Halogenation of Peptides, Drugs and (Hetero)aromatic Compounds with a Nucleophilic Hydrazide Catalyst
Authors: Mondal Haripriyo , Patra Subimal , Saha Shuvendu , Nayak Tarak , Sengupta Uddalak , Sudan Maji Modhu
Published: November 2023

Unlike its other halogen atom siblings, chlorination of a bioactive compound can change its physiological characteristics, improve its pharmacological profile, and function as a point of diversification through cross‐coupling reactions. As a result, it has been a crucial strategy for drug discovery and development. However, functional groups such as amines, amides, hydroxy groups, or carboxylic acids trap the Cl+, severely limiting the reactivity and making direct chlorination far too difficult to be practical. Herein, we introduce a nucleophilic sulfonohydrazide catalyst for late‐stage halogenation of peptides and drugs. This direct, mild and metal‐free protocol shows high functional‐group tolerance and is compatible with a range of structurally diverse peptides, drugs and aromatic compounds. Furthermore, DFT studies indicate that the reaction most likely proceeds via a cationic transition state. The gram‐scale synthesis, high stability and efficiency of the catalyst provide a facile route for late‐stage functionalization and intermediates for further derivatization.
Spatial Distribution of Nitrogen Binding Sites in Metal‐Organic Frameworks for Selective Ethane Adsorption and One‐Step Ethylene Purification
Authors: Song Changhua , Zheng Fang , Liu Ying , Yang Qiwei , Zhang Zhiguo , Ren Qilong , Bao Zongbi
Published: November 2023

The one‐step purification of ethylene (C2H4) from mixtures containing ethane (C2H6) and acetylene (C2H2) is an industrially important yet challenging process. In this work, we present a site‐engineering strategy aimed at manipulating the spatial distribution of binding sites within a confined pore space. We realized successfully by incorporating nitrogen‐containing heterocycles, such as indole‐5‐carboxylic acid (Ind), benzimidazole‐5‐carboxylic acid (Bzz), and indazole‐5‐carboxylic acid (Izo), into the robust MOF‐808 platform via post‐synthetic modification. The resulting functionalized materials, namely MOF‐808‐Ind, MOF‐808‐Bzz, and MOF‐808‐Izo, demonstrated significantly improved selectivity for C2H2 and C2H6 over C2H4. MOF‐808‐Bzz with two uniformly distributed nitrogen binding sites gave the optimal geometry for selective ethane trapping through multiple strong C−H⋅⋅⋅N hydrogen bonds, leading to the highest C2H2/C2H4 and C2H6/C2H4 combined selectivities among known MOFs. Column breakthrough experiments validated its ability to purify C2H4 from ternary C2H2/C2H4/C2H6 mixtures in a single step.
A compliance control strategy of lower‐limb exoskeletons for energy‐efficient stance‐squat transitions with a payload
Authors: Hsiao Tesheng , Yu Kai‐Jung
Published: November 2023

This paper proposes an admittance control algorithm for lower‐limb exoskeletons to assist able‐bodied wearers in performing energy‐efficient stance‐squat transitions while carrying a payload of up to 20 kg. A two‐degree‐of‐freedom (DOF) model dedicated to the stance‐squat transition is derived, which takes into account the wearer's torso inclination angle and the vertical displacement of the hip joint. The torso inclination angle is obtained from an inertial measurement unit (IMU) located at the backpack of the exoskeleton. In addition, the moment caused by the torso plus the payload with respect to the hip joint is estimated. Then a model‐based disturbance observer (DOB) is used to estimate the wearer's joint torque as an indication of the motion intention, and the exoskeleton complies with the intention by following the desired joint angular velocity generated from the estimated wearer's joint torque through an admittance function. Experiments with different admittance parameters are conducted, and the energy consumption of the wearer is evaluated in terms of the normalized energy consumption index (NECI) and the physiological cost index (PCI). Furthermore, experimental comparisons of energy consumption are made for a subject carrying a payload of up to 20 kg and performing repeated stance‐squat transitions with and without the exoskeleton. The results show that a 50% reduction of energy consumption (in terms of PCI) is achieved by the exoskeleton with the proposed admittance control strategy.
Impact of training on awareness and Knowledge of Birth Defects among Community Health Workers in tribal district of Maharashtra, India
Authors: Surve Suchitra , Kulkarni Ragini , Gawai Priyanka , Salvi Neha , Begum Shahina , Bodade Sanjay , Suryawanshi Dayanand , Chavan Milind , Pachalkar Ujwal , Pagi Pradeep , Chauhan Sanjay
Published: November 2023

Objective

Early identification, referrals and timely treatment is crucial to improve the outcome of Birth Defects (BDs). The role of Community Health Workers (CHWs) in India is largely fulfilled by Accredited Social Health Activists (ASHAs) who can play an important role in community‐based reporting and referrals of BDs in newborn. In the study area, ASHAs have been previously trained for identification of BDs under Rashtriya Bal Swasthya Karyakram (RBSK); however, reporting through them was found to be sub‐optimal.

Methods

To strengthen the community based reporting of BDs through ASHAs, audio visual based training was provided to 1225 ASHAs in 6 tribal blocks of Palghar district in Maharashtra, India. The change in knowledge about BDs before and after training among 1023 participants was analyzed using paired sample t test & McNemar test.

Results

Findings reveal a significant increase in the knowledge of participants with regards to prevention, risk factors and identification of BDs after intervention as compared to before intervention.

Discussion

The study suggests that audio‐visual based refresher training increased knowledge of ASHAs with respect to identification, prevention and risk factors of BDs which may eventually improve reporting and referrals of BDs at community level.
Association between gaming disorder and regional homogeneity in highly involved male adult gamers: A pilot resting‐state fMRI study
Authors: Jiang Wen‐tao , Liu Xia , Xu Zi‐yun , Zhou Zhi‐feng , Tie Chang‐jun , Liu Xiao‐ying , Yang Ji‐hui , Li Hai , Lai Wen‐tao
Published: November 2023

Background

Gaming behavior can induce cerebral changes that may be related to the neurobiological features of gaming disorder (GD). Additionally, individuals with higher levels of depression or impulsivity are more likely to experience GD. Therefore, the present pilot study explored potential neurobiological correlates of GD in the context of depression and impulsivity, after accounting for video gaming behavior.

Methods

Using resting‐state functional magnetic resonance imaging (fMRI), a cross‐sectional study was conducted with 35 highly involved male adult gamers to examine potential associations between GD severity and regional homogeneity (ReHo) in the entire brain. A mediation model was used to test the role of ReHo in the possible links between depression/impulsivity and GD severity.

Results

Individuals with greater GD severity showed increased ReHo in the right Heschl's gyrus and decreased ReHo in the right hippocampus (rHip). Furthermore, depression and impulsivity were negatively correlated with ReHo in the rHip, respectively. More importantly, ReHo in the rHip was found to mediate the associations between depression/impulsivity and GD.

Conclusions

These preliminary findings suggest that GD severity is related to ReHo in brain regions associated with learning/memory/mood and auditory function. Higher levels of depression or impulsivity may potentiate GD through the functional activity of the hippocampus. Our findings advance our understanding of the neurobiological differences behind GD symptoms in highly involved gamers.
From green hype to green habits: Understanding the factors that influence young consumers' green purchasing decisions
Authors: Lopes João M. , Pinho Micaela , Gomes Sofia
Published: November 2023

It is believed that environmental causes will grow in fervor with members of Gen Z. This study explores the main factors of green marketing affecting young Portuguese green purchasing decisions and the relationship between them. An online questionnaire was used to collect data from 708 young Portuguese consumers of eco‐friendly products. The quantitative analysis was performed using the partial least square (PLS) method. We found that the marketing factors of green willingness to purchase, green awareness of price, green perceived benefits, and green perceived quality were positively associated with young peoples' environmental concerns, and they also proved to be positively related to their green purchasing decisions when mediated by the environmental concern variable. This study contributes to the literature on green marketing, having empirically evaluated, for the first time, the role of environmental concerns as mediators of consumers' perceptions of green products and their purchase intentions. Furthermore, it pioneeringly explores the determinants of Generation Z's environmental concerns and green purchasing decisions, making an essential contribution to the literature on consumer behavior and generational cohorts. The breadth of influence of each determinant is not balanced, and producers, marketers, and policymakers must consider these results in their strategy of attracting young consumers to purchase green products.
Real‐world effectiveness and safety of RC48‐ADC alone or in combination with PD‐1 inhibitors for patients with locally advanced or metastatic urothelial carcinoma: A multicenter, retrospective clinical study
Authors: Xu Jingwei , Zhang Hongqiao , Zhang Li , Chu Xiufeng , Li Yu , Li Guangyuan , Nie Caiyun , Wang Meng , Guo Yanwei
Published: November 2023

Introduction

Previous RC48 (Disitamab Vedotin) studies established that the safety and efficacy of RC48‐antibody–drug conjugate (ADC), either alone or combined with toripalimab, for metastatic urothelial carcinoma (mUC) patients exhibiting human epidermal growth factor receptor 2 (HER2)‐positive or even HER2‐negative status after standard chemotherapy failure.

Methods

With locally advanced or metastatic urothelial carcinoma (la/mUC), patients who received RC48‐ADC monotherapy or a combination with programmed cell death protein 1 (PD‐1) inhibitors between August 2021 and October 2022 were enrolled in this retrospective observational study to evaluate the real‐world antitumor effectiveness and safety.

Results

Among the 38 enrolled patients (29 males; median age 67.5 years [38–93]), 8 received RC48‐ADC monotherapy, while 30 received combination therapy. Initially, 63.2% (24/38) of the patients had received ≥1 line of prior treatment, and 63.2% (24/38) had visceral metastasis. UC of the bladder represented the majority type in 68.4% (26/38) of cases. By the data cutoff in March 2023, the overall objective response rate (ORR) was 63.2% (95% CI, 47.1%–79.2%), with a disease control rate (DCR) of 89.5% (95% CI, 79.3%–99.7%). Median follow‐up time was 10.6 months. The median progression‐free survival (PFS) was 8.2 months (95% CI, 5.9–10.5), with a 6‐month PFS rate of 63.2% and a 12‐month PFS rate of 34.1%. Median overall survival (OS) was not reached, with a 12‐month OS rate of 76.7%. The median duration of response was 7.3 months (95% CI, 4.6–10.0) among 24 patients evaluated as partial response (PR). The most common treatment‐related adverse events (TRAEs) included anemia (71.1%), anorexia (57.9%), asthenia (52.6%), hypoesthesia (52.6%), bone marrow suppression (47.4%), alopecia (47.4%), nausea (44.7%), proteinuria (36.8%), vomiting (34.2%), and hypoalbuminemia (31.6%). No patient experienced TRAEs of Grade ≥3. One patient had an immune‐related adverse event (irAE) of rash related to toripalimab.

Conclusions

Both as monotherapy and in combination with PD‐1 inhibitors, RC48‐ADC exhibits promising effectiveness and manageable safety profile for mUC patients in real‐world settings.
Psychotherapy students' experiences of supervisee‐centred supervision based on deliberate practice, feedback‐informed treatment and self‐compassion
Authors: Axelsson Susanne , Kihlberg Sara , Davis Paul , Nyström Markus B. T.
Published: November 2023

Objective

There are few methods that focus on therapists' experiences of supervision. To facilitate the development of psychologist students, a supervisee‐centred supervision, based on deliberate practice, feedback informed treatment and self‐compassion, was introduced.

Methods

This study examines six supervisees’ experiences of a supervisee‐centred supervision. A semi‐ structured interview was used for the collection of the data, which identified two main themes: Learning and Development and five associated sub‐themes: structure and purposesfulness, prerequisites, experience‐based learning, therapeutic skills and personal development.

Conclusion

The experience‐ and feedback‐based approach was perceived as efficient, structured and goal oriented. This created high‐focused activity and participation, a strong group dynamic and a good alliance with the supervisors, providing a good climate for learning and development. Focusing on performance and feedback was perceived as a potential obstacle that could create stress and anxiety.
Management of gingival hyperpigmentation induced by increased ferritin level in aHbS‐β+thalassemia patient using diode laser
Authors: Darkazali Raneem , Hamadah Omar
Published: November 2023

Key Clinical Message

Diode lasers can be employed for the treatment of gingival hyperpigmentation in HbS‐β+thalassemia patients due to the advantages that lasers provide including good hemostatic effect and less postoperative complications.
Acute soft head syndrome in a teenager with sickle cell anemia: A case report
Authors: Magitta Ng'weina F. , Komanya Francisca B. , Alphonce Baraka O. , Bitesigilwe Mbelwa D. , Sindato Emmanuel M. , Meda John R.
Published: November 2023

Key Clinical Message

Sickle cell disease (SCD) rarely presents with acute soft head syndrome (ASHS) often posing a diagnostic dilemma. Recovery is typically spontaneous, however, in the context of lack of awareness and limited brain imaging it could potentially lead to poor outcome.

ASHS is a rare complication of SCD, invariably occurring near puberty with hitherto elusive pathogenic mechanisms. ASHS often resolves spontaneously on conservative management, however, lack of awareness in the context of limited access to brain imaging could pose diagnostic challenges resulting in inappropriate management and untoward outcome. We present a case of a teenager who presented with subtle symptoms for which the diagnosis of sickle cell anemia (SCA) was delayed until he developed ASHS. LTM was a 16 years old boy with a history of recurrent joints pain since the age of 6 years, with a family history of SCA, but had initial negative sickling test. He presented with episodes of multiple joints pain, unprovoked scalp and left orbital swelling, low‐grade fever and mild headache without any evidence for bleeding diathesis. The diagnosis of SCA was confirmed by hemoglobin electrophoresis. Computed tomography (CT) scan of the head revealed subgaleal heamatoma (SGH) and intraorbital haematoma without intracranial hemorrhage (ICH). He was managed conservatively with analgesics and hydration together with antibiotics for associated sepsis with complete resolution of clinical symptoms within 2 weeks. This case represents a rare scenario for a relatively mild SCA phenotype presenting with ASHS whose diagnosis poses an enigma in the resource‐limited contex. It is therefore, prudent to recognize ASHS to avoid judicious interventions which could potentially result in untoward clinical outcome.
H2[Pt(C2O4)2] as a Tailor‐made Halide‐free Precursor for the Preparation of Diesel Oxidation Catalysts: Nanoparticles Formation, Thermal Stability and Catalytic Performance
Authors: Spolaore F. , Hengst C. , Dornhaus F. , Votsmeier M. , Gross S.
Published: November 2023

The aim of this study was to investigate a tailor‐made metal precursor and its chemical properties to tune the properties of supported metal nanoparticles (NPs) and their catalytic performance when used as Diesel Oxidation Catalyst (DOC). The formation of extremely small Pt NPs from a new halide‐free Pt complex was investigated, namely bis(oxalato)platinate, H2[Pt(C2O4)2]. The size evolution of the supported NPs, from the formation upon the Pt precursor decomposition on γ‐alumina to the sintering of the NPs at high temperatures, was followed by thermogravimetric analysis coupled with mass spectrometry (TG‐MS) and differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. A correlation between the NPs’ size of the catalyst and the performance for the CO, C3H6, C3H8 and NO oxidation reactions pointed out a retained activity during test cycles, showing low sensitivity to the test conditions applied (i. e., temperature and gas composition). The overall catalytic performance was better in the fresh catalysts compared to the reference catalyst prepared from platinum nitrate, Pt(NO3)4. In particular, the different dispersion of the Pt NPs over the support obtained from the two precursors was identified as the reason for the different catalytic performance, retaining small NPs size after the tests cycles.
One‐Pot Synthesis of ZnO‐Activated Eggshell@kaolinite: Sorbents for Phosphate Capture in Water
Authors: Bayode Ajibola A. , Badamasi Hamza , Olusola Johnson Adedeji , Durodola Solomon S. , Akeremale Olaniran K. , Ore Odunayo T. , Helmreich Brigitte , Omorogie Martins O.
Published: November 2023

The availability of colossal amounts of phosphate in water bodies has led to serious environmental challenges all over the world. In this study, a new adsorbent was synthesized using treated kaolinite clay, pulverized eggshells, and ZnCl2. Surface characterizationof these adsorbents showed the availability of functional moieties, morphological variations, pore sizes, particle sizes, etc. Adsorption of phosphate occurs via multiple mechanisms, comprising ligand exchange, complexation, hydrogen bonding, and electrostatic interaction, among others. The effect of pH, showed that maximum adsorption of 93.3 % was achieved at pH 3.0. It was also shown that these cost‐effective adsorbents could be regenerated in six cycles, hence increasing their applicability.
Unraveling the Fundamental Concepts of Superaerophobic/Superhydrophilic Electrocatalysts for Highly Efficient Water Electrolysis: Implications for Future Research
Authors: Shen Jingjun , Zheng Yihao , Lei Wen , Shao Huaiyu
Published: November 2023

Electrochemical water splitting is a highly effective method for carbon‐free hydrogen production. While significant efforts have been made to develop efficient and cost‐effective electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), the optimization of electrode surface properties has been largely overlooked. Inadequate mass diffusion, especially at high bath voltage, hampers the energy transfer efficiency of water electrolysis. To overcome these challenges, precise design of superaerophobic/superhydrophilic electrodes can effectively separate gas bubbles from the catalyst surface and enhance mass transfer, improving overpotential and Faraday efficiency. This article underscores the importance of designing electrocatalysts with well‐designed surface properties to address these challenges. It also discusses characterization techniques for evaluating surface properties and provides examples of applications for superaerophobic/superhydrophilic electrodes in energy storage and conversion systems, electrochemical biosensors, and industrial processes, etc. Overall, optimizing the surface properties of electrocatalysts holds promise for enhancing the efficiency of gas‐involving reactions and energy conversion systems.
Direct Spectroscopic Identification of BN‐Arynes and Subtle Steric Effects on Nitrogen Fixation**
Authors: Gupta Divanshu , Keck Constanze , Tönshoff Christina , Bhagat Virinder , Strobel Raphael , Eder Manuel , Baylère Patrick , Labat Stéphane , Chrostowska Anna , Bettinger Holger F.
Published: November 2023

1,2‐Azaborinines are the BN analogues of arynes through exchange of the formal CC triple bond by an isoelectronic BN bond. The BN‐arynes are an underexplored class of reactive intermediates. Dibenzo[c,e][1,2]azaborinine (10,9‐BN‐phenanthryne) 1 was inferred as reactive intermediate by trapping reactions. Here it is shown that 1 can be generated in the gas phase by thermolysis from the pyridine adduct of 9‐azido‐9‐borafluorene by cleavage of the dative bond with pyridine and dinitrogen extrusion. The ionization potential of 1 is 8.2 eV with ionization resulting from the π HOMO. Under cryogenic matrix isolation conditions, 9‐azido‐9‐borafluorene photolysis results in isomerization to the dinitrogen adduct of 1 without involvement of a triplet borylnitrene intermediate. Photochemical nitrogen extrusion from 1 ⋅ N2 is not possible and nitrogen fixation is irreversible under cryogenic conditions. In contrast, 2,4,7,9‐tetra‐tert‐butyldibenzo[c,e][1,2]azaborinine can be photogenerated from the corresponding azidoborole precursor under cryogenic matrix isolation conditions, and nitrogen fixation is precluded due to steric hindrance. The BN stretching vibration at about 1750 cm−1 is much weaker than in typical linear diaryl iminoboranes.
Preparation of a Compound with a SiII−SiIV−SiII Bonding Arrangement
Authors: Kushvaha Saroj Kumar , Kallenbach Paula , Gorantla Sai Manoj N. V. T. , Herbst‐Irmer Regine , Stalke Dietmar , Roesky Herbert W.
Published: November 2023

Herein, we report the synthesis of a rare bis‐silylene, 1, in which two SiIIatoms are bridged by a SiIV atom. Compound 1 contains an unusual SiII−SiIV−SiII bonding arrangement with SiII−SiIV bond distances of 2.4212(8) and 2.4157(7) Å. Treatment of 1 with Fe(CO)5 afforded a dinuclear Fe0 complex 2 with two unusually long Si−Si bonds (2.4515(8) and 2.4488(10) Å). We have also carried out a detailed computational study to understand the nature of the Si−Si bonds in these compounds. Natural bond orbital (NBO) and energy decomposition analysis–natural orbital for chemical valence (EDA‐NOCV) analyses reveal that the Si−Si bonds in 1 and 2 are of an electron‐sharing nature.
Isolation of (Aryl)‐(Imino) Phosphide and (Aryl)‐(Phosphaalkene) Amide Complexes of Alkali Metals from Carbene‐Phosphinidenes under Reductive‐Thermal Rearrangements
Authors: Nag Ekta , Francis Maria , Putta Divya , Roy Sudipta
Published: November 2023

Invited for the cover of this issue are Sudipta Roy and co‐workers at the Indian Institute of Science Education and Research (IISER) Tirupati. The image depicts the rearrangement of cyclic alkyl(amino) carbene (cAAC)‐supported chloro‐phosphinidenes affording two ligands, of which one was used for the solid‐state isolation of three cyclic alkyl(amino‐boryl) phosphaalkenes and two coinage metal clusters. Read the full text of the article at 10.1002/chem.202302120.
Moral, Verantwortung, Nachhaltigkeit
Authors: Wöhrle D.
Published: November 2023

Im Anthropozän kam es aufgrund der Folgen der Industrialisierung zu immer dramatischeren Veränderungen des Zustands des Planeten Erde. Die globale Wirtschaft und das Verhalten der Menschen führten im begrenzten Erdsystem zu Umweltbelastungen und ‐schäden. Ein Umdenken in vielen Bereichen muss stattfinden, um weitere Folgen zu vermeiden. Wegen der Bedeutung der Chemie auch für die Zukunft ist Ethik als moralisches Wertesystem zu verankern. Hier sind die Wissenschaftler durch ihre Verantwortung bei der Anwendung von Ergebnissen der Wissenschaft gefragt. Weiter ist die Nachhaltigkeit für die Bewahrung der Regenerationsfähigkeit von Ökosystemen und dem schonenden Umgang mit Ressourcen wichtig. Notwendig ist, dass in Schulen und Hochschulen die Ethik in der Chemie im Zusammenhang mit Moral, Verantwortung und Nachhaltigkeit behandelt wird.
Polyhydroxyurethanes from Biobased Monomers and CO2: A Bridge between Sustainable Chemistry and CO2 Utilization†
Authors: Theerathanagorn Tharinee , Kessaratikoon Tanika , Rehman Hafeez Ur , D'Elia Valerio , Crespy Daniel
Published: November 2023

Comprehensive Summary

Polyhydroxyurethanes (PHUs) have received considerable attention in the last decade as potential alternatives to traditional phosgene‐based polyurethanes (PUs). The development of suitable 5CC (five membered‐ring cyclic carbonate) precursors bearing multiple carbonate moieties (multi‐5CCs) is a key requisite for preparing PHUs by polyaddition reaction with bis‐ or polyamines. Producing sustainable PHUs from CO2‐based five‐membered cyclic carbonates (5CCs) obtained from biobased epoxides is a valuable strategy to bridge CO2 utilization and the upcycling of renewable substrates. In this context, while many multi‐5CC monomers reported in the literature are oil‐based, recent efforts have led to the development of a large variety of multifunctional 5CCs that are produced by the combination of CO2 and renewable resources such as fatty acids and vegetable oils, lignin, terpenes, and sugars. In this work, recent crucial advances (2019—2023) on PHUs prepared from bis‐ and multi‐5CCs produced from CO2 and (partially/potentially) biobased substrates are reviewed with respect to their synthesis, thermal and mechanical properties, and their recent, emerging applications.
Recent Advances in Deciphering the Mechanisms and Biological Functions of DNA Demethylation
Authors: Feng Yang , Chen Sheng‐Jun , Yuan Bi‐Feng
Published: November 2023

Comprehensive Summary

5‐Methylcytosine (5mC) is a dynamic and reversible epigenetic modification in genomic DNA of higher eukaryotes. It has been well‐established that the demethylation of 5mC occurs through the ten‐eleven translocation (TET)‐mediated oxidation of 5mC followed by thymine DNA glycosylase (TDG)‐initiated base excision repair (BER). Recent findings also have identified an alternative pathway of DNA demethylation. In this pathway, TET enzymes directly oxidize 5mC to form 5‐formylcytosine (5fC) or 5‐carboxylcytosine (5caC). These modified bases can undergo direct deformylation or decarboxylation, respectively. Additionally, DNA demethylation can also occur through the deamination of 5mC and 5hmC, resulting in the production of thymine and 5‐hydroxymethyluracil (5hmU), respectively. Various DNA demethylation pathways possess critical functional implications and roles in biological processes. This Recent Advances article will focus on the studies of mechanisms and biological functions of DNA demethylation, shedding light on the reversible nature of the epigenetic modification of 5mC.
Iron‐Catalyzed Reductive C(aryl)—Si Cross‐Coupling of Diaryl Ethers with Chlorosilanes
Authors: Liu Pei , Wu Baowei , Cong Xuefeng , Kong Jie
Published: November 2023

Comprehensive Summary

The reductive cross‐coupling between C(aryl)—O and Si—Cl bonds is of much importance as a valuable strategy for the construction of C(aryl)—Si bonds but has remained a great challenge. Herein, we report a reductive cross‐coupling of diaryl ethers and chlorosilanes via strong electrophilic C(aryl)—O and Si—Cl bonds cleavage by iron catalysis, which constitutes an efficient protocol for the synthesis of a range of functionalized arylsilanes. The combination of low cost FeCl2 as the precatalyst and iPrMgCl as the reductant shows high activity in the successive cleavage of unactivated C(aryl)—O bonds of diaryl ethers and strong electrophilic Si—Cl bonds of chlorosilanes, allowing their cross‐coupling in a reductive fashion. The low‐valent iron species generated in situ by reduction of FeCl2 with iPrMgCl was proposed, which prefers to initially cleavage the C(aryl)—O bond of diaryl ethers with the chelation help of an o‐amide auxiliary.
Maladaptive daydreaming, emotional dysregulation, affect and internalized stigma in persons with borderline personality disorder and depression disorder: A network analysis
Authors: Pyszkowska Anna , Celban Julia , Nowacki Ari , Dubiel Izabela
Published: November 2023

Maladaptive daydreaming (MD) manifests through experiences of excessive, long‐lasting daydreaming resulting in significant suffering, including isolation, distress and shame. Considering that one of its functions is a distraction from painful feelings, it is linked with escapism and plays a significant role in disorders associated with emotional dysregulation, maintaining negative symptoms, including internalized stigmatization and social withdrawal. The current study aimed to examine cognitive (internalized stigma), affective (affect, anhedonia, emotional dysregulation) and behavioural (escapism) aspects of MD in borderline personality disorder (BPD) and depression groups. The sample consisted of 188 persons, including 102 individuals with BPD. The results showed higher scores in emotional dysregulation, internalized stigma and escapism in the BPD group compared to the depression group; the subgroups did not vary in MD rates. The network analysis revealed significant differences between groups in variables dynamics, with links between MD and self‐suppression escapism, negative affect in the BPD group and MD with self‐suppression escapism and social withdrawal in the depression group. Emotionally dysregulation and internalized stigma factors posed as the most robust expected influence components in both networks, suggesting that the cognitive and affective factors, not strictly behavioural, are pivotal for one's functioning and regulation strategies in the groups studied. The current study allows for clinical implications in interventions focused on persons developing MD and emotional dysregulation symptoms, including persons with BPD and depression.
Influence of gender and combined estrogen–progestin oral contraceptive on parotid saliva flow rate, pH, and electrolytes concentration
Authors: Rovera Angela , Anderson Paul
Published: November 2023

Objectives

Endocrinal variations within an individual impact the electrolyte composition, pH, and flow‐rate (FR) of saliva. The aim of this study was to evaluate the gender‐specific differences and the effect of combined estrogen‐progestin oral contraceptives (COCs) on FR, pH, and electrolyte concentrations in the parotid saliva (PS) of a group of healthy adults.

Material and Methods

Stimulated PS was collected from 20 healthy adults using a Lashley cup; 11 males, 8 females, and 1 female undertaking combined contraceptive therapy (levonorgestrel/ethinyloestradiol 0.1 mg + 0.02 mg). FR and pH were recorded for each saliva sample. Electrolytes concentrations (Na+, Ca2+, K+, Mg2+) were measured using inductively coupled plasma optical emission spectrometer (ICP‐OES). Statistical analysis was performed, and the significance level was set atp < .05.

Results

PS FR varied from 0.13 to 0.42 mL/min in females not taking any medication and from 0.08 to 0.5 mL/min in males not taking any medication. PS pH of females and males not taking any medication ranged from 6.23 to 7.50 and from 6.15 to 7.55. PS pH and FR of the female taking COCs were 6.5 and 0.1 mL/min. PS pH, FR, and electrolytes concentrations (Ca2+, Na+, K+, Mg2+) were not statistically significantly different between females and males not taking any medication. PS concentrations of Ca2+ and Na+were significantly higher in the females taking COCs than in the females not taking any medication. Whereas, concentrations of K+and Mg2+did not differ significantly between the females taking COCs and the females not taking any medication.

Conclusions

There are no significant gender‐specific differences in PS flow rate, pH, and electrolyte concentrations of Na+, Ca2+, Mg2+, and K+. Combined hormonal oral contraceptive has a significant effect on PS flow rate, pH, Ca2+, and Na+concentrations. Whereas the PS concentration of K+and Mg2+are not influenced by COCs. These results warrant further investigation.
Auto‐dentin platelet‐rich fibrin matrix is an alternative biomaterial for different augmentation procedures: A retrospective case series report
Authors: Alrmali Abdusalam , Saleh Muhammad H. A. , Mazzocco John , Zimmer Jacob M. , Testori Tiziano , Wang Hom‐Lay
Published: November 2023

Objectives

Autologous dentin grafts derived from extracted teeth have shown promise as bone graft materials for promoting bone regeneration. This retrospective case series aimed to evaluate clinical, radiographic, and histologic outcomes of using autologous dentin matrices in various bone regeneration procedures.

Materials and Methods

This case series included 26 eligible patients and encompassed 4 socket preservation cases, 5 cases of guided tissue regeneration, 5 cases of guided bone regeneration (GBR), 10 cases of sinus augmentation procedures, 2 immediate placement implants, and 2 socket shields. Dentin grafts were prepared from extracted teeth, cleaned, and processed. These grafts were combined with platelet‐rich fibrin (PRF) to create adhesive dentin matrices, then covered with collagen membranes for simultaneous guided bone augmentation cases. Cone beam computed tomography (CBCT) scans were conducted before surgery and 4 months postoperatively to assess ridge dimensions. Histologic evaluation was performed through bone core biopsies for socket preservation cases at the 4‐month mark.

Results

A total of 42 implants were placed in 26 patients, with an average follow‐up of 32 months. Notably, two implant failures occurred following lateral maxillary sinus augmentation. CBCT scans at the 4‐month interval revealed bone coverage over implant platforms in the majority of cases. Histologic analysis from two cases of socket preservation demonstrated dentin granules enveloped by newly formed bone undergoing continuous remodeling. The quantitative histomorphometric assessment revealed a bone area of 42.8 ± 3.56%, a remaining graft area of 19.05 ± 4.58%, and a viable bone of 38.15 ± 7.84%.

Conclusions

The utilization of autologous dentin particles mixed with PRF proved effective as an alternative to conventional bone graft materials in GBR and maxillary sinus augmentation procedures. Larger controlled clinical trials are recommended to further substantiate these findings.
Relationship between baseline plasma p‐tau181 and longitudinal changes in cognition and structural brain measures in a cohort of cognitively unimpaired older adults
Authors: Pais Marcos V. , Kuo Chia‐Ling , Ances Beau M. , Wetherell Julie Loebach , Lenze Eric J. , Diniz Breno S.
Published: November 2023

INTRODUCTION

Preclinical Alzheimer's disease (AD) affects a significant proportion of cognitively unimpaired (CU) older adults. Currently, blood‐based biomarkers detect very early changes in the AD continuum with great accuracy.

METHODS

We measured baseline plasma phosphorylated tau (p‐tau)181 using electrochemiluminescence (ECL)‐based assay (MesoScale Discovery) in 533 CU older adults. Follow‐up lasted up to 18 months. Cognitive performance assessment included memory and cognitive control. Structural brain measures included cortical thickness, which includes the AD magnetic resonance imaging (AD MRI) signature, and hippocampal volume.

RESULTS

In this cohort of CU older adults, baseline plasma p‐tau181 levels were not associated with short‐term changes in cognition and structural brain measures. Also, baseline plasma p‐tau levels did not influence the effects of behavioral interventions (exercise or mindfulness) on cognitive and structural brain changes.

DISCUSSION

The short follow‐up and healthy status of this CU cohort might have limited the sensitivity of plasma p‐tau181 in detecting changes associated with AD pathology.
How mothers help children learn to use everyday objects
Authors: Kaplan Brianna E. , Kasaba Isabella , Rachwani Jaya , Adolph Karen E. , Tamis‐LeMonda Catherine S.
Published: November 2023

Children must learn specific motor actions to use everyday objects as their designers intended. However, designed actions are not obvious to children and often are difficult to implement. Children must know what actions to do and how to execute them. Previous work identified a protracted developmental progression in learning designed actions—from nondesigned exploratory actions, to display of the designed action, to successful implementation. Presumably, caregivers can help children to overcome the challenges in discovering and implementing designed actions. Mothers of 12‐, 18‐ to 24‐, and 30‐ to 36‐month‐olds (N = 74) were asked to teach their children to open containers with twist‐off or pull‐off lids. Mothers’ manual and verbal input aligned with the developmental progression and with children's actions in the moment, pointing to the role of attuned social information in helping children learn to use objects for activities of daily living. However, mothers sometimes “overhelped” by implementing designed actions for children instead of getting children to do it themselves, highlighting the challenges of teaching novices difficult motor actions.
Fan‐hinged shear instead of frictional stick–slip as the main and most dangerous mechanism of natural, induced, and volcanic earthquakes in the earth's crust
Authors: Tarasov Boris G.
Published: November 2023

Frictional stick–slip instability along pre‐existing faults has been accepted as the main mechanism of earthquakes for about 60 years, since it is believed that fracture of intact rocks cannot reflect such features inherent in earthquakes as low shear stresses activating instability, low stress drop, repetitive dynamic instability, and connection with pre‐existing faults. This paper demonstrates that all these features can be induced by a recently discovered shear rupture mechanism (fan‐hinged), which creates dynamic ruptures in intact rocks under stress conditions corresponding to seismogenic depths. The key element of this mechanism is the fan‐shaped structure of the head of extreme ruptures, which is formed as a result of an intense tensile cracking process, with the creation of inter‐crack slabs that act as hinges between the shearing rupture faces. The preference of the fan mechanism over the stick–slip mechanism is clear due to the extraordinary properties of the fan structure, which include the ability to generate new faults in intact dry rocks even at shear stresses that are an order of magnitude lower than the frictional strength; to provide shear resistance close to zero and abnormally large energy release; to cause a low stress drop; to use a new physics of energy supply to the rupture tip, providing supersonic rupture velocity; and to provide a previously unknown interrelation between earthquakes and volcanoes. All these properties make the fan mechanism the most dangerous rupture mechanism at the seismogenic depths of the earth's crust, generating the vast majority of earthquakes. The detailed analysis of the fan mechanism is presented in the companion paper “New physics of supersonic ruptures” published in DUSE. Further study of this subject is a major challenge for deep underground science, earthquake and fracture mechanics, volcanoes, physics, and tribology.