bluuebunny/crossref_metadata_2025 huggingface dataset:
Electrically Conductive Liquid Metal Composite Adhesives for Reversible Bonding of Soft Electronics
Authors: Haque A. B. M. Tahidul , Ho Dong Hae , Hwang Dohgyu , Tutika Ravi , Lee Chanhong , Bartlett Michael D.
Published: July 2023

Conductive adhesives are required for the integration of dissimilar material components to create soft electronic and robotic systems. Here, a heterogeneous liquid metal‐based conductive adhesive is developed that reversibly attaches to diverse surfaces with high stretchability (>100% strain), low modulus (<100 kPa), and strain‐invariant electrical conductivity. This SofT integrated composite with tacK through liquid metal (STICK‐LM) adhesive consists of a heterogeneous graded film with a liquid metal‐rich side that is embossed at prescribed locations for electrical conductivity and an electrically insulating adhesive side for integration. Adhesion behavior is tuned for adhesion energies > 70 Jm−2 (≈ 25x enhancement over unmodified composites) and described with a viscoelastic analysis, providing design guidelines for controllable yet reversible adhesion in electrically conductive systems. The architecture of STICK‐LM adhesives provides anisotropic and heterogeneous electrical conductivity and enables direct integration into soft functional systems. This is demonstrated with deformable fuses for robotic joints, repositionable electronics that rapidly attach on curvilinear surfaces, and stretchable adhesive conductors with nearly constant electrical resistance. This study provides a methodology for electrically conductive, reversible adhesives for electrical and mechanical integration of multicomponent systems in emerging technologies.
Self‐Healing and ‐Repair of Nanomechanical Damages in Lead Halide Perovskites
Authors: Parida Santanu , Kumar Sujit , Cherf Shiraz , Aharon Sigalit , Cahen David , Eren Baran
Published: July 2023

Recovery from damage in materials helps extend their useful lifetime and of devices that contain them. Given that the photodamages in HaP materials and based devices are shown to recover, the question arises if this also applies to mechanical damages, especially those that can occur at the nanometer scale, relevant also in view of efforts to develop flexible HaP‐based devices. Here, this question is addressed by poking HaP single crystal surfaces with an atomic force microscope (AFM) tip under both ultra‐high vacuum (UHV) and variably controlled ambient water vapor pressure conditions. Sequential in situ AFM scanning allowed real‐time imaging of the morphological changes at the damaged sites. Using methylammonium (MA) and cesium (Cs) variants for A‐site cations in lead bromide perovskites, the experiments show that nanomechanical damages on methylammonium lead bromide (MAPbBr3) crystals heal an order of magnitude faster than Cs‐based ones in UHV. However, surprisingly, under ≥40% RH conditions, cesium lead bromide (CsPbBr3) shows MAPbBr3‐like fast healing kinetics. Direct evidence for ion solvation on CsPbBr3 is presented, leading to the formation of a surface hydration layer. The results imply that moisture improves the ionic mobility of degradation components and leads to water‐assisted improved healing, i.e., repair of nanomechanical damages in the HaPs.
Soft Robotic‐Adapted Multimodal Sensors Derived from Entirely Intrinsic Self‐Healing and Stretchable Cross‐Linked Networks
Authors: Dai Xingyi , Wu Yinghui , Liang Qihua , Yang Jingkun , Huang Long‐Biao , Kong Jie , Hao Jianhua
Published: July 2023

Flexible sensing technologies that play a pivotal role in endowing robots with detection capabilities and monitoring their motions are impulsively desired for intelligent robotics systems. However, integrating and constructing reliable and sustainable flexible sensors with multifunctionality for robots remains an everlasting challenge. Herein, an entirely intrinsic self‐healing, stretchable, and attachable multimodal sensor is developed that can be conformally integrated with soft robots to identify diverse signals. The dynamic bonds cross‐linked networks including the insulating polymer and conductive hydrogel with good comprehensive performances are designed to fabricate the sensor with prolonged lifespan and improved reliability. Benefiting from the self‐adhesiveness of the hydrogel, strong interfacial bonding can be formed on various surfaces, which promotes the conformable integration of the sensor with robots. Due to the ionic transportation mechanism, the sensor can detect strain and temperature based on piezoresistive and thermoresistive effect, respectively. Moreover, the sensor can work in triboelectric mode to achieve self‐powered sensing. Various information can be identified from the electrical signals generated by the sensor, including hand gestures, soft robot crawling motions, a message of code, the temperature of objects, and the type of materials, holding great promise in the fields of environmental detection, wearable devices, human‐machine interfacing, and robotics.
Electrical and Thermal Transport Properties of Ge1–xPbxCuySbyTeSe2y
Authors: Jin Yang , Ren Dudi , Qiu Yuting , Zhao Li‐Dong
Published: July 2023

Balancing the contradictory relationship between thermoelectric parameters, such as effective mass and carrier mobility, is a challenge to optimize thermoelectric performance. Herein, the exceptional thermoelectric performance is realized in GeTe through collaboratively optimizing the carrier and phonon transport via stepwise alloying Pb and CuSbSe2. The formation energy of Ge vacancy is efficiently bolstered by alloying Pb, which reduces carrier density and carrier scattering to maintain superior carrier mobility in GeTe. Additionally, CuSbSe2, acting as an n‐type dopant, further modulates carrier density and validly equilibrates carrier mobility and effective mass. Accordingly, the promising power factor of 45 µW cm−1 K−2 is achieved at 723 K. Meanwhile, point defects are found to significantly suppress phonons transport to descend lattice thermal conductivity by Pb and CuSbSe2 alloying, which barely impacts the carrier mobility. A combination with superior carrier mobility and lower lattice thermal conductivity, a maximum ZT of 2.2 is attained in Ge0.925Pb0.075Cu0.005Sb0.005TeSe0.01, which corresponds to a 100% promotion compared with that of intrinsic GeTe. This study provides a new indicator for optimizing carrier and phonon transport properties by balancing interrelated thermoelectric parameters.
Lithiation Enhances Electrocatalytic Iodine Conversion and Polyiodide Confinement in Iodine Host for Zinc–Iodine Batteries
Authors: Du Yiqun , Kang Rongkai , Jin Huixin , Zhou Wei , Zhang Wenyang , Wang Han , Qin Jingyu , Wan Jiaqi , Chen Guowen , Zhang Jianxin
Published: July 2023

Aqueous static zinc–iodine batteries attract tremendous attention because of their abundant reserves of iodine, nonflammable electrolyte, and facile assembly. Currently, scientific challenges for static zinc–iodine batteries include self‐discharge and sluggish kinetics. Herein, a lithiation approach for the iodine host to suppress the shuttle effect and catalyze iodine conversion is reported. Through regulating the d‐ and p‐band center and lowering the I−/I0 conversion barrier, Li+ intercalation into VS2 reinforces interaction with I3− and achieves catalytic conversion of iodine, ameliorating self‐discharge, and accelerating kinetics. Zinc–iodine batteries featuring LiVS2 as the iodine host reach a high iodine utilization, high Coulombic efficiencies, and a long cyclic lifespan. Notably, the performance enhancement mechanism is the thermodynamically favorable iodine conversion reaction, inhibition of the I3− appearance, and promotion of I3− consumption due to the Li+ insertion. The findings provide fundamental insights into tackling issues of static zinc–iodine batteries.
Pre‐buried Interface Strategy for Stable Inverted Perovskite Solar Cells Based on Ordered Nucleation Crystallization
Authors: Dai Runying , Meng Xiangchuan , Zhang Jiaqi , Cai Zhixing , Tan Licheng , Chen Yiwang
Published: July 2023

The buried interface has important effect on carrier extraction and nonradiative recombination of perovksite solar cells (PSCs). Herein, to inactivate the buried interfacial defects of perovskite and boost the crystallization quality of perovskite film, 3‐amino‐1‐adamantanol (AAD) serves as a pre‐buried interface modifier on nickel oxide (NiOx) surface to regulate the nucleation and crystallization process of perovskite precursor. The amino and hydroxyl groups in AAD molecule can synchronously coordinate with nickel ion (Ni3+) in NiOx and lead ion in perovskite, respectively. The dual action favors the ordered arrangement of AAD molecules between NiOx and perovskite, which not only enhances hole extraction in hole transport layer, but also provides active sites for homogeneous nucleation. Furthermore, AAD modifier blocks the unfavorable reaction between Ni3+ and perovskite, and effectively passivates the buried interfacial defects. The optimal inverted PSCs achieve a champion power conversion efficiency of 22.21% with negligible hysteresis, favorable thermal, optical, and long‐term stability. Thus, this strategy of modulating perovskite nucleation and crystallization by pre‐buried modifier is feasible for achieving efficient and stable inverted perovskite solar cells.
Interstitial Injection of Hydrogels with High‐Mechanical Conductivity Relieves Muscle Atrophy Induced by Nerve Injury
Authors: Li Kai , Zhu Yuting , Zhang Qiang , Shi Yahong , Yan Tun , Lu Xi , Sun Huizhen , Li Tingting , Li Zhongxian , Shi Xiaoli , Han Dong
Published: July 2023

Injectable hydrogels have been extensively used in tissue engineering where high mechanical properties are key for their functionality at sites of high physiological stress. In this study, an injectable, conductive hydrogel is developed exhibiting remarkable mechanical strength that can withstand a pressure of 500 kPa (85% deformation rate) and display good fatigue resistance, electrical conductivity, and tissue adhesion. A stable covalent cross‐linked network with a slip‐ring structure by threading amino β‐cyclodextrin is formed onto the chain of a four‐armed (polyethylene glycol) amino group, and then reacted with the four‐armed (polyethylene glycol) maleimide under physiological conditions. The addition of silver nanowires enhances the hydrogel's electrical conductivity, enabling it to act as a good conductor in vivo. The hydrogel is injected into the fascial space, and the results show that the weight and muscle tone of the atrophied gastrocnemius muscle improve, subsequently alleviating muscle atrophy. Overall, this study provides a simple method for the preparation of a conductive hydrogel with high mechanical properties. In addition, the interstitial injection provides a strategy for the use of hydrogels in vivo.
Designing a Dipole‐Scheme Heterostructure Based on Janus TMDCs for Highly Efficient Photocatalytic Overall Water Splitting
Authors: Liu Xinyi , Cheng Peng , Li Shuang , Liu Wei
Published: July 2023

Direct Z‐scheme heterostructures, with strong redox abilities, are promising candidates for solar‐driven water splitting. However, carriers' recombination at the interface results in the loss of at least half of the photogenerated carriers, leading to low efficiency of carrier utilization. To solve this issue, a novel dipole‐scheme for photocatalytic water splitting is proposed, by utilizing the synergistic effects of the intrinsic dipole in Janus materials and the interfacial electric field. This approach can separate the photogenerated carriers with strong redox ability and suppress the recombination of photogenerated carriers at interface. Density functional theory calculations indicate that, for the heterostructures including Janus materials, the total electric dipole points to the oxygen evolution photocatalyst from the hydrogen evolution photocatalyst decreases the redox potential for water splitting. Additionally, the opposite intrinsic dipole of two Janus layers can offset the total dipole of Janus heterostructure to obtain a moderate vacuum level difference ΔV for reducing the redox potential. Based on these findings, a highly efficient dipole‐scheme photocatalyst CrSSeCrSeTe (SeTe interface), with opposite intrinsic Janus dipole is predicted, which achieves a high solar‐to‐hydrogen efficiency of 44%. This study provides a promising avenue for the design of highly efficient photocatalysts for overall water splitting with potential commercial applications.
C358X: A 2D Hexagon‐Free Carbon‐Based Anode Material for Li‐Ion Batteries
Authors: Zhuang Jie , Li Zhihui , Cui Tian , Li Da
Published: July 2023

Despite reports of 2D hexagon‐free carbon allotrope anode materials for Li‐ion batteries (LIBs), rate performance enhancement and the practical application of these materials are still major challenges. Here, a novel 2D hexagon‐free carbon allotrope C358X with a unique combination of triangular, pentagonal, octagonal, and decagonal rings is predicted to be a high‐performance anode material in LIBs. The special hexagon‐free configuration enables C358X to introduce many serviceable local strain regions and electron‐deficient regions on the surface. The formation of these regions is very important for enhancing the rate performance of C358X as an anode material for LIBs. C358X has rich adsorption active sites for lithium ions, a lower lithium‐ion diffusion energy barrier of 0.29 eV, a lower average open circuit voltage of 0.31 V, and a high theoretical capacity of 1116.7 mA h g−1. This work may facilitate the utilization of 2D carbon‐based anode materials for cost‐effective LIBs.
Fluorinated Solvent Molecule Tuning Enables Fast‐Charging and Low‐Temperature Lithium‐Ion Batteries
Authors: Mo Yanbing , Liu Gaopan , Yin Yue , Tao Mingming , Chen Jiawei , Peng Yu , Wang Yonggang , Yang Yong , Wang Congxiao , Dong Xiaoli , Xia Yongyao
Published: July 2023

Popularly‐used fluorination can effectively weaken Li+‐solvent interaction to facilitate the desolvation process at low temperature; however, high fluorination degree sacrifices salt dissociation and ionic conductivity. Herein, functional fluorinations are well tuned with different amounts of F atoms to balance Li+‐solvent binding energy and ion movement, which reveals the fluorination effect on the solvation behavior and low‐temperature performance. Noteworthily, the moderately‐fluorinated ethyl difluoroacetate (EDFA) successfully favors a lower binding energy than less‐fluorinated ethyl fluoroacetateand superior salt dissociation more than highly‐fluorinated ethyl trifluoroacetate, realizing the trade‐off between weak affinity and sufficient ionic conductivity. The well‐formulated EDFA‐based electrolyte exhibits a unique solvation sheath and generates inorganic‐rich solid electrolyte interphase with low resistance for smooth Li+ diffusion, which enables graphite anodes with excellent fast‐charging capability (196 mAh g−1 at 6 C) and impressive low‐temperature performance with a reversible capacity of 279 mAh g−1 under −40 °C. Subsequently, the wide electrochemical potential window of EDFA‐based electrolyte endows the 1.2 Ah LiNi0.8Co0.1Mn0.1O2 (NCM811)||graphite pouch cells with a high reversible capacity retention of 58.3% at −30 °C and discharge capacity of 790 mAh at −40 °C. Such solvent molecules with a moderately‐fluorinated strategy promise advanced electrolyte design for lithium‐ion batteries operating under harsh conditions.
Topology and porosity control on zirconium–fumarate frameworks boosting xenon/krypton separation
Authors: Chen Rundao , Sheng Bin , Zheng Fang , Li Jiaqi , Sun Haoran , Zhou Fangru , Chen Lihang , Zhang Zhiguo , Yang Qiwei , Ren Qilong , Bao Zongbi
Published: July 2023

The designability and ultrahigh stability of zirconium–organic frameworks make them attractive adsorbents for noble gases xenon (Xe) and krypton (Kr), but their Xe/Kr separation performance needs to be further enhanced. In this study, we rationally control the topology and porosity of zirconium–fumarate frameworks by simply changing the synthesis conditions, and successfully construct an adsorbent (named as MIP‐203‐F) with one‐dimensional pore instead of the original cage‐like fcu metal–organic framework MOF‐801. The Xe/Kr separation performance of MIP‐203‐F is thoroughly evaluated by isotherm measurements and breakthrough experiments, while the adsorption mechanism is elucidated in detail by Monte Carlo and density functional theory calculations. Due to the uniform pore with suitable size and abundant polarization groups, MIP‐203‐F can differentially polarize and recognize atomic Xe/Kr gases, and establishes a new record among zirconium–organic frameworks for the capture and separation of Xe/Kr.
Explicit model predictive control through robust optimization
Authors: Pappas Iosif , Diangelakis Nikolaos A. , Pistikopoulos Efstratios N.
Published: July 2023

A strategy that calculates an explicit state feedback policy to regulate constrained uncertain discrete‐time uncertain linear systems is presented. We consider uncertain processes, affected by box‐bounded multiplicative uncertainty as well as bounded additive uncertainty with linear state and inputs constraints. The proposed method includes (i) the calculation of a terminal set constraint and (ii) the robust reformulation of state constraints in the prediction horizon. These features allow the derivation of the desired policy by solving a single multiparametric quadratic programming problem that guarantees feasible operation in the presence of uncertainty. Additionally, we employ variable and constraint elimination approaches to enhance the computational performance of the strategy. We demonstrate the steps and benefits of these developments with a numerical example and a chemical engineering case study.
Demographic and reproductive impacts of hybridization unrelated to hybrid viability in a native plant
Authors: Greaves Elaina , Kron Paul , Husband Brian C.
Published: July 2023

Premise

Introduced species can influence native congeners through production of hybrids and introgression, but impacts not involving viable hybrids, such as reduced conspecific offspring and increased asexual seed production, are rarely examined. Here we tested for these demographic and reproductive consequences of hybridization between introduced, domesticated apple (Malus domestica) and native crabapple (M. coronaria) in southern Canada.

Methods

We applied four pollination treatments (open,M. coronaria,M. domestica, open +M. coronaria) to focalM. coronariatrees across multiple years and assessed the number and reproductive origins of resulting seeds (hybrid or conspecific endosperm and, for each, sexual or asexual embryo) using flow cytometry.

Results

In open‐pollinated fruit, 27% of seeds had hybrid endosperm; 52% of embryos were asexual. The number of conspecific embryos (sexual or asexual) per fruit did not decline significantly with increasing hybridization, indicating no seed discounting, but hand pollinations using only domestic apple or crabapple pollen reduced the number of conspecific embryos significantly. Hybridization was not associated with a change in percentage asexual embryos, overall, but there was an increase in asexual embryos in tetraploid seeds, the maternal and most common offspring ploidy.

Conclusions

We conclude that hybridization can influence nativeMalusin ways beyond the production of viable hybrids, with significant implications for population dynamics and genetic structure.
Skeletal, dental, and sexual maturation as an indicator of pubertal growth spurt
Authors: Ercan Derviş Emre , Yüksel Sema
Published: July 2023

Objectives

The aims of this study were to determine the skeletal, dental, and sexual maturation stages of individuals at the peak of the pubertal growth spurt and to analyze the correlations between these parameters.

Methods

The study included 98 patients, 49 females (mean chronological age 12.05 ± 0.96 years) and 49 males (mean chronological age: 13.18 ± 0.86 years), in the MP3cap stage. Skeletal maturation stages were determined using the cervical vertebral maturation (CVM) method on lateral cephalometric radiographs. The Demirjian index was used to determine dental maturation stages and dental ages on panoramic radiographs. The sexual maturation of the patients was evaluated in the pediatric endocrinology clinic by a pediatrician according to the Tanner stages. The frequencies of the variables were determined, and the Spearman rank correlation coefficients were used to analyze the correlations between the variables.

Results

It was determined that the cervical vertebral maturation stage was CS3 in 81.6% (n = 40) of both female and male patients, and 81.6% of the female and 89.8% of the male patients were in stage G in terms of mandibular second molar tooth development. According to the Tanner pubic hair staging, 73.5% of the male and 51.0% of the female patients were in Stage 3. A significant correlation was found between the cervical vertebra stages and mandibular second molar tooth development stages in both sexes and between the cervical vertebra and Tanner pubic hair stages only among the male patients (r = 0.357;p < .05). There was also a significant and strong correlation between the Tanner pubic hair stages and breast development stages (r = 0.715;p < .05).

Conclusion

Cervical vertebral development in the CS3 stage and mandibular molar tooth development in the G stage can be considered the peak of the pubertal growth spurt. Tanner Stage 3 marks the peak of the pubertal growth spurt in males.
Organocatalyst‐Controlled Divergent Asymmetric Aza‐Friedel‐Crafts Reactions of Indol‐3‐ones with 1‐ and 2‐Naphthols
Authors: Zheng Jie , Rong Meng‐Yu , Feng Fang‐Fang , Zhang Fa‐Guang , Cheung Chi Wai , Ma Jun‐An
Published: July 2023

Indol‐3‐ones are readily available reaction substrates, but their utility in asymmetric reactions is underdeveloped. Herein, we describe the organocatalytic asymmetric aza‐Friedel‐Crafts‐type reaction of indol‐3‐ones with 1‐ and 2‐naphthols. By using spirocyclic chiral phosphoric acids and quinine‐incorporated squaramides as the organocatalysts, two classes of structurally distinct chiral compounds, namely 2‐(hydroxylnaphthyl)‐indolin‐3‐ones and tetrahydrofuroindoles, are formed respectively. These quaternary centre‐containing indoline derivatives may find use in the synthesis of biologically active molecules.
Facile Synthesis of Bis‐Coumarins Using [BCMIM][Cl] Zwitter Ionic Liquid and Their Binding with Bovine Serum Albumin
Authors: Deepak Pasuparthy Sai , Joseph Suman , Somkuwar Pranati , S. K. Ashok Kumar , Maiti Barnali
Published: July 2023

Herein, we report a novel synthetic pathway for synthesizing bis‐coumarins using 5 mol% [BCMIM][Cl] ionic liquid via the facile, one‐pot, metal‐free synthesis in aqueous ethanol at room temperature. A series of 24 derivatives were furnished in up to 94% yields in 15 min to 1.5 h and were characterized using different spectroscopic techniques. The photophysical properties of bis‐coumarin derivatives were explored through UV‐Visible and fluorescence spectroscopy. The absorption and emission spectra demonstrate a peak wavelength (λmax), within the range of 297–311 nm and 486–505 nm, respectively. An analogous pattern to the experimental results is seen in density functional calculations. The binding affinities of all the synthesised derivatives with Bovine Serum Albumin (BSA) were determined using AutoDock Vina which exhibited a range from −8.4 to −11.5 kcal mol−1. The computed binding constant (KBSA) by tryptophan (Trp) emission quenching values illustrate strong binding interactions of the selected ligands in the order of 104. The calculated binding affinities were validated by performing molecular dynamics simulations of the best docking pose using GROMACS software over a period of 1 ns for studying the stability of protein‐ligand complexes.
Dynamic Control of Cyclic Peptide Assembly to Form Higher‐Order Assemblies
Authors: Wu Chongyang , Zhang Hongyue , Kong Nan , Wu Bihan , Lin Xinhui , Wang Huaimin
Published: July 2023

Chirality correction, asymmetry, ring‐chain tautomerism and hierarchical assemblies are fundamental phenomena in nature. They are geometrically related and may impact the biological roles of a protein or other supermolecules. It is challenging to study those behaviors within an artificial system due to the complexity of displaying these features. Herein, we design an alternating D,L peptide to recreate and validate the naturally occurring chirality inversion prior to cyclization in water. The resulting asymmetrical cyclic peptide containing a 4‐imidazolidinone ring provides an excellent platform to study the ring‐chain tautomerism, thermostability and dynamic assembly of the nanostructures. Different from traditional cyclic D,L peptides, the formation of 4‐imidazolidinone promotes the formation of intertwined nanostructures. Analysis of the nanostructures confirmed the left‐handedness, representing chirality induced self‐assembly. This proves that a rationally designed peptide can mimic multiple natural phenomena and could promote the development of functional biomaterials, catalysts, antibiotics, and supermolecules.
Supramolecular Polymer Ion Conductor with Weakened Li Ion Solvation Enables Room Temperature All‐Solid‐State Lithium Metal Batteries
Authors: Zhou Hang‐Yu , Ou Yu , Yan Shuai‐Shuai , Xie Jin , Zhou Pan , Wan Lei , Xu Zi‐Ang , Liu Feng‐Xiang , Zhang Wei‐Li , Xia Yin‐Chun , Liu Kai
Published: July 2023

Improved durability, enhanced interfacial stability, and room temperature applicability are desirable properties for all‐solid‐state lithium metal batteries (ASSLMBs), yet these desired properties are rarely achieved simultaneously. Here, in this work, it is noticed that the huge resistance at Li metal/electrolyte interface dominantly impeded the normal cycling of ASSLMBs especially at around room temperature (<30 °C). Accordingly, a supramolecular polymer ion conductor (SPC) with “weak solvation” of Li+ was prepared. Benefiting from the halogen‐bonding interaction between the electron‐deficient iodine atom (on 1,4‐diiodotetrafluorobenzene) and electron‐rich oxygen atoms (on ethylene oxide), the O‐Li+ coordination was significantly weakened. Therefore, the SPC achieves rapid Li+ transport with high Li+ transference number, and importantly, derives a unique Li2O‐rich SEI with low interfacial resistance on lithium metal surface, therefore enabling stable cycling of ASSLMBs even down to 10 °C. This work is a new exploration of halogen‐bonding chemistry in solid polymer electrolyte and highlights the importance of “weak solvation” of Li+ in the solid‐state electrolyte for room temperature ASSLMBs.
Tetraazacoronenes and Their Dimers, Trimers and Tetramers
Authors: Eichelmann Robert , Ballmann Joachim , Gade Lutz H.
Published: July 2023

Tetraazacoronenes were synthesized from bay‐functionalized tetraazaperylenes by Zr‐mediated cyclization and four‐fold Suzuki–Miyaura cross coupling. In the Zr‐mediated approach, an η4‐cyclobutadiene‐zirconium(IV) complex was isolated as an intermediate to cyclobutene‐annulated derivatives. Using bis(pinacolatoboryl)vinyltrimethylsilane as a C2 building block gave the tetraazacoronene target compound along with the condensed azacoronene dimer as well as higher oligomers. The series of extended azacoronenes show highly resolved UV/Vis absorption bands with increased extinction coefficients for the extended aromatic cores and fluorescence quantum yields of up to 80 % at 659 nm.
Facile chemical modification of poly(vinyl alcohol) to an organosoluble, flame‐retardant copolymer using dichloroacetic acid
Authors: Km Shelly , Ravishankar Kartik , Raghavachari Dhamodharan
Published: July 2023

Applications of poly(vinyl alcohol) (PVOH) are largely limited due to its poor flame resistance. In this work, organosolubility, and flame resistance are imparted to PVOH through green chemical transformation using dichloroacetic acid (DCAA). Unlike the conventional solvent‐based strategies, PVOH was modified by simply mixing it with DCAA and heating the mixture without employing any additional reagents/catalysts/solvents. This resulted in the formation of a random copolymer, poly(vinyl alcohol‐co‐vinyl dichloroacetate), which was not soluble in water but was soluble in organic solvents such as acetone, methanol, and dimethylsulfoxide. Furthermore, the copolymer was inherently self‐extinguishing, and did not melt drip or show glowing combustion. Additionally, dummy currency notes coated with this copolymer displayed exceptional self‐extinguishing and non‐glowing properties when removed from the flame, proving the copolymer's suitability for flame‐retardant sizing/coating applications.
Measuring imagery strength in schizophrenia: no evidence of enhanced mental imagery priming
Authors: Wagner Sophie , Monzel Merlin
Published: July 2023

Introduction

Recent research shows ambivalent results regarding the relationship between mental imagery and schizophrenia. The role of voluntary visual imagery in schizophrenic hallucinations remains unclear. The aim of the study was to investigate the association between visual imagery, schizophrenia, and the occurrence of schizophrenic hallucinations using an objective visual imagery task.

Methods

The sample consisted of 16 participants with schizophrenia (59.1% female; MAge = 45.55) and 44 participants without schizophrenia (62.5% female; MAge = 43.94). Visual imagery was measured using the Vividness of Visual Imagery Questionnaire (VVIQ) as well as the well‐validated Binocular Rivalry Task (BRT). Occurrences of hallucinations were assessed using the Launay–Slade Hallucination Scale.

Results

Participants with schizophrenia showed more hallucinatory experiences but did not score higher on either the VVIQ or the BRT than participants without schizophrenia. A correlation between the VVIQ and the BRT was found, validating the measurement of visual imagery and enabling the interpretation that visual imagery vividness is not enhanced in people with schizophrenia.

Conclusion

The association between mental imagery vividness and schizophrenia found in previous studies may be based on other facets of mental imagery than visual imagery.
A nomogram model for predicting the risk of checkpoint inhibitor‐related pneumonitis for patients with advanced non‐small‐cell lung cancer
Authors: Zhang Yao , Zhang Lincheng , Cao Shuhui , Wang Yue , Ling Xuxinyi , Zhou Yan , Zhong Hua
Published: July 2023

Objective

Immunotherapy extensively treats advanced non‐small‐cell lung cancer (NSCLC). Although immunotherapy is generally better tolerated than chemotherapy, it can cause multiple immune‐related adverse events (irAEs) involving multiple organs. Checkpoint inhibitor‐related pneumonitis (CIP) is a relatively uncommon irAE that, in severe cases, can be fatal. Potential risk factors for the occurrence of CIP are currently poorly understood. This study sought to develop a novel scoring system for predicting the risk of CIP based on a nomogram model.

Methods

We retrospectively collected advanced NSCLC patients who received immunotherapy at our institution between January 1, 2018, and December 30, 2021. All patients who met the criteria were randomly divided into the training set and testing set (in a ratio of 7:3), and cases fulfilling the CIP diagnostic criteria were screened. The patients' baseline clinical characteristics, laboratory tests, imaging, and treatment information were extracted from the electronic medical records. The risk factors associated with the occurrence of CIP were identified based on the results of logistic regression analysis on the training set, and a nomogram prediction model was developed. The discrimination and prediction accuracy of the model was evaluated using the receiver operating characteristic (ROC) curve, the concordance index (C‐index), and the calibration curve. Decision curve analysis (DCA) was used to evaluate the clinical applicability of the model.

Results

The training set comprised 526 (CIP: 42 cases), and the testing set comprised 226 (CIP: 18 cases) patients, respectively. In the training set, the final multivariate regression analysis revealed that age (p = 0.014; odds ratio [OR] = 1.056; 95% Confidence Interval [CI] =1.011–1.102), Eastern Cooperative Oncology Group performance status (p = 0.002; OR = 6.170; 95% CI = 1.943–19.590), history of prior radiotherapy (p < 0.001; OR = 4.005; 95% CI = 1.920–8.355), baseline white blood cell count (WBC) (p < 0.001; OR = 1.604; 95% CI = 1.250–2.059), and baseline absolute lymphocyte count (ALC) (p = 0.034; OR = 0.288; 95% CI = 0.091–0.909) were identified as independent risk factors for the occurrence of CIP. A prediction nomogram model was developed based on these five parameters. The area under the ROC curve and C‐index of the prediction model in the training set and testing set were 0.787 (95% CI: 0.716–0.857) and 0.874 (95% CI: 0.792–0.957), respectively. The calibration curves are in good agreement. The DCA curves indicate that the model has good clinical utility.

Conclusion

We developed a nomogram model that proved to be a good assistant tool for predicting the risk of CIP in advanced NSCLC. This model has the potential power to help clinicians in making treatment decisions.
Booster effect of a third mRNA‐based COVID‐19 vaccine dose in patients with myeloid malignancies
Authors: Mori Akio , Onozawa Masahiro , Kobayashi Mirei , Tsukamoto Shihori , Senjo Hajime , Ishio Takashi , Yokoyama Emi , Kanaya Minoru , Izumiyama Koh , Saito Makoto , Muraki Haruna , Morioka Masanobu , Teshima Takanori , Kondo Takeshi
Published: July 2023

Background

We have reported that seroconversion rates after the second dose of mRNA‐based COVID‐19 vaccines for myelodysplastic syndrome (MDS) and acute myeloid leukemia (AML) were 100% and 95% respectively, with no significant difference from healthy controls (HCs).However, there are very limited data for the response to a third vaccine dose in those patients.

Aims

In this complementary study, we investigated the booster effect of a third mRNA‐based COVID‐19 vaccine dose in patients with myeloid malignancies.

Materials & Methods

A total 58 patients including 20 patients with MDS and 38 patients with AML were enrolled. Anti‐SARS‐CoV‐2S immunoassays were performed at 3, 6, and 9 months after the second vaccine dose.

Results

Seventy‐five percent of the MDS patients and 37% of the AML patients were receiving active treatment at the time of the third vaccination. Both the initial and third vaccine response in AML patients were comparable to those in HCs. In MDS patients, although the initial vaccine immunogenicity was inferior to that in HCs and AML patients, the third vaccine improved the response to a level not inferior to those in HCs and AML patients. Of note, the third vaccine resulted in a significant increase of antibodies in actively treated MDS patients who had shown a response inferior to that in untreated patients after two doses of vaccination.

Discussion

In patients with myeloid malignancies, the third vaccine dose showed a booster effect, and disease‐ and therapy‐related factors associated with the booster response have been identified.

Conclusion

The third dose of an mRNA‐based COVID‐19 vaccine showed a booster effect in patients with myeloid malignancies. Such a good booster response has not been reported in other haematological malignancies.
Innovative Approaches to Enhanced Enzymatic Microalgae‐to Biodiesel Production
Authors: Sowan Eyad , Mozumder Mohammad Sayem , Taher Hanifa , Al‐Zuhair Sulaiman
Published: July 2023

Despite the increasing interest in biodiesel production from microalgae, the high cost of multistage production processes still hinders its commercialization. The high oil productivity of microalgae and their ability to grow rapidly under harsh conditions and in saline water make them a favorable feedstock for biodiesel production. In this review, conventional methods of producing biodiesel from microalgae are thoroughly discussed and compared to state‐of‐the‐art technologies. Considerable emphasis has been put on the adoption of biocatalysts as alternative greener and more effective catalysts. Challenges facing the biocatalytic process and innovative ways to overcome them are also presented. The main focus is on the in‐situ biodiesel production processes, which are promising to pave the way for industrial application of microalgae‐to‐biodiesel process. The use of state‐of the‐art thermoresponsive switchable solvents, coupled with immobilized lipase, for simultaneous cell disruption, oil extraction‐reaction, and product separation in one pot has shown to be highly favorable. Because enzymes are expensive, finding ways to enhance their stability and reusability for a greater number of cycles is essential for the process to be economically viable and competitive.
Recent Advances in MXenes Based Composites as Photocatalysts: Synthesis, Properties and Photocatalytic Removal of Organic Contaminants from Wastewater
Authors: Kitchamsetti Narasimharao , de Barros Ana L. F.
Published: July 2023

MXene has indeed gained significant attention in recent years as a promising photocatalyst for various applications, including photocatalytic degradation of pollutants. MXene possesses several unique physical and chemical properties that make it suitable for such applications, including its uniform planar structure, strong metal conductivity, effective functional groups, and numerous derivatives. These properties contribute to the excellent photodegradation performance and long‐term stability exhibited by MXene‐based photocatalysts compared to other photocatalysts. MXene‐based composites, which are formed by incorporating MXene with other materials, demonstrate even better photodegradation activity due to their abundant active sites and porous structure. One crucial factor influencing the photodegradation performance of MXene‐based photocatalysts is the presence of active functional groups on the surface of MXene. These functional groups play a significant role in the photocatalytic process and contribute to the overall efficiency of the catalyst. To provide a broader understanding of MXene‐based photocatalysts, the physicochemical properties of MXene are briefly described in this review. This includes its structural characteristics, electrical conductivity, and the presence of functional groups. This review also investigates the physical and chemical synthesis routes for preparing MXene, both in its natural state and as composites with other materials. These synthesis methods are essential for tailoring the properties of MXene‐based photocatalysts to meet specific requirements. Finally, the review discusses future work and challenges in MXene‐based photocatalysis. This field holds great promise for addressing environmental concerns and improving the degradation of organic compounds. However, further research is needed to optimize the synthesis methods, enhance the photocatalytic efficiency, and explore the practical applications of MXene‐based photocatalysts.
Light‐Driven NADPH Cofactor Recycling by Photosystem I for Biocatalytic Reactions
Authors: Medipally Hitesh , Guarneri Alice , Pospisil Lars , Franssen Maurice C. R. , van Berkel Willem J. H. , Paul Caroline E. , Nowaczyk Marc M.
Published: July 2023

Biocatalytic asymmetric reduction of C=C and C=O bonds is highly attractive to produce valuable (chiral) chemicals for the fine and pharmaceutical industry, yet occurs at the expense of reduced nicotinamide adenine dinucleotide coenzyme NADPH that requires recycling. Established methods each have their challenges. Here we developed a light‐driven approach based on photosystem I (PSI) by mimicking the natural electron transfer from PSI via ferredoxin (Fd) towards ferredoxin NADP+ reductase (FNR) in vitro. Illumination with red light led to reduction of NADP+ to NADPH with a turnover frequency of 2.55 s−1 (>9000 h−1) at pH 7.5. Light‐driven NADPH regeneration by PSI‐Fd‐FNR was coupled with three oxidoreductases for asymmetric reduction of C=C and C=O bonds, reaching up to 99 % conversion with a turnover number of 3035, and retaining enantioselectivity. This study demonstrates the capacity of a PSI system to drive continuous NADPH‐dependent biocatalytic conversions with light.
Computational Fluid Dynamics Simulation of a Membrane Contactor for CO2 Separation: Two Types of Membrane Evaluation
Authors: Sayyah Alborzi Zahra , Amini Younes , Amirabedi Parya , Raveshiyan Saba , Hassanvand Amin
Published: July 2023

Two different types of hollow‐fiber membrane contactors were used for CO2 separation from the gas stream with monoethanolamine (MEA) absorbent and numerically investigated. After the model validation with experimental data, CO2 removal efficiency, MEA concentration, and pressure drop variation were examined under different conditions by variation of some effective parameters such as gas stream velocity, absorption solution velocity, membrane porosity, and membrane tortuosity. Membrane tortuosity and porosity enhancement led to light decrease and light increase in CO2 removal efficiency, respectively, but gas stream velocity enhancement significantly reduced the CO2 removal efficiency.
Total Synthesis of UCS1025A via Tandem Carbonylative Stille Cross Coupling and Diels‐Alder Reaction†
Authors: Cui Chengsen , Dai Mingji
Published: July 2023

Comprehensive Summary

We report an efficient and convergent strategy for the total synthesis of UCS1025A and its diastereomer tetra‐epi‐UCS1025A. UCS1025A is a representative member of the naturally occurring pyrrolizidinone polyketides, from which members with potent antibacterial, antifungal, and anticancer activities have been identified. Our approach features a tandem carbonylative Stille cross coupling and Diels‐Alder reaction to forge a key C—C bond and build the trans‐decalin system. This tandem process utilizes carbon monoxide as a one‐carbon linchpin to stitch a vinyl triflate and a vinylstannane together and form the desired enone moiety for the subsequent intramolecular Diels‐Alder cyclization. Our synthesis also provides a versatile approach for the synthesis of other related pyrrolizidinone‐containing polyketides.
Mechanisms of change in treatments for transdiagnostic emotion dysregulation: The roles of skills use, perceived control and mindfulness
Authors: Wyatt Kristin P. , Eberle Jeremy W. , Ruork Allison K. , Neacsiu Andrada D.
Published: July 2023

Emotion dysregulation (ED) is a key target for change among empirically supported treatments for emotional disorders, including dialectical behaviour therapy skills training (DBT‐ST), yet how treatments improve ED is poorly understood. Using data from a randomised trial of DBT‐ST versus supportive group therapy for transdiagnostic ED, we tested whether three mechanistic variables—behavioural skills use, mindfulness, and perceived control—explain variability in ED within people over time. We additionally explored the mediating roles of these variables between conditions. Adults with transdiagnostic ED (N = 44) participated in weekly groups for 4 months, with assessments at pre‐, mid‐ and post‐treatment and at 2‐month follow‐up. As hypothesised, multilevel models disaggregating within‐ and between‐person effects indicated that skills use, mindfulness, and perceived control each had significant total and unique within‐person associations with ED at concurrent time points, net the effect of time. Unexpectedly, these within‐person relations were not significant for mechanistic variables predicting ED 2 months later. Further, unique between‐person variability in skills use, mindfulness, and perceived control did not significantly mediate the relationship between condition and ED improvements. The present study is an important step in clarifying ED mechanisms of change, both within and between persons.
An integrative view on the systematic position of the cupressophyteCephalotaxus
Authors: Yang Yong , Yang Zhi , Ferguson David Kay , Shong Jia‐Yi
Published: July 2023

We made an in‐depth review of historical studies of the cupressophyte conifer genusCephalotaxusSiebold & Zucc. with an emphasis on its systematic position. We suggest that the systematic position of the genus is better understood using an integrative approach, so the evolution of phenetic characters is discussed within the context of recent phylogenomics. We propose that the genus should be classified as a separate family Cephalotaxaceae belonging to the clade consisting of Cupressaceae, Cephalotaxaceae, and Taxaceae; the family Cephalotaxaceae is sister to the Taxaceae but not nested within the Taxaceae and is characterized by a unique set of characters including morphology, anatomy, embryology, and chemistry. The family Cephalotaxaceae shows transitional characters between the Cupressaceae and the Taxaceae; the family possesses female cones with a primary cone axis bearing 5–8 pairs of decussate bracts, which is similar to the typical female cones of the Cupressaceae, on the one hand, and may have given rise to the reduced female cone of the Taxaceae with one terminal ovule partially or completely enclosed in a fleshy aril. In parallel, the compound male cone of the Cephalotaxaceae evolved into the seemingly “simple” male cones of the Taxaceae by means of reduction, elimination, and fusion.
Diuretic dose is a strong prognostic factor in ambulatory patients awaiting heart transplantation
Authors: Baudry Guillaume , Coutance Guillaume , Dorent Richard , Bauer Fabrice , Blanchart Katrien , Boignard Aude , Chabanne Céline , Delmas Clément , D'Ostrevy Nicolas , Epailly Eric , Gariboldi Vlad , Gaudard Philippe , Goéminne Céline , Grosjean Sandrine , Guihaire Julien , Guillemain Romain , Mattei Mathieu , Nubret Karine , Pattier Sabine , Vermes Emmanuelle , Sebbag Laurent , Duarte Kevin , Girerd Nicolas
Published: July 2023

Aims

The prognostic value of ‘high dose’ loop diuretics in advanced heart failure outpatients is unclear. We aimed to assess the prognosis associated with loop diuretic dose in ambulatory patients awaiting heart transplantation (HT).

Methods and results

All ambulatory patients (n = 700, median age 55 years and 70% men) registered on the French national HT waiting list between 1 January 2013 and 31 December 2019 were included. Patients were divided into ‘low dose’, ‘intermediate dose’, and ‘high dose’ loop diuretics corresponding to furosemide equivalent doses of ≤40, 40–250, and >250 mg, respectively. The primary outcome was a combined criterion of waitlist death and urgent HT. N‐terminal pro‐B‐type natriuretic peptide, creatinine levels, pulmonary capillary wedge pressure, and pulmonary pressures gradually increased with higher diuretic dose. At 12 months, the risk of waitlist death/urgent HT was 7.4%, 19.2%, and 25.6% (P = 0.001) for ‘low dose’, ‘intermediate dose’, and ‘high dose’ patients, respectively. When adjusting for confounders, including natriuretic peptides, hepatic, and renal function, the ‘high dose’ group was associated with increased waitlist mortality or urgent HT [adjusted hazard ratio (HR) 2.23, 1.33 to 3.73; P = 0.002] and a six‐fold higher risk of waitlist death (adjusted HR 6.18, 2.16 to 17.72; P < 0.001) when compared with the ‘low dose’ group. ‘Intermediate doses’ were not significantly associated with these two outcomes in adjusted models (P > 0.05).

Conclusions

A ‘high dose’ of loop diuretics is strongly associated with residual congestion and is a predictor of outcome in patients awaiting HT despite adjustment for classical cardiorenal risk factors. This routine variable may be helpful for risk stratification of pre‐HT patients.