bluuebunny/crossref_metadata_2025 huggingface dataset:
Atomically Dispersed Interstitial Phosphorus Boosts Alkaline Hydrogen Evolution Performance of Co Catalysts
Authors: Shi Yue , Wang Mengna , Zhang Dan , Li Hongdong , Li Caixia , Zhan Tianrong , Lai Jianping , Wang Lei
Published: August 2024

Introducing interstitial light atoms shows great potential in improving the intrinsic activity and stability of metal catalysts owing to strongly affecting the electronic structure and adsorption properties. However, filling atomically dispersed light atoms into metal lattices and further unveiling their interstitial effects are still limited by tightly arranged metal lattices. Herein, the study reports a calcination reduction assisted trace light atoms filling strategy to form a series of interstitial light single atoms filled Co‐based catalysts (Co‐X@NF, X = P, N and NF = nickel foam), therefore constructing monometallic atomic interfaces between P‐coordinated Coδ+ and Co0 to promote alkaline hydrogen evolution reaction (HER). Noteworthy, the optimal Co‐P0.43@NF with rich monometallic atomic interfacial structure shows very high turnover frequency values (5.64 s−1), which is close to noble metal level and far exceeds non‐noble metal catalysts. Meanwhile, it maintains excellent stability of 150 h at 100 mA cm−2. Theoretical studies prove that P‐coordinated Coδ+ promotes H2O dissociation and Co0 optimizes H* adsorption energy, thus forming highly active monometallic atomic interfaces, which greatly accelerates the alkaline HER kinetics.
Surface‐Confined Winding Assembly of SiO2 on the Surface of BaTiO3 Leading to Enhanced Performance of Dielectric Nanocomposites
Authors: Wang Fan , Luo Hang , Chen Haiyan , Zhai Di , Jiang Xun , Liu Yuan , Zhang Dou
Published: August 2024

In response to the demand for miniaturization and lightweighting in the electronics industry, achieving enhanced energy density of dielectrics is crucial. Constructing nanocomposites consist of ceramic fillers and polymer matrix is an effective strategy in this regard. To address the adverse coupling between polarization and breakdown strength of the nanocomposites, a series of BaTiO3@SiO2 nanofillers with customizable SiO2 shell coverage degrees (90°, 180°, and 360°) is designed and synthesized by surface‐confined winding assembly of SiO2 on the surface of BaTiO3. When a half area of BaTiO3 core is coated by SiO2 layer, it is defined as 180°. A larger coverage degree implies better reduction of leakage current injection, and more effective suppression of local electric field concentration. However, it also leads to a more pronounced reduction in the polarization. 180° BaTiO3@SiO2 demonstrates the most effective mitigation of the adverse coupling between polarization and breakdown strength in nanocomposites. The 180° BaTiO3@SiO2/Poly(vinylidene fluoride) (PVDF) nanocomposite achieves high breakdown strength while maintaining relatively higher polarization intensity, for example, the energy density reaches 20.64 J cm−3 at 650 MV m−1, which is 2.62 times of pure PVDF. This work reveals the growth mechanism of customizable SiO2 shell coverage degrees on BaTiO3 surfaces, providing an effective strategy for high‐performance dielectrics
Asymmetric π‐Bridge Strategy Regulating Film‐Forming Kinetics for Over 19% Efficiency Organic Solar Cells
Authors: Wang Pengchao , Bi Fuzhen , Jiang Huanxiang , Wang Xiaoning , Cui Chuanlong , Li Yonghai , Bao Xichang
Published: August 2024

Blending morphologies are critical to bulk‐heterojunction (BHJ) organic solar cells (OSCs) to realize satisfactory photovoltaic performance. Therefore, rationally manipulating film‐forming kinetics is of great importance to building suitable phase‐separations to balance exciton dissociation and charge transport. Herein, by employing a unilateral π‐bridge approach, a new acceptor, WA6 is reported to optimize the film‐forming process of active layers and their microstructures. Meanwhile, the possible influencing factors are proposed, including intermolecular electrostatic interactions and donor/acceptor compatibility in the vital solution‐to‐film transformation stage. Beneficial from the appropriate fibrous phase‐separation, the PM6:WA6 based solar cells refined exciton/charge properties, leading to 15.39% high efficiency and much greater than the control device based on the counterpart acceptor without π‐bridge. Furthermore, the WA6 can serve as efficient guest component as well, and achieved 19.21% efficiency in the resultant ternary solar cells. This study provides a feasible approach to modulate the molecular aggregation and film‐forming procedure, for the construction of high‐performance OSCs with eligible blending morphologies.
Rapid Hole Transfer and Molecular Enrichment at Amorphous‐Crystalline Interfaces of Pt0.25%/TO(B)‐FCP for Efficient Photocatalysis
Authors: Sun Qimeng , Xia Xiaoyong , He Weijie , Liu Xiaofang , Chen Dongyun , Li Hua , Li Najun , Dong Huilong , Xu Qingfeng , Lu Jianmei
Published: August 2024

The construction of amorphous‐crystalline interfaces of heterogeneous metal oxide systems is an effective approach to modulate the interfacial adsorption behavior and carrier transfer pathways for the photocatalytic process. In this work, the amorphous‐crystalline interface is constructed by covalently linking a flexible crosslinked polymer (FCP) layer to a Pt0.25%/TO(B) substrate. Adsorption‐photodegradation experiments show that Pt0.25%/TO(B)‐FCP can ultimately enrich bisphenol A molecules to the interface within 5 min and in situ‐photodegrade >97.0% of bisphenol A within 10 min (50 ppm), which is 6.21 times than pure TO(B). In addition to the efficient accumulation of BPA molecules, the rapid hole transfer pathway at the amorphous‐crystalline interface is revealed by theoretical calculations, Kelvin probe force microscopy, and photoelectrochemical characterization. The coexistence of Pt single atoms (SAs) and nanoclusters (NCs) optimizes the transfer kinetics and reduces the energy barrier of photogenerated holes of TO(B). Meanwhile, the covalent hole transfer channels between the FCP layer and Pt0.25%/TO(B) significantly accelerate the separation and transfer of photogenerated carrier, promoting the photodegradation of adsorbed BPA molecules.
Self‐Assembled Peptide Hydrogels Loaded with Umbilical Cord‐Derived Mesenchymal Stem Cells Repairing Injured Endometrium and Restoring Fertility
Authors: Lv Xue , Niu Wenjing , Zhang Bin , Chen Jingbo , Yang Shicong , Xue Yuhuan , Dong Yutian , Yuan Peiyan , Pan Yue , Tan Jeremy , Yang Yi Yan , Ding Xin , Zhao Xiaomiao
Published: August 2024

Endometrial injury is a major cause of infertility and recurrent miscarriage. However, no clinically available methods currently exist to effectively repair the damaged endometrium. Mesenchymal stem cells (MSCs) have emerged as a promising therapeutic approach for promoting tissue regeneration, yet a biocompatible scaffold capable of delivering MSCs and supporting their growth is needed. Herein, the study reports a peptide hydrogel scaffold, self‐assembled from a peptide IVK8‐RGD consisting of an ionic complementary peptide sequence IEVEIRVK and a bioactive sequence RGD, to load umbilical cord‐derived mesenchymal stem cells (UC‐MSCs). This peptide forms a hydrogel under the physiological condition through self‐assembly, and the peptide hydrogel exhibits injectability and adhesiveness to uterus, making it suitable for endometrial repair. Importantly, this hydrogel supports the adhesion and proliferation of UC‐MSCs in a 3D environment. In vivo experiments using rats with endometrial injury have shown that treatment with IVK8‐RGD hydrogel loaded with UC‐MSCs effectively restores endometrial thickness, inhibits fibrosis, and facilitates angiogenesis through activating Raf/MEK/ERK pathway, leading to significantly improved fertility and live birth rate. These findings demonstrate the potential of the UC‐MSCs‐loaded hydrogel in repairing damaged endometrium and may address the unmet clinical needs of treating recurrent miscarriage and infertility induced by endometrial damage.
Immunometabolic Approaches Mitigating Foreign Body Response and Transcriptome Characterization of the Foreign Body Capsule
Authors: Macias Sabrina L. , Palmer Olivia , Simonovich Jennifer A. , Clark Ryan A. , Hudalla Gregory A. , Keselowsky Benjamin G.
Published: August 2024

Directing immunometabolism presents new opportunities to modulate key cell types associated with the formation of foreign body response (FBR) capsule. Contrasting approaches directing immunometabolism are investigated to mitigate FBR: a broadly suppressive metabolic inhibitor (MI) cocktail comprised of 2‐deoxyglucose (2‐DG), metformin, and 6‐diazo‐5‐oxo‐l‐norleucine (DON) with daily systemic dosing regimen, and local weekly injection of the more narrowly focused tryptophan catabolizing IDO‐Gal3 fusion protein. Treatments significantly decrease FBR capsule formed around subcutaneously implanted cellulose disks. MI cocktail results in a substantially thinner FBR capsule (40% of control), while weekly local injection of IDO‐Gal3 also results in a thinner FBR capsule (69% of control). RNA‐sequencing capsule transcripts reveal MI cocktail promotes quiescence, with decreased antigen processing and presentation, T helper subset differentiation, and cytokine‐cytokine receptor pathway. IDO‐Gal3 promotes pro‐regenerative, alternatively activated M2‐like macrophages and T helper 2 cells, with increased expression of type 2 response‐associated genes (Il4, Il13, Arg1, Mrc1, Chil3, Gata3). IDO‐Gal3 decreases pro‐inflammatory innate sensing pathways, and C‐type lectin receptor, NOD‐like receptor, RIG‐I‐like receptor, and Toll‐like receptor signaling. This work helps define key gene targets and pathways concomitantly regulated in the FBR capsule during immunometabolic modulation compared to control FBR capsule.
Ruthenium Single‐Atom Modulated Protonated Iridium Oxide for Acidic Water Oxidation in Proton Exchange Membrane Electrolysers
Authors: Tang Jialin , Liu Xinyan , Xiong Xiaoxia , Zeng Qisheng , Ji Yuan , Liu Chunxiao , Li Jiawei , Zeng Hongliang , Dai Yizhou , Zhang Xinyan , Li Chengbo , Peng Hongjie , Jiang Qiu , Zheng Tingting , Pao Chih‐Wen , Xia Chuan
Published: August 2024

Proton exchange membrane water electrolysers promise to usher in a new era of clean energy, but they remain a formidable obstacle in designing active and durable electrocatalysts for the acidic oxygen evolution reaction (OER). In this study, a protonated iridium oxide embedded with single‐atom dispersed ruthenium atoms (H3.8Ir1−xRuxO4) that demonstrates exceptional activity and stability in acidic water oxidation is introduced. The single Ru dopants favorably induce localized oxygen vacancies in the Ir─O lattice, synergistically strengthening the adsorption of OOH* intermediates and enhancing the intrinsic OER activity. In addition, the preferential oxidation of Ru and the electronegativity of the oxygen vacancies significantly stabilize the Ir─O active sites, improving the OER stability. Consequently, the H3.8Ir1─xRuxO4 catalyst shows an overpotential of 255 mV at 10 mA cm−2 and displays exceptional catalytic endurance in acidic electrolytes, surpassing 1100 h, representing a remarkable one‐order‐of‐magnitude increase in stability compared to that of pristine H3.8IrO4. A proton exchange membrane electrolyser utilizing the H3.8Ir1−xRuxO4 catalyst as an anode exhibits stable performance for more than 1280 h under a high current density of 2 A cm−2.
Modulating the Electronic Structure of Cobalt‐Vanadium Bimetal Catalysts for High‐Stable Anion Exchange Membrane Water Electrolyzer
Authors: Liang Zhijian , Shen Di , Wei Yao , Sun Fanfei , Xie Ying , Wang Lei , Fu Honggang
Published: August 2024

Modulating the electronic structure of catalysts to effectively couple the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is essential for developing high‐efficiency anion exchange membrane water electrolyzer (AEMWE). Herein, a coral‐like nanoarray composed of nanosheets through the synergistic layering effect of cobalt and the 1D guiding of vanadium is synthesized, which promotes extensive contact between the active sites and electrolyte. The HER and OER activities can be enhanced by modulating the electronic structure through nitridation and phosphorization, respectively, enhancing the strength of metal‐H bond to optimize hydrogen adsorption and facilitating the proton transfer to improve the transformation of oxygen‐containing intermediates. Resultantly, the AEMWE achieves a current density of 500 mA cm–2 at 1.76 V for 1000 h in 1.0 M KOH at 70 °C. The energy consumption is 4.21 kWh Nm–3 with the producing hydrogen cost of $0.93 per kg H2. Operando synchrotron radiation and Bode phase angle analyses reveal that during the high‐energy consumed OER, the dissolution of vanadium species transforms distorted Co−O octahedral into regular octahedral structures, accompanied by a shortening of the Co−Co bond length. This structural evolution facilitates the formation of oxygen intermediates, thus accelerating the reaction kinetics.
Polymeric Nanocarriers Autonomously Cross the Plant Cell Wall and Enable Protein Delivery for Stress Sensing
Authors: Zhang Yilin , Cao Yunteng , Jiang Wenzhi , Ma Qingquan , Shin Jinwoo , Sun Hui , Cui Jianqiao , Chen Yongsheng , Giraldo Juan Pablo , Strano Michael S. , Lowry Gregory V. , Sheen Jen , Marelli Benedetto
Published: August 2024

Delivery of proteins in plant cells can facilitate the design of desired functions by modulation of biological processes and plant traits but is currently limited by narrow host range, tissue damage, and poor scalability. Physical barriers in plants, including cell walls and membranes, limit protein delivery to desired plant tissues. Herein, a cationic high aspect ratio polymeric nanocarriers (PNCs) platform is developed to enable efficient protein delivery to plants. The cationic nature of PNCs binds proteins through electrostatic. The ability to precisely design PNCs’ size and aspect ratio allowed us to find a cutoff of ≈14 nm in the cell wall, below which cationic PNCs can autonomously overcome the barrier and carry their cargo into plant cells. To exploit these findings, a reduction‐oxidation sensitive green fluorescent protein (roGFP) is deployed as a stress sensor protein cargo in a model plant Nicotiana benthamiana and common crop plants, including tomato and maize. In vivo imaging of PNC‐roGFP enabled optical monitoring of plant response to wounding, biotic, and heat stressors. These results show that PNCs can be precisely designed below the size exclusion limit of cell walls to overcome current limitations in protein delivery to plants and facilitate species‐independent plant engineering.
Probing Charge Transport and Microstructural Attributes in Solvent‐ versus Water‐Based Electrodes with a Spotlight on Li–S Battery Cathode
Authors: Yari Saeed , Bird Liam , Rahimisheikh Sepideh , Reis Albin Conde , Mohammad Mahsa , Hadermann Joke , Robinson James , Shearing Paul R. , Safari Mohammadhosein
Published: August 2024

In the quest for environmentally benign battery technologies, this study examines the microstructural and transport properties of water‐processed electrodes and compares them to conventionally formulated electrodes using the toxic solvent, N‐Methyl‐2‐pyrrolidone (NMP). Special focus is placed on sulfur electrodes utilized in lithium‐sulfur batteries for their sustainability and compatibility with diverse binder/solvent systems. The characterization of the electrodes by X‐ray micro‐computed tomography reveals that in polyvinylidene fluoride (PVDF)/NMP, sulfur particles tend to remain in large clusters but break down into finer particles in carboxymethyl cellulose‐styrene butadiene rubber (CMC‐SBR)/water and lithium polyacrylate (LiPAA)/water dispersions. The findings reveal that in the water‐based electrodes, the binder properties dictate the spatial arrangement of carbon particles, resulting in either thick aggregates with short‐range connectivity or thin films with long‐range connectivity among sulfur particles. Additionally, cracking is found to be particularly prominent in thicker water‐based electrodes, propagating especially in regions with larger particle agglomerates and often extending to cause local delamination of the electrodes. These microstructural details are shown to significantly impact the tortuosity and contact resistance of the sulfur electrodes and thereby affecting the cycling performance of the Li‐S battery cells.
Ultrahigh Energy Density and Ultrafast Response in Symmetric Microsupercapacitors with 3D Bicontinuous Pseudocapacitance
Authors: Kim Min Ji , Kim Minjeong , Sohn Won Bae , Kang JoonHyun , Kim Woong , Kang Jin Gu
Published: August 2024

Achieving a high storage capability while maintaining good rate performance using symmetric microsupercapacitors (MSCs) remains challenging. Herein, a 3D symmetric MSC based on interdigitated 3D bicontinuous pseudocapacitive electrodes is proposed to simultaneously attain ultrahigh energy density and ultrafast response. The 3D electrodes comprise electrolytically active MnO2 layers conformally coated onto a 3D periodic porous Ni current collector. In this architecture, the low conductivity of MnO2 can be compensated by efficient charge transport and facile charge transfer without compromising its high capacitance. The 3D MSC with a 1‐V window exhibits an ultrahigh volumetric energy density of 15.8 mWh cm−3 with a high power density of 4.95 W cm−3, outperforming all previously reported MnO2‐based symmetric MSCs. Benefitting from its ultrafast response, the 3D MSC exhibits superiority in terms of the phase angle (−66°), areal capacitance (1400 µF cm−2), and time constant (0.6 ms) at an alternating‐current (AC) frequency of 120 Hz. By using the 3D MSC as a line‐filtering capacitor in a real circuit, the AC signal is effectively smoothed with small residual ripples (≈1.35 mV). Additionally, the device achieves excellent performance in an all‐solid‐state form.
Revealing Phase Transitions in Poly(Ethylene Oxide)‐Based Electrolyte for Room‐Temperature Solid‐State Batteries
Authors: Ding Ning , Chien Sheau Wei , Tam Teck Lip Dexter , Li Xiaodong , Wu Gang , Lee Won Jun , Chiam Sing Yang , Meng Ying Shirley , Fam Derrick Wen Hui
Published: August 2024

Solid‐state electrolytes (SSEs) offer enhanced safety, extended cycle life, and increased energy density when replacing flammable liquid electrolytes in lithium‐ion batteries. Poly(ethylene oxide) (PEO)‐based SSE is the only candidate that has been commercially implemented in electric vehicles. However, the equipped battery needs to operate at temperatures above 50 °C, and its phase transitions at room temperature are still unclear. Herein, the solidification of the PEO‐lithium bis(trifluoromethanesulfonyl)imide (PEOn‐LiTFSI) system is revisited. Contrary to the prevailing view of forming PEO(6)‐LiTFSI spherulites, the presence of crystalline PEO(8)‐LiTFSI complexes is quantitatively confirmed. The nucleation and growth processes of crystalline PEO and PEO(8)‐LiTFSI spherulites are also visually elucidated, and phase transitions with the impedance change are correlated. In addition, it is demonstrated that the crystalline PEO shell surrounding the PEO(8)‐LiTFSI spherulites hinders the kinetics of crystal growth, thereby enabling the highest ionic conductivity at n = 10. Importantly, it is pointed out that instead of the poor ionic conductivity of the electrolyte layer, the heterogeneous nucleation of PEO(8)‐LiTFSI within the electrodes is the limiting factor in constructing room‐temperature all‐solid‐state batteries.
Double somatic mosaicism in Marfan syndrome
Authors: Carrera Ignacio Arroyo , Amor‐Salamanca Almudena , Isidro Elena Márquez , Pérez‐Barbeito Marlene , Sacristán Ana Raquel Barrio , Ochoa Juan Pablo
Published: August 2024

Marfan syndrome (MFS) is a hereditary systemic connective tissue disorder with great clinical variability. It is caused by heterozygous pathogenic variants in the FBN1 gene. Cardinal manifestations involve the cardiovascular, ocular, and skeletal systems. Clinical diagnosis is based on the revised Ghent nosology. We present the case of a child with a Marfan systemic score of 9 whose genetic study revealed two pathogenic mosaic frameshift variants in the FBN1 gene. Mosaicism is very rare in patients diagnosed with MFS, and this is the first description of a patient with two pathogenic mosaic variants in the FBN1 gene. Both variants are present in cells derived from ectodermal (buccal swab) and mesodermal (leukocyte) tissues, suggesting a mutation prior to gastrulation. We propose a defective repair of the de novo variant in the complementary strand as the mechanism that led this individual to be a carrier of two different populations of mutant cells carrying adjacent variants.
CNOT1 p.Arg535Cys variant in holoprosencephaly with late onset diabetes mellitus
Authors: de Queiroz Júnior Amaro Freire , Sanseverino Maria Teresa Vieira , Collares Marcus Vinicius Martins , Fornari Adriana , do Virmond Luiza Amaral , Filho João Bosco Oliveira , Artigalás Osvaldo , Félix Têmis Maria
Published: August 2024

Holoprosencephaly (HPE) results from a lack of cleavage of the prosencephalon. It has a complex etiology, resulting from chromosome abnormalities or single gene variants in the Sonic hedgehog signaling pathway. A single variant, p.Arg535Cys in CNOT1, has been described in HPE in association with pancreatic agenesis and neonatal diabetes. Here, we report on a case of HPE and p.Arg535Cys in CNOT1 without pancreatic agenesis where the patient presented with diabetes mellitus in adolescence. This case reinforces the role of CNOT1 in pancreatic development. We suggest that individuals with p.Arg535Cys in CNOT1 with no pancreas abnormalities observed at birth should be screened for diabetes during follow‐up.
Longitudinal echocardiography in pediatric patients with hypermobile Ehlers‐Danlos syndrome
Authors: Lahey Hannah , Shin Haewon , Myers Katherine , McBride Kim L.
Published: August 2024

Vascular Ehlers‐Danlos, Marfan and Loeys‐Dietz syndromes have increased risk of aortic dilation and dissection. Previous early studies showed hypermobile Ehlers‐Danlos syndrome (hEDS) may also have increased risk, with echocardiography screening recommended; subsequent studies have not confirmed the risk or recommended echocardiography. This pediatric‐based study assessed aortic dilation prevalence in those with hEDS by serial echocardiographic examinations and assessed family history for aortic dissections. We retrospectively identified individuals with hEDS who had echocardiography studies from the electronic medical records at one pediatric center. Aortic root Z‐scores >2.0 were found in 15/225 subjects (average age 12.9 years) on initial echocardiograms, with no Z‐score >3.0. Subsequent studies (n = 68) found statistically significant decline in aortic root Z‐scores. Repeat echocardiography in those with initial aortic root Z‐score >2.0 (n = 10) demonstrated a decline in Z score <2.0 in seven. On final examination, 9/225 (4.0%) had a Z‐score >2.0, not statistically different from the general population. No aortic dissection occurred in first‐ or second‐degree relatives. In conclusion, aortic root dilation rate in hEDS is likely not different from the general population. We propose that in the absence of other cardiac findings or suspicion for another disorder, echocardiography is not required in hEDS.
Atypical presentation of ACCES syndrome resembling dominant Spondyloepiphyseal dysplasia tarda
Authors: Sezer Abdullah , Özdemir Zeynep , Özkan Erdem , Çetinkaya Semra
Published: August 2024

Aplasia Cutis Congenita with Ectrodactyly Skeletal Syndrome (ACCES, OMIM #619959) is an extremely rare multiple congenital anomalies syndrome caused by haploinsufficiency of the UBA2 gene. This syndrome presents with growth retardation, dysmorphic facial features, neurodevelopmental delay, skeletal problems including ectrodactyly, developmental dysplasia of the hip (DDH) and scoliosis, skin findings such as aplasia cutis, and some internal organ abnormalities. Our 13‐year‐old female patient and her 38‐year‐old father had a skeletal dysplasia phenotype with disproportionate short stature, bilateral DDH, mild epiphyseal involvement, scoliosis, and increased lumbar lordosis. Both were neurodevelopmentally normal and had mild dysmorphic facial features and mild ectodermal findings. The dominant inheritance pattern in the pedigree suggested a pre‐diagnosis of spondyloepiphyseal dysplasia tarda. The exome sequencing analysis of the patient has identified a novel heterozygous variant, NM_005499.2:c.460‐2A >G, in the UBA2 gene, and the father was found heterozygous either. The isolated spondyloepiphyseal involvement of our patients was an unusual presentation compared to patients with ACCES syndrome previously reported in the literature. Considering the highly variable expressiveness of ACCES syndrome and the co‐occurrence of familial hip dysplasia and vertebral problems, we suggest that this syndrome can also be classified under “Spondyloepi(meta)physial dysplasia (SE(M)D)” in the nosology of genetic skeletal disorders.
The DNH 7 endocast of Paranthropus robustus from Drimolen, South Africa: Reconsidering the functional significance of an enlarged occipital‐marginal (O/M) sinus system in robust australopithecines
Authors: Falk Dean , Marom Assaf
Published: August 2024

This paper presents a detailed analysis of the endocast of one of the most complete Paranthropus robustus crania known, DNH 7, from the Drimolen site (South Africa), and compares it with the morphology of other australopithecine endocasts. We focus on endocranial volume, the impressions of cortical sulci, cranial sutures, and the pattern of cranial venous sinuses on the endocast. A noteworthy observation is the estimated endocranial capacity of 403 cm3, which is small for an adult Paranthropus. Fragmentary sulci identified in the frontal and temporal lobes of DNH 7 exhibit similarities with patterns observed in chimpanzees and gracile australopithecines. We observe the presence of a large remnant of an occipital‐marginal sinus on DNH 7 and provide an updated table of 13 Paranthropus endocasts that are scorable for this trait, which reinforces the hypothesis that an enlarged occipital‐marginal (O/M) sinus system was fixed across the three species of Paranthropus. In light of this, the possible functional significance of the occipital‐marginal sinus system is reevaluated considering the ontogenetic development of cranial venous blood flow in human children. This leads us to hypothesize that the ontogenetic development of cranial blood flow in Paranthropus and Australopithecus africanus infants were different and to suggest that Taung 1 was the only A. africanus specimen known to have exhibited an enlarged O/M sinus system because it was an immature individual.
One‐Stone‐For‐Three‐Birds Strategy Using a Fullerene Modifier for Efficient and Stable Inverted Perovskite Solar Cells
Authors: Jiang Xiaofen , Jia Lingbo , Zhang Shantao , Gao Yan , Yan Nan , Hou Tianao , Gao Shuang , Wang Xue , Li Xinyu , Chen Wenjing , Xiao Zhengguo , Wu Xiaojun , Fang Zhimin , Liu Shengzhong (Frank) , Yang Shangfeng
Published: August 2024

The electron extraction from perovskite/C60 interface plays a crucial role in influencing the photovoltaic performance of inverted perovskite solar cells (PSCs). Here, we develop a one‐stone‐for‐three‐birds strategy via employing a novel fullerene derivative bearing triple methyl acrylate groups (denoted as C60‐TMA) as a multifunctional interfacial layer to optimize electron extraction at the perovskite/C60 interface. It is found that the C60‐TMA not only passivates surface defects of perovskite via coordination interactions between C=O groups and Pb2+ cations but also bridge electron transfer between perovskite and C60. Moreover, it effectively induces the secondary grain growth of the perovskite film through strong bonding effect, and this phenomenon has never been observed in prior art reports on fullerene related studies. The combination of the above three upgrades enables improved perovskite film quality with increased grain size and enhanced crystallinity. With these advantages, C60‐TMA treated PSC devices exhibit a much higher power conversion efficiency (PCE) of 24.89 % than the control devices (23.66 %). Besides, C60‐TMA benefits improved thermal stability of PSC devices, retaining over 90 % of its initial efficiency after aging at 85 °C for 1200 h, primarily due to the reinforced interfacial interactions and improved perovskite film quality.
Molecular Design of Hole Transport Materials to Immobilize Ion Motion for Photostable Perovskite Solar Cells
Authors: Zhang Zheng , Duan Chenghao , Wang Sijing , Xie Tianyou , Zou Feilin , Luo Yang , Tang Ruijia , Guo Kunpeng , Yuan Ligang , Zhang Kaicheng , Wang Yao , Qiu Jianhang , Yan Keyou
Published: August 2024

Poor operational stability is a crucial factor limiting the further application of perovskite solar cells (PSCs). Organic semiconductor layers can be a powerful means for reinforcing interfaces and inhibiting ion migration. Herein, two hole‐transporting molecules, pDPA‐SFX and mDPA‐SFX, are synthesized with tuned substituent connection sites. The meta‐substituted mDPA‐SFX results in a larger dipole moment, more ordered packing, and better charge mobility than pDPA‐SFX, accompanying with strong interface bonding on perovskite surfaces and suppressed ion motion as well. Importantly, mDPA‐SFX‐based PSCs exhibit an efficiency that has significantly increased from 22.5 % to 24.8 % and a module‐based efficiency of 19.26 % with an active area of 12.95 cm2. The corresponding cell retain 94.8 % of its initial efficiency at maximum power point tracking (MPPT) after 1,000 h (T95=1,000 h). The MPPT T80 lifetime is as long as 2,238 h. This work illustrates that a small degree of structural variation in organic compounds leaves considerable room for developing new HTMs for light stable PSCs.
Three‐Dimensional Covalent Organic Frameworks Based on Linear and Trigonal Linkers for High‐Performance H2O2 Photosynthesis
Authors: Zhu Ruo‐Meng , Liu Yong , Han Wang‐Kang , Feng Jing‐Dong , Zhang Jinfang , Pang Huan , Zhang Jiangwei , Gu Zhi‐Guo
Published: August 2024

The design of three‐dimensional covalent organic frameworks (3D COFs) using linear and trigonal linkers remains challenging due to the difficulty in achieving a specific non‐planar spatial arrangement with low‐connectivity building units. Here, we report the novel 3D COFs with linear and trigonal linkers, termed TMB‐COFs, exhibiting srs topology. The steric hindrance provides an additional force to alter the torsion angles of peripheral triangular units, guiding the linear unit to connect with the trigonal unit into 3D srs frameworks, rather than the more commonly observed two‐dimensional (2D) hcb structures. Furthermore, we comprehensively examined the hydrogen peroxide photocatalytic production capacity of the TMB‐COFs in comparison with analogous 2D COFs. The experimental results and DFT calculations demonstrate a significant enhancement in photocatalytic hydrogen peroxide production efficacy through framework regulation. This work emphasizes the steric configuration using low connectivity building units, offering a fresh perspective on the design and application of 3D COFs.
[4+1] Heteroannulation to Form 1‐Pyrrolines through Alder‐Ene Reaction of in situ Generated Ynimines: Development and Application in Total Synthesis of Borrecapine
Authors: Lavernhe Rémi , Wang Qian , Zhu Jieping
Published: August 2024

We report in this paper a novel Cu‐catalyzed synthesis of polysubstituted 1‐pyrrolines. The reaction of β,γ‐unsaturated oxime esters 4 with terminal alkynes 5 in the presence of a catalytic amount of Cu(OAc)2 and 2,2′‐biquinoline affords the corresponding 1,6‐enynimines, which undergo a highly stereoselective Alder‐ene reaction to afford 1‐pyrrolines with concomitant generation of a quaternary carbon and a 2‐azadiene motif. It represents an unusual [4+1] heteroannulation reaction wherein terminal alkynes act as a one carbon donor and are 1,1‐difunctionalized. Mechanistic studies suggest that the allylic hydrogen trans to the oxime ester main chain is selectively transferred to the electron‐rich alkyne during the pericyclic reaction. The resulting 1‐pyrrolines undergo facile acid‐catalyzed regioselective Wagner–Meerwein rearrangement to provide 2H‐pyrroles in excellent yields. The 2H‐pyrroles are also accessible from 4 and 5 in a one‐pot manner without isolation of the 1‐pyrrolines. Leveraging this heteroannulation reaction as a key step, the first total synthesis of borrecapine, a 2,3,3,5‐tetrasubstituted pyrrolidine, is accomplished.
Synthesis, in vitro and in silico evaluation of gallamide and selenogallamide derivatives as inhibitors of the SARS‐CoV‐2 main protease
Authors: Carvalho Maryelle A. G. de , Souza Gabriella B. , Tizziani Tiago , Pontes Carime L. M. , Dambrós Bibiana P. , Sousa Natália F. de , Scotti Marcus T. , Steindel Mario , Braga Antonio L. , Sandjo Louis P. , Assis Francisco F. de
Published: August 2024

The present work reports the inhibitory effect of amides derived from gallic acid (gallamides) against severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) main protease (Mpro), along with cytotoxicity evaluation and molecular docking studies. In addition to gallamides, other relevant compounds were also synthesized and evaluated against Mpro, making a total of 25 compounds. Eight compounds presented solubility issues during the inhibitory assay and one showed no inhibitory activity. Compounds 3a, 3b, and 3f showed the highest enzymatic inhibition with IC50 = 0.26 ± 0.19 µM, 0.80 ± 0.38 µM, and 2.87 ± 1.17 µM, respectively. Selenogallamide 6a exhibited IC50 values of 5.42 ± 2.89 µM and a comparison with its nonselenylated congener 3c shows that the insertion of the chalcogen moiety improved the inhibitory capacity of the compound by approximately 10 times. Regarding the cellular toxicity in THP‐1 and Vero cells, compounds 3e and 3g, showed moderate cytotoxicity in Vero cells, while for THP‐1 both were nontoxic, with CC50 > 150 µM. Derivative 3d showed moderate cytotoxicity against both cell lines, whereas 6d was moderatly toxic to THP‐1. Other compounds analyzed do not induce substantial cellular toxicity at the concentrations tested. The molecular docking results for compounds 3a, 3b, and 3f show that hydrogen bonding interactions involving the hydroxyl groups (OH) of the gallate moiety are relevant, as well as the carbonyl group.
Quality of reporting health behaviors for multiple sclerosis (QuoRH‐MS): A scoping review to inform intervention planning and improve consistency of reporting
Authors: Probst Yasmine , Kinnane Emily
Published: August 2024

Background

Multiple sclerosis (MS) is a neurological condition that necessitates a multidisciplinary approach to aid those living with MS in managing their disease. Health behavior, or lifestyle modification, is an emerging approach to MS self‐management. MS researchers utilize measurement tools to ensure that interventions are best suited to the outcomes, thereby potentially influencing practice. The aim of this study was to investigate which tools are being used for health behavior management studies in people living with MS and develop an aid for tool selection.

Methods

A scoping review guided by the PRISMA‐Sc checklist and the JBI manual for evidence synthesis was employed with a systematic search strategy executed across four scientific databases: Medline, PubMed, CINAHL, and Cochrane Libraries. The types of assessment tools used were extracted from the included studies. Each tool was categorized into the health behavior intervention discipline (nutrition, exercise, and psychology) and then subcategorized by the tool's purpose. The frequency of use was determined for each tool. Reporting of validation of the assessment tools were collated to inform a tool selection checklist.

Results

The review identified a total of 248 tools (12 nutrition, 55 exercise, and 119 psychology unique reports) from 166 studies. Seventy‐seven multidimensional tools were identified including measures of quality of life, fatigue, and functional scales. Only 88 studies (53%) referred to the validity of the tools. The most commonly reported tools were the dietary habits questionnaire (n = 4, nutrition), 6‐minute walk test (n = 17, exercise), Symbol Digits and Modalities Test, and Hospital Anxiety and Depression Scale (n = 15 each, psychology) with the Expanded Disability Status Scale reported 43 times.

Conclusion

Evidence from interventions may inform practice for health professionals. This review provides insights into the range of tools reported across health behavior intervention studies for MS and offers a guide toward more consistent reporting of study methods.
Factors affecting consumer purchases of natural foods: Prioritizing health consciousness and environmental sustainability
Authors: Pahari Subhajit , Chakraborty Debarun , Polisetty Aruna , Dash Ganesh , Camilleri Mark Anthony , Zhang Justin
Published: August 2024

To date, there are still limited studies that have devoted their attention to the customers' demand for natural food products. Notwithstanding, to the best of the authors' knowledge, there are no articles that integrate the theory of consumption values with the stimuli‐organism‐behavior‐consequence framework, to explore the intricate connections between consumption values, purchase intentions, and actual buying behaviors of natural food products. Primary data were gathered from 793 survey respondents, and a covariance‐based structural equations modeling approach was used to evaluate the robustness of the proposed model. The findings indicate that the various benefits of natural food products have a significant impact on how consumers perceive and approach these products. The results also suggest that consumer behaviors are greatly influenced by their environmental concerns and health considerations. Furthermore, they underline the significance of the consumers' incomes and education levels on the causal paths between attitudes, intentions to purchase, and actual purchase behaviors. This contribution advances a novel theoretical model that is empirically tested, as well as reasonable implications for industry practitioners.
Consumers' purchase behavior of Cradle to Cradle Certified® products—The role of trust and supply chain transparency
Authors: Damberg Svenja , Saari Ulla A. , Fritz Morgane , Dlugoborskyte Vytaute , Božič Katerina
Published: August 2024

Consumers' trust in eco‐labels is declining due to the growing number of different kinds of eco‐labels that can be uncertified and related to greenwashing. This paper argues that providing more transparency regarding green supply chains (GSCs) through eco‐labels (such as Cradle to Cradle Certified®) is critical for creating trust and convincing consumers to buy eco‐products over conventional ones. Building on previous literature related to sustainable consumption behavior, green purchasing behavior, Cradle to Cradle certification and GSC management, we develop and test a conceptual model to empirically investigate the links between consumers' trust in eco‐product labels and GSC perceptions in influencing green purchase behavior (GPB) in the case of eco‐friendly fast‐moving consumer goods (FMCGs). By studying a sample of 276 German consumers and applying structural equation modeling, we find that the trust in eco‐product labels and positive perceptions of GSCs are important drivers of GPB. Our research contributes by expanding the knowledge on the factors influencing the acceptance of eco‐products, highlighting the importance of supply chain transparency and trust in GSCs among consumers. We discuss theoretical implications for green product innovation and marketing including eco‐product labeling based on transparent GSCs.
Promising first‐line immuno‐combination therapies for unresectable hepatocellular carcinoma: A cost‐effectiveness analysis
Authors: Wen Feng , Huang Peng , Wu Qiuji , Yang Yang , Zhou Kexun , Zhang Mengxi , Li Qiu
Published: August 2024

Background and Aims

Hepatocellular carcinoma (HCC) is one of the leading causes of cancer‐related death all over the world, and brings a heavy social economic burden especially in China. Several immuno‐combination therapies have shown promising efficacy in the first‐line treatment of unresectable HCC and are widely used in clinical practice. Nevertheless, which combination is the most affordable one is unknown. Our study assessed the cost‐effectiveness of the immuno‐combinations as first‐line treatment for patients with unresectable HCC from the perspective of Chinese payers.

Methods

A Markov model was built according to five multicenter, phase III, open‐label, randomized trials (Himalaya, IMbrave150, ORIENT‐32, CARES‐310, LEAP‐002) to investigate the cost‐effectiveness of tremelimumab plus durvalumab (STRIDE), atezolizumab plus bevacizumab (A + B), sintilimab plus bevacizumab biosimilar (IBI305) (S + B), camrelizumab plus rivoceranib (C + R), and pembrolizumab plus lenvatinib (P + L). Three disease states were included: progression free survival (PFS), progressive disease (PD) as well as death. Medical costs were searched from West China Hospital, published literatures or the Red Book. Cost‐effectiveness ratios (CERs) and incremental cost‐effectiveness ratios (ICERs) were evaluated to compare costs among different combinations. Sensitivity analyses were performed to assess the robust of the model.

Results

The total cost and quality‐adjusted life years (QALYs) of C + R, S + B, P + L, A + B and STRIDE were $12,109.27 and 0.91, $26,961.60 and 1.12, $55,382.53 and 0.83, $70,985.06 and 0.90, $84,589.01 and 0.73, respectively, resulting in the most cost‐effective strategy of C + R with CER of $13,306.89 per QALY followed by S + B with CER of $24,072.86 per QALY. Compared with C + R, the ICER of S + B strategy was $70,725.38 per QALY, which would become the most cost‐effective when the willing‐to‐pay threshold exceeded $73,500/QALY. In the subgroup analysis, with the application of Asia results in Leap‐002 trial, the model results were the same as global data. In the sensitivity analysis, with the variation of parameters, the results were robust.

Conclusion

As one of the promising immuno‐combination therapies in the first‐line systemic treatment of HCC, camrelizumab plus rivoceranib demonstrated the potential to be the most cost‐effective strategy, which warranted further studies to best inform the real‐world clinical practices.
The miRNAs 203a/210‐3p/5001‐5p regulate the androgen/androgen receptor/YAP‐induced migration in prostate cancer cells
Authors: Huo Chieh , Kuo Ying‐Yu , Lin Ching‐Yu , Shiah Shine‐Gwo , Li Chia‐Yang , Huang Shu‐Pin , Chen Jen‐Kun , Wang Wen‐Ching , Kung Hsing‐Jien , Chuu Chih‐Pin
Published: August 2024

Background

Prostate cancer (PCa) patients with elevated level of androgen receptor (AR) correlate with higher metastatic incidence. Protein expression of AR and its target gene prostate‐specific antigen (PSA) are elevated in metastatic prostate tumors as compared to organ‐confined tumors. Androgen treatment or elevation of AR promotes metastasis of PCa in cell culture and murine model. However, under androgen depleted condition, AR suppressed cell mobility and invasiveness of PCa cells. Androgen deprivation therapy in PCa patients is associated with higher risk of cancer metastasis. We therefore investigated the dual roles of AR and miRNAs on PCa metastasis.

Methods

The PC‐3AR (PC‐3 cells re‐expressing AR) and LNCaP cells were used as PCa cell model. Transwell migration and invasion assay, wound‐healing assay, zebrafish xenotransplantation assay, and zebrafish vascular exit assay were used to investigate the role of AR and androgen on PCa metastasis. Micro‐Western Array, co‐immunoprecipitation and Immunofluorescence were applied to dissect the molecular mechanism lying underneath. The miRNA array, miRNA inhibitors or plasmid, and chromatin immunoprecipitation assay were used to study the role of miRNAs on PCa metastasis.

Results

In the absence of androgen, AR repressed the migration and invasion of PCa cells. When androgen was present, AR stimulated the migration and invasion of PCa cells both in vitro and in zebrafish xenotransplantation model. Androgen increased phospho‐AR Ser81 and yes‐associated protein 1 (YAP), decreased phospho‐YAP Ser217, and altered epithelial‐mesenchymal transition (EMT) proteins in PCa cells. Co‐IP assay demonstrated that androgen augmented the interaction between YAP and AR in nucleus. Knockdown of YAP or treatment with YAP inhibitor abolished the androgen‐induced migration and invasion of PCa cells, while overexpression of YAP showed opposite effects. The miRNA array revealed that androgen decreased hsa‐miR‐5001‐5p but increased hsa‐miR‐203a and hsa‐miR‐210‐3p in PC‐3AR cells but not PC‐3 cells. Treatment with inhibitors targeting hsa‐miR‐203a/hsa‐miR‐210‐3p, or overexpression of hsa‐miR‐5001‐5p decreased YAP expression as well as suppressed the androgen‐induced migration and invasion of PCa cells. Chromatin immunoprecipitation (ChIP) assay demonstrated that AR binds with promoter region of has‐miR‐210‐3p in the presence of androgen.

Conclusions

Our observations indicated that miRNAs 203a/210‐3p/5001‐5p regulate the androgen/AR/YAP‐induced PCa metastasis.
Bridging the Gap in the Structure–Function Paradigm of Enzymatic PET Degradation–Aromatic Residue Driven Balanced Interactions with Catalytic and Anchoring Subsite
Authors: James Anjima , Bhasi Anjitha , De Susmita
Published: August 2024

Understanding all parameters contributing to enzyme activity is crucial in enzyme catalysis. For enzymatic PET degradation, this involves examining the formation of the enzyme‐PET complex. In IsPETase (WT), a PET‐degrading enzyme from Ideonella sakaiensis, mutating two non‐catalytic residues (DM) significantly enhances activity. Such mutations, depending on their position in the tertiary structure, fine‐tune enzyme function. However, detailed molecular insights into these mutations’ structure‐function relationship for PET degradation are lacking. This study characterizes IsPETase's catalytic ability compared to WT TfCut2 using molecular dynamics simulations and quantum mechanical methods. We explore the conformational landscape of the enzyme‐PET complex and quantify residue‐wise interaction energy. Notably, aromatic and hydrophobic residues Tyr, Trp, and Ile in the catalytic subsite S1, and aromatic Phe and polar Asn in the anchoring subsite S3, crucially optimize PET binding. These residues enhance PET specificity over non‐aromatic plastics. Our findings suggest that the balance between binding at subsite S1 and subsite S3, which is influenced by cooperative mutations, underlies catalytic activity. This balance shows a positive correlation with experimentally obtained kcat/Km values: WT TfCut2<WT IsPETase≪DM IsPETase.
Rare case of complete gonadal dysgenesis in a female patient with primary amenorrhea and a 46XY karyotype
Authors: Monolov Nurbek , Nurbekova Ulbolsun , Mamytova Elmira , Unusov Abdurashid , Osmonova Meerim , Makambaeva Meerim , Vityala Yethindra , Tagaev Tugolbai
Published: August 2024

Key Clinical Message

A comprehensive diagnostic approach is crucial for patients with primary amenorrhea and short stature. Karyotyping and imaging studies help to detect hidden chromosomal abnormalities and anatomical differences, emphasizing their value in this context.

A 16‐year‐old girl with absent menstruation and short stature. Further examination revealed constitutional stunting and primary amenorrhea. Karyotyping revealed a 46, XY chromosomal abnormality, whereas pelvic ultrasonography showed uterine hypoplasia and a unicornuate uterus with a rudimentary horn. After 11 months of therapy, she experienced menarche and improved secondary sexual characteristics.