bluuebunny/crossref_metadata_2025 huggingface dataset:
Immunological Impact of Fermented Soybean Condiments Produced from Indigenous Fermenters
Authors: Iheukwumere C. M. , Iheukwumere I. H. , Okoli U. O. , Ugwu C. H.
Published: September 2023

Several studies have shown that most condiments consumed in Nigeria today are fortified with chemicals that alter the nature and stripped the natural immunological adjuvants designed by nature to protect the body system. Several condiments have been developed from fermented foods in order to control this ugly situation but there is still controversial thought in the choice of microorganism to be used in order to produce a non-toxic condiment with an improved immunological function. The aim of this study was to evaluate the toxicity, nutritive value and immunological impact of fermented soybean condiments. Soybean (Glycine max) sample was fermented with indigenous microorganisms isolated from 7 days old fermented soybean sample; this was oven-dried, pulverized and packaged in a cleaned sterile screw capped container. The immunological impact, pro-inflammatory and anti-inflammatory activities were determined using in vivo and instrumentation techniques. Lactobacillus plantarum strain ZS 2058 (L), Bacillus subtilis strain 168 (B) and Saccharomyces cerevisiae strain YJM555 (Y) were the indigenous microbes used both singly and in consortium for the production of light to dark brown condiments with water activity ranging from 0.27 – 0.37 for the fermented soybean in the plate and 0.22 - 0.36 for the fermented soybean wrapped with Thaumatococcus danielli leaves (called Uma in Igbo and Ewe eran in Yoruba). There was pronounced delay type hypersensitivity (DTH) and significant (P<0.05) elevation of lymphocyte population, rosette counts, antibody titers, phagocytic indices, total lymphocytes and malondialdehyde (MDA) values, of which pronounced activities were mostly seen on those condiments prepared with consortium of the organisms (BLY). Therefore condiments produced from fermentation of soybean using indigenous B, L, Y, BL and BLY are recommended as this would enhance its immunological impact and also safe, and those fermented in plastic plates using BLY were most efficient, preferable and acceptable.
Evaluation of the Effects of Green Tea (Camellia sinensis) on Markers of Liver Function and Liver Histology in Wistar Rats
Authors: Ogar Faith Onyedikachi , Ibubeleye Victor Tamunotonye , Uahomo Precious Ojo , Kofii Nwibana Barisuka
Published: September 2023

Background: Green tea is rich in flavonoids and catechins, compounds reported to have antioxidant, anti-inflammatory, and anticancer properties. However, there is a need to evaluate the effects of green tea on vital organs like the liver. This study aimed to investigate the effects of Camellia sinensis on markers of liver function, and liver histology in Wistar rats.

Methods: Forty-eight adult male Wistar rats were divided into four equal groups and orally administered 250mg/kg, 500mg/kg and 1000mg/kg of Camellia sinensis extract or 1ml of distilled water for up to 28 days. AST, ALT, ALP, TP, ALB, TB, and CB levels were measured at various time points. Effect on liver histology was also assessed using haematoxylin and eosin staining. Results: Camellia sinensis had varying effects on biomarkers of liver injury in a dose-dependent manner. Higher doses (500mg/kg and 1000mg/kg) of Camellia sinensis led to significant increases in AST, ALT, and ALP levels when consumed for up to 21 days. TP and ALB levels were not significantly altered. TB levels significantly increased in the highest dose group while CB levels did not significantly change at any time point studied. Also, higher doses of Camellia sinensis were associated with the development of fatty liver and mild inflammation from the histology. Conclusion: Camellia sinensis extract at low dose may not be harmful to the liver, however, the potential toxicity of green tea on the liver (at higher doses) should be further studied. Moderate use of green tea is therefore, recommended to ensure its safe and beneficial effects on liver health.
Georgia Pathways—Partial Medicaid Expansion With Work Requirements and Premiums
Authors: Gordon Sarah H. , Cole Megan B. , Huberfeld Nicole
Published: September 2023

This Viewpoint discusses the Georgia Pathways to Coverage program, which is the first state program that partially expands Medicaid eligibility to low-income adults with work requirements.
A Prescription for Americans Dually Eligible for Medicare and Medicaid
Authors: Cassidy Bill , Letchuman Sunjay
Published: September 2023

This Viewpoint discusses the lack of coordination of care that individuals who are eligible for both Medicare and Medicaid services face.
The Problem of Limited-Supply Agreements for Medicare Price Negotiation
Authors: Gabriele Sarah M. E. , Feldman William B.
Published: September 2023

This Viewpoint discusses how limited-supply agreements (introduction of generic products in reduced volumes) might thwart efforts to negotiate lower prices on prescription drugs in the US.
Physical Activity Intervention for Leisure-Time Activity Levels Among Older Adults
Authors: Li Nanyan , Ye Qin , Deng Qian , Wang Yufei , Hu Julinling , Li Xianlan , Liu Qianqian , Jiang Meili , Zhao Xing , Zhou Junmin
Published: September 2023

Importance

Current randomized trial evidence of the effects of physical activity interventions in older adults is mainly from developed countries, with little reliable evidence from low- and middle-income countries, such as China, where race, culture, and lifestyles differ substantially from those in Western populations.

Objective

To evaluate the effects of a multilevel intervention for increasing leisure-time activity levels in Chinese older adults.

Design, Setting, and Participants

This cluster randomized trial was conducted from May 2021 to May 2023, including an 8-week intervention period and a follow-up period of 24 months. Eight villages in China were randomly assigned to the intervention (4 villages) or the control (4 villages) group. Potentially eligible participants were 60 years or older. A total of 511 older adults from the selected 8 villages were enrolled.

Interventions

The intervention group received an 8-week socioecological model–based intervention, comprising individual, interpersonal, and community-level components, whereas the control group did not.

Main Outcome and Measure

The primary outcome was the change in leisure-time activity at 8 weeks, measured by the Physical Activity Scale for the Elderly (PASE). Possible PASE scores for leisure-time activity range from 0 to 502, with higher scores indicating higher activity levels.

Results

A total of 511 older adults from 8 villages were recruited and randomly allocated to the intervention (240 participants, 4 villages) or control (271 participants, 4 villages) groups. The mean (SD) age was 70.95 (5.72) years, and 284 (55.6%) were female participants. Seven serious adverse events (unrelated deaths) were reported. Participants in the intervention group increased leisure-time activity more than those in the control group, with a mean difference in PASE scores of 13.74 points (95% CI, 8.58-18.91 points) between the groups at 8 weeks (P < .001). Significant differences in leisure-time activity were also found over 24 months (mean difference in scores at 4 weeks, 11.66 points; 95% CI, 6.41-16.90 points; P < .001; at 6 months, 12.35 points; 95% CI, 7.19-17.50 points; P < .001; at 12 months, 11.55 points; 95% CI, 6.32-16.78 points; P < .001; and at 24 months, 14.51 points; 95% CI, 9.28-19.75 points; P < .001).

Conclusions and Relevance

In this cluster randomized trial, the multilevel intervention was effective in promoting leisure-time activity over 24 months of follow-up in older adults from China. This finding suggests that implementation of such interventions could be an important step in addressing physical inactivity in older adults in low- and middle-income countries.

Trial Registration

Chinese Clinical Trial Registry Identifier: ChiCTR2100045653
The impact of mechanical devices for lifting and transferring of patients on low back pain and musculoskeletal injuries in health care personnel—A systematic review and meta-analysis
Authors: Richarz Hans-Udo , Tamayo Arturo , Rahmig Jan , Siepmann Timo , Barlinn Jessica
Published: September 2023

Objectives

Heavy lifting in nursing is highly associated with low back pain (LBP) and musculoskeletal injuries (MSI). We aimed to evaluate the impact of mechanical devices used for patient lifting and transferring on risk of LBP and MSI of health care personnel.

Methods

We conducted a systematic review and meta-analysis. The literature search was performed during 1st and 12th September 2021 using 17 electronic databases and handsearching of bibliographies of included studies. Twenty studies were included in the qualitative synthesis and eight studies with in total 2087 participants in the meta-analysis. Dependent on the study design, risk of bias was assessed by Cochrane RoB 2.0, EPOC, and MINORS. We conducted random-effects meta-analyses assessing Hedges’s g and 95% CI of MSI rate, perceived LBP, and peak compressive spinal load. We calculated prediction intervals and conducted a cost-benefit analysis (CBA).

Results

All outcomes showed significant, adjusted pooled effect sizes (MSI rate: g = 1.11, 95% CI 0.914–1.299; perceived LBP: g = 1.54, 95% CI −0.016–3.088; peak compressive spinal load: g = 1.04, 95% CI −0.315 to 2.391). True effect sizes in 95% of all comparable populations fell in the following prediction intervals: MSI rate = −1.07-3.28, perceived LBP = −0.522–3.594, and peak compressive spinal load = −15.49 to 17.57. CBA revealed cost-benefit ratios of 1.2 and 3.29 between cumulative total savings and investment costs of intervention.

Conclusions

Prediction intervals confirmed strong true effect sizes for MSI rate and perceived LBP in 95% of all comparable populations but not for peak compressive spinal load. Mechanical lifting and transferring devices displayed a favorable cost-benefit ratio and should be considered for clinical implementation.
Trend analysis of CASBEE Wellness Office certified properties
Authors: Hiyama Kyosuke , Hayashi Tatsuya , Kubo Ryutaro
Published: September 2023

CASBEE Wellness Office, a tool assessing buildings and workplaces in terms of worker health, workplace productivity, and resilience, has been in operation since 2019 and has certified more than 90 properties in Japan. In this study, the trends of certified properties were analyzed. Most of them were accredited with high ranks, S or A. CASBEE allows self‐certification, and properties with high potential tend to be applied for third‐party certification. Buildings occupied or owned by a single company tend to have higher scores than buildings with multiple tenants. Among buildings with multiple tenants, those with larger floor areas tend to be accredited with higher scores. In some categories of the assessment systems, it might be easier to obtain higher scores for large‐scale properties, such as serving various refreshment spaces. Questionnaire surveys using the CASBEE Office Health Checklist were conducted on properties evaluated by the CASBEE Wellness Office. A strong correlation was identified between the scores. Owing to the evident correlations between the CASBEE Office health checklist, workplace productivity, and worker health, it can be concluded that the CASBEE Wellness Office can appropriately measure the planning and operation of properties in terms of worker performance related to wellness.
Order of Valency‐Changing Morphemes
Authors: Alsina Alex
Published: September 2023

Valency‐changing morphemes, in those languages that allow more than one in the same word, show ordering restrictions and effects of syntactic and semantic scope. In some languages, a given pair of valency‐changing morphemes (e.g. causative and passive) may be restricted to appearing in a fixed order. When both orders of a given pair of morphemes are attested, often the syntax and semantics associated with one of the orders are different from those associated with the other order. Three different approaches to explaining the constraints on the ordering of valency‐changing morphemes are considered. One line of research assumes that scope is not the primary force at play, but rather a template is, and that scope is stipulated as a constraint that interacts with the template. Another line of research assumes that words with valency‐changing morphemes are derived through syntactic movement and that scope effects (or the mirror principle) follow from the syntactic principles involved in the derivation. The third line of research discussed here assumes that all words, including those with valency‐changing affixes, are formed in the lexicon and that scope effects are derived from the idea that, within a layered morphology, stems are formed through the pairwise combination of a stem with an affix and every such operation implies simultaneously a concatenation of morphs and a composition of syntactic and semantic information. Problems with and advantages of each approach are presented.
Ordering Restrictions between Affixes
Authors: Manova Stela
Published: September 2023

A language possesses a limited set of affixes; and, of all possible combinations of those affixes, only a relatively small number exists. This gives rise to questions about the nature of the restrictions on affix combinability. In the literature, grammatical and extragrammatical restrictions have been reported. The former refer to the levels of grammar (phonology, morphology, semantics, syntax), the latter concern statistical or psycholinguistic information (or both). Phonological restrictions rely on regular phonology. Morphological restrictions use morphological information and, as a rule, produce fixed combinations of two or three affixes. Semantic restrictions are cognitive in nature and refer to scopal relationships or compositionality of meaning (or both). Syntactic restrictions are due to mirroring of syntactic derivations. Two types of morphological organization, layered and template morphology, provide the canvas for affix order analyses. Layered morphology operates with hierarchically organized layers and derives morphological structure step by step, which implies syntactic ordering and semantic compositionality. Layered morphology may produce variable orders of the same morphemes. Template morphology is flat and the order of affixes in a template is stipulated. Templates derive fixed combinations of affixes and are incompatible with variation. Although a clear distinction between layered and template morphology is made at a theoretical level, there is hardly a language that falls under only one of the two types. All grammatical restrictions on affix ordering are compatible with both layered and template morphology, and no language's affixation system can be explained with a single affix‐ordering principle. As regards the length of the affix sequences examined in different studies, affix order analyses are usually based on combinations of two and three affixes. Bigrams and trigrams appear to be the most appropriate sequences for learning affix ordering patterns, both for humans and for machines.
Cell Communication‐Mediated Selective Drug Delivery for Epitope‐Specific Deletion of Alloreactive T Cells in Organ Transplant
Authors: Shi Yingying , Lou Zeliang , Liu Yu , Huang Jiaxin , Wang Yi , You Jian
Published: September 2023

Allogeneic grafts are vulnerable to the attack launched by host alloreactive T cells, which accounts primarily for allograft failure in the clinic. Conventional pharmacological intervention mainly involves broad‐acting, nonspecific immunosuppressants that provide limited protection over the graft and may cause deleterious side effects due to insufficient allospecificity. Here, core–shell structured nanoparticles co‐loaded with allogeneic antigen (Ag) and immunosuppressive agent Tacrolimus (Ag@FK506‐NPs) are constructed. Dendritic cells (DCs) pulsed with Ag@FK506‐NPs present alloantigenic epitopes on the cell surface as a bait to capture specific T cells, especially CD8+ T cells, for intercellular FK506 transfer and alloreactive T‐cell deletion. Meanwhile, DCs are maintained in an immature tolerogenic state that induces the functional inactivation of recruited T cells. Compared with free FK506, the adoptive transfer of low immunosuppressant dose (25 000‐fold lower) of Ag@FK506‐NPs pulsed DCs is enough to yield a superior antirejection effect in a major histocompatibility complex‐mismatched murine skin transplant model. Of note, due to the cell–cell communication conferred selective T‐cell suppression, the recipient mouse is able to respond to the subsequent stimulation of an irrelevant Ag, indicating that off‐target toxicity is bypassed. Overall, this work may address some of the limitations of current allograft therapeutics.
Wet‐Etching‐Boosted Charge Storage in 1D Nitride‐Based Systems for Imitating Biological Synaptic Behaviors
Authors: Huang Chang‐Hsun , Wu Chia‐Yi , Lin Yen‐Fu , Chou Yi‐Chia , Lee Ko‐Tao
Published: September 2023

Nitride materials for memristors are benefited from their high response speed and high power density. The memristive effects on 1D nitride structures has not yet been elucidated. Hence, the activation of the memristive capability of nanowire (NW)‐based nitride memristors using an uncomplicated fabrication as single‐step anisotropic wet etching is proposed. Among nitrides, gallium nitride, a third‐generation semiconductor, exhibits properties potentially suitable for neuromorphic applications. The wet etchant considerably alters the chemisorbed molecules and dangling bonds associated with the surface states of the nanowires. A device based on such NWs which exhibits low power consumption with no required compliance current and forming voltage for operation is demonstrated. It can integrate all memristive capabilities, including multiple state switching, nonvolatile bipolar memory, and Ca2+ dynamics‐imitating synaptic actions. The examination of the memristive process also highlights the significance of altering surfaces in the devices, in addition to the shared principles that underlie biological and artificial synapses. The operating mode of the nitride‐nanowire devices can be controlled by controlling the formation/dissolution of the oxygen‐conductive path along the nanowires. Thus, the study realizes nanowire memristors based on a nitride material framework, that is promising for application in the 1D–1D system downsizing required for the bio‐inspired artificial synapse.
Hierarchically Porous Cellulose Membrane via Self‐Assembly Engineering for Ultra High‐Power Thermoelectrical Generation in Natural Convection
Authors: Sun Haodong , Tang Fengjie , Bi Yinghao , Sun Hao , Huang Liulian , Jiang Feng , Chen Lihui , Li Jianguo
Published: September 2023

Renewable heat‐to‐power conversion based on thermoelectric strategy holds strong prospect toward clean electricity generation in low‐carbon society, in which its conversion performance is mainly decided by the temperature gradient. However, achieving a high temperature gradient spontaneously throughout the day in natural convection remains a significant challenge. Herein, cost‐effective, sustainable, and hierarchically porous cellulose membrane (HPCM) created through a simple self‐assembly engineering of cellulose molecules is proposed. Such HPCM boasts a unique structure of layered micro‐ and nanoscaled pores with ≈95% porosity, and correspondingly demonstrates >94% solar reflectance and >0.9 mid‐infrared emissivity. As a result, HPCM enables average temperature gradient of 14.5 °C and 76 mV output voltage of thermoelectric module during daytime natural convection, which are 17‐ and 30‐time higher than those of pristine device, respectively. Note that HPCM‐based thermoelectric module consistently generates an average output voltage of 44.2 mV all day. Such modules are seamlessly integrated into thermoelectric arrays to achieve high output voltage of ≈1.5 V and power density of ≈3 W m−2 over 90‐d period. The prepared HPCM marks a significant advancement in environmentally friendly, scalable, and viable thermoelectric conversion to power the low‐carbon society.
Sustained Release of Nitric Oxide‐Mediated Angiogenesis and Nerve Repair by Mussel‐Inspired Adaptable Microreservoirs for Brain Traumatic Injury Therapy
Authors: Liu Hsiu‐Ching , Huang Chu‐Han , Chiang Min‐Ren , Hsu Ru‐Siou , Chou Tsu‐Chin , Lu Tsai‐Te , Lee I‐Chi , Liao Lun‐De , Chiou Shih‐Hwa , Lin Zhong‐Hong , Hu Shang‐Hsiu
Published: September 2023

Traumatic brain injury (TBI) triggers inflammatory response and glial scarring, thus substantially hindering brain tissue repair. This process is exacerbated by the accumulation of activated immunocytes at the injury site, which contributes to scar formation and impedes tissue repair. In this study, a mussel‐inspired nitric oxide‐release microreservoir (MINOR) that combines the features of reactive oxygen species (ROS) scavengers and sustained NO release to promote angiogenesis and neurogenesis is developed for TBI therapy. The injectable MINOR fabricated using a microfluidic device exhibits excellent monodispersity and gel‐like self‐healing properties, thus allowing the maintenance of its structural integrity and functionality upon injection. Furthermore, polydopamine in the MINOR enhances cell adhesion, significantly reduces ROS levels, and suppresses inflammation. Moreover, a nitric oxide (NO) donor embedded into the MINOR enables the sustained release of NO, thus facilitating angiogenesis and mitigating inflammatory responses. By harnessing these synergistic effects, the biocompatible MINOR demonstrates remarkable efficacy in enhancing recovery in mice. These findings benefit future therapeutic interventions for patients with TBI.
Liquid Metal‐Based Stable and Stretchable Zn‐Ion Battery for Electronic Textiles
Authors: Pu Jie , Cao Qinghe , Gao Yong , Wang Qiangzheng , Geng Zeyu , Cao Leiqing , Bu Fan , Yang Nute , Guan Cao
Published: September 2023

Electronic textiles harmoniously interact with the human body and the surrounding environment, offering tremendous interest in smart wearable electronics. However, their wide application faces challenges due to the lack of stable and stretchable power electrodes/devices with multifunctional design. Herein, an intrinsically stretchable liquid metal‐based fibrous anode for a stable Zn‐ion battery (ZIB) is reported. Benefiting from the liquid feature and superior deformability of the liquid metal, optimized Zn ion concentration distribution and Zn (002) deposition behavior are observed, which result in dendrite‐free performance even under stretching. With a strain of 50%, the ZIB maintains a high capacity of 139.8 mAh cm−3 (corresponding to 83.0% of the initial value) after 300 cycles, outperforming bare Zn fiber‐based ZIB. The fibrous ZIB seamlessly integrates with the sensor, Joule heater, and wirelessly charging device, which provides a stable power supply for human signal monitoring and personal thermal management, holding promise for the application of wearable multifunctional electronic textiles.
Multicrystalline, Highly Oriented Thick‐Film Silicon from Reduction of Soda‐Lime Glass
Authors: Schall Ingrid , Ebbinghaus Stefan G. , Strelow Christian , Peiner Erwin
Published: September 2023

The study describes synthesis and characterization of > 10 µm thick multicrystalline (mc), highly oriented,p‐doped silicon layers by aluminothermic reduction of low‐cost soda‐lime glass. X‐ray diffraction shows a highly preferred (111)‐orientation and excellent crystallinity. Low compressive stress and very good crystallinity are confirmed by the peak position and width of the Raman LO‐phonon line, approaching the one of bulk single‐crystalline wafer material. Due to strong bonding to the glass substrate layer, spalling is not observed. A conductive aluminum‐rich oxide layer is formed underneath the silicon, serving as an electrical back‐contact for electronic devices. Using secondary ion mass spectrometry very low concentrations of 1014–1015 cm−3of impurities are found originating from the soda‐lime glass with an iron content below the detection limit. Furthermore, a plateau‐like, very homogenous Al concentration of ≈4 × 1018 cm−3over a thickness of ≈10 µm is found, which corresponds to the solubility of Al in Si at the process temperature. Complete electronic activation within the plateau region is confirmed by carrier concentration measurements using electrochemical capacitance–voltage profiling and Raman spectroscopy. Hole concentrations in the range of few 1018 cm−3are beneficial for thep‐type base material of full‐emitter cell mc‐silicon photovoltaic devices.
Resorbable Layered Double Hydroxides‐Based Composite Implants Synergistically Accelerates Critical‐Sized Defect Closure
Authors: Mohan Vimala Devi , V. K. Anupama Devi , Haridoss Pushkin Raj , Uthirappan Mani , Thada Raja Rajeshwari , Manikantan Syamala Kiran , Tiruchirapalli Sivagnanam Uma
Published: September 2023

The study focuses on the fabrication of a composite implant composed of MgAl layered double hydroxides (LDH), gelatin, and diosgenin and its regeneration potential in experimentally‐induced tibial defect in rabbits. The implant is fabricated by blending and lyophilization technique and eventually cross‐linked using glutaraldehyde. The implant is characterized by attenuated total reflectance (ATR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and compressive strength. A sustained release of diosgenin occurs over a period of 28 days. The osteogenic activity is analyzed by alkaline phosphatase activity and alizarin red S staining; that aid in determining the extent of biomineralization. The results also demonstrate that LGD100 implant stimulates the expression of genes associated with osteoblastic activities in MG‐63 cells, namely type I collagen, osteocalcin, and osteopontin. The bone regeneration capacity of diosgenin‐loaded gelatin‐based LDH implant is then tested by creating critical bone defects in the tibia of rabbits by using empty bone defects as controls. Periodic radiographs are taken which show promising results. Histological and immunohistochemical staining confirm that after treatment with LGD100, new bone is formed at the defect site. This study suggests that LGD100 implant aids in faster bone formation as it mimics the natural properties of bone.
Adipose‐Derived Mesenchymal Stem Cell‐Derived Exosomes Biopotentiated Extracellular Matrix Hydrogels Accelerate Diabetic Wound Healing and Skin Regeneration
Authors: Song Yanling , You Yuchan , Xu Xinyi , Lu Jingyi , Huang Xiajie , Zhang Jucong , Zhu Luwen , Hu Jiahao , Wu Xiaochuan , Xu Xiaoling , Tan Weiqiang , Du Yongzhong
Published: September 2023

Wound healing is an urgent clinical challenge, particularly in the case of chronic wounds. Traditional approaches to wound healing have limited therapeutic efficacy due to lengthy healing times, risk of immune rejection, and susceptibility to infection. Recently, adipose‐derived mesenchymal stem cell‐derived exosomes (ADSC‐exos) have emerged as a promising modality for tissue regeneration and wound repair. In this study, the development of a novel extracellular matrix hydrogel@exosomes (ECM@exo) is reported, which entails incorporation of ADSC‐exos into an extracellular matrix hydrogel (ECM hydrogel). This solution forms a hydrogel at physiological temperature (≈37 °C) upon local injection into the wound site. ECM@exo enables sustained release of ADSC‐exos from the ECM hydrogel, which maintains high local concentrations at the wound site. The ECM hydrogel displays good biocompatibility and biodegradability. The in vivo and in vitro results demonstrate that ECM@exo treatment effectively reduces inflammation and promotes angiogenesis, collagen deposition, cell proliferation, and migration, thereby accelerating the wound healing process. Overall, this innovative therapeutic approach offers a new avenue for wound healing via a biological hydrogel with controlled exosome release.
Deep Electronic State Regulation through Unidirectional Cascade Electron Transfer Induced by Dual Junction Boosting Electrocatalysis Performance
Authors: Zhang Wenlin , Shu Chonghong , Zhan Jiayu , Zhang Shenghu , Zhang Lu‐Hua , Yu Fengshou
Published: September 2023

Unidirectional cascade electron transfer induced by multi‐junctions is essential for deep electronic state regulation of the catalytic active sites, while this advanced concept has rarely been investigated in the field of electrocatalysis. In the present work, a dual junction heterostructure (FePc/L‐R/CN) is designed by anchoring iron phthalocyanine (FePc)/MXene (L‐Ti3C2‐R, R═OH or F) heterojunction on g‐C3N4 nanosheet substrates for electrocatalysis. The unidirectional cascade electron transfer (g‐C3N4 → L‐Ti3C2‐R → FePc) induced by the dual junction of FePc/L‐Ti3C2‐R and L‐Ti3C2‐R/g‐C3N4 makes the Fe center electron‐rich and therefore facilitates the adsorption of O2 in the oxygen reduction reaction (ORR). Moreover, the electron transfer between FePc and MXene is facilitated by the axial Fe─O coordination interaction of Fe with the OH in alkalized MXene nanosheets (L‐Ti3C2‐OH). As a result, FePc/L‐OH/CN exhibits an impressive ORR activity with a half‐wave potential (E1/2) of 0.92 V, which is superior over the catalysts with a single junction and the state‐of‐the‐art Pt/C (E1/2 = 0.85 V). This work provides a broad idea for deep regulation of electronic state by the unidirectional cascade multi‐step charge transfer and can be extended to other proton‐coupled electron transfer processes.
Regulating Lattice Oxygen of Co3O4/CeO2 Heterojunction Nanonetworks for Enhanced Oxygen Evolution
Authors: Zhao Ziyu , Yu Meng , Liu Yawen , Zeng Tao , Ye Rongkai , Liu Yuchan , Hu Jianqiang , Li Aiqing
Published: September 2023

Developing efficient and cost‐effective electrocatalysts as substitutes for noble metals remains a big challenge, which demands significant advancements in both material designing and mechanistic understanding. Herein, Co3O4/CeO2 heterojunction nanonetworks are successfully synthesized through metal organic framework precursor. Notably, Co3O4/CeO2 heterojunctions can effectively regulate electronic structure of Co3O4, thus inducing oxygen atom from Co3O4 lattice to participating in oxygen evolution reaction (OER) via lattice oxygen‐mediated mechanism, which reduces reaction overpotential. Additionally, the porous network structure can facilitate electrolyte transfer and provide more active sites for electrocatalytic reactions. Consequently, Co3O4/CeO2 heterojunction nanonetworks exhibit great electrocatalytic performance and high durability, requiring only an OER overpotential of 259 mV at current density of 100 mA cm−2 in 1 M KOH, markedly outperforming Co3O4 nanocatalysts (309 mV) and showing promising potential as substitutable non‐noble OER catalysts.
An atypical Aymé‐Gripp phenotype detected by exome sequencing
Authors: Caiazza Martina , Budillon Alberto , Monda Emanuele , Aruta Giustina , Esposito Augusto , Del Vecchio Blanco Francesca , Piluso Giulio , Nigro Vincenzo , Scarano Gioacchino , Limongelli Giuseppe
Published: September 2023

Aymé‐Gripp Syndrome (AGS) is an ultra‐rare syndrome characterized by peculiar facial traits combined with early bilateral cataracts, sensorineural hearing loss, and variable neurodevelopmental abnormalities. Only a few cases carrying a pathogenic variant in MAF have been described to date. A significant effort is then required to expand the genotypic and phenotypic spectrum of this condition. In this paper, we report the peculiar case of a 6‐year‐old girl carrying a de novo missense pathogenic variant in MAF, being the first case reported to show a milder phenotype with no cataracts and deafness displayed. Furthermore, we performed a systematic review of previously published cases, focusing on clinical manifestation and genotype.
Copper‐Catalyzed Asymmetric Acylboration of 1,3‐Butadienylboronate with Acyl Fluorides
Authors: Gao Shang , Liu Jiaming , Troya Diego , Chen Ming
Published: September 2023

We report herein a Cu‐catalyzed regio‐, diastereo‐ and enantioselective acylboration of 1,3‐butadienylboronate with acyl fluorides. Under the developed conditions, the reactions provide (Z)‐β,γ‐unsaturated ketones bearing an α‐tertiary stereocenter with high Z‐selectivity and excellent enantioselectivities. While direct access to highly enantioenriched E‐isomers was not successful, we showed that such molecules can be synthesized with excellent E‐selectivity and optical purities via Pd‐catalyzed alkene isomerization from the corresponding Z‐isomers. The orthogonal chemical reactivities of the functional groups embedded in the ketone products allow for diverse chemoselective transformations, which provides a valuable platform for further derivatization.
Aldol Condensation for the Construction of Organic Functional Materials
Authors: Zhu Xiuyuan , Duan Jiayao , Chen Junxin , Liu Riping , Qin Ze , Chen Hu , Yue Wan
Published: September 2023

Aldol condensation is a cost‐effective and sustainable synthetic method, offering the advantages of low complexity, substrate universality, and high efficiency. Over the past decade, it has become popular for creating next‐generation organic functional materials, particularly rigid‐rod conjugated (semi)conductors. This review focuses on conjugated small molecules, oligomers, and polymeric (semi)conductors synthesized through aldol condensation, with emphasis on their remarkable features in advancing n‐type organic field‐effect transistors (OFETs), organic electrochemical transistors (OECTs), organic photovoltaics (OPVs), and organic thermoelectrics (OTEs) as well as NIR‐II photothermal conversion. Coherence character, optical properties, microstructure, and chain conformation are investigated to understand material‐property relationships. Future applications and challenges in this area are also discussed.
Relative Local Electron Density Tuning in Metal‐Covalent Organic Frameworks for Boosting CO2Photoreduction
Authors: Zhang Mi , Huang Pei , Liao Jia‐Peng , Yang Ming‐Yi , Zhang Shuai‐Bing , Liu Yu‐Fei , Lu Meng , Li Shun‐Li , Cai Yue‐Peng , Lan Ya‐Qian
Published: September 2023

The high local electron density and efficient charge carrier separation are two important factors to affect photocatalytic activity, especially for the CO2photoreduction reaction. However, the systematic studies on the structure‐functional relationship regarding the above two factors based on precisely structure model are rarely reported. Herein, as a proof‐of‐concept, we developed a new strategy on the evaluation of local electron density by controlling the relative electron‐deficient (ED) and electron‐rich (ER) intensity of monomer at a molecular level based on three rational‐designed vinylene‐linked sp2carbon‐covalent organic frameworks (COFs). As expected, the as‐prepared vinylene‐linked sp2carbon‐conjugated metal‐covalent organic framework (MCOFs) (VL‐MCOF‐1) with molecular junction exhibited excellent activities for CO2‐to‐HCOOH conversion (283.41 μmol g−1 h−1) and high selectivity of 97.1 %, much higher than the VL‐MCOF‐2 and g‐C34N6‐COF, which is due to the synergistic effect of the multi‐electronic metal clusters (Cu3(PyCA)3) (PyCA=pyrazolate‐4‐carboxaldehyde) as strong ER roles and cyanopyridine units as ED roles and active sites, as well as the boosted photo‐induced charge separation efficiency of vinyl connection and increased light utilization ability. These results not only provide a strategy for regulating the electron‐density distribution of photocatalysts at the molecular level but also offers profound insights for metal clusters‐based COFs to effective CO2conversion.
Function of revolute zygapophyses in the lumbar vertebrae of early placental mammals
Authors: Kort Anne E. , Jones Katrina E.
Published: September 2023

The unique morphology of mammalian lumbar vertebrae allows the spine to flex and extend in the sagittal plane during locomotion. This movement increases stride length and allows mammals to efficiently breathe while running with an asymmetric gait. In extant mammals, the amount of flexion that occurs varies across different locomotor styles, with dorsostable runners relying more on movement of long limbs to run and dorsomobile runners incorporating more flexion of the back. Although long limbs and a stabilized lumbar region are commonly associated with each other in extant mammals, many “archaic” placental mammals with short limbs had lumbar vertebrae with revolute zygapophyses. These articulations with an interlocking S‐shape are found only in artiodactyls among extant mammals and have been hypothesized to stabilize against flexion of the back. This would suggest that archaic placental mammals may not have incorporated dorsoventral flexion into locomotion to the same extent as extant mammals with similar proportions. We tested the relative mobility of fossil lumbar vertebrae from two early placental mammals, the creodonts Patriofelis and Limnocyon, to see how these vertebrae may have functioned. We compared range of motion (ROM) between the original vertebrae, with revolute morphology and digitally altered vertebrae with a flat morphology. We found that the revolute morphology had relatively little effect on dorsoventral flexion and instead that it likely prevented disarticulation due to shear forces on the spine. These results show that flexion of the spine has been an important part of mammalian locomotion for at least 50 million years.
Proprioceptive innervation of the human lips
Authors: Martín‐Cruces José , Cuendias Patricia , García‐Mesa Yolanda , Cobo Juan L. , García‐Suárez Olivia , Gaite Juan J. , Vega José A. , Martín‐Biedma Benjamín
Published: September 2023

The objective of this study was to analyze the proprioceptive innervation of human lips, especially of the orbicularis oris muscle, since it is classically accepted that facial muscles lack typical proprioceptors, that is, muscle spindles, but recently this has been doubted. Upper and lower human lips (n = 5) from non‐embalmed frozen cadavers were immunostained for detection of S100 protein (to identify nerves and sensory nerve formations), myosin heavy chain (to label muscle fibers within muscle spindles), and the mechano‐gated ion channel PIEZO2. No muscle spindles were found, but there was a high density of sensory nerve formations, which were morphologically heterogeneous, and in some cases resemble Ruffini‐like and Pacinian sensory corpuscles. The axons of these sensory formations displayed immunoreactivity for PIEZO2. Human lip muscles lack typical proprioceptors but possess a dense sensory innervation which can serve the lip proprioception.
Regioselective Synthesis of 3‐Substituted Isocoumarin‐1‐imines via Palladium‐Catalyzed Denitrogenative Transannulation of 1,2,3‐Benzotriazin‐4(3H)‐ones and Terminal Alkynes
Authors: Balakrishnan Madasamy Hari , Sureshbabu Popuri , Korivi Ramaraju , Mannathan Subramaniyan
Published: September 2023

A palladium‐catalyzed denitrogenative transannulation strategy to access various 3‐substituted isocoumarin‐1‐imine frameworks using 1,2,3‐benzotriazin‐4(3H)‐ones and terminal alkynes is described. The reaction is highly regioselective and tolerates a wide range of functional groups. The reaction is believed to proceed via a five‐membered palladacycle intermediate extruding environmentally benign molecular nitrogen as a by‐product. The utility of this method was showcased through the one‐pot synthesis of biologically relevant 3‐substituted isocoumarin scaffolds.
Synthesis of Naphthalene‐ and Phenanthrene‐Fused Smaragdyrins and Their BF2Complexes
Authors: Liu Pingting , Wang Kaisheng , Xu Ling , Rao Yutao , Zhou Mingbo , Osuka Atsuhiro , Song Jianxin
Published: September 2023

Naphthalene‐ and phenanthrene‐fused [22]smaragdyrin BF2‐complexes were synthesized by 1) Suzuki‐Miyaura coupling ofβ‐brominated [22]smaragdyrin BF2complexes with 2‐formylarylboronates, 2) Witting‐type methoxymethylenation of the formyl group, and 3) methanesulfonic acid‐catalyzed cyclization reaction. Subsequently these BF2complexes were deboronized and oxidized to the corresponding antiaromatic [20]smaragdyrin free bases. The installed fused structures led to decrease of the aromatic characters of the [22]smaragdyrin BF2complexes and the antiaromatic characters of the [20]smaragdyrin free bases.
Assessing the utility of molecular diagnostic classification for cancers of unknown primary
Authors: Moore Elle C. , Blobe Gerard C. , DeVito Nicholas C. , Hanks Brent A. , Harrison Michael R. , Hoimes Christopher J. , Jia Jingquan , Morse Michael A. , Jayaprakasan Parvathy , MacKelfresh Andrew , Mulder Hillary , Hockenberry Adam J. , Zander Alia , Stumpe Martin C. , Michuda Jackson , Beauchamp Kyle A. , Perakslis Eric , Taxter Timothy , George Daniel J.
Published: September 2023

Background

Roughly 5% of metastatic cancers present with uncertain origin, for which molecular classification could influence subsequent management; however, prior studies of molecular diagnostic classifiers have reported mixed results with regard to clinical impact. In this retrospective study, we evaluated the utility of a novel molecular diagnostic classifier by assessing theoretical changes in treatment and additional testing recommendations from oncologists before and after the review of classifier predictions.

Methods

We retrospectively analyzed de‐identified records from 289 patients with a consensus diagnosis of cancer of uncertain/unknown primary (CUP). Two (or three, if adjudication was required) independent oncologists separately reviewed patient clinical information to determine the course of treatment before they reviewed results from the molecular diagnostic classifier and subsequently evaluated whether the predicted diagnosis would alter their treatment plan.

Results

Results from the molecular diagnostic classifier changed the consensus oncologist‐reported treatment recommendations for 235 out of 289 patients (81.3%). At the level of individual oncologist reviews (n = 414), 64.7% (n = 268) of treatment recommendations were based on CUP guidelines prior to review of results from the molecular diagnostic classifier. After seeing classifier results, 98.1% (n = 207) of the reviews, where treatment was specified (n = 211), were guided by the tissue of origin‐specific guidelines. Overall, 89.9% of the 414 total reviews either expressed strong agreement (n = 242) or agreement (n = 130) that the molecular diagnostic classifier result increased confidence in selecting the most appropriate treatment regimen.

Conclusions

A retrospective review of CUP cases demonstrates that a novel molecular diagnostic classifier could affect treatment in the majority of patients, supporting its clinical utility. Further studies are needed to prospectively evaluate whether the use of molecular diagnostic classifiers improves clinical outcomes in CUP patients.
Radiation‐Induced Transfer of Charge, Atoms, and Energy within Isolated Biomolecular Systems
Authors: Chevalier François , Schlathölter Thomas , Poully Jean‐Christophe
Published: September 2023

In biological tissues, ionizing radiation interacts with a variety of molecules and the consequences include cell killing and the modification of mechanical properties. Applications of biological radiation action are for instance radiotherapy, sterilization, or the tailoring of biomaterial properties. During the first femtoseconds to milliseconds after the initial radiation action, biomolecular systems typically respond by transfer of charge, atoms, or energy. In the condensed phase, it is usually very difficult to distinguish direct effects from indirect effects. A straightforward solution for this problem is the use of gas‐phase techniques, for instance from the field of mass spectrometry. In this review, we survey mainly experimental but also theoretical work, focusing on radiation‐induced intra‐ and inter‐molecular transfer of charge, atoms, and energy within biomolecular systems in the gas phase. Building blocks of DNA, proteins, and saccharides, but also antibiotics are considered. The emergence of general processes as well as their timescales and mechanisms are highlighted.
Use of Constrained G‐Quadruplexes for Enantioselective Sulfoxidation Site Mapping
Authors: Colas Yoann , Ménage Stéphane , Marchi‐Delapierre Caroline , Spinelli Nicolas
Published: September 2023

Catalysis using G‐quadruplexes (G‐4) has shown promise as a way to perform asymmetric sulfoxidation of thioanisole derivatives. However, despite the relative simplicity of G‐4, the mechanism of chiral control of sulfoxidation is still unknown, mainly because G‐4 can adopt different topologies. To better understand the mechanism of G‐4‐catalyzed sulfoxidation, G‐4 was chemically constrained into a unique topology. It was shown that either sulfoxidation can occur at the outer tetrads or at the grooves of G‐4 and that different enantiomers can be generated depending on the region where catalysis occurs. By means of these G‐4 mimics, the enantioselective control of the sulfoxidation reaction was unraveled.
Synthesis and Anticancer Activity of Phosphinoylated and Phosphonoylated N‐Heterocycles Obtained by the Microwave‐Assisted Palladium Acetate‐Catalyzed Hirao Reaction
Authors: Huszár Bianka , Szolga Renáta , Bősze Szilvia , Oláhné Szabó Rita , Simon András , Karaghiosoff Konstantin , Czugler Mátyás , Drahos László , Keglevich György
Published: September 2023

A literature survey showed that different derivatives with the 9‐phenyl‐9H‐carbazole or the dihydroindoline scaffold may be of biological activity including cytotoxic effect. Driven by this experience, P‐functionalized derivatives of these N‐heterocycles were synthesized. Three N‐heterocycles, 9‐(4‐bromophenyl)‐9H‐carbazole, 3‐bromo‐9‐phenyl‐9H‐carbazole and 1‐(5‐bromoindolin‐1‐yl)ethan‐1‐one, were coupled with dialkyl phosphites and diarylphosphine oxides using Pd(OAc)2 (10 %) as the catalyst precursor and triethylamine as the base in ethanol under microwave irradiation. The excess of the Y2P(O)H reagent (Y=alkoxy, aryl) (30 %) served as the P‐ligand in its trivalent tautomeric form (Y2POH), hence there was no need for the usual P‐ligands meaning cost and environmental burden. Hence, the presented method is a “green” approach that proved to be more efficient than the preparation by the traditional method. The products, dialkyl phosphonates and tertiary phosphine oxides obtained in 58–84 % yields were characterized, one of them also by single crystal X‐ray analysis, and were subjected to in vitro biological activity evaluation. A (carbazol)yl‐phenylphosphonate, an N‐phenyl‐(carbazol)yl‐phosphonate, a (carbazol)yl‐phenylphosphine oxide and an N‐phenyl‐(carbazol)ylphosphine oxide revealed a significant cytotoxic activity on A549 human non‐small‐cell lung carcinoma and MonoMac‐6 acute monocytic leukemia cancer cells. The cytotoxic effect was significant as compared to that of the reference compounds.
Exceptionally Stable And Super‐Efficient Electrocatalysts Derived From Semiconducting Metal Phosphonate Frameworks
Authors: Beglau Thi Hai Yen , Fetzer Marcus N. A. , Boldog Istvan , Heinen Tobias , Suta Markus , Janiak Christoph , Yücesan Gündoğ
Published: September 2023

Two new isostructural semiconducting metal‐phosphonate frameworks are reported. Co2[1,4‐NDPA] and Zn2[1,4‐NDPA] (1,4‐NDPA4− is 1,4‐naphthalenediphosphonate) have optical bandgaps of 1.7 eV and 2.5 eV, respectively. The electrocatalyst derived from Co2[1,4‐NPDA] as a precatalyst generated a low overpotential of 374 mV in the oxygen evolution reaction (OER) with a Tafel slope of 43 mV dec−1 at a current density of 10 mA cm−2 in alkaline electrolyte (1 mol L−1 KOH), which is indicative of remarkably superior reaction kinetics. Benchmarking of the OER of Co2[1,4‐NPDA] material as a precatalyst coupled with nickel foam (NF) showed exceptional long‐term stability at a current density of 50 mA cm−2 for water splitting compared to the state‐of‐the‐art Pt/C/RuO2@NF after 30 h in 1 mol L−1 KOH. In order to further understand the OER mechanism, the transformation of Co2[1,4‐NPDA] into its electrocatalytically active species was investigated.