bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hierarchical LTL Zeolite as an Efficient and Sustainable Solid Acid Catalyst for Replacing HCl in the Production of Polyurethane Intermediates
Authors: Lee Susung , Park Younghwan , Baik Yaejun , Kim Jeong‐Chul , Lee Yongjin , Choi Minkee 
Published: June 2023

AbstractIn many industrially important reactions, caustic mineral acid catalysts have been successfully replaced with green solid acids such as zeolites. In this context, extensive efforts have been devoted to replacing HCl to produce methylenedianiline (MDA), a key intermediate in polyurethane production. Unfortunately, limited success has been achieved thus far due to low activity, selectivity towards the desired 4,4′‐MDA, and rapid catalyst deactivation. Here we report that meso‐/microporous hierarchical LTL zeolite exhibits unprecedentedly high activity, selectivity, and stability. The one‐dimensional cage‐like micropores of LTL promote the bimolecular reaction between two para‐aminobenzylaniline intermediates to selectively produce 4,4′‐MDA and inhibit the formation of undesired isomers and heavy oligomers. Meanwhile, the secondary mesopores alleviate mass transfer limitations, resulting in a 7.8‐fold higher MDA formation rate compared to solely microporous LTL zeolite. Due to suppressed oligomer formation and fast mass transfer, the catalyst exhibits inappreciable deactivation in an industrially relevant continuous flow reactor.
ATP Drives the Formation of a Catalytic Hydrazone through an Energy Ratchet Mechanism
Authors: Marchetti Tommaso , Frezzato Diego , Gabrielli Luca , Prins Leonard J. 
Published: June 2023

AbstractAn energy ratchet mechanism is exploited for the synthesis of a molecule. In the presence of adenosine triphosphate (ATP), hydrazone‐bond formation between an aldehyde and hydrazide is accelerated and the composition at thermodynamic equilibrium is shifted towards the hydrazone. Enzymatic hydrolysis of ATP installs a kinetically stable state, at which hydrazone is present at a higher concentration compared to the composition at thermodynamic equilibrium in the presence of the degradation products of ATP. It is shown that the kinetic state has an enhanced catalytic activity in the hydrolysis of an RNA‐model compound.
Dual‐Site Activation Coupling with a Schottky Junction Boosts the Electrochemiluminescence of Carbon Nitride
Authors: Wu Zhichao , Wen Jing , Qin Ying , Ling Ling , Jiao Lei , Zhang Ruizhong , Luo Zhen , Xi Mengzhen , Hu Liuyong , Gu Wenling , Zhu Chengzhou 
Published: June 2023

AbstractRobust electrochemiluminescence (ECL) of carbon nitride (CN) requires efficient electron‐hole recombination and the suppression of electrode passivation. In this work, Au nanoparticles and single atoms (AuSA+NP) loaded on CN serve as dual active sites that significantly accelerate charge transfer and activate peroxydisulfate. Meanwhile, the well‐established Schottky junctions between Au NPs and CN act as electron sinks, effectively trapping over‐injected electrons to prevent electrode passivation. As a result, the porous CN modified with AuSA+NP exhibits an enhanced and stable ECL emission, with a minimal relative standard deviation of 0.24 %. Furthermore, the designed ECL biosensor based on AuSA+NP‐CN shows a remarkable performance in detecting organophosphorus pesticides. This innovative strategy has the potential to offer new insights into strong and stable ECL emission for practical applications.
Production, health implications and applications of oleogels as fat replacer in food system: A review
Authors: Tan Tzyi Horng , Chan Eng‐Seng , Manja Maslia , Tang Teck‐Kim , Phuah Eng‐Tong , Lee Yee‐Ying 
Published: June 2023

AbstractVarious food formulations widely utilized solid fats to provide specific textural properties and sensory attributes. Partially hydrogenated oil was commonly used as solid fat before being banned by FDA recently because of the existence of trans fats. Oleogels, semi‐solid gel typically prepared from liquid vegetable oil and food‐grade oleogelators, is developed as an alternative for solid fats that is free of trans fat and low in saturated fats. Oleogels are prepared via indirect or direct oleogelation technology by which the liquid oil is entrapped in a three‐dimensional network with the aid of low molecular weight oleogelators (LMOGs) and high molecular weight oleogelators (HMOGs). Oleogels received tremendous attention from food scientists to be used in various food applications, particularly high‐fat products such as comminuted meat, chocolates, ice cream, shortening and margarine and even as a deep‐frying medium. They satisfy not only the current trends of consumers for healthy food products (free of trans fat and low in saturated fat) but also provide viscoelastic solid‐ and gel‐ like properties to structure high fat food products. More importantly, recent studies showed that oleogels tend to be metabolized differently from conventional fats and oils giving them an additional advantage in improving the nutritional value of high‐fat foods. Therefore, this review aims to provide an overview that captures the latest studies on oleogels from their production via direct dispersion and indirect dispersion methods, processing conditions that influence the physical properties, metabolism and health attributes as well as recent application in food products.
Conformation changes in stiff‐chain poly‐n‐butyl isocyanate. The dilute regime
Authors: Romo‐Uribe Angel , Rodriguez‐Talavera Rogelio , Hernandez‐Morales Maria Guadalupe 
Published: June 2023

AbstractA change of conformation of the rod‐like poly‐n‐butyl isocyanate (PBIC), in the dilute regime, was induced by temperature and observed via an abrupt change of index of refraction increment, Δn, and of viscosity, η. PBIC was dissolved in carbon tetrachloride where it exhibits its most extended conformation, with persistence length of 15 nm. The index of refraction increment Δn and viscosity η were measured as a function of temperature in the dilute regime, that is, the concentration range below the threshold concentration c* where intermolecular interactions are negligible. Strikingly, increasing the temperature an abrupt change of Δn was observed, at a given solution concentration. The change of Δn is associated to a change in macromolecular size per the Clausius‐Mossotti relation. At the same solution concentration and temperature range, the shear viscosity also exhibited an abrupt increase Δη. This investigation showed that the conformation transition temperature Ttr is independent of the wavelength utilized to measure Δn, and it is an increasing function of the solution concentration and of PBIC molecular weight. Static light scattering confirmed that the sudden changes of Δn and η are not associated to macromolecular aggregation. Finally, the magnitude of the change of Δn and Δη was gradually reduced when increasing the solution concentration c, that is, when c > c*, therefore suggesting that the conformation transition was screened by intermolecular interactions.
Evaluation of the viscoelastic behavior, thermal transitions, and self‐healing efficiency of microcapsules‐based composites with and without a catalyst using dynamic mechanical analysis technique
Authors: Ahmed Abdalla , Ali Alamry , Alzahrani Bandar , Sanada Kazuaki 
Published: June 2023

AbstractThis comprehensive study investigates the viscoelastic behavior, thermal transitions, and self‐healing efficiency of microcapsule‐based composites with and without a catalyst. The composites consist of urea‐formaldehyde/dicyclopentadiene microcapsules embedded in an epoxy matrix, with the addition of Grubbs' catalyst. Our research examines the impact of repetitive dynamic mechanical analysis (DMA) testing and the presence of Grubbs' catalyst on the composites' self‐healing efficiency and dynamic mechanical properties. Using laser microscopy, optical microscopy, Fourier‐transform infrared spectroscopy, and thermogravimetric analysis, we employ various characterization techniques to enhance our understanding of the composite behavior. The findings emphasize the importance of evaluating self‐healing efficiency through DMA, which is a reliable, expeditious, and non‐destructive method. The results show that incorporating Grubbs' catalyst significantly enhances the self‐healing performance of the composites, effectively mitigating the degradation of mechanical properties due to aging. Furthermore, the inclusion of catalyst particles improves stiffness, rigidity, and energy dissipation characteristics, facilitating the self‐healing process. However, careful consideration is necessary to balance mechanical properties and the glass transition temperature when designing self‐healing composites. This study demonstrates a promising self‐healing efficiency of approximately 73% and 44% in the second and third DMA tests, respectively, for composites containing microcapsules and Grubbs' catalyst.
Solvent‐Induced Modulation in the Optical Properties of Copper Nanoclusters and Revealing the Isomeric Effect of Templates
Authors: Mahato Paritosh , Thomas Amar S , Yadav Rahul , Rai Saurabh , Shekhar Shashi , Mukherjee Saptarshi 
Published: June 2023

AbstractThe solvent plays an influential role in controlling the nucleation process of metal nanoclusters (MNCs) and thereby significantly modulates their optical signatures. Herein, we have demonstrated the solvent‐induced modulation in the optical properties of copper nanoclusters (CuNCs), primarily governed by the solvent polarity. During the preparation of para‐mercaptobenzoic acid (p‐MBA)‐templated CuNCs, the simultaneous formation of blue‐emitting CuNCs (B‐CuNCs) and red‐emitting CuNCs (R‐CuNCs) were observed up to 7 h of reaction time, reflected from the systematic increment in the photoluminescence (PL) intensity at 420 nm and 615 nm, respectively. However, after 7 h of reaction time, the exclusive formation of B‐CuNCs was observed. Such simultaneous growth and depletion dynamics of CuNCs result in a significant modulation in their optical properties. The variation of the solvent from water to less polar solvents such as DMSO and DMF restricts this inter‐cluster dynamics by stabilizing both the CuNCs (B‐CuNCs and R‐CuNCs). Thereby, a single‐component White Light Emission (WLE) was realized in DMSO with CIE coordinates (0.37, 0.36). The isomeric effect of the templates has also been investigated which extensively controls the optical and catalytic properties of the CuNCs.
Design and Synthesis of Far‐Red to Near‐Infrared Chromophores with Pyrazine‐Based Boron Complexes
Authors: Takahashi Hiromasa , Watanabe Hiroyuki , Ito Shunichiro , Tanaka Kazuo , Chujo Yoshiki 
Published: June 2023

AbstractWe synthesized new binuclear boron complexes based on pyrazine with ortho and para substitution patterns. It was demonstrated that the para‐linked complexes possess a significantly narrow energy gap between highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), leading to their far‐red to near‐infrared emission properties. Meanwhile, the ortho‐substituted complex showed orange emission. Considering the HOMO and LUMO distributions of pyrazine, the boron complexation to the nitrogen atoms would stabilize its LUMO more efficiently than its HOMO because a nodal plane in the HOMO passes through the two nitrogen atoms. The theoretical study suggests that the para‐substitution would not significantly perturb such a characteristic HOMO distribution originating from pyrazine in stark contrast to the ortho‐substituted one. As a result, the HOMO‐LUMO gap of the para‐linked complex is dramatically narrower than that of the ortho‐linked one.
Controlled release of adeno‐associated virus from alginate hydrogel microbeads with enhanced sensitivity to ultrasound
Authors: Takatsuka Shuhei , Kubota Takeshi , Kurashina Yuta , Kurihara Sho , Hirabayashi Motoki , Fujioka Masato , Okano Hirotaka James , Onoe Hiroaki 
Published: June 2023

AbstractAdeno‐associated virus (AAV)‐based gene therapy holds promise as a fundamental treatment for genetic disorders. For clinical applications, it is necessary to control AAV release timing to avoid an immune response to AAV. Here we propose an ultrasound (US)‐triggered on‐demand AAV release system using alginate hydrogel microbeads (AHMs) with a release enhancer. By using a centrifuge‐based microdroplet shooting device, the AHMs encapsulating AAV with tungsten microparticles (W‐MPs) are fabricated. Since W‐MPs work as release enhancers, the AHMs have high sensitivity to the US with localized variation in acoustic impedance for improving the release of AAV. Furthermore, AHMs were coated with poly‐l‐lysine (PLL) to adjust the release of AAV. By applying US to the AAV encapsulating AHMs with W‐MPs, the AAV was released on demand, and gene transfection to cells by AAV was confirmed without loss of AAV activity. This proposed US‐triggered AAV release system expands methodological possibilities in gene therapy.
The superior vesical artery: A review of conflicting definitions and how these could affect invasive procedures
Authors: Hampel Gilad A. , Shekhawat Devendra , Chaiyamoon Arada , Cardona Juan J. , Carrera Ana , Reina Francisco , Anadkat Samir , Iwanaga Joe , Tubbs R. Shane 
Published: June 2023

AbstractSince the superior umbilical artery is the only functioning branch of the patent umbilical artery, some anatomical and surgical books/atlases fail to clarify that it is a branch of the umbilical artery and not a direct branch of the anterior division of the internal iliac artery and so specifically state that it is a direct branch of the internal iliac artery. This discrepancy in nomenclature can obviously affect invasive procedures and communication between physicians. Therefore, the present review is intended to highlight this issue. The term “superior vesical artery” was searched using standard search engines, for example, PubMed and Google Scholar. Several standard and specialized anatomy textbooks were also examined to ascertain how the superior vesical artery was described. Thirty‐two articles were identified that used the terms “superior vesical artery” or “superior vesical arteries.” After applying exclusion criteria, in 28 papers, the definition of the superior vesical artery was undetermined in eight, described as a direct branch of the internal iliac artery in 13, described as a branch of the umbilical artery in six, and defined as being equivalent to the umbilical artery in one. Of the sampled textbooks, some defined the superior vesicle artery as a branch of the umbilical artery, some as a direct branch of the internal iliac artery and some as both. Taken all together, most define the superior vesical artery as a branch of the umbilical artery. As the superior vesical artery is described as a branch of the umbilical artery in the internationally accepted terminology (Terminologia Anatomica), we recommend that this definition be used by anatomists and physicians alike so that communication is clear.
Prognostic and immune infiltration significance of ARID1A in TCGA molecular subtypes of gastric adenocarcinoma
Authors: Zhang Zhenkun , Li Qiujing , Sun Shanshan , Ye Jing , Li Zhe , Cui Zhengguo , Liu Qian , Zhang Yujie , Xiong Sili , Zhang Shukun 
Published: June 2023

AbstractBackgroundAT‐rich interaction domain 1A (ARID1A) is an essential subunit of the switch/sucrose non‐fermentable chromatin remodeling complex and is considered to be a tumor suppressor. The Cancer Genome Atlas (TCGA) molecular classification has deepened our understanding of gastric cancer at the molecular level. This study explored the significance of ARID1A expression in TCGA subtypes of gastric adenocarcinoma.MethodsWe collected 1248 postoperative patients with gastric adenocarcinoma, constructed tissue microarrays, performed immunohistochemistry for ARID1A, and obtained correlations between ARID1A and clinicopathological variables. We then carried out the prognostic analysis of ARID1A in TCGA subtypes. Finally, we screened patients by random sampling and propensity score matching method and performed multiplex immunofluorescence to explore the effects of ARID1A on CD4, CD8, and PD‐L1 expression in TCGA subtypes.ResultsSeven variables independently associated with ARID1A were screened out: mismatch repair proteins, PD‐L1, T stage, differentiation status, p53, E‐cadherin, and EBER. The independent prognostic variables in the genomically stable (GS) subtype were N stage, M stage, T stage, chemotherapy, size, and ARID1A. PD‐L1 expression was higher in the ARID1A negative group than in the ARID1A positive group in all TCGA subgroups. CD4 showed higher expression in the ARID1A negative group in most subtypes, while CD8 did not show the difference in most subtypes. When ARID1A was negative, PD‐L1 expression was positively correlated with CD4/CD8 expression; while when ARID1A was positive, this correlation disappeared.ConclusionsThe negative expression of ARID1A occurred more frequently in the Epstein–Barr virus and microsatellite instability subtypes and was an independent adverse prognostic factor in the GS subtype. In the TCGA subtypes, ARID1A negative expression caused increased CD4 and PD‐L1 expression, whereas CD8 expression appeared independent of ARID1A. The expression of CD4/CD8 induced by ARID1A negativity was accompanied by an increase in PD‐L1 expression.
Management of cervical external root resorption following connective tissue grafting
Authors: Thibault Émilie , Dhalla Suraya , Deporter Douglas 
Published: June 2023

AbstractBackgroundCervical external root resorption (CERR) is not a common occurrence, but can result in a hopeless tooth prognosis. Its etiology is poorly understood and its management can be challenging. The present case report describes the late presentation and management of CERR at both maxillary first premolar teeth following connective tissue grafting (CTG) procedures including use of citric acid as a chemical root surface conditioner.Methods and ResultsA 55‐year‐old female was diagnosed with bilateral external cervical root resorption of both maxillary first premolar teeth 28 years after CTG procedures that had included the use of citric acid root conditioning. As both teeth were asymptomatic, the patient opted for repair of the lesions via full‐thickness flap elevation, meticulous removal of all granulation tissue, and restoration of the lesions with a resin‐modified glass ionomer. A 2‐year follow‐up has been completed with no significant complications to report.ConclusionsCERR usually develops asymptomatically and is found by chance in radiographs. Its etiology is unclear, but may appear some years after soft tissue grafting to manage gingival recession. Early detection is key to be able to repair the lesions with minimal intervention.
Multiple group identifications and identity compatibility in eating disorder recovery: A mixed methods study
Authors: McNamara Niamh , Wakefield Juliet R. H. , Mair Elizabeth , Rennoldson Mike , Stevenson Clifford , Fitzsimmons Wendy 
Published: June 2023

AbstractEating disorder recovery is an identity transition characterised by ambivalence, in which group memberships play an important part. However, our understanding of how memberships of groups with different recovery norms (i.e., supportive vs. unsupportive of recovery) can facilitate or inhibit recovery is limited. To address this gap, this study adopted the Social Identity Model of Recovery to examine how recovery is manifest through the changing composition of an individual's group memberships. We employed a convergent mixed methods design to quantitatively determine whether specific groups (i.e., family, friends, and online groups) are more helpful to eating disorder recovery than others, and to qualitatively explore how group (in)compatibility shapes recovery efforts. There was a high level of convergence across survey (N = 112) and interview (N = 12) data: groups could have a positive or negative impact according to their recovery norms; different groups provided different forms of support and identity‐expression; incompatibility was not always experienced as a problem and could afford strategic benefits. Our findings are amongst the first to attest to the importance of considering identity networks (and their normative content) during eating disorder recovery.
Co‐Immobilization of a Multi‐Enzyme Cascade: (S)‐Selective Amine Transaminases, l‐Amino Acid Oxidase and Catalase
Authors: Heinks Tobias , Koopmeiners Simon , Montua Nicolai , Sewald Norbert , Höhne Matthias , Bornscheuer Uwe T. , Fischer von Mollard Gabriele 
Published: June 2023

AbstractAn enzyme cascade was established previously consisting of a recycling system with an l‐amino acid oxidase (hcLAAO4) and a catalase (hCAT) for different α‐keto acid co‐substrates of (S)‐selective amine transaminases (ATAs) in kinetic resolutions of racemic amines. Only 1 mol % of the co‐substrate was required and l‐amino acids instead of α‐keto acids could be applied. However, soluble enzymes cannot be reused easily. Immobilization of hcLAAO4, hCAT and the (S)‐selective ATA from Vibrio fluvialis (ATA‐Vfl) was addressed here. Immobilization of the enzymes together rather than on separate beads showed higher reaction rates most likely due to fast co‐substrate channeling between ATA‐Vfl and hcLAAO4 due to their close proximity. Co‐immobilization allowed further reduction of the co‐substrate amount to 0.1 mol % most likely due to a more efficient H2O2‐removal caused by the stabilized hCAT and its proximity to hcLAAO4. Finally, the co‐immobilized enzyme cascade was reused in 3 cycles of preparative kinetic resolutions to produce (R)‐1‐PEA with high enantiomeric purity (97.3 %ee). Further recycling was inefficient due to the instability of ATA‐Vfl, while hcLAAO4 and hCAT revealed high stability. An engineered ATA‐Vfl‐8M was used in the co‐immobilized enzyme cascade to produce (R)‐1‐(3‐ethoxy‐4‐methoxyphenyl)‐2‐(methylsulfonyl)ethanamine, an apremilast‐intermediate, with a 1,000 fold lower input of the co‐substrate.
A novel adenosine signalling‐based prognostic signature in gastric cancer and its association with cancer immune features and immunotherapy response
Authors: Yu Yang , Wang Yidian , Xi Dayong , Wang Na , Gao Lei , Shi Qianling , Yu Rong , Li Haiyuan , Xiang Lin , Maswikiti Ewetse Paul , Chen Hao 
Published: June 2023

AbstractReliable prognostic signatures that can reflect the intrinsic characteristics of gastric cancer (GC) are still rare. Here, we developed an adenosine‐based prognostic signature and explored its association with the tumour immune in GC patients, aiming at confirming the prognostic value of adenosine‐related genes and guiding the GC risk stratification and immunotherapeutic response prediction. We collected adenosine pathway‐related genes from STRING websites and manual searching. We enrolled the The Cancer Genome Atlas cohort and four gene expression omnibus cohorts of GC for generating and validating the adenosine pathway‐based signature using the Cox regression method. Gene expression in the signature was verified using polymerase chain reaction. We also performed gene set enrichment analysis, immune infiltration assessment and immunotherapy response prediction based on this signature. Our study resulted in a six‐gene adenosine signature (GNAS, CXCR4, PPP1R1B, ADCY6, NT5E and NOS3) for risk stratification of GC prognosis, with the highest area under the receiver operating characteristic curve up to 0.767 for predicting 10‐year overall survival (OS). In the training cohort, patients with signature‐defined high risk had significantly poorer OS than those with low risk (p < .001). Multivariate analysis identified the signature as an independent prognostic factor (hazard ratio 2.863, 95% confidence interval [1.871–4.381], p < .001). These findings were confirmed in four independent cohorts. Expression detection showed that all signature genes were upregulated in both GC tissues and cell lines. Further analysis revealed that the signature‐defined high‐risk patients were characterised by immunosuppressive states and associated with a poor immunotherapy response. In conclusion, the adenosine pathway‐based signature represents a promising risk stratification tool for GC in guiding individualised prognostication and immunotherapy.