bluuebunny/crossref_metadata_2025_split huggingface dataset:
Motorized Photomodulator: Making A Non‐photoresponsive Supramolecular Gel Switchable by Light
Authors: Shan Yahan , Zhang Qi , Sheng Jinyu , Stuart Marc C. A. , Qu Da‐Hui , Feringa Ben L. 
Published: September 2023

AbstractIntroducing photo‐responsive molecules offers an attractive approach for remote and selective control and dynamic manipulation of material properties. However, it remains highly challenging how to use a minimal amount of photo‐responsive units to optically modulate materials that are inherently inert to light irradiation. Here we show the application of a light‐driven rotary molecular motor as a “motorized photo‐modulator” to endow a typical H‐bond‐based gel system with the ability to respond to light irradiation and create a reversible sol‐gel transition. The key molecular design feature is the introduction of a minimal amount (2 mol %) of molecular motors into the supramolecular network as photo‐switchable non‐covalent crosslinkers. Advantage is taken of the subtle interplay of the large geometry change during photo‐isomerization of the molecular motor guest and the dynamic nature of a supramolecular gel host system. As a result, a tiny amount of molecular motors is enough to switch the mechanical modulus of the entire supramolecular systems. This study proves the concept of designing photo‐responsive materials with minimum use of non‐covalent light‐absorbing units.
Preparation of polyethylene glycol/polyacrylamide interpenetrating network hydrogel for simultaneously enhancing the fire protection and aging resistance of fireproof glass
Authors: Yi Liang , Zhou Longxiadi , Yan Long , Xu Zhisheng 
Published: September 2023

AbstractTo enhance the flame retardancy and aging resistance of grouting fireproof glass, different molecular weights of polyethylene glycol (PEG) were mixed with acrylamide (AM) to construct interpenetrating network hydrogels, then the obtained hydrogels were mixed with flame retardants to prepare a series of transparent flame‐retarded hydrogels applied in the fireproof glass. The effects of PAM/PEG hydrogel with varying PEG molecular weight on the optical transparency, heat insulation and aging resistance of fireproof glass were investigated. Optical transparency analysis shows that the light transmittance of grouting fireproof glass decreases with the increase of PEG molecular weight in the PAM/PEG interpenetrating network. Fire tests show that PAM/PEG hydrogel significantly enhances the heat insulation and aging resistance of the grouting fireproof glass compared to the single PAM network hydrogel. The flame‐retarded and anti‐aging effects of PAM/PEG hydrogel in the fireproof glass varies with the PEG molecular weight, and the order is PAM/PEG2000 > PAM/PEG1500 > PAM/PEG1000 > PAM/PEG800. Accelerated aging test shows that PAM/PEG interpenetrating network hydrogel is less affected by aging conditions and exerts durable heat insulation and transmittance. Especially, the backside temperature of 3600 s and transmittance of PAM/PEG2000 system after 264 h aging test only changed 38.3°C and 1.3%, respectively, compared to the unaged PAM/PEG2000 system.
Combined effects of vitamin B12 and fumarate on rumen propionate production and methanogenesis in dairy cow in vitro
Authors: Liu Zihao , Wang Kun , Zhao Yiguang , Nan Xuemei , Yang Liang , Zhou Mengting , Tang Xiangfang , Xiong Benhai 
Published: September 2023

AbstractThis study explored the combined effects of vitamin B12 and fumarate supplementation on methane (CH4) emission and propionate synthesis in dairy cows through simulated rumen fermentation in vitro. The experimental animals were 3 cows with an average milk yield of 23 ± 2.8 kg/d, a body weight of 618 ± 100 kg, and a parity of 3 ± 1 that were selected as rumen fluid donors. The TMR diet fed to cows is a fermentation substrate. Experiments adopted 2 × 2 factorial design, including control group, vitamin group (1 mg/g DM vitamin B12), fumarate group (100 mg/g DM), and combined addition group (1 mg/g DM vitamin B12 and 100 mg/g DM). All treatments had no effect on the dry matter degradation (DMD). Both vitamin B12 and fumarate reduced CH4 emission, increased the propionate concentration, and reduced the acetate/propionate ratio without any observed interaction. Vitamin B12 made Prevotella and Prevotellaceae_ UCG‐003 increase in quantity, and fumarate increased the abundance of Succinivibrionaceae_UCG‐002 and Selenomonas, both of which are propionate‐producing bacteria. At the species level, the supplementation of vitamin B12 and fumarate slightly changed the abundance of some strains, but it was not statistically significant. Shifts in the abundance of propionate‐producing bacteria and methanogenic archaea species suggest an increase in propionate production and a decrease in CH4 emission. In conclusion, the addition of vitamin B12 and fumarate changed the fermentation mode of the rumen and reduced the emission of CH4 by affecting the structure of the rumen microbial community, but no obvious interaction was found between the two.
Targeting Ultrafast Spectroscopic Insights into Red Fluorescent Proteins
Authors: Krueger Taylor D. , Chen Cheng , Fang Chong 
Published: September 2023

AbstractRed fluorescent proteins (RFPs) represent an increasingly popular class of genetically encodable bioprobes and biomarkers that can advance next‐generation breakthroughs across the imaging and life sciences. Since the rational design of RFPs with improved functions or enhanced versatility requires a mechanistic understanding of their working mechanisms, while fluorescence is intrinsically an ultrafast event, a suitable toolset involving steady‐state and time‐resolved spectroscopic techniques has become powerful in delineating key structural features and dynamic steps which govern irreversible photoconverting or reversible photoswitching RFPs, and large Stokes shift (LSS)RFPs. The pertinent cis‐trans isomerization and protonation state change of RFP chromophores in their local environments, involving key residues in protein matrices, lead to rich and complicated spectral features across multiple timescales. In particular, ultrafast excited‐state proton transfer in various LSSRFPs showcases the resolving power of wavelength‐tunable femtosecond stimulated Raman spectroscopy (FSRS) in mapping a photocycle with crucial knowledge about the red‐emitting species. Moreover, recent progress in noncanonical RFPs with a site‐specifically modified chromophore provides an appealing route for efficient engineering of redder and brighter RFPs, highly desirable for bioimaging. Such an effective feedback loop involving physical chemists, protein engineers, and biomedical microscopists will enable future successes to expand fundamental knowledge and improve human health.
A machine learning model for predicting congenital heart defects from administrative data
Authors: Shi Haoming , Book Wendy , Raskind‐Hood Cheryl , Downing Karrie F. , Farr Sherry L. , Bell Mary N. , Sameni Reza , Rodriguez Fred H. , Kamaleswaran Rishikesan 
Published: September 2023

AbstractIntroductionInternational Classification of Diseases (ICD) codes recorded in administrative data are often used to identify congenital heart defects (CHD). However, these codes may inaccurately identify true positive (TP) CHD individuals. CHD surveillance could be strengthened by accurate CHD identification in administrative records using machine learning (ML) algorithms.MethodsTo identify features relevant to accurate CHD identification, traditional ML models were applied to a validated dataset of 779 patients; encounter level data, including ICD‐9‐CM and CPT codes, from 2011 to 2013 at four US sites were utilized. Five‐fold cross‐validation determined overlapping important features that best predicted TP CHD individuals. Median values and 95% confidence intervals (CIs) of area under the receiver operating curve, positive predictive value (PPV), negative predictive value, sensitivity, specificity, and F1‐score were compared across four ML models: Logistic Regression, Gaussian Naive Bayes, Random Forest, and eXtreme Gradient Boosting (XGBoost).ResultsBaseline PPV was 76.5% from expert clinician validation of ICD‐9‐CM CHD‐related codes. Feature selection for ML decreased 7138 features to 10 that best predicted TP CHD cases. During training and testing, XGBoost performed the best in median accuracy (F1‐score) and PPV, 0.84 (95% CI: 0.76, 0.91) and 0.94 (95% CI: 0.91, 0.96), respectively. When applied to the entire dataset, XGBoost revealed a median PPV of 0.94 (95% CI: 0.94, 0.95).ConclusionsApplying ML algorithms improved the accuracy of identifying TP CHD cases in comparison to ICD codes alone. Use of this technique to identify CHD cases would improve generalizability of results obtained from large datasets to the CHD patient population, enhancing public health surveillance efforts.
Digestibility, starch morphology, and nutritive value of rusks made from wheat flour with the addition of proso
Authors: Pavlicevic Milica , Vucinic Dajana , Stosic Miljana , Boely Elise , Filipcev Bojana , Dokic Ljubica , Pavlovic Vladimir , Rac Vladislav , Demin Mirjana , Radovic Biljana V. , Rakic Vesna 
Published: September 2023

AbstractBackground and Objectives“Modern diseases” that are the result of a “high sugar, low nutrient” diet are becoming more prevalent. Incorporation of “traditional” gluten‐free cereals, like proso, in “everyday” food, such as rusks, would allow diabetics and people looking to increase fiber and nutrient content to include rusks in their diet.FindingsCompared to wheat rusks, rusks with the addition of proso showed a higher content of microelements and essential amino acids. Also, higher content of dietary fiber and smaller and more regularly arranged starch granules increased the digestibility of rusks with the addition of proso. Additionally, rusks with the addition of proso showed better antioxidative properties and had a lower glycemic index when compared with wheat rusks.ConclusionsIncorporation of proso flour in rusk production could be beneficial not only to people suffering from diabetes but also as a way of improving general well‐being. However, due to the decreased water absorption and, therefore, greater hardness and fracturability, our results suggested that the addition of proso flour should be capped at 20%.Significance and NoveltyTo our knowledge, this is the first description of the effects of different additions of proso on digestibility, starch morphology, glycemic index, and nutritive and antioxidative properties of rusks.
A case of retro‐auricular panfolliculoma mimicking basal cell carcinoma: A rare adnexal tumor with a review of the literature
Authors: Al‐Zahawi Saman , Ghanadan Alireza , Etesami Ifa 
Published: September 2023

Key Clinical MessageA rare case of slow‐growing retro‐auricular panfolliculoma is presented. The lesion was biopsied to rule out basal cell carcinoma but histopathology revealed a follicular tumor with differentiation toward all segments of the hair follicle. Panfolliculoma is a benign follicular tumor with no report of recurrence after surgical excision and no malignant transformation of the previously reported cases.AbstractPanfolliculoma is a rare slow growing adnexal tumor, characterized by differentiation toward all parts of the hair follicle including the infundibulum, isthmus, stem, and bulbs. Clinically this adnexal tumor may mimick basal cell carcinoma and other adnexal neoplasm including trichoblastoma and trichoepithelioma. In this study, we present a rare case of slow‐growing retro‐auricular panfolliculoma of a 70‐year‐old female mimicking basal cell carcinoma that was successfully excised without recurrence.
Hypoglycemia as first presentation of presumed immune checkpoint inhibitor‐induced type 1 diabetes
Authors: Kamal Rayyan Syed , Dean Arleigh , Dutt Hanna , Rajeh Adnan , Fernandes Ricardo 
Published: September 2023

Key Clinical MessageWe present a case of a 60‐year‐old male diagnosed with metastatic clear cell renal cell carcinoma who developed hypoglycemia during induction ipilimumab and nivolumab treatment. This was diagnosed as presumed type 1 diabetes mellitus secondary to immunotherapy.
Preparation and Characterization of Hollow CeO2 Nanoparticles for the Efficient Conversion of CO2 into Dimethyl Carbonate
Authors: Hu Lihua , Hu Kairan , Xu Zhihao , Yao Wenxuan , Wang Aili , Wu Gongde , Xu Wei 
Published: September 2023

AbstractThe hollow CeO2 (H‐CeO2) nanoparticles with mesoporous defects structure were prepared by a solid template method under ambient pressure and applied to catalyze the conversion of CO2 into dimethyl carbonate (DMC). The textural properties of H‐CeO2 were investigated by various characterization techniques. The results showed that H‐CeO2 have higher surface area, more mesoporous defects and higher surface oxygen vacancies concentration than those of conventional CeO2 with block morphology (C‐CeO2). Therefore, H‐CeO2 exhibited better catalytic performance for the conversion of CO2 into DMC. Additionally, the Ce(NO3)3 ⋅ 6H2O amount in preparation procedure was important for the formation of hollow structure and mesoporous defects. The DMC yield could reach 4.96 % on H‐CeO2‐1.2 (Ce(NO3)3 ⋅ 6H2O amount: 1.2 g) catalyst when the reaction was performed at 140 °C and 4.5 MPa for 4 h. This work proposed a facile strategy for designing CeO2 catalysts for the CO2 conversion by creating mesoporous defective structure.
Iron‐Based Nanoparticles Oxygen Scavenger for Suppressing Heat‐Stable Salts Formation in Amine
Authors: Chin Sim Yee , Lim Soh Fong , Lau Kok Keong , Thangavel Mythili , Kamaruzaman Muhammad Ridzuan 
Published: September 2023

AbstractHeat‐stable salts (HSS), which trigger excessing foaming in absorber, are formed when protonated methyl diethanolamine (MDEA) reacts with the more acidic degraded products in the presence of dissolved oxygen (DO). The aim is to suppress the HSS formation in MDEA solution inaugurally employing a hybrid iron‐based nanoparticles (HINP) oxygen scavenger. It was discovered that the oxygen‐scavenging performance of a more cost‐effective 20 %Fe/HZSM5 was one‐fold higher than the 20 %Fe/MCM‐41. The former was verified for its superior structural properties. The Fe2+ on its surface first reacted with DO, preventing DO from oxidizing the MDEA. Consequently, the absence of hydroxyl radicals eliminated the potential of formic acid formation, hence suppressing the MDEA‐acid HSS formation.
Controlled Potential Electrolysis: Transition from Fast to Slow Regimes in Homogeneous Molecular Catalysis. Application to the Electroreduction of CO2 Catalyzed by Iron Porphyrin
Authors: Deeba Rana , Collard Alexandra , Rollin Camille , Molton Florian , Chardon‐Noblat Sylvie , Costentin Cyrille 
Published: September 2023

AbstractMolecular catalysis of electrochemical reactions is a field of intense activity because of the current interest in electrifying chemical transformations, including both electrosynthesis of organic molecules and production of fuels via small molecule activation. Controlled potential electrolysis (CPE) is often coupled with in situ in operando spectroscopic methods with the aim to gather mechanistic information regarding the catalytic species involved. Herein, considering a simple mechanism for a homogeneous molecular catalysis of an electrochemical reaction, we establish the concentration profile of the catalyst in the electrolysis cell enabling to envision the information that can be obtained from the coupling of this CPE with a spectroscopic probe in the cell compartment. We show how the characteristic parameters of the system (catalytic rate constant, cell dimensions and stirring rate) affect the response with particular emphasis on the transition between two limiting cases, namely a ‘fast’ catalysis regime where catalysis only takes place in a small layer adjacent to the electrode surface and a ‘slow’ catalysis regime where catalysis takes place in the bulk of the solution. These formal concepts are then illustrated with an experimental example, the electroreduction of CO2 in dimethylformamide homogeneously catalyzed by iron tetraphenylporphyrin and followed by UV‐vis spectroscopy.
Modulating Strain in Twisted Pyrene‐Fused Azaacenes
Authors: Mateos‐Martín Javier , Dhbaibi Kais , Melle‐Franco Manuel , Mateo‐Alonso Aurelio 
Published: September 2023

AbstractThe design and synthesis of strained aromatics provide an additional insight into the relationship between structure and properties. In the last years, several approaches to twist pyrene‐fused azaacenes have been developed that allow to introduce twists of different sizes. Herein, we describe the synthesis of a new set of twisted dibenzotetraazahexacenes constituted by fused pyrene and quinoxaline residues that have been distorted by introducing increasingly larger substituents on the quinoxaline residues. Their twisted structure has been demonstrated by single‐crystal X‐ray diffraction. Furthermore, absorption, fluorescence, electrochemical and theoretical studies shine light on the effects of the substituents and twists on the optoelectronic and redox properties.
One Ligand to Bind them All: S~C~S2− Carbon‐ and Sulfur‐Based Gem‐Dianion as Structuring Ligand for Iron Polymetallic Assemblies
Authors: Ravel‐Massol Raphaël , Munshi Sandip , Pujol Anthony , Garcia‐Serres Ricardo , Saffon‐Merceron Nathalie , Mézailles Nicolas , Fustier‐Boutignon Marie 
Published: September 2023

AbstractNumerous synthetic models of the FeMo‐co cluster of nitrogenases have been proposed to find the simplest structure with relevant reactivity. Indeed, such structures are able to perform multi‐electrons reduction processes, such as the conversion of N2 to ammonia, and of CO2 into methane and alkenes. The most challenging parameter to imitate is indeed the central carbide ligand, which is believed to maintain the integrity of iron sulfide assembly during the course of catalytic cycles. The study proposes the use of bis(diphenylthiophosphinoyl)methanediide (SCS)2− as an ideal platform for the synthesis of bi‐ and tetra‐metallic iron complexes, in which the iron‐carbon interaction is maintained upon structural diversification and redox state changes.
Yet Another Case of Lithium Metal Atoms and Germanium Atoms Sharing Chemistry in the Solid State: Synthesis and Structural Characterization of Ba2LiGe3
Authors: Ghosh Kowsik , Bobev Svilen 
Published: September 2023

AbstractSeveral Ba−Li−Ge ternary phases are known and structurally characterized, including the title compound Ba2LiGe3. Its structure is reported to contain [Ge6]10− anions that exhibit delocalized bonding with a Hückel‐like aromatic character. The Ge atoms are in the same plane with the Li atoms, and if both types of atoms are considered as covalently bonded, [LiGe3]4− honeycomb‐like layers will result. The latter are separated by slabs of Ba2+ cations. However, based on the systematic work detailed herein, it is necessary to re‐evaluate the phase as Ba2Li1−xGe3+x (x<0.05). Although small, the homogeneity range is clearly demonstrated in the gradual change of the unit cell for four independent samples. Subsequent characterization by single‐crystal X‐ray diffraction methods shows that the Ba2Li1−xGe3+x structure, responds to the varied number of valence electrons and the changes are most pronounced for the refined lengths of the Li−Ge and Ge−Ge bonds. Indirectly, the changes in the Ge−Li/Ge distances within layers affect the stacking too, and these changes can be correlated to the variation of the c‐cell parameter. Chemical bonding analysis based on TB‐LMTO‐ASA level calculations affirms the notion for covalent character of the Ge−Ge bonds; the Ba−Ge and Li−Ge interactions also show some degree of covalency.
PI and PIII Ions Supported by BZIMPY Ligands
Authors: LaFortune James H. W. , Swidan Ala'aeddeen , Ovens Jeffrey S. , Qu Zheng‐Wang , Grimme Stefan , Land Michael A. , Macdonald Charles L. B. 
Published: September 2023

AbstractWe report a class of compounds in which both PIII−X and PI forms featuring the same ligand are stable and readily cycled with each other. A series of PIII−X (X=Cl, Br, I) dicationic triflate salts supported by benzyl‐ and allyl‐substituted 2,6‐bis(benzimidazole‐2‐yl)pyridine (BZIMPY) ligands is synthesized. Surprisingly, treatment of these with R3PO (R=Et, Oct) results in reduction to BZIMPY‐ligated PI monocationic triflate salts while treatment with Ph3P reduces but also substitutes the compound to produce Ph3P‐BZIMPY‐ligated PI dicationic triflate salts. The mechanisms of these surprising reductions are probed experimentally and rationalized computationally. The PIII−X dications are shown to be strong Lewis acids both experimentally and computationally and to readily behave as X+, PX, and P+ transfer agents in reactions with phosphines, NHCs, and diazabutadienes. The PI mono‐ and dications are shown to be very effective P+ transfer agents when treated similarly. Oxidation from a monocationic PI salt back to the dicationic PIII−X (X=Cl, Br) salt was achieved by treatment with N‐chlorosuccinimide (NCS) or N‐bromosuccinimide (NBS). Full characterization is reported using multinuclear nuclear magnetic resonance spectroscopy, elemental analysis, and single‐crystal X‐ray diffractometry where suitable crystals were isolated.
Composite dietary antioxidant index and the risk of heart failure: A cross‐sectional study from NHANES
Authors: Ma Yazhe , Liu Jiangwen , Sun Jianying , Cui Yanju , Wu Peng , Wei Feiyu , Gao Xiaolong , Ma Tao , Zhang Xi , Kuang Xiaohui , Fan Jie 
Published: September 2023

AbstractBackgroundPrevious studies show that oxidative stress is important in heart failure (HF) pathogenesis. The composite dietary antioxidant index (CDAI), which reflects the antioxidant profile of nutrient supplements, is associated with cardiovascular mortality risk. However, the association between CDAI and the risk of HF remains unknown.HypothesisIn this study, we investigated the relationship between CDAI and HF risk using National Health and Nutritional Examination Survey (NHANES) data.MethodsThe data of participants aged >40 years old from the NHNANES between 2001 and 2018 were obtained and used to assess the relationship between CDAI and the risk of HF. Logistic regression was used to calculate the odds ratio (OR) of CDAI for the risk of HF.ResultsA total of 29 101 participants were divided into the HF (n = 1419; 4.88%) and non‐HF groups (n = 27 682; 95.12%), HF group participants had lower CDAI than the non‐HF group (−0.32 ± 0.14 vs. 0.67 ± 0.05, p < .0001). Compared with the lowest CDAI quartile (Q1), the OR for HF risk was 0.88 (0.68−1.13) for Q2 (p = .30), 0.77 (0.61−0.99) for Q3 (p = .04), and 0.68 (0.52−0.89) for Q4 (p = .01).ConclusionsCDAI was negatively associated with the risk of HF. Our findings show that the intake of an antioxidant‐rich dietary is a potential method to reduce the risk of HF.