bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cooperative Rheological State‐Switching of Enzymatically‐Driven Composites of Circular DNA And Dextran
Authors: Marfai Juexin , McGorty Ryan J. , Robertson‐Anderson Rae M. 
Published: July 2023

AbstractPolymer topology, which plays a principal role in the rheology of polymeric fluids, and non‐equilibrium materials, which exhibit time‐varying rheological properties, are topics of intense investigation. Here, composites of circular DNA and dextran are pushed out‐of‐equilibrium via enzymatic digestion of DNA rings to linear fragments. These time‐resolved rheology measurements reveal discrete state‐switching, with composites undergoing abrupt transitions between dissipative and elastic‐like states. The gating time and lifetime of the elastic‐like states, and the magnitude and sharpness of the transitions, are surprisingly decorrelated from digestion rates and non‐monotonically depend on the DNA fraction. These results are modeled using sigmoidal two‐state functions to show that bulk state‐switching can arise from continuous molecular‐level activity due to the necessity for cooperative percolation of entanglements to support macroscopic stresses. This platform, coupling the tunability of topological composites with the power of enzymatic reactions, may be leveraged for diverse material applications from wound‐healing to self‐repairing infrastructure.
Bi‐Directional Shape Morphing in 4D‐Bioprinted Hydrogels on a Single Stimulation
Authors: Mondal Pritiranjan , Mandal Arkodip , Chatterjee Kaushik 
Published: July 2023

AbstractA generalizable 4D bioprinting technique utilizing graded semi‐interpenetrating network (IPN) hydrogels is introduced with versatile ink design, which exhibits rapid, sequential shape‐morphing transformations in two opposite directions on a single stimulation (immersion in water). The bi‐directional shape morphing behavior is governed by the sequential activation of two distinct actuation mechanisms, namely, anisotropic water uptake due to photocrosslinking gradient and subsequent temporal water redistribution as a consequence of differential swelling‐induced osmolarity gradient. This study demonstrates that the spatiotemporal characteristics of these bi‐directional shape‐morphing hydrogels can be precisely programmed according to desired part specifications by rationally designing dual‐component hydrogel systems based on a mechanistic understanding of the underlying phenomena. Additionally, a proof‐of‐concept demonstration is provided where the bi‐directional, shape‐morphing behavior is leveraged for the design of soft, deployable hydrogel devices. Lastly, a systematic guideline is proposed facilitating the selection of the second hydrogel component for tuning the extent and pace of shape changes. Owing to their excellent biocompatibility and mild enabling conditions, these hydrogels stand to transform the capacity to precisely design soft, deployable devices for the delivery of therapeutic agents in a minimally invasive manner inside the human body, among other potential applications.
Water‐Stable 0D Hybrid Manganese Halides with Adjustable Crystal Structure and Emission Color
Authors: Liu Yu‐Hang , Yan Xue , Xiao Li , Jiang Wei , Liu Qi , Liu Tian‐Ci , Yan Tian‐Yu , Yue Cheng‐Yang , Lei Xiao‐Wu 
Published: July 2023

AbstractDespite the ultra‐high photoluminescence quantum yield (PLQY) of 0D hybrid manganese halides as state‐of‐the‐art luminescent materials, intrinsic water stability remains an unsurpassable barrier due to the serious hygroscopicity of the hydrogen‐bonding structure. Herein, a synthetic strategy that realizes adjustable emission color and high water resistance in a 0D hybrid manganese chloride family based on the same cation of [H2TMDAP]2+ (TMDAP = N,N,N′,N′‐tetramethyl‐1,3‐diaminopropane) is reported. Specifically, direct solution or solid‐state reaction of precursor materials generates [H2TMDAP]3[MnCl4]2[Mn2Cl6], while additional Zn2+‐doping as a structural directing agent results in [H2TMDAP]Mn0.63Zn0.37Cl4. Functionally, the [Mn/ZnCl4]2− tetrahedron based [H2TMDAP]Mn0.63Zn0.37Cl4 displays green light emission at 521 nm with a PLQY of 63.9%. [H2TMDAP]3[MnCl4]2[Mn2Cl6] is composed of a [MnCl6]4− octahedron based [Mn2Cl6]2− chain and a discrete [MnCl4]2− tetrahedron, but it only exhibits single red emission at 628 nm with a PLQY of 48.1%. Compared with water‐instable [H2TMDAP]Mn0.63Zn0.37Cl4, [H2TMDAP]3[MnCl4]2[Mn2Cl6] represents extraordinary chemical stability in humid air and water over 1 month, manifested by an unchanged structural lattice and sufficient emission intensity. Significantly, the ultra‐high water proof performance of [H2TMDAP]3[MnCl4]2[Mn2Cl6] is nearly unmatchable among all previously reported manganese halides as far as is known. The combined merits of tunable emission wavelength, high PLQY, and stability highlight the potential applications of title materials in solid‐state lighting and display diodes.
L‐Proline Derived Thioamide Small Organic Molecule for the α‐Stereoselective Synthesis of 2‐Deoxyglycosides
Authors: Tiwari Ashwani , Khanam Ariza , Kumar Ashwani , Lal Mohan , Kumar Mandal Pintu 
Published: July 2023

AbstractL‐Prolinethioamide catalyzes direct stereoselective glycosylation of glycal donors to access 2‐deoxyglycosides under moderate reaction conditions. This proposed glycosylation protocol produced the desired products in up to 88% yield and shows greater tolerance of glycosyl acceptors and a broad substrate scope with better stereoselectivity. This method is also applicable for less nucleophilic acceptors such as phenol. In addition, 1,1′‐linked trehalose‐type analogues can also be accessed through this methodology. Further, mechanistic studies suggest that, in this glycosylation, L‐prolinethioamide operates via Brønsted acid/base catalysis.
Single‐Atom Cobalt‐Catalyzed Transfer Hydrogenation of Azides and One‐Pot Synthesis of Pyrroles
Authors: Panja Dibyajyoti , Sau Anirban , Thakur Seema D. , Dey Sadhan , Sahu Rajib , Kundu Sabuj 
Published: July 2023

AbstractIn this work, a single‐atom cobalt‐catalyzed transfer hydrogenation (TH) of azides is reported under mild conditions (at 30 °C in 30 min) using NH2NH2 ⋅ H2O as the hydrogen source. Employing this protocol, a wide range of azides were transformed to their corresponding amines. This methodology was extended towards the synthesis of several important N‐substituted pyrroles from azides in one‐pot manner. The control experiments suggested, the transfer hydrogenation favoured by electron withdrawing substituents and one‐pot pyrrole synthesis favoured by electron‐donating substituents. The recyclability test revealed the catalysts could be recycled up to 7th times without significant loss in the catalytic activity.
Visible Light‐Driven, Persulfate‐Mediated Hydrocarboxylation of Vinylsulfones
Authors: Pálvölgyi Ádám Márk , Scharinger Fabian , Bauhoff Thomas , Bica‐Schröder Katharina 
Published: July 2023

AbstractWe report a visible light‐mediated approach for the radical hydrocarboxylation of vinylsulfone derivatives. Using cheap and easily accessible sodium formate as C1‐source and K2S2O8 as reagent, a set of vinylsulfone substrates could be efficiently hydrocarboxylated in aqueous medium without any additional catalyst or reagent; and the concept could be also applied for direct hydroacylations, hydroalkylations and hydrophosphorylations. The control experiments clearly indicated that the reaction proceeds via radical mechanism without the generation of electron donor‐acceptor (EDA) complexes; supporting the working model of K2S2O8‐initiated in situ formation of CO2 radical anion.
Substituent‐Controlled Regiodivergent Palladium‐Catalyzed Annulative Dearomatization of Phenols toward Skeletally Diverse Spirocyclohexadienones
Authors: Mao Hui‐Lin , Yu Jun , Shen Yi‐Ting , Li Qiuyun , Hao Wen‐Juan , Jiang Bo 
Published: July 2023

AbstractA palladium‐catalyzed intermolecular dearomative formal [4+2] annulation of phenols with propargyl electrophiles is reported, enabling substituent‐controlled regiodivergent synthesis of a wide range of skeletally diverse spirocyclohexadienones with good yields. The regiodivergence could be precisely controlled by adjusting the steric hindrance of O‐ and N‐substituents from binucleophilic substrates, where substrates with an O‐nucleophilic site were converted into spiro[chromane‐4,1′‐cyclohexane]‐2′,5′‐dien‐4′‐ones with complete regioselectivity and (Z)‐selectivity, whereas N‐nucleophiles enabled a different regiodivergent process to access spiro[cyclohexane‐1,4′‐quinoline]‐2,5‐dien‐4‐ones.
Responsive Regulation of Energy Transfer in Lanthanide‐Doped Nanomaterials Dispersed in Chiral Nematic Structure
Authors: Luo Yuxia , Liu Qingdi , He Ping , Li Liang , Zhang Zhao , Li Xinping , Bao Guochen , Wong Ka‐Leung , Tanner Peter A. , Jiang Lijun 
Published: July 2023

AbstractThe responsive control of energy transfer (ET) plays a key role in the broad applications of lanthanide‐doped nanomaterials. Photonic crystals (PCs) are excellent materials for ET regulation. Among the numerous materials that can be used to fabricate PCs, chiral nematic liquid crystals are highly attractive due to their good photoelectric responsiveness and biocompatibility. Here, the mechanisms of ET and the photonic effect of chiral nematic structures on ET are introduced; the regulation methods of chiral nematic structures and the resulting changes in ET of lanthanide‐doped nanomaterials are highlighted; and the challenges and promising opportunities for ET in chiral nematic structures are discussed.
Ultra‐Tough Self‐Healing Hydrogel via Hierarchical Energy Associative Dissipation
Authors: Zhao Zhi , Li Yurong , Wang Haibin , Shan Yupeng , Liu Xuemei , Wu Mengfei , Zhang Xinping , Song Xiaoyan 
Published: July 2023

AbstractOwing to high water content and homogeneous texture, conventional hydrogels hardly reach satisfactory mechanical performance. Tensile‐resistant groups and structural heterogeneity are employed to fabricate tough hydrogels. However, those techniques significantly increase the complexity and cost of material synthesis, and have only limited applicability. Here, it is shown that ultra‐tough hydrogels can be obtained via a unique hierarchical architecture composed of chemically coupled self‐assembly units. The associative energy dissipation among them may be rationally engineered to yield libraries of tough gels with self‐healing capability. Tunable tensile strength, fracture strain, and toughness of up to 19.6 MPa, 20 000%, and 135.7 MJ cm⁻3 are achieved, all of which exceed the best known records. The results demonstrate a universal strategy to prepare desired ultra‐tough hydrogels in predictable and controllable manners.
Designing Electrolytes With Controlled Solvation Structure for Fast‐Charging Lithium‐Ion Batteries
Authors: Kautz David J. , Cao Xia , Gao Peiyuan , Matthews Bethany E. , Xu Yaobin , Han Kee Sung , Omenya Fredrick , Engelhard Mark H. , Jia Hao , Wang Chongmin , Zhang Ji‐Guang , Xu Wu 
Published: July 2023

AbstractRecharging battery‐powered electric vehicles (EVs) in a similar timeframe as those used for refueling gas‐powered internal combustion vehicles is highly desirable for rapid penetration of the EV market. It is well known that the electrolyte in a battery plays a critical role in fast‐charging capability of the battery because it determines the rate of ion transport together with its derived electrode/electrolyte interphases on both cathode and anode of the battery. In this study, the effects of contents of salt, coordinating solvent, and noncoordinating diluent on salt dissociation degree and electrolyte ionic conductivity are investigated, and a controlled solvation structure electrolyte is developed to improve the lithium ion mobility and conductivity in the electrolyte and to enhance the kinetics and stability of the electrode/electrolyte interphases in the battery. This electrolyte enables fast‐charging capability of high energy density lithium‐ion batteries (LIBs) at up to 5 C rate (12‐min charging), which significantly outperforms the state‐of‐the‐art electrolyte. The controlled solvation structure sheds light on the future electrolyte design for fast‐charging LIBs.
Intraspecific variation of long bone cross‐sectional properties in Pan troglodytes troglodytes and Gorilla gorilla gorilla
Authors: Cosman Miranda Nicole , MacLatchy Laura M. , Schlecht Stephen H. , Devlin Maureen J. 
Published: July 2023

AbstractObjectivesMorphological intraspecific variation is due to the balance between skeletal plasticity and genetic constraint on the skeleton. Osteogenic responses to external stimuli, such as locomotion, have been well documented interspecifically across the primate order, but less so at the intraspecific level. Here, we examine the differences in cross‐sectional variability of the femur, humerus, radius, and tibia in Pan troglodytes troglodytes versus Gorilla gorilla gorilla. We investigate whether there are sex, species, bone, and trait differences in response to variable body size and locomotion.Materials and MethodsAdult male and female P. t. troglodytes and G. g. gorilla long bones from the Cleveland Museum of Natural History were scanned with a peripheral quantitative computer tomography system. Scans were taken at the midshaft of each bone according to functional bone length. Coefficients of variation were used to provide a size‐independent measure of variation. We applied a Bonferroni correction to account for the multiple pairwise tests.ResultsThere were limited significant differences between males and females, however, females tended to be more variable than males. Variation in Gorilla, when significant, was greater than in Pan, although significant differences were limited. There were no differences between bone variability in male and female Gorilla, and female Pan.DiscussionIncreased female variability may be due to more variable locomotor behavior, particularly during periods of pregnancy, lactation, and caring for an offspring compared to consistent locomotion over the life course by males. Body size may be a contributing factor to variability; more work is needed to understand this relationship.
Optimizing the timing of biologic and surgical therapy for patients with refractory chronic rhinosinusitis with nasal polyposis (CRSwNP)
Authors: Garvey Emily , Naimi Bita , Duffy Alexander , Hannikainen Paavali , Kahn Chase , Farquhar Douglas , Rosen Marc , Rabinowitz Mindy , Toskala Elina , Nyquist Gurston 
Published: July 2023

AbstractIntroductionChronic rhinosinusitis with nasal polyposis (CRSwNP) is often treated with endoscopic sinus surgery (ESS); however, patients may require revision surgery due to recurrence. To date, no studies have compared outcomes for combined surgery and biologic therapy for CRSwNP compared with biologic therapy alone.MethodsRetrospective case–control study of CRSwNP patients who underwent ESS while on dupilumab or mepolizumab (ESS‐biologic cohort) compared with CRSwNP patients on biologic therapy (biologic‐only controls). Cohorts were matched according to indication, aspirin‐exacerbated respiratory disease (AERD), sinonasal outcome test‐22 (SNOT‐22), and total polyp scores.ResultsSixteen patients underwent ESS while on biologic therapy (13 dupilumab and 3 mepolizumab). Sixteen patients were biologic‐only controls. There were no significant differences between indication, baseline SNOT‐22 scores, polyp scores, and AERD status between cohorts. Patients underwent surgery a median of 33 days after starting biologic therapy. After 12 months of follow‐up, the total polyp score for the ESS‐biologic cohort decreased from 4.73 to 0.09 compared with a decrease from 5.22 to 3.38 for the biologic‐only controls (95% confidence interval [CI] of difference: −5.37 to −1.38, Cohen's d: 2.40, p = 0.005). In the ESS‐dupilumab subanalysis, the ESS‐dupilumab cohort had a significant reduction in polyp burden from 4.85 to 0.00 compared with 4.88 to 3.50 for the controls (95% CI of difference: −5.68 to −1.32, Cohen's d: −1.69, p = 0.009).ConclusionIn CRSwNP patients, combined ESS and biologic therapy results in a significant and sustained decrease in polyp burden compared with biologic therapy alone. Larger studies are warranted to further examine the impact of combined therapy.
Automatisierte Generierung von Mikrokinetiken für heterogen katalysierte Reaktionen unter Berücksichtigung korrelierter Unsicherheiten**
Authors: Kreitz Bjarne , Lott Patrick , Studt Felix , Medford Andrew J. , Deutschmann Olaf , Goldsmith C. Franklin 
Published: July 2023

AbstractDie Studie stellt eine ab initio basierte Methode für die automatische Konstruktion von detaillierten Mikrokinetiken vor, welche korrelierte Unsicherheiten in allen energetischen Parametern und Schätzroutinen berücksichtigt. Hierfür wurden innerhalb des Unsicherheitsraums des BEEF‐vdW Funktionals 2000 Mikrokinetiken für die Oxidationsreaktionen repräsentativer Abgasemissionen von stöchiometrischen Verbrennungsmotoren auf Pt(111) generiert und durch Multiskalenmodellierung mit Experimenten verglichen. Das Ensemble der Simulationsergebnisse unterstreicht die Bedeutung der Berücksichtigung von Unsicherheiten. Innerhalb dieses Ensembles ist es möglich, eine Mikrokinetik zu identifizieren, welche mit den experimentellen Daten übereinstimmt. Diese Mikrokinetik lässt sich auf ein einziges Austausch‐Korrelations‐Funktional zurückführen und legt nahe, dass Pt(111) das aktive Zentrum für die Oxidation leichter Kohlenwasserstoffe sein könnte. Die Studie bietet einen universellen Rahmen für die automatisierte Konstruktion von Reaktionsmechanismen unter Berücksichtigung korrelierter Unsicherheiten und ermöglicht eine DFT‐basierte Optimierung der Mikrokinetik auch für andere heterogen katalysierte Systeme.
Automated Generation of Microkinetics for Heterogeneously Catalyzed Reactions Considering Correlated Uncertainties**
Authors: Kreitz Bjarne , Lott Patrick , Studt Felix , Medford Andrew J. , Deutschmann Olaf , Goldsmith C. Franklin 
Published: July 2023

AbstractThe study presents an ab‐initio based framework for the automated construction of microkinetic mechanisms considering correlated uncertainties in all energetic parameters and estimation routines. 2000 unique microkinetic models were generated within the uncertainty space of the BEEF‐vdW functional for the oxidation reactions of representative exhaust gas emissions from stoichiometric combustion engines over Pt(111) and compared to experiments through multiscale modeling. The ensemble of simulations stresses the importance of considering uncertainties. Within this set of first‐principles‐based models, it is possible to identify a microkinetic mechanism that agrees with experimental data. This mechanism can be traced back to a single exchange‐correlation functional, and it suggests that Pt(111) could be the active site for the oxidation of light hydrocarbons. The study provides a universal framework for the automated construction of reaction mechanisms with correlated uncertainty quantification, enabling a DFT‐constrained microkinetic model optimization for other heterogeneously catalyzed systems.
Stereodivergent Zweifel Olefination and its Mechanistic Dichotomy
Authors: Manna Samir , Paul Swagata , Kong Wang‐Yeuk , Aich Debasis , Sahoo Rupam , Tantillo Dean J. , Panda Santanu 
Published: July 2023

AbstractStereoselective Zweifel olefination using boronate complexes carrying two different reactive π‐systems was achieved to synthesize vinyl heteroarenes and conjugated 1,3‐dienes in good yield and up to 100 % stereoselectivity, which remains unexplored until now. Most importantly, we report the unprecedented formation of E vs. Z‐vinyl heteroarenes for different heteroarenes under identical conditions. Density functional theory (DFT) investigations unveil the mechanistic dichotomy between olefin and heteroarene activation followed by 1,2‐migration, leading to E or Z‐vinyl heteroarenes respectively. We also report a previously unknown reversal of stereoselectivity by using 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) as an electrophile. The Zweifel olefination using a boronate complex that carries two different olefins was previously unexplored due to significant challenges associated with the site‐selective activation of olefins. We have solved this problem and reported the site‐selective activation of olefins for the stereoselective synthesis of 1,3‐dienes.
Catalytic water oxidation mediated by copper‐triazolylpyridine complexes
Authors: Zhao Si‐Yang , Zhu Xue‐Ling , Wang Xue‐Han , Cao Yuan‐Yang , Li Qing‐An , Qin Shu‐Yi , Wang Tian‐Shun , Zhang Hua‐Xin 
Published: July 2023

Water oxidation reaction (WOR) is a rather sluggish process in the water splitting that hampers the extraction of hydrogen gas from water in a large scale. It is highly desirable to develop low‐cost WOR catalysts to increase the efficacy. Herein two Cu(II) complexes [Cu (DTEL)2]n(ClO4)2n (1) and [Cu(DTE)2(ClO4)2] (2) of two triazolylpyridines, 1‐(2‐hydroxy)‐4‐(2‐pyridyl)1,2,3‐triazole (DTEL) and 1‐(2‐acetoxymethyl)‐4‐(2‐pyridyl)1,2,3‐triazole (DTE), have been synthesized and characterized. The X‐ray diffraction analysis revealed that the copper centers of 1 and 2 adopted the octahedral coordination geometry with four N atoms from two DTEL or DTE ligands in the equatorial plane. The two axial sites were weakly ligated by the hydroxyl group of DTEL or perchlorate. Both complexes 1 and 2 were homogenous molecular catalysts boosting the WOR in pH 9.0 phosphate buffer solution with the overpotentials being 568 and 478 mV, rate constants (kcat) of 0.1 and 0.39 s−1, and Faradaic efficiencies of 90% and 93%, respectively. The pendant substituent on the two triazolylpyridine ligands DTEL and DTE apparently influenced the catalysis. A mechanism for the catalytic WOR mediated by 1 and 2 was suggested on the basis of the experimental data. This work illustrated that triazolylpyridines were promising scaffolds for forming metal complexes working as WOR catalysts.
Crystallization and polymorphic behaviors of cocoa butter alternatives: A review
Authors: Ramos Ramos María Regina , García Londoño Víctor Alonso , Borroni Virginia , Candal Roberto Jorge , Herrera María Lidia 
Published: July 2023

AbstractAlthough cocoa butter (CB) has remarkable physical properties, its high price, growing difficulties, and increased consumption have been the main incentive to explore alternatives to replace or improve it. The potential of fats systems obtained from tropical butters, mixtures of them with vegetable oils, or marine fats as cocoa butter equivalent (CBE), extender (CBEx), substitute (CBS), replacer (CBR), or improver (CBI) have been deeply investigated and their physical chemical properties have been compared to those of CB. The TAGs composition of fats systems is a key factor that determines fats crystallization and polymorphic behaviors, and the suitability for an application. Fats with high concentrations of the TAGs StOSt, StOA, or StOB and low concentrations of POP compared to CB show some incompatibility with CB as analyzed by iso‐solid diagrams and a more complex polymorphic behavior. The presence of low melting TAGs such as POO, StOO, and AOO also leads to significant differences in physical behavior compared to CB. In those fats systems, co‐crystallization and polymorphic transitions of co‐existing solid solutions were reported. A few of the studied fat systems may behave as CBE. However, most of them have potential as CBS, CBR, CBEx or CBI in confectionery products. Studies reported the relevance of fractionation and interesterification processes to modify TAGs composition and the need of finding the right processing conditions and additives to extend fats applications.