bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Modular Co‐assembly Strategy for Ordered Mesoporous Perovskite Oxides with Abundant Surface Active Sites
Authors: Zheng Yuenan , Wang Luoqi , Liu Hongyu , Yang Jiaqi , Zhang Rui , Zhang Ling , Qiao Zhen‐An 
Published: July 2022

AbstractThe ordered mesoporous perovskite oxides with well‐defined mesostrcture and versatile metal sites are attractive, but their successful synthesis faces challenges of complicated assembly dynamics and pore collapse in crystalline calcination. Here, we propose an energy balance concept to reveal interplay relationship in assembly process and realize regulation of porous structure for mesoporous perovskite oxides. A series of ordered mesoporous perovskite oxides with unique porous structure were prepared by a modular co‐assembly method. Mesoporous La2Zr2O7 shows 94 % conversion and 99 % selectivity for hydrogenation of 5‐hydroxymethylfurfural (HMF) to 2,5‐bis(hydroxymethyl)furan. Experiments reveal that rich Lewis acid sites, active Zr species, and favorable porous structure promote interaction between mesoporous La2Zr2O7 and HMF and reduce catalytic energy barrier. This work provides the insight into molecule co‐assembly and developing multiple component ordered mesoporous materials.
Chemical Investigations of Differentially Oxidized Polycylic Pyrroles from Bipolaris Fungi: Synthetic Entry Into the Bipolamine Alkaloids
Authors: Xuan Jun , Machicao Paulo A. , Haelsig Karl T. , Maimone Thomas J. 
Published: July 2022

Abstractindolizidine alkaloids of unusual biosynthetic origin have recently been characterized from several species of fungi within the Pleosporaceae family. Possessing distinct polycyclic architectures with two embedded electron‐rich pyrroles as well as reported antibacterial activity against gram positive and negative pathogens, these natural products represent attractive targets for total synthesis. Herein we survey the differential functionalization of a chemically sensitive bispyrrole framework resulting in the preparation of multiple bipolamine alkaloids, work which sheds light on their innate chemical reactivity and potential biosynthetic relationships.
Leveraging Isothermal Titration Calorimetry to Explore Structure–Property Relationships of Protein Immobilization in Metal–Organic Frameworks
Authors: Tai Tzu‐Yi , Sha Fanrui , Wang Xiaoliang , Wang Xingjie , Ma Kaikai , Kirlikovali Kent O. , Su Shengyi , Islamoglu Timur , Kato Satoshi , Farha Omar K. 
Published: July 2022

AbstractProteins immobilized in metal–organic frameworks (MOFs) often show extraordinary stability. However, most efforts to immobilize proteins in MOFs have only been exploratory. Herein, we present the first systematic study on the thermodynamics of protein immobilization in MOFs. Using insulin as a probe, we leveraged isothermal titration calorimetry (ITC) to investigate how topology, pore size, and hydrophobicity of MOFs influence immobilization. ITC data obtained from the encapsulation of insulin in a series of Zr‐MOFs reveals that MOFs provide proteins with a hydrophobic stabilizing microenvironment, making the encapsulation entropically driven. In particular, the pyrene‐based NU‐1000 tightly encapsulates insulin in its ideally sized mesopores and stabilizes insulin through π‐π stacking interactions, resulting in the most enthalpically favored encapsulation process among this series. This study reveals critical insights into the structure–property relationships of protein immobilization.
Synergistic effect of polyphosphazene nanotubes and graphene on enhancing ablative resistance of ethylene propylene diene monomer insulation composites
Authors: Chen Junming , Huang Xiaobin , He Yongzhu , Liu Longquan , Sheng Haoqiang , Hu Wenbin , Zhao Zhengchuang , He Jinxuan 
Published: July 2022

AbstractMany advanced fillers were used in ethylene propylene diene monomer (EPDM) insulation composites to enhance the ablative resistance by strengthening char layer. However, the structures of fillers and char layer were usually neglected. In this work, a new type of cross‐linked network‐like polyphosphazene nanotubes (PNTs) was added in EPDM composites in combination with graphene. The results showed that the ablation performance of EPDM composites was improved by 21.6% with the synergistic effect of PNTs and graphene. Moreover, the ablation mechanism was studied by analyzing ablated char layer using X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy disperse spectroscopy (EDS) and Raman spectroscopy. PNTs served as skeleton to build the cross‐linked network char layer and graphene played a role in enhancing the properties of char layer. The findings of this work emphasize the synergistic effect of structures and properties of fillers when performing ablative modification, which provides a new idea to enhance the ablation properties of EPDM composites.
Delivery of bioactive albumin from multi‐functional polyampholyte hydrogels
Authors: Haag Stephanie L. , Martinez‐Alvarez Jacquelin , Schiele Nathan R. , Bernards Matthew T. 
Published: July 2022

AbstractTissue engineered scaffolds are currently being explored to aid in healing and regeneration of non‐union fractures in bone. Additionally, albumin has been demonstrated to provide benefits to healing when applied to injury sites. This article focuses on delivery of calcium modified, bioactive bovine serum albumin (BSA) from a multi‐functional polyampholyte polymer scaffold. First, the inherent nonfouling and conjugation properties of the polyampholyte hydrogel were verified to determine the impact of calcium exposure. The polyampholyte hydrogel delivery platform was then assessed with calcium titrations and osteoblast‐like cell (MC3T3‐E1) adhesion, proliferation, and viability evaluations. Finally, integrin inhibitors were used to identify the binding mechanisms that mediate cell adhesion to the calcium‐modified BSA‐conjugated hydrogels. An increase in cell adhesion was observed following calcium exposure up to 0.075 M, although this and higher calcium concentrations affected hydrogel stability and cell growth. BSA exposed to 0.05 M calcium and delivered from polyampholyte hydrogels promoted the most promising viable cell adhesion over 7 days. Cell adhesion to the calcium‐modified BSA‐conjugated hydrogels appeared to be regulated by arginine‐glycine‐aspartic acid (RGD) and collagen‐specific integrins. These results demonstrate that the delivery of calcium modified BSA from an implantable polymer scaffold is promising for bone tissue engineering applications.
Shear and elongational rheometry for determination of spinnability window of polymer solutions in solution blow spinning
Authors: Wojasiński Michał , Ciach Tomasz 
Published: July 2022

AbstractRecently, processes for stable and efficient production of polymeric nano‐ and submicron fibrous materials, like solution blow spinning, have developed rapidly. However, the application of new polymers, synthetic or natural, for the fabrication of innovative fibrous materials still requires a trial‐and‐error approach to determine the spinnability window of polymer concentration in the solution. In this study, we investigated the use of shear and elongational rheometry to determine the spinnability window of polymer solutions of two synthetic polymers—poly‐L‐lactic acid (PLLA) and polyurethane (PU). Based on measured values of four polymer solution properties: density, surface tension, zero shear viscosity, and relaxation time, we calculated Ohnesorge (Oh) and Deborah (De) numbers corresponding to the polymer concentration ranges from 1 to 9%w/w for PLLA and 1–12%w/w for PU. After blow spinning each of the investigated solutions and using images from the scanning electron microscope and calculated values of Oh and De numbers, we determined the spinnability window for both polymers in the solution blow spinning process to be Oh >0.5, De/Oh >1, and Oh < 25.
Dynamic alterations of metabolites revealed the vascularization progression of bioengineered liver
Authors: Zhou Qian , Guo Beibei , Chen Deying , Yao Heng , Liang Xi , Xin Jiaojiao , Shi Dongyan , Ren Keke , Yang Hui , Jiang Jing , Li Jun 
Published: July 2022

AbstractVascularization is a critical but challenging process in developing functional bioengineered livers with the decellularized liver scaffolds (DLSs) and the process is accompanied by cell‐specific metabolic alterations. To elucidate the dynamic alterations of metabolites during vascularization, rat DLSs were vascularized with human umbilical vein endothelial cells and liquid chromatography mass spectrometry‐based metabolomics was performed on culture supernatants collected at 0, 1, 3, 7, 14, and 21 days. Overall, 1698 peak pairs or metabolites were detected in the culture supernatants, with 309 metabolites being positively identified. The orthogonal partial least‐squares discriminant analysis and functional enrichment analysis revealed three phases that could be clearly discriminated, including Phase D1 (cell proliferation and migration), Phase D3D7 (vascular lumen formation), and Phase D14D21 (functional endothelial barrier formation). Seventy‐two common differentially abundant metabolites of known identity were detected in these three phases when compared with Day 0. Of these metabolites, a high level of β‐Alanine indicated a better degree of vascularization and 14 days of in vitro dynamic culture is required to develop a functionalized vascular structure. These results enriched our understanding of the metabolic mechanism of DLS vascularization and indicated that β‐Alanine could function as a potential predictor of the patency of vascularized bioengineered livers.
Synthesis of New Cinnamoyl‐Amino Acid Conjugates and in Vitro Cytotoxicity and Genotoxicity Studies
Authors: Çalışkan Eray , Öztürk Dilara Altay , Koran Kenan , Tekin Suat , Sandal Süleyman , Erkan Sultan , Görgülü Ahmet Orhan , Çetin Ahmet 
Published: July 2022

AbstractAmino acid conjugates are described by the reaction of amino acids with bioactive organic groups such as vitamins, hormones, flavonoids, steroids, and sugars. In this study, 12 new conjugates were synthesized by reaction of cinnamic acid derivatives with various amino acids. Cytotoxic studies against four different human cancer cells (MCF7, PC‐3, Caco‐2, and A2780) were carried out by MTT assay method at five different concentrations. The structure‐activity relationships based on the cell viability rates were evaluated. To compare the anticancer activities of the compounds using computational chemistry methods, they were docked against A2780 human ovarian cancer, Michigan Cancer Foundation‐7 (MCF7), human prostate cancer (PC‐3) and human colon epidermal adenocarcinoma (Caco‐2) cell lines and compared with the standard 5‐Fluorouracil. The results indicate that the efficacy of cinnamic acid derivatives increases with the presence of amino acids. Comet assay was conducted to understand whether the cell deaths occur through DNA damage mechanism and the results exhibit that the changes in the specified parameters were statistically significant (p<0.05). Our study demonstrated that the compounds cause cell death through the formation of DNA damage mechanism.
Post‐Synthetic Modification of a Porous Hydrocarbon Cage to Give a Discrete Co24 Organometallic Complex**
Authors: Thomas Chriso M. , Liang Weibin , Preston Dan , Doonan Christian J. , White Nicholas G. 
Published: July 2022

AbstractA new alkyne‐based hydrocarbon cage was synthesized in high overall yield using alkyne‐alkyne coupling in the cage forming step. The cage is porous and displays a moderately high BET surface area (546 m2 g−1). The cage loses crystallinity on activation and thus is porous in its amorphous form, while very similar cages have been either non‐porous, or retained crystallinity on activation. Reaction of the cage with Co2(CO)8 results in exhaustive metalation of its 12 alkyne groups to give the Co24(CO)72 adduct of the cage in good yield.
Switching Chirophilic Self‐assembly: From meso‐structures to Conglomerates in Liquid and Liquid Crystalline Network Phases of Achiral Polycatenar Compounds
Authors: Alaasar Mohamed , Cao Yu , Liu Yan , Liu Feng , Tschierske Carsten 
Published: July 2022

AbstractSpontaneous generation of chirality from achiral molecules is a contemporary research topic with numerous implications for technological applications and for the understanding of the development of homogeneous chirality in biosystems. Herein, a series of azobenzene based rod‐like molecules with an 3,4,5‐trialkylated end and a single n‐alkyl chain involving 5 to 20 aliphatic carbons at the opposite end is reported. Depending on the chain length and temperature these achiral molecules self‐assemble into a series of liquid and liquid crystalline (LC) helical network phases. A chiral isotropic liquid (Iso1[*]) and a cubic triple network phase with chiral I23 lattice were found for the short chain compounds, whereas non‐cubic and achiral cubic phases dominate for the long chain compounds. Among them a mesoscale conglomerate with I23 lattice, a tetragonal phase (Tetbi) containing one chirality synchronized and one non‐synchronized achiral network, an achiral double network meso‐structure with Ia
d space group and an achiral percolated isotropic liquid mesophase (Iso1) were found. This sequence is attributed to an increasing strength of chirality synchronization between the networks, combined with a change of the preferred mode of chirophilic self‐assembly between the networks, switching from enantiophilic to enantiophobic with decreasing chain length and lowering temperature. These nanostructured and mirror symmetry broken LC phases exist over wide temperature ranges which is of interest for potential applications in chiral and photosensitive functional materials derived from achiral compounds.
Chemically Laminated 2D Bis(terpyridine)metal Polymer Films: Formation Mechanism at the Liquid–Liquid Interface and Redox Rectification
Authors: Komeda Joe , Takada Kenji , Maeda Hiroaki , Fukui Naoya , Tsuji Takuya , Nishihara Hiroshi 
Published: July 2022

AbstractInvited for the cover of this issue is the group of Hiroshi Nishihara at Tokyo University of Science. The image depicts the moment of the growth of the second layer at the liquid–liquid interface to form a heterolaminated film. Read the full text of the article at 10.1002/chem.202201316.
Goals of care documentation by medical oncologists and oncology patient end‐of‐life care outcomes
Authors: Epstein Andrew S. , Riley Michael , Nelson Judith E. , Bernal Camila , Martin Steven , Xiao Han 
Published: July 2022

BackgroundGoals of care (GOC) documentation is important but underused. We aimed to improve oncologist GOC documentation and end‐of‐life (EOL) care.MethodsIn April 2020, our cancer center launched a GOC note template, including optional fields for documenting discussion with the patient about: cancer natural history, goals, and/or EOL (resuscitation preferences, hospice receptivity). Associations between GOC notes and EOL care were evaluated.ResultsAmong 1721 patients dying between June 1, 2020 and June 30, 2021, median days from first GOC note (± with documentation of EOL discussion) to death was 92, whereas a GOC note including EOL discussion (“GOC EOL note”), specifically, was 31. Patients with a first GOC note >60 days before death spent fewer days inpatient (6.7 vs 10.6 days, p < .001). Among patients with GOC EOL notes, those with such documentation >30 days before death had fewer inpatient (5 vs 11, p < .001) and intensive care unit days (0.5 vs 1.5, p < .001), more hospice referrals (57% vs 44%, p = .003), and less chemotherapy ≤14 days before death (6% vs 11%, p = .010). Of 925 admissions of patients dying within ≤30 days, those with GOC EOL notes were shorter (7 vs 9 days, p = .013) but not associated with more hospice discharge (30% vs 25%, p = .163). Oncologist (vs nononcologist) GOC documentation and earlier documentation of EOL discussion were associated in subset analyses with less inpatient care and more hospice referrals.ConclusionsDocumentation of GOC, including EOL discussions, is associated with favorable performance on accepted indicators of quality EOL care.
High Mobility and ON/OFF Ratio of Solution‐Processable p‐Channel OFETs from Arylacetylene End‐Capped Alkoxyphenanthrenes
Authors: Balambiga Balu , Devibala Paneerselvam , Imran Predhanekar Mohamed , Bhuvanesh Nattamai S. P. , Nagarajan Samuthira 
Published: July 2022

AbstractNew arylacetylene end‐capped alkoxyphenanthrenes were synthesized and demonstrated as the best active layer for solution‐processable p‐channel organic field‐effect transistors. The alkoxy chain embedded compounds exhibited enhanced solubility and induced non‐covalent interactions resulting in effective molecular packing. The ′Lewis soft′ heteroatoms direct the most stable conformation with dihedral angles possible for molecular interactions, and energy levels. DFT studies supported the fine‐tuning of FMOs, with high HOMO levels ∼−5.2 eV ensuring a low barrier for charge injection. OFET devices exhibited a maximum charge carrier mobility up to 1.30 cm2/Vs with the highest ON/OFF ratio of 107. The strong π–π interactions and the crystallinity of the films are well supported by GIXRD and SEM analysis.
Thermally‐Activated Tunneling in the Two‐Water Bridge Catalyzed Tautomerization of Phosphinylidene Compounds**
Authors: Nandi Ashim , Martin Jan M. L. 
Published: July 2022

AbstractPhosphinylidenes are an important class of organophosphorus compounds that can exhibit tautomerization between tricoordinated P(III) hydroxide (R1R2POH) and a pentacoordinated P(V) oxide (R1R2P(O)H) form. Herein we show, using the canonical variational transition state theory combined with multidimensional small‐curvature tunneling approximation, the dominance of proton tunneling in the two‐water‐bridged tautomerizations of phosphinous acid and model phosphinylidenes comprising phosphosphinates, H‐phosphonates, H‐phosphinates and secondary phosphine oxides. Based on the studied system, the contribution of thermally‐activated tunneling is predicted to speed up the semiclassical reaction rate by ca. threefold to as large as two orders of magnitude at 298.15 K in the gas phase. The large KIE and the concavity in the Arrhenius plots are further fingerprints of tunneling. The simulations also predicted that the rapid tunneling rate and short half‐life span for the forward reaction, as opposed to the reverse reaction in fluorinated secondary phosphine oxides, would result in P(V) being elusive and only P(III) being isolable, which agrees with previous experiments where only P(III) was detected by IR and NMR spectroscopy. We also explored the role of solvent and predicted tunneling to be substantial.
Hydrazine Energy Storage: Displacing N2H4 from the Metal Coordination Sphere
Authors: McNeece Andrew J. , Jaroš Adam , Batista Enrique R. , Yang Ping , Scott Brian L. , Davis Benjamin L. 
Published: July 2022

AbstractHydrogen carriers, such as hydrazine (N2H4), may facilitate long duration energy storage, a vital component for resilient grids by enabling more renewable energy generation. Lanthanide coordination chemistry with N2H4 as well as efforts to displace N2H4 from the metal coordination sphere to develop an efficient catalytic production cycle were detailed. Modeling the equilibrium of different ligand coordination, it was predicted that strong sigma donor molecules would be required to displace N2H4. Monitoring competition experiments with nuclear magnetic resonance confirmed that trimethyl phosphine oxide, dimethylformamide, and dimethyl sulfoxide displaced N2H4 in large or small lanthanide complexes.
Mutually coupled circuits based on modified voltage differencing transconductance amplifier with tuneable characteristics
Authors: Petrović Predrag 
Published: July 2022

AbstractThe paper presents a new mutually coupled circuit (MCC) based on a modified voltage differencing transconductance amplifier (MVDTA), designed using the modified Gorski‐Popiel technique. The proposed synthetic transformer (ST) circuit uses two MVDTAs as active elements, and all passive elements are grounded—two capacitors and two resistors. Thanks to the newly established coupling method‐connections, it is provided with independent electronic control of primary and secondary self‐inductance, as well as mutual inductance, via bias voltages of MVDTAs. In addition, it is very easy to provide the conditions by which symmetrical couplings are achieved. Monte Carlo analysis is carried out to verify the example application's robustness against the variation of the active and passive elements. In order to verify the results and conclusions reached through theoretical analysis, simulation testing was performed in the PSPICE software environment, both in the time and frequency domains. The functionality of the proposed MCC is shown in the example of a double‐bandwidth filter (double‐tuned band‐pass filter [DTBP]), while in order to accurately illustrate the superiority of the proposed solution, a comparison was made with similar circuits that are known from the professional literature. The proposal is also supported by experimental results (with off‐the‐shelf components IC MAX435) in order to confirm the workability of the proposed solution.
Effects of steroidal mineralocorticoid receptor antagonists on acute and chronic estimated glomerular filtration rate slopes in patients with chronic heart failure
Authors: Vaduganathan Muthiah , Ferreira João Pedro , Rossignol Patrick , Neuen Brendon L. , Claggett Brian L. , Pfeffer Marc A. , McMurray John J.V. , Pitt Bertram , Zannad Faiez , Solomon Scott D. 
Published: July 2022

AbstractAimsSteroidal mineralocorticoid receptor antagonists (MRAs) form a cornerstone of the management of heart failure (HF), but little is known about the long‐term effects of MRA therapy on kidney function. We evaluated acute and chronic estimated glomerular function (eGFR) slopes in the two largest completed trials testing steroidal MRAs in chronic HF.Methods and resultsWe conducted parallel post hoc eGFR slope analyses in two multinational, double‐blind randomized, placebo‐controlled trials of steroidal MRAs in chronic HF with reduced ejection fraction (EMPHASIS‐HF) and preserved ejection fraction (TOPCAT Americas region). GFR was estimated using the Chronic Kidney Disease Epidemiology Collaboration equation. Annual slopes of eGFR were assessed by generalized random coefficient models. Least square mean differences in eGFR slopes between steroidal MRA and placebo arms were assessed. Median follow‐up was 1.8 years (EMPHASIS‐HF) and 3.3 years (TOPCAT Americas). From baseline to month 4–6 (‘acute eGFR slope’), compared to placebo, MRA treatment led to an acute decline in eGFR of −2.4 ml/min/1.73 m2 (95% confidence interval [CI] −3.4 to −1.4; p < 0.001) and −2.0 ml/min/1.73 m2 (95% CI −3.0 to −1.8; p < 0.001) in EMPHASIS‐HF and TOPCAT Americas, respectively. From month 4–6 to end of study, there was no difference in ‘chronic eGFR slope’ between MRA and placebo arms (−0.3 ml/min/1.73 m2/year [95% CI −1.3 to 0.7; p = 0.53] and 0.1 ml/min/1.73 m2/year [95% CI −1.4 to 1.7; p = 0.86]) in EMPHASIS‐HF and TOPCAT Americas, respectively.ConclusionsSteroidal MRAs result in acute declines in eGFR but do not modify long‐term kidney disease trajectories in chronic HF with reduced or preserved ejection fraction.Clinical Trial Registration: EMPHASIS‐HF (ClinicalTrials.gov NCT00232180) and TOPCAT (ClinicalTrials.gov NCT00094302).