bluuebunny/crossref_metadata_2025_split huggingface dataset:
LaOCl‐Coupled Polymeric Carbon Nitride for Overall Water Splitting through a One‐Photon Excitation Pathway
Authors: Lin Yuan , Su Wenyue , Wang Xuxu , Fu Xianzhi , Wang Xinchen 
Published: August 2020

AbstractIt is a challenge to explore photocatalytic materials for sunlight‐driven water splitting owing to the limited choice of a single semiconductor with suitable band energy levels but with a minimized band gap for light harvesting. Here, we report a one‐photon excitation pathway by coupling polymeric carbon nitride (PCN) semiconductor with LaOCl to achieve overall water splitting. This artificial photosynthesis composite catalyzes the decomposition of H2O into H2 and O2, with evolution rates of 22.3 and 10.7 μmol h−1, respectively. The high photocatalytic performance of PCN/LaOCl can be ascribed to the simultaneously accomplished reduction and oxidation of water on LaOCl and PCN domains, respectively, as well as the fast charge separation and migration induced by the interfacial electric field related to LaOCl modification. This study provides new insights on the development of composite photocatalysts for pure water splitting based on polymer‐based materials via charge modulation.
Damage and Repair in Informational Poly(N‐substituted urethane)s
Authors: Mondal Tathagata , Charles Laurence , Lutz Jean‐François 
Published: August 2020

AbstractThe degradation and repair of uniform sequence‐defined poly(N‐substituted urethane)s was studied. Polymers containing an ω‐OH end‐group and only ethyl carbamate main‐chain repeat units rapidly degrade in NaOH solution through an ω→α depolymerization mechanism with no apparent sign of random chain cleavage. The degradation mechanism is not notably affected by the nature of the side‐chain N‐substituents and took place for all studied sequences. On the other hand, depolymerization is significantly influenced by the molecular structure of the main‐chain repeat units. For instance, hexyl carbamate main‐chain motifs block unzipping and can therefore be used to control the degradation of specific sequence sections. Interestingly, the partially degraded polymers can also be repaired; for example by using a combination of N,N′‐disuccinimidyl carbonate with a secondary amine building‐block. Overall, these findings open up interesting new avenues for chain‐healing and sequence editing.
Enantiospecific Solid Solution Formation Triggers the Propagation of Homochirality
Authors: Baglai Iaroslav , Leeman Michel , Wurst Klaus , Kellogg Richard M. , Noorduin Willem L. 
Published: August 2020

AbstractPropagation of homochirality plays a crucial role in the discussion on the origin of life. We investigated the role of structurally related enantiopure additives in chiral symmetry breaking during reactive crystallizations. We demonstrate that symmetry breaking can be driven towards the same absolute configuration as the additive if this additive forms an enantiospecific solid solution with the racemate. We observe two antagonistic processes: enantiospecific growth inhibition directs symmetry breaking to the opposite enantiomer following “the rule of reversal”, and enantiospecific solid solution formation that favors homochiral outcome. During continuous grinding, contributions of solid solution formation override contributions of enantiospecific growth inhibition, directing the process towards the absolute configuration of the additive. Collectively, our findings offer a potential mechanism for the propagation of homochirality.
A Robust Mixed‐Lanthanide PolyMOF Membrane for Ratiometric Temperature Sensing
Authors: Feng Tongtong , Ye Yingxiang , Liu Xiao , Cui Hui , Li Zhiqiang , Zhang Ying , Liang Bin , Li Huanrong , Chen Banglin 
Published: August 2020

AbstractTemperature sensors play a significant role in biology, chemistry, and engineering, especially those that can work accurately in a noninvasive manner. We adopted a photoinduced post‐synthetic copolymerization strategy to realize a membranous ratiometric luminescent thermometer based on the emissions of two lanthanide ions. This novel mixed‐lanthanide polyMOF membrane exhibits not only the integrity and temperature sensing behaviour of the Ln‐MOF powder but also excellent mechanical properties, such as flexibility, elasticity, and processability. Moreover, the polyMOF membrane shows remarkable stability under harsh conditions, including high humidity, strong acid and alkali (pH 0–14), which allowed the mapping of temperature distributions in extreme circumstances. This work highlights a simple strategy for polyMOF membrane formation and pushes forward the further practical application of Ln‐MOF‐based luminescent thermometers in various fields and conditions.
Duale Emission: Klassen, Mechanismen und Bedingungen
Authors: Behera Santosh Kumar , Park Soo Young , Gierschner Johannes 
Published: August 2020

AbstractDual emittierende (DE‐)Verbindungen finden starkes Interesse in den Material‐ and Biowissenschaften; allerdings fehlt eine systematische Zusammenfassung der zugrundeliegenden Prozesse. Diese erfolgt hier durch eine Klassifizierung der DE‐Phänomene, wobei zwischen Prozessen unterschieden wird, die einerseits auf nur einem Emitter mit zwei emittierenden Zuständen oder andererseits auf zwei unbhängigen Emittern oder zwei korrelierten Emittern beruhen. Danach werden die für die Materialwissenschaften relevanten DE‐Mechnismen beschrieben, wobei die elektronischen und geometrischen Bedingungen herausgearbeitet werden, unter denen sie erfolgen; die weiterführende Literatur, auf die verwiesen wird, soll einen genaueren Einblick in die mechanistischen Aspekte der DE‐Prozesse und einen Überblick über die Substanzklassen und ihre Anwendungen geben. Indem Zweideutigkeiten vermieden werden und auf Fehlinterpretationen hingewiesen wird, mag diese Übersicht die weitere gezielte Entwicklung von DE‐Materialien fördern.
Ein einfach koordiniertes Silizium(II)‐Kation: Ein kristallines “Supersilylen”
Authors: Hinz Alexander 
Published: August 2020

AbstractEinfach koordinierte Silizium(II)‐Kationen werden als reaktive Ambiphile angesehen, die die typische hohe Lewis‐Acidität von Siliziumkationen mit Nucleophilie durch die Gegenwart eines freien Elektronenpaars am selben Atom vereinigen. Nun wurde ein Carbazolderivat als Substituent genutzt, um Salze mit einem einfach koordinierten Silizium(II)‐Kation [RSi]+, (R=sterisch anspruchsvoller Carbazolylsubstituent), durch Halogenidabstraktion von einem basenfreien Iodosilylen mit Ag[Al(OtBuF)4] darzustellen. Trotz der sterischen Abschirmung beweist das Silylenyliumkation [RSi]+ hohe Reaktivität. Es wurde gezeigt, dass durch Umsetzung mit einem Amin drei Bindungen am Siliziumatom in einer Reaktion gebildet werden können, was mit dem Konzept eines “Supersilylens” einhergeht. Das so durch oxidative Addition einer NH‐Bindung an [RSi]+ erhaltene Silyliumion [RSi(H)NR′2]+ (in der Oxidationsstufe SiIV) ist noch acider als das Silylenyliumion (SiII), da kein freies Elektronenpaar am Siliziumatom mehr vorhanden ist.
Hydroxamic Acids Immobilized on Resins (HAIRs): Synthesis of Dual‐Targeting HDAC Inhibitors and HDAC Degraders (PROTACs)
Authors: Sinatra Laura , Bandolik Jan J. , Roatsch Martin , Sönnichsen Melf , Schoeder Clara T. , Hamacher Alexandra , Schöler Andrea , Borkhardt Arndt , Meiler Jens , Bhatia Sanil , Kassack Matthias U. , Hansen Finn K. 
Published: August 2020

AbstractInhibition of more than one cancer‐related pathway by multi‐target agents is an emerging approach in modern anticancer drug discovery. Here, based on the well‐established synergy between histone deacetylase inhibitors (HDACi) and alkylating agents, we present the discovery of a series of alkylating HDACi using a pharmacophore‐linking strategy. For the parallel synthesis of the target compounds, we developed an efficient solid‐phase‐supported protocol using hydroxamic acids immobilized on resins (HAIRs) as stable and versatile building blocks for the preparation of functionalized HDACi. The most promising compound, 3 n, was significantly more active in apoptosis induction, activation of caspase 3/7, and formation of DNA damage (γ‐H2AX) than the sum of the activities of either active principle alone. Furthermore, to demonstrate the utility of our preloaded resins, the HAIR approach was successfully extended to the synthesis of a proof‐of‐concept proteolysis‐targeting chimera (PROTAC), which efficiently degrades histone deacetylases.
Dual Emission: Classes, Mechanisms, and Conditions
Authors: Behera Santosh Kumar , Park Soo Young , Gierschner Johannes 
Published: August 2020

AbstractThere has been much interest in dual‐emission materials in the past few years for materials and life science applications; however, a systematic overview of the underlying processes is so‐far missing. We resolve this issue herein by classifying dual‐emission (DE) phenomena as relying on one emitter with two emitting states (DE1), two independent emitters (DE2), or two correlated emitters (DE3). Relevant DE mechanisms for materials science are then briefly described together with the electronic and/or geometrical conditions under which they occur. For further reading, references are given that offer detailed insight into the complex mechanistic aspects of the various DE processes or provide overviews on materials families or their applications. By avoiding ambiguities and misinterpretations, this systematic, insightful Review might inspire future targeted designs of DE materials.
A Mono‐Substituted Silicon(II) Cation: A Crystalline “Supersilylene”
Authors: Hinz Alexander 
Published: August 2020

AbstractMono‐coordinated silicon(II) cations are predicted to be reactive ambiphiles, combining the typically high Lewis acidity of silicon cations with nucleophilicity due to the presence of an electron pair at the same atomic centre. Here, a carbazole‐derived scaffold was used to isolate salts with a mono‐coordinated silicon(II) cation, [RSi]+ (R=bulky carbazolyl substituent), by halide abstraction from a base‐free halosilylene, RSiI, with Ag[Al(OtBuF)4]. Despite the bulk of the carbazolyl moiety, the silylenylium cation [RSi]+ retains high reactivity. It was shown to react with an amine to form three bonds at the silicon atom in one reaction which conforms with the notion of a “supersilylene”. The resulting silylium cation [RSi(H)NR′2]+ (in the formal oxidation state SiIV) obtained by oxidative addition of an NH bond at [RSi]+ is even more acidic than the silylenylium cation (SiII) due to the absence of a lone pair of electrons the silicon atom.
Screening of Bombyx mori brain proteins interacting with protein tyrosine phosphatase of BmNPV
Authors: Wang Guobao , Na Shuang , Qin Li 
Published: August 2020

AbstractIn this study, glutathione‐S‐transferase pull‐down combined with mass spectrometry techniques were used to identify the candidate proteins interacting with protein tyrosine phosphatase of the Bombyx Mori nucleopolyhedrovirus in the B. mori (BmNPV‐PTP) brain. A total of 36 proteins were identified from BmNPV‐PTP coprecipitate samples by searching the NCBI_Bombyx Mori database with the original mass spectrum data. Among those proteins, the interaction between BmNPV‐PTP and B. mori cyclophilin A may accelerate the apoptosis of certain nerve cells involved in regulating behavior, and thus may be an inducer of enhanced locomotor activity (ELA). After the BmNPV invasion, BmNPV‐PTP binding to peripheral‐type benzodiazepine receptors may initiate a series of abnormal cascades of the nervous system, which results in abnormal hyperactive behavior in B. mori. Besides this, vacuolar ATP synthase catalytic subunit A, annexin, and several enzymes for energy conversion were identified, which may play a role in enhancing viral entry and infectivity and provide energy for enhancing the locomotor activity of B. mori. In general, the results of this study will facilitate the understanding of the molecular mechanisms underlying the ELA of B. mori larva induced by BmNPV.
Synthesis of novel 4,5‐dihydropyrrolo[1,2‐a]quinoxalines, pyrrolo[1,2‐a]quinoxalin]‐2‐ones and their antituberculosis and anticancer activity
Authors: Makane Vitthal B. , Vamshi Krishna Eruva , Karale Uattam B. , Babar Dattatraya A. , Kalari Saradhi , Rekha Estharla M. , Shukla Manjulika , Kaul Grace , Sriram Dharmarajan , Chopra Sidharth , Misra Sunil , Rode Haridas B. 
Published: August 2020

AbstractA facile strategy was developed for the synthesis of biologically important 4,5‐dihydropyrrolo[1,2‐a]quinoxalines and pyrrolo[1,2‐a]quinoxalin]‐2‐ones by treating 2‐(1H‐pyrrol‐1‐yl)anilines with imidazo[1,2‐a]pyridine‐3‐carbaldehyde or isatin, using amidosulfonic acid (NH3SO3) as a solid catalyst in water at room temperature. The protocol has been extended to electrophile ninhydrin. The catalyst could be recycled for six times without the loss of activity. The compounds were evaluated for their antituberculosis, antibacterial, and anticancer activities. It is worth noting that compounds 3d and 3e demonstrated a minimum inhibitory concentration value of 6.25 µM against Mycobacterium tuberculosis H37Rv, whereas compounds 3d, 3g, 5d, 5e, and 5i showed a remarkable inhibition of A549, DU145, HeLa, HepG2, MCF‐7, and B16‐F10 cell lines, respectively. Staphylococcus aureus was inhibited by compounds 5b, 5e, 5d, 5g, and 5l at 32 µg/ml.
Phase II Open Label Study of Anakinra in Intravenous Immunoglobulin–Resistant Kawasaki Disease
Authors: Koné‐Paut Isabelle , Tellier Stéphanie , Belot Alexandre , Brochard Karine , Guitton Corinne , Marie Isabelle , Meinzer Ulrich , Cherqaoui Bilade , Galeotti Caroline , Boukhedouni Nadja , Agostini Helene , Arditi Moshe , Lambert Virginie , Piedvache Céline 
Published: August 2020

ObjectiveAnakinra has been shown to be successful in preventing and treating cardiovascular lesions both in experimental murine models of Kawasaki disease (KD) and in several studies on intravenous immunoglobulin (IVIG)– and steroid‐resistant patients with KD. This study was undertaken to determine the safety of blocking interleukin‐1 in patients with IVIG‐resistant KD.MethodsSixteen patients were included in the present study. Patients with KD who were not responsive to 1 or more courses of 2 mg/kg of IVIG received anakinra by subcutaneous daily injections. Starting doses were 2 mg/kg of IVIG (4 mg/kg in patients who were age <8 months and who weighed ≥5 kilograms), and the dose was increased up to 6 mg/kg every 24 hours if the patient’s body temperature remained >38°C, indicative of a fever. Treatment duration was 14 days. The last visit was on day 45. Primary outcome was abatement of fever. Secondary measures included disease activity, coronary artery Z score, and C‐reactive protein (CRP) levels.ResultsSeventy‐five percent of patients in the intention‐to‐treat group and 87.5% in the per‐protocol group became afebrile within 48 hours of the last escalation dose of anakinra. Reduction of disease activity by 50% was indicated on 93.3% (95% confidence interval [95% CI] 68.1–99.8%) of physician evaluations and on 100% (95% CI 73.5–100%) of parent evaluations. CRP values normalized by day 30. At the initial screening, 12 of 16 patients had a maximum coronary artery Z score of >2, and 10 of 16 patients had a maximum Z score of >2.5. At day 45, 5 of 10 patients (50% [95% CI 18.7–81.3%]) and 6 of 12 patients (50% [95% CI 21.1–78.9%]) had achieved coronary artery Z scores of <2.5 and <2, respectively. Five serious adverse events were observed in 3 patients, but no serious infections or deaths occurred.ConclusionAnakinra was well tolerated in the study patients and may have some efficacy in reducing fever, markers of systemic inflammation, and coronary artery dilatation in individuals with IVIG‐refractory KD.
Synergistic Roles of Macrophages and Neutrophils in Osteoarthritis Progression
Authors: Hsueh Ming‐Feng , Zhang Xin , Wellman Samuel S. , Bolognesi Michael P. , Kraus Virginia B. 
Published: August 2020

ObjectiveTo evaluate the role of immune cells and their effector cytokines in the pathogenesis and progression of knee osteoarthritis (OA) in matched OA synovial fluid (SF) and synovial tissue samples.MethodsCells from matched samples of synovial tissue and SF acquired from individuals undergoing total knee replacement for OA (n = 39) were characterized for immune cell–associated surface markers and intracellular cytokine expression using polychromatic flow cytometry. Additional individuals with radiographic knee OA (Kellgren/Lawrence severity grades ≥1) who had available etarfolatide (inflammatory cell) imaging (n = 26) or baseline and 3‐year data on progression of radiographic knee OA (n = 85) were also assessed. SF cytokine concentrations in all cohorts were evaluated for associations with synovial tissue and SF cell phenotypes and severity of radiographic knee OA.ResultsMacrophages (predominant in the synovial tissue, 53% of total cells) and neutrophils (predominant in the SF, 26% of total cells) were the major immune cell populations identified in the OA knee joints, exhibiting expression of or association with transforming growth factor β1 (TGFβ1) and elastase, respectively, in the SF. Expression levels of TGFβ1 and elastase were significantly associated with severity of radiographic knee OA. Baseline SF concentrations of TGFβ1 and elastase along with radiographic knee OA severity scores were predictive of knee OA progression, with areas under the receiver operating characteristic curves of 0.810 (for TGFβ1), 0.806 (for elastase), and 0.846 (for both TGFβ1 and elastase combined), with greater stability of prediction when both markers were utilized.ConclusionOur findings demonstrate the hitherto underappreciated role of neutrophils in the sterile inflammatory process and progression of OA. Two soluble mediators, SF elastase and TGFβ1, are strong predictors of knee OA progression, reflecting a synergistic role of neutrophil and macrophage populations in the pathogenesis and worsening of OA that could potentially be utilized to identify patients who may have a greater risk of more rapid disease progression.
Tapering Canakinumab Monotherapy in Patients With Systemic Juvenile Idiopathic Arthritis in Clinical Remission: Results From a Phase IIIb/IV Open‐Label, Randomized Study
Authors: Quartier Pierre , Alexeeva Ekaterina , Constantin Tamàs , Chasnyk Vyacheslav , Wulffraat Nico , Palmblad Karin , Wouters Carine , I. Brunner Hermine , Marzan Katherine , Schneider Rayfel , Horneff Gerd , Martini Alberto , Anton Jordi , Wei Xiaoling , Slade Alan , Ruperto Nicolino , Abrams Ken ,   the Paediatric Rheumatology International Trials Organisation and the Pediatric Rheumatology Collaborative Study Group
Published: August 2020

ObjectiveTo evaluate the efficacy and safety of 2 canakinumab monotherapy tapering regimens in order to maintain complete clinical remission in children with systemic juvenile idiopathic arthritis (JIA).MethodsThe study was designed as a 2‐part phase IIIb/IV open‐label, randomized trial. In the first part, patients received 4 mg/kg of canakinumab subcutaneously every 4 weeks and discontinued glucocorticoids and/or methotrexate as appropriate. Patients in whom clinical remission was achieved (inactive disease for at least 24 weeks) with canakinumab monotherapy were entered into the second part of the trial, in which they were randomized 1:1 into 1 of 2 treatment arms. In arm 1, the dose of canakinumab was reduced from 4 mg/kg to 2 mg/kg and then to 1 mg/kg, followed by discontinuation. In arm 2, the 4 mg/kg dose interval was prolonged from every 4 weeks, to every 8 weeks, and then to every 12 weeks, followed by discontinuation. In both arms, canakinumab exposure could be reduced provided systemic JIA remained in clinical remission for 24 weeks with each step. The primary objective was to assess whether >40% of randomized patients in either arm maintained clinical remission of systemic JIA for 24 weeks in the first part of the study.ResultsIn part 1 of the study, 182 patients were enrolled, with 75 of those patients randomized before entering part 2 of the trial. Among the 75 randomized patients, clinical remission was maintained for 24 weeks in 27 (71%) of 38 patients in arm 1 (2 mg/kg every 4 weeks) and 31 (84%) of 37 patients in arm 2 (4 mg/kg every 8 weeks) (P ≤ 0.0001 for arm 1 versus arm 2 among those meeting the 40% threshold). Overall, 25 (33%) of 75 patients discontinued canakinumab, and clinical remission was maintained for at least 24 weeks in all 25 of these patients. No new safety signals were identified.ConclusionReduction of canakinumab exposure may be feasible in patients who have achieved clinical remission of systemic JIA, but consistent interleukin‐1 inhibition appears necessary to maintain this response.
A Diaminodiacid (DADA) Strategy for the Development of Disulfide Surrogate Peptides
Authors: Qi Yun‐Kun , Qu Qian , Bierer Donald , Liu Lei 
Published: August 2020

AbstractDisulfide bond‐containing peptides are useful molecular scaffolds with diagnostic and therapeutic applications due to their good biological activity and good target selectivity, but their utility is sometimes limited by the lability of the disulfide moiety under reducing conditions and in the presence of disulfide bond isomerase. The development of disulfide surrogates with improved redox stability has been an area of ongoing research; and one possible strategy is based on a diaminodiacid (DADA) moiety, which can be used to synthesize the disulfide bond replacement peptides with precise structures and enhanced stability through automated solid‐phase peptide synthesis (SPPS). This review summarizes recent developments in the DADA‐based SPPS of peptide disulfide surrogates. Some representative applications and structural studies on the DADA‐based disulfide surrogates are described.
Sequestering Ability of a Synthetic Chelating Agent towards Copper(II) and Iron(III): A Detailed Theoretical and Experimental Analysis
Authors: Ritacca Alessandra G. , Malacaria Luana , Algieri Vincenzo , De Nino Antonio , Russo Nino , Furia Emilia , Maiuolo Loredana , Sicilia Emilia 
Published: August 2020

AbstractIn the continuous effort to identify selective chelators towards bioavailable and toxic metal ions, the potential selectivity of a novel N,O chelating ligand, recently synthesized and claimed to be able to bind to Cu(II) ions forming stable complexes while leaving unaltered the level of essential metal ions, was scrutinized using a combined theoretical and experimental approach. A multistep synthetic procedure was used to synthesize the ligand, whose chelating properties along with the stability of the complexes formed binding Cu(II) and, for comparison, Fe(III) ions were evaluated using potentiometric measurements and UV‐Vis spectroscopy. DFT analysis allowed to disclose the structural characteristics of the formed complexes. In the plethora of all the possible structures, a selection of the most reliable ones was achieved by means of a stringent comparison between experimental and simulated UV‐Vis spectra. The outcomes of the present investigation demonstrate that the Cu(II) sequestering ability of the ligand is smaller than that towards Fe(III). The strategy used here should allow to check the propensity of ligands in selectively binding metal ions.