bluuebunny/crossref_metadata_2025_split huggingface dataset:
Molecular Oligothiophene–Fullerene Dyad Reaching Over 5% Efficiency in Single‐Material Organic Solar Cells
Authors: Aubele Anna , He Yakun , Kraus Teresa , Li Ning , Mena‐Osteritz Elena , Weitz Paul , Heumüller Thomas , Zhang Kaicheng , Brabec Christoph J. , Bäuerle Peter 
Published: August 2021

AbstractA novel donor–acceptor dyad, 4, in which the conjugated oligothiophene donor is covalently connected to fullerene PC71BM by a flexible alkyl ester linker, is synthesized and applied as photoactive layer in solution‐processed single‐material organic solar cells (SMOSCs). Excellent photovoltaic performance, including a high short‐circuit current density (JSC) of 13.56 mA cm−2, is achieved, leading to a power conversion efficiency of 5.34% in an inverted cell architecture, which is substantially increased compared to other molecular single materials. Furthermore, dyad 4‐based SMOSCs display excellent stability maintaining 96% of the initial performance after 750 h (one month) of continuous illumination and operation under simulated AM 1.5G irradiation. These results will strengthen the rational molecular design to further develop SMOSCs for potential industrial application.
A Topological Stitching Strategy for Biocompatible Wet Adhesion Using Mussel‐Inspired Polyurethane
Authors: Chen Buyun , Lei Kun , Zhu Dandan , Yang Chongchong , Sun Chengyuan , Xiao Wei , Zheng Zhen , Wang Xinling 
Published: August 2021

AbstractThe biomedical and surgical applications of hydrogels demand effective methods to adhere hydrogels to diverse substrates including living tissues. Here a mussel mimetic polyurethane as topological suture material for tough adhesion of hydrogels by introducing catechol moieties into polymer chains is presented. Solution of the stitching polyurethane can be injected onto the surface of a hydrogel, followed by diffusing spontaneously into the hydrogel, then get triggered by oxidant for in situ gelation. Oxidative cross‐linkage of catechol‐modified polyurethane after penetration into hydrogels or living tissues can establish enough covalently entangled networks to afford desired adhesion strength. The mussel mimetic polyurethane demonstrates excellent adhesion strength of hydrogels to versatile substrates including inorganics, polymers, and biomaterials, with no requirements for specific functional groups or chemical modification. The adhesion energy achieved by the topological stitching strategy can reach up to 350 J m−2. Moreover, the stitching polymer shows potential for debonding under the catalysis of elastase. This work will possibly become a promising strategy candidate for adhesion in wet environments.
Ultrastrong Spontaneous Surface Wetting of Room Temperature Liquid Metal on Treated Metal Surface
Authors: Lin Weiguang , Qiu Wangkang , Tuersun Yisimayili , Huang Xu , Chu Sheng 
Published: August 2021

AbstractThe low melting gallium‐based liquid metal (LM) is showing tremendous potential in many technologies due to its unique properties. However, the high surface tensions as well as oxidations result in poor wetting capability on most solid surfaces, which limits its practical application. In this work, a simple chemical method is utilized to enable spontaneous wetting of LM on various metal surfaces, such as copper, nickel, and iron. It is found that LM can spread rapidly on the metal substrates treated with CuCl2 solution through reactive‐wetting and metallic bond‐enabled wetting mechanism. The redox reaction between Ga and copper compound and the formation of intermetallic compound via LM phagocytosis help drive LM to wet metal substrates spontaneously. Many factors affecting the wetting behaviors of LM, including surface roughness, crystal size, and ambient environment, are systematically studied. This finding provides a novel strategy to solve the wetting problem of LM and will enable wider applications.
2D Organic Radical Conjugated Skeletons with Paramagnetic Behaviors
Authors: Li Hao , Zhang Weifeng , Xu Jie , Cai Le , Yu Zhiwei , Ma Tianbao , Zheng Yuanhui , Wang Liping , Yu Gui 
Published: August 2021

Abstract2D conjugated polymers (2D CPs) with high crystallinity and proper bandgaps have attracted much attention. However, the development of magnetic 2D CPs still remains a challenge. It is urgently needed to develop graphene‐like 2D CPs with tunable structural properties under relatively mild reaction conditions. Herein, two 2D CPs (TAPA‐HKH and HAB‐HKH) with fused rings bridged by pyrazine are synthesized by reacting 2,3,7,8‐tetraaminephenazine (TAPA) and 1,2,3,4,5,6‐hexaaminebenzene (HAB) with hexaketocyclohexane octahydrate (HKH), respectively. Both the TAPA‐HKH and HAB‐HKH have nanoporous graphene‐like skeletons with unique N‐embedded zigzag edges. Moreover, few‐layer nanosheets of the 2D CPs are further obtained by liquid‐phase exfoliation. The magnetic properties and radical characteristics of the TAPA‐HKH and HAB‐HKH nanosheets are further studied by superconducting quantum interference device magnetometer and electron spin resonance spectroscopy, respectively. At 2 K, the saturation magnetizations of the TAPA‐HKH and HAB‐HKH nanosheets reach up to 0.30 and 0.10 emu g−1, respectively. In addition, TAPA‐HKH nanosheets even show a high localized spin magnetic moments of 12.4 μB in 1000 nitrogen atoms. The intrinsic magnetism of TAPA‐HKH and HAB‐HKH nanosheets can be attributed to the highly stable radicals, nanoporous structures, and N‐doped zigzag edges existing in their graphene‐like skeletons.
Green and Fire Resistant Nanocellulose/Hemicellulose/Clay Foams
Authors: Carosio Federico , Medina Lilian , Kochumalayil Joby , Berglund Lars A. 
Published: August 2021

AbstractLightweight polymer foams from synthetic polymers are commonly used in a wide‐spread spectrum of application fields. Their intrinsic flammability coupled with restrictions on flame retardant chemicals poses a severe threat to safety. Here, fire resistant foams comprising biobased components capable of replacing petroleum‐based foams are investigated. Cellulose nanofibers are combined with 2D montmorillonite nanoplatelets and a native xyloglucan hemicellulose binder, using a water‐based freeze casting approach. Due to the silicate nanoplatelets, these lightweight foams self‐extinguish the flame during flammability tests. The limiting oxygen index is as high as 31.5% and in the same range as the best fire‐retardant synthetic foams available. In cone calorimetry, the foams display extremely low combustion rates. Smoke release is near the detection limit of the instrument. In addition, the foams are withstanding the penetration of a flame torch focused on one side of the specimen (Ton surface 800 °C) and structural integrity is maintained. At the same time, the unexposed side is insulated, as demonstrated by a through‐thickness temperature drop of 680 °C cm−1. The results represent a tremendous opportunity for the development of fire‐safe foams combining excellent sustainability with multifunctional performance.
Mechanochemistry Enabled Construction of Isoxazole Skeleton via CuO Nanoparticles Catalyzed Intermolecular Dehydrohalogenative Annulation
Authors: Vadivelu Murugan , Sampath Sugirdha , Muthu Kesavan , Karthikeyan Kesavan , Praveen Chandrasekar 
Published: August 2021

AbstractA dehydrohalogenative approach for isoxazole annulation by partnering β‐vinyl halides and α‐nitrocarbonyls under mechanochemical setting was accomplished. This chemistry is operative under the cooperative catalysis of cupric oxide nanoparticles (<50 nm) and DABCO. The key beneficial aspects of this protocol include: (i) broad substrate scope, (ii) no vigorous work‐up, (iii) short reaction time, (iv) solvent‐free condition, (v) commercial viability of substrates/reagents (vi) good chemical yields and selectivity. The other merit of this chemistry is the ease with which CuO can be recuperated and reused after the reaction with not much drop in catalytic activity for six runs. With no confinement to β‐vinyl halides, the validated condition is also open to alkynes for isoxazole preparation, thereby establishing the broader utility of the current methodology.magnified image
Cytogenetic and molecular abnormalities in Waldenström's macroglobulinemia patients: Correlations and prognostic impact
Authors: Krzisch Daphné , Guedes Nayara , Boccon‐Gibod Clémentine , Baron Marine , Bravetti Clotilde , Davi Frédéric , Armand Marine , Smagghe Luce , Caron Jonathan , Bernard Olivier A. , Susin Santos , Chapiro Elise , Leblond Véronique , Nguyen‐Khac Florence , Roos‐Weil Damien ,   on behalf the FILO (French Innovative Leukemia Organization) group
Published: August 2021

AbstractWhile Waldenström macroglobulinemia (WM) is characterized by an almost unifying mutation in MYD88, clinical presentation at diagnosis and response to therapy can be widely different among WM patients. Current prognostic tools only partially address this clinical heterogeneity. Limited data compiling both molecular and cytogenetic information have been used in risk prognostication in WM. To investigate the clinical impact of genetic alterations in WM, we evaluated cytogenetic and molecular abnormalities by chromosome banding analyses, FISH and targeted NGS in a retrospective cohort of 239 WM patients, including 187 patients treated by first‐line chemotherapy or immunochemotherapy. Most frequent mutations were identified in MYD88 (93%), CXCR4 (29%), MLL2 (11%), ARID1A (8%), TP53 (8%), CD79A/B (6%), TBL1XR1 (4%) and SPI1 (4%). The median number of cytogenetic abnormalities was two (range, 0–22). Main cytogenetic abnormalities were 6q deletion (del6q) (27%), trisomy 4 (tri4) (12%), tri18 (11%), del13q (11%), tri12 (7.5%) and del17p (7%). Complex karyotype (CK) was observed in 15% (n = 31) of cases, including 5% (n = 12) of highly CK (high‐CK). TP53 abnormalities (TP53abn) were present in 15% of evaluable patients. TP53abn and del6q were associated with CK/high‐CK (p < .05). Fifty‐three percent of patients with hyperviscosity harbored CXCR4 mutations. Cytogenetic and molecular abnormalities did not significantly impact time to first treatment and response to therapy. Prognostic factors associated with shorter PFS were del6q (p = .01), TP53abn (p = .002) and high‐CK (p = .01). These same factors as well as IPSSWM, tri4, CXCR4 frameshift and SPI1 mutations were significantly associated with lower OS (p < .05). These results argue for integration of both cytogenetic and molecular screening in evaluation of first‐line WM patients.
Exploring the impacts of the COVID‐19 crisis for the employment prospects of refugees and people seeking asylum in Australia
Authors: Cooney‐O'Donoghue Diarmuid , Adamovic Mladen , Sojo Victor 
Published: August 2021

AbstractAs recent research indicates, refugees and people seeking asylum are suffering disproportionately from the COVID‐19 pandemic and have become more and more “shut out” and marginalised. An important pathway to integration and self‐reliance is sustainable employment. To explore the impacts of COVID‐19 on the employment prospects of refugees and people seeking asylum, we conducted 35 interviews with managers from Australian organisations that employ or assist refugees and asylum seekers in finding employment and 20 interviews with refugees and people seeking asylum. Our interviews indicate that the labour market has become more difficult for these groups in the COVID‐19 era due to (1) declines in job availabilities, (2) loss of jobs, (3) increased competition in the labour market and (4) increased discrimination and an “Australian first” mentality. Our interviews further suggest four strategies to improve employment prospects in the current situation: (1) pathways to permanent residency and citizenship for people seeking asylum; (2) access to healthcare and a financial safety net; (3) online training and education; and (4) social procurement.
Oxyenamide als vielseitige Bausteine für eine hochgradig stereoselektive Eintopf‐Synthese der 1,3‐Diamino‐2‐ol‐Einheit mit drei fortlaufenden Stereozentren
Authors: Krieg Sara‐Cathrin , Grimmer Jennifer , Kramer Philipp , Bolte Michael , Kelm Harald , Manolikakes Georg 
Published: August 2021

AbstractEs wird eine hochgradig diastereoselektive Eintopf‐Synthese der 1,3‐Diamino‐2‐Alkohol‐Einheit mit drei fortlaufenden Stereozentren beschrieben. Bei dieser Methode werden 2‐Oxyenamide als neue Bausteine für den raschen Aufbau des 1,3‐Diamin‐Gerüsts, mit einer zusätzlichen stereogenen Sauerstofffunktionalität in C2‐Position, eingesetzt. Zusätzlich wird über eine stereoselektive Synthese der erforderlichen (Z)‐Oxyenamide berichtet.
Oxyenamides as Versatile Building Blocks for a Highly Stereoselective One‐Pot Synthesis of the 1,3‐Diamino‐2‐ol‐Scaffold Containing Three Continuous Stereocenters
Authors: Krieg Sara‐Cathrin , Grimmer Jennifer , Kramer Philipp , Bolte Michael , Kelm Harald , Manolikakes Georg 
Published: August 2021

AbstractA highly diastereoselective one‐pot synthesis of the 1,3‐diamino‐2‐alcohol unit bearing three continuous stereocenters is described. This method utilizes 2‐oxyenamides as a novel type of building block for the rapid assembly of the 1,3‐diamine scaffold containing an additional stereogenic oxygen functionality at the C2 position. A stereoselective preparation of the required (Z)‐oxyenamides is reported as well.
Isolable Geminal Bisgermenolates: A New Synthon in Organometallic Chemistry
Authors: Drusgala Manfred , Frühwirt Philipp , Glotz Gabriel , Hogrefe Katharina , Torvisco Ana , Fischer Roland C. , Wilkening H. Martin R. , Kelterer Anne‐Marie , Gescheidt Georg , Haas Michael 
Published: August 2021

AbstractWe have synthesized the first isolable geminal bisenolates L2K2Ge[(CO)R]2 (R=2,4,6‐trimethylphenyl (2 a,b), L=THF for (2 a) or [18]‐crown‐6 for (2 b)), a new synthon for the synthesis of organometallic reagents. The formation of these derivatives was confirmed by NMR spectroscopy and X‐ray crystallographic analysis. The UV/Vis spectra of these anions show three distinct bands, which were assigned by DFT calculations. The efficiency of 2 a,b to serve as new building block in macromolecular chemistry is demonstrated by the reactions with two different types of electrophiles (acid chlorides and alkyl halides). In all cases the salt metathesis reaction gave rise to novel Ge‐based photoinitiators in good yields.
Preparation of poly(lactic acid) with excellent comprehensive properties via simple deformation or microfibrillation of spherulites
Authors: Xiang Pei , Fan Lijun , Li Shen , Cao Nuo , Wan Chao , Bi Siwen , Chen Xuhang , Yu Peng 
Published: August 2021

AbstractOur work overcomes the long‐standing challenge to achieve comprehensive improvements in thermo/mechanical properties of poly(lactic acid) (PLA), especially for impact toughness, strength, ductility, stiffness, and heat resistance. Simple deformation or microfibrillation of spherulites can create excellent thermo/mechanical properties making PLA compete against conventional petrochemical‐based polymers. It was performed by pressure‐induced‐flow (PIF) processing, and produced typical deformed spherulite structure and brick‐mud structure. It was found that the critical deformation degree of spherulites was around 2.7, beyond which spherulites would fragment. Through three transition stages of spherulite structures, deformed spherulite structures, and brick‐mud structure, PLA exhibited an enhancement of orientation, storage modulus and glass transition temperature. And a substantial increase was proved in impact strength (105.6 kJ/m2), tensile strength (148.4 MPa) and elongation at break (107.7%), which can be comparable to most engineering plastics. Both the deformed spherulite structures and the brick‐mud structures can enhance the impact toughness of PLA by increasing the fracture path of cracks. Besides, the evolution of the microstructure for a sandwich structure during PIF‐processing was proposed.
Preparation and anticorrosion properties of GO‐Ce‐MOF nanocomposite coatings
Authors: Chen Legang , Yu Zongxue , Yin Di , Cao Kunyao , Xie Chunxia , Zhu Lijuan , Jiang Yong 
Published: August 2021

AbstractHerein, a new strategy for improving epoxy coatings' anti‐corrosion performance has been developed, which combined NH2‐Ce‐MOF with graphene oxide (GO) by hydrothermal method. First, the nanocomposite material's morphology and structure (GO‐Ce‐MOF) were confirmed by Fourier transform infrared, X‐ray diffraction, TG, X‐ray photoelectron spectroscopy, and scanning electron microscope (SEM) studies. The dispersity of the composite in the epoxy coating was evaluated by SEM and mapping analysis. Meanwhile, the anti‐corrosion of as‐prepared composite coatings was investigated in detail by the electrochemical impedance spectroscopy (EIS) and the Tafel polarization curve test. The results illustrated that 2.0 wt% GO‐Ce‐MOF/EP greatly enhanced the composite coating's anti‐corrosion performance compared to other coatings. The reasons for the improvement of the anti‐corrosion performance of the composite coating are attributed to the following two aspects: On the one hand, the addition of GO can provide a physical barrier to form a labyrinth effect to slow down the invasion of corrosive media into the metal substrate, on the other hand, the modification of GO can GO‐Ce‐MOF achieve better compatibility and dispersion in epoxy resin.
Effect of size, concentration, and nature of fillers on crystallinity, thermal, and mechanical properties of polyetheretherketone composites
Authors: Doumeng Marie , Berthet Florentin , Delbé Karl , Marsan Olivier , Denape Jean , Chabert France 
Published: August 2021

AbstractPolyetheretherketone (PEEK) composites exhibit high stiffness, chemical stability, and heat resistance and they are therefore employed in applications under severe operating environments. This work aims to provide insight into the effect of the size, concentration, and type of fillers on the thermal and mechanical properties of PEEK. A total of 32 composites are used to highlight the influence of nature (lamellae, such as boron nitride and graphite and silicon carbide and alumina), size (nano and micrometric), and content (2.5, 5, 7.5, and 10 vol%) of fillers. The melting temperature and lamellar thickness did not change regardless of the nature of the filler. The thermomechanical analysis demonstrates that lamellar fillers form a percolating network and contribute significantly to the enhancement of the storage modulus. The increase in the storage modulus is proportional to the filler content, and it is more pronounced for micro composites. As expected, the percolating network is formed at lower concentrations for lamellar fillers than for spherical ones. The highest conductivity is achieved with graphite at 0.823 W m−1 K−1, which is twice that of PEEK for 10 vol%. Moreover, the use of micrometric fillers results in thermal conductivity enhancement attributed to the higher amount of efficient hot zones for heat transfer.
Association of Bone Erosions and Osteophytes With Systemic Bone Involvement on High‐Resolution Peripheral Quantitative Computed Tomography in Premenopausal Women With Longstanding Rheumatoid Arthritis
Authors: Perez Mariana O. , Figueiredo Camille P. , Sales Lucas P. , Medeiros‐Ribeiro Ana Cristina , Takayama Liliam , Domiciano Diogo S. , Bonfiglioli Karina , Caparbo Valeria F. , Pereira Rosa M. R. 
Published: August 2021

ObjectiveTo evaluate premenopausal women with longstanding rheumatoid arthritis (RA) for potential associations between parameters of localized bone involvement and parameters of systemic bone involvement in the affected joints.MethodsEighty consecutively evaluated premenopausal women with RA were included in the study, along with 160 healthy female control subjects who were matched to the patients by age and body mass index. Volumetric bone mineral density (vBMD), bone microarchitecture, and finite elements of biomechanical bone strength (bone stiffness and estimated failure load) at the distal radius and distal tibia were analyzed by high‐resolution peripheral quantitative computed tomography (HR‐pQCT) in patients with RA compared to healthy controls. In addition, in patients with RA, localized bone involvement in the metacarpophalangeal and proximal interphalangeal joints was analyzed by HR‐pQCT, to identify bone erosions and osteophytes.ResultsAmong the 80 premenopausal women with longstanding RA, the mean ± SD age was 39.4 ± 6.7 years and mean ± SD disease duration was 9.8 ± 5.3 years. Trabecular and cortical bone parameters and bone strength at the distal radius and distal tibia were all impaired in patients with RA compared to healthy controls (each P < 0.05). In total, 75% of RA patients had evidence of bone erosions, and 41.3% of RA patients had detectable osteophytes on HR‐pQCT. RA patients with bone erosions, as compared to RA patients without bone erosions, had lower cortical vBMD (at the distal radius, mean ± SD 980 ± 72 mg HA/cm3 versus 1,021 ± 47 mg HA/cm3 [P = 0.03]; at the distal tibia, 979 ± 47 mg HA/cm3 versus 1,003 ± 34 mg HA/cm3 [P = 0.04]) and higher cortical bone porosity (at the distal radius, mean ± SD 2.8 ± 2.5% versus 1.8 ± 1.6% [P = 0.04]; at the distal tibia, 3.7 ± 1.6% versus 2.7 ± 1.6% [P = 0.01]). In patients with RA, osteophyte volume at the distal radius was positively correlated with trabecular vBMD (r = 0.392, P = 0.02), trabecular number (r = 0.381, P = 0.03), and trabecular stiffness (r = 0.411, P = 0.02), and negatively correlated with trabecular separation (r = −0.364, P = 0.04), as determined by Pearson's or Spearman's correlation test.ConclusionThe findings show that premenopausal women with longstanding RA have systemic bone fragility at peripheral joint sites. Moreover, the presence of bone erosions is mainly associated with cortical bone fragility at the distal radius and tibia, and presence of osteophytes is associated with repair of trabecular bone at the distal radius.
Metal Effect Meets Volcano Plots: A DFT Study on Tris(phosphino)borane‐Transition Metal Complexes Catalyzed H2 Activation
Authors: Su Peifeng , Li Yinwu , Ke Zhuofeng 
Published: August 2021

AbstractBifunctional transition metal complexes are of particular interest in metal‐ligand cooperative activation of small molecules. As a novel type of bifunctional catalyst, Lewis acid transition metal (LA‐TM) complexes have attracted increasing interest in hydrogen activation and storage. To advance the catalyst design, herein the metal effect of LA‐TM complexes on the hydrogen activation has been systematically studied with a series of tris(phosphino)borane (TPB) complexes with V, Cr, Mn, Fe, Co, and Ni as metal centers. The metal effect not only influences the mechanism of hydrogen activation, but also notably casts a volcano plot for the activity. TPB complexes of V, Cr, Mn, Fe, and Co tend to activate H2 through a stepwise mechanism, while TPB‐Ni prefers a synergetic mechanism for H2 activation. More importantly, the metal effect significantly influences the activity of H2 activation and the formation of the LA‐H‐TM bridging hydride. The trend of changes in the LA‐H‐TM structures, the second‐order perturbation stabilization energies, and the Laplacian bond orders, along with different metals (from V to Ni), are all interestingly constitute volcano plots for the performance of TPB‐TM complexes catalyzed H2 activation. TPB‐Mn and TPB‐Fe are found to be the optimal catalysts among the discussed TPB‐TM complexes. The volcano plots disclosed for the metal effects should be informative and instructive for homogeneous and heterogeneous LA‐TM catalysts development.