bluuebunny/crossref_metadata_2025_split huggingface dataset:
A new frontier of image guidance: Organs at risk avoidance with MRI‐guided respiratory‐gated intensity modulated radiotherapy: Technical note and report of a case
Authors: Massaccesi Mariangela , Cusumano Davide , Boldrini Luca , Dinapoli Nicola , Fionda Bruno , Teodoli Stefania , Azario Luigi , Mattiucci Gian Carlo , Balducci Mario , Cellini Francesco , Valentini Vincenzo 
Published: May 2019

AbstractThe case of a 50‐year‐old man affected by a rhabdomiosarcoma metastatic lesion in the left flank Is reported. The patient was addressed to 50.4 Gy radiotherapy with concomitant chemotherapy in order to locally control the lesion. A Tri‐60‐Co magnetic resonance hybrid radiotherapy unit was used for treatment delivery and a respiratory gating protocol was applied for the different breathing phases (Free Breathing, Deep Inspiration Breath Hold and Final Expiration Breath Hold). Three intensity modulated radiation therapy (IMRT) plans were calculated and Final Expiration Breath Hold plan was finally selected due to the absence of PTV coverage differences and better organs at risk sparing (i.e. kidneys). This case report suggests that organs at risk avoidance with MRI‐guided respiratory‐gated Radiotherapy is feasible and particularly advantageous whenever sparing the organs at risk is of utmost dosimetric or clinical importance.
Five‐Year Follow‐Up of Coronary Microvascular Dysfunction and Coronary Artery Disease in Systemic Lupus Erythematosus: Results From a Community‐Based Lupus Cohort
Authors: Sandhu Vaneet K. , Wei Janet , Thomson Louise E. J. , Berman Daniel S. , Schapira Jay , Wallace Daniel , Weisman Michael H. , Bairey Merz C. Noel , Ishimori Mariko L. 
Published: May 2019

ObjectiveThe present study was undertaken to investigate prospective change in the prevalence of coronary microvascular dysfunction (CMD) and obstructive coronary artery disease (CAD) in a cohort of subjects with systemic lupus erythematosus (SLE) initially evaluated for anginal chest pain (CP). Prior work documented a relatively high prevalence of CMD in the absence of obstructive CAD in subjects with SLE.MethodsTwenty female SLE subjects with CP who underwent stress cardiac magnetic resonance imaging (CMRI) and coronary computed tomography angiography at baseline were reevaluated at 5 years.ResultsSeventeen subjects (85%) were available and reenrolled, of which 11 (65%) had persistent CP at follow‐up. Fourteen subjects had complete follow‐up CMRI, of which 36% (n = 5) demonstrated CMD at follow‐up. Further, 25% (1 of 4) of the originally abnormal myocardial perfusion reserve index (MPRI) findings at baseline were lower at follow‐up, while 2 additional abnormal MPRI findings at follow‐up were noted in previously normal MPRI results. The prevalence of CMD and nonobstructive/obstructive CAD both was unchanged between baseline and follow‐up, respectively (both P values not significant). During follow‐up, 33% of subjects (5 of 15) had adverse cardiac outcomes, including pericarditis, unstable angina, or intracranial aneurysm clipping procedure.ConclusionAt the 5‐year follow‐up of SLE subjects with CP who were evaluated at baseline and follow‐up, a majority had persistent CP, and nearly one‐half had similar or worse myocardial perfusion consistent with CMD without obstructive CAD. These findings propose an alternative explanation for CP in SLE subjects compared to the more common SLE‐related accelerated obstructive CAD accounting for CP and adverse outcomes. These findings support further studies of CMD as an etiology for cardiac morbidity and mortality in SLE.
Preparation of Tortuous 3D γ‐CsPbI3 Films at Low Temperature by CaI2 as Dopant for Highly Efficient Perovskite Solar Cells
Authors: Zhao Hang , Xu Jia , Zhou Shijie , Li Zhenzhen , Zhang Bing , Xia Xin , Liu Xiaolong , Dai Songyuan , Yao Jianxi 
Published: May 2019

AbstractInorganic cubic CsPbI3 perovskite (α‐CsPbI3) has been widely explored for perovskite solar cells (PSCs) due to its thermal stability and suitable bandgap of 1.73 eV. However, α‐CsPbI3 usually requires high synthesis temperatures (>320 °C). Additionally, it usually undergoes phase transition to the nonperovskite structure phase (β‐CsPbI3), which results in poor photoelectric performance in devices. In this study, it is first found that the tortuous 3D CsPbI3 phase (γ‐CsPbI3) can be prepared and used for PSCs by solution process without any additive at low temperature (60 °C). The γ‐CsPbI3 exhibits suitable bandgap of 1.75 eV and favorable photoelectric properties. However, γ‐CsPbI3 is a metastable phase and easily transforms into β‐CsPbI3 in ambient moisture. In order to improve the stability of γ‐CsPbI3, calcium ions (Ca2+) with a relatively small radius of 100 pm are used to partially substitute lead ions (119 pm). This research proves that Ca2+ can effectively improve the stability of the γ‐CsPbI3 at room temperature. By optimizing the doping concentration of Ca2+ (CsPb1−xCaxI3, x is from 0% to 2%), the Ca2+‐doped γ‐CsPbI3 PSCs achieve a hysteresis‐free J–V curve and a maximum power conversion efficiency (PCE) of 9.20%.
Unconjugated Side‐Chain Engineering Enables Small Molecular Acceptors for Highly Efficient Non‐Fullerene Organic Solar Cells: Insights into the Fine‐Tuning of Acceptor Properties and Micromorphology
Authors: Liu Tao , Gao Wei , Wang Yilin , Yang Tao , Ma Ruijie , Zhang Guangye , Zhong Cheng , Ma Wei , Yan He , Yang Chuluo 
Published: May 2019

Abstract2D conjugated side‐chain engineering is an effective strategy that is widely utilized to construct benzodithiophene‐based polymers. Herein, an unconjugated side‐chain strategy to design fused‐benzodithiophene‐based non‐fullerene small molecule acceptors (SMAs) via vertical aromatic side‐chain engineering on the ladder‐type core is employed. Three SMAs named BTTIC‐Th, BTTIC‐TT, and BTTIC‐Ph with thiophene, thieno[3,2‐b]thiophene, and benzene, respectively, as side chains, are designed and synthesized. Three SMAs exhibit similar absorption ranges but different lowest unoccupied molecular orbital (LUMO) energy levels due to the different strength of the δ‐inductive effect between vertical aromatic side chains and their electron‐rich core. Organic solar cells based on PBDB‐T:BTTIC‐TT achieve a power conversion efficiency (PCE) of 13.44%, which is higher than the PCE of devices based on PBDB‐T:BTTIC‐Th (12.91%) and PBDB‐T:BTTIC‐Ph (9.14%). The difference in device performance is investigated by electrical and morphological characterizations. A large domain size and different types of π–π stacking are found in the bulk heterojunction layer of PBDB‐T:BTTIC‐Ph blend film, which are detrimental to exciton dissociation and charge transport. Overall, it is demonstrated that when designing unconjugated side chains, thieno[3,2‐b]thiophene is superior to thiophene and benzene through its dual roles of promoting the LUMO energy level and optimizing the morphology. These results shed light on the side‐chain engineering of high‐performance non‐fullerene SMAs.
Microfluidic Model for Evaluation of Immune Checkpoint Inhibitors in Human Tumors
Authors: Beckwith Ashley L. , Velásquez‐García Luis F. , Borenstein Jeffrey T. 
Published: May 2019

AbstractPresented is the first demonstration of real‐time monitoring of the response of resident lymphocyte populations in biopsied tumor tissue to immunotherapeutic agents in a perfused tumor microenvironment. This technology comprises a microfluidic tumor trapping device constructed from a novel 3D‐printed, transparent, noncytotoxic substrate. The 3D‐printed device sustains viability of biopsied tissue fragments under dynamic perfusion for at least 72 h while enabling simultaneous administration of various drug treatments, illustrating a useful tool for drug development and precision medicine for immunotherapy. Confocal microscopy of the tumor tissue and resident lymphocytes in the presence of fluorescent tracers provides real‐time monitoring of tumor response to various immunotherapies. Devices are additively manufactured in Pro3dure GR‐10 (i.e., a relatively new, high‐resolution stereolithographic resin with properties suitable for biomedical applications), allowing integration of a set of finely featured functional components into a monolithically constructed platform. The presented platform comprises a new methodology for modeling and analyzing tumor response for the improved prediction of patient‐specific immunotherapy efficacy. It is acknowledged that this is the first report of human tumor fragments cultured in a dynamic perfusion system capable of testing the effect of circulating immune checkpoint inhibitors on resident tumor‐infiltrating lymphocytes.
Surface‐Halogenation‐Induced Atomic‐Site Activation and Local Charge Separation for Superb CO2 Photoreduction
Authors: Hao Lin , Kang Lei , Huang Hongwei , Ye Liqun , Han Keli , Yang Songqiu , Yu Hongjian , Batmunkh Munkhbayar , Zhang Yihe , Ma Tianyi 
Published: May 2019

AbstractSolar‐energy‐driven CO2 conversion into value‐added chemical fuels holds great potential in renewable energy generation. However, the rapid recombination of charge carriers and deficient reactive sites, as two major obstacles, severely hampers the photocatalytic CO2 reduction activity. Herein, a desirable surface halogenation strategy to address the aforementioned concerns over a Sillén‐related layer‐structured photocatalyst Bi2O2(OH)(NO3) (BON) is demonstrated. The surface halogen ions that are anchored on the Bi atoms by replacing surface hydroxyls on the one hand facilitate the local charge separation, and, on the other hand, activate the hydroxyls that profoundly boost the adsorption of CO2 molecules and protons and facilitate the CO2 conversion process, as evidenced by experimental and theoretical results collectively. Among the three series of BON‐X (X = Cl, Br, and I) catalysts, BON‐Br shows the most substantially enhanced CO production rate (8.12 µmol g−1 h−1) without any sacrificial agents or cocatalysts, ≈73 times higher than that of pristine Bi2O2(OH)(NO3), also exceeding that of the state‐of‐the‐art photocatalysts reported to date. This work presents a surface polarization protocol for engineering charge behavior and reactive sites to promote photocatalysis, which shows great promise to the future design of high‐performance materials for clean energy production.
From Nonluminescent to Blue‐Emitting Cs4PbBr6 Nanocrystals: Tailoring the Insulator Bandgap of 0D Perovskite through Sn Cation Doping
Authors: Zou Shenghan , Liu Caiping , Li Renfu , Jiang Feilong , Chen Xueyuan , Liu Yongsheng , Hong Maochun 
Published: May 2019

AbstractAll‐inorganic cesium lead halide perovskite nanocrystals (NCs) with different dimensionalities have recently fascinated the research community due to their extraordinary optoelectronic performance such as tunable bandgaps over the entire visible spectral region. However, compared to well‐developed 3D CsPbX3 perovskites (X = Cl, Br, and I), the bandgap tuning in 0D Cs4PbX6 perovskite NCs remains an arduous task. Herein, a simple but valid strategy is proposed to tailor the insulator bandgap (≈3.96 eV) of Cs4PbBr6 NCs to the blue spectral region by changing the local coordination environment of isolated [PbBr6]4− octahedra in the Cs4PbBr6 crystal through Sn cation doping. Benefitting from the unique Pb2+‐poor and Br−‐rich reaction environment, the Sn cation is successfully introduced into the Cs4PbBr6 NCs, forming coexisting point defects comprising substitutional SnPb and interstitial Bri, thereby endowing these theoretically nonluminescent Cs4PbBr6 NCs with an ultranarrow blue emission at ≈437 nm (full width at half maximum, ≈12 nm). By combining the experimental results with first‐principles calculations, an unusual electronic dual‐bandgap structure, comprising the newly emerged semiconducting bandgap of ≈2.87 eV and original insulator bandgap of ≈3.96 eV, is found to be the underlying fundamental reason for the ultranarrow blue emission.
Highly Reversible Electrofluorochromism from Electrochemically Decoupled but Electronically Coupled Molecular Dyads
Authors: Kim Sinheui , You Youngmin 
Published: May 2019

AbstractAlthough electrofluorochromism enables unique optoelectronic applications, its utility has been limited by poor reversibility. It is demonstrated that high reversibility in electrofluorochromism is obtainable from molecular dyads having a redox‐stable acceptor and an aromatic or antiaromatic donor. The structural control aims to generate excited‐state conjugation that produces twisted intramolecular charge‐transfer fluorescence, while suppressing the ground‐state conjugation in order to confine electrochemical processes exclusively within the acceptor unit. Overpotential‐free electrofluorochromism can be achieved with a high fatigue resistance against repeated electrochemical cycles. The electrofluorochromism is investigated using structural, spectroscopic, electrochemical, spectroelectrochemical, and quantum chemical techniques. The studies reveal that electrochemical gating of intramolecular charge transfer is the key mechanism underlying the improved electrofluorochromism performance. The study will provide novel insights into the future development and applications of electrofluorochromic devices.
The Enigmatic Roles of PPR‐SMR Proteins in Plants
Authors: Zhang Yi , Lu Congming 
Published: May 2019

AbstractThe pentatricopeptide repeat (PPR) protein family, with more than 400 members, is one of the largest and most diverse protein families in land plants. A small subset of PPR proteins contain a C‐terminal small MutS‐related (SMR) domain. Although there are relatively few PPR‐SMR proteins, they play essential roles in embryo development, chloroplast biogenesis and gene expression, and plastid‐to‐nucleus retrograde signaling. Here, recent advances in understanding the roles of PPR‐SMR proteins and the SMR domain based on a combination of genetic, biochemical, and physiological analyses are described. In addition, the potential of the PPR‐SMR protein SOT1 to serve as a tool for RNA manipulation is highlighted.
Manipulation of Ni Interstitials for Realizing Large Power Factor in TiNiSn‐Based Materials
Authors: Ren Wuyang , Zhu Hangtian , Mao Jun , You Li , Song Shaowei , Tong Tian , Bao Jiming , Luo Jun , Wang Zhiming , Ren Zhifeng 
Published: May 2019

AbstractDefect engineering has been identified as an effective strategy for improving thermoelectric performance by tailoring electron and phonon transport. TiNiSn is unique due to its naturally formed Ni interstitials, where the interstitial atoms enable strong phonon scattering that results in reduced lattice thermal conductivity, although an adverse effect on mobility is inevitable. Rather than pursuing the conventional strategy of strengthening the interstitial scattering to improve the performance of TiNiSn‐based materials, an attempt is made to minimize the atomic disorder in order to enhance the mobility, which in turn favors a higher power factor. The altered bandgap, and electrical and thermal properties demonstrate that the interstitials can be effectively controlled by intentionally reducing the amount of Ni. Benefiting from the manipulation of the interstitials, significantly enhanced mobility is achieved in the Ni‐deficient composition, resulting in peak power factor of ≈50 µW cm−1 K−2, which is comparable to the best n‐type half‐Heusler compounds. Additionally, the well‐designed composition employing Ni interstitial manipulation and heavy‐element doping exhibits peak ZT of ≈0.73, higher than that of all other reported TiNiSn‐based materials. The unique role of interstitials in either electron or phonon transport is emphasized, and further encouragement for engineering thermoelectric properties by manipulating intrinsic disorder, especially in materials with complex structures, is provided.
Myelodysplasia as assessed by multiparameter flow cytometry refines prognostic stratification provided by genotypic risk in systemic mastocytosis
Authors: Mannelli Francesco , Gesullo Francesca , Rotunno Giada , Pacilli Annalisa , Bencini Sara , Annunziato Francesco , Zanotti Roberta , Scaffidi Luigi , Giona Fiorina , Santopietro Michelina , Grifoni Federica , Pieri Lisa , Guglielmelli Paola , Vannucchi Alessandro M. 
Published: May 2019

AbstractSystemic mastocytosis (SM) is characterized by extreme heterogeneity of manifestations and prognosis. Several disease‐related biomarkers, including clinical, hematological and molecular variables, have been correlated with prognosis. Although relevant, the mutation profile closely reflects the WHO classification that has per se prognostic value. High‐risk mutations (HRM) are largely confined to advanced forms, and thus fail in providing information regarding progression and outcome in the not‐advanced variants. In this work, we studied hematopoietic cells by multi‐parameter flow cytometry (MFC) in order to highlight dysplastic traits that might provide insights into outcome. A score previously validated for myelodysplastic syndromes, with high reproducibility in standard diagnostics, was used. The application of an MFC score to a cohort of 71 SM cases, concurrently genotyped for configuring a HRM category, resulted in the identification of two separate patients' categories (MFC+ and MFC‐) characterized by significantly different clinical and laboratory features at presentation. The extent of dysplasia by MFC tended to parallel WHO‐category and genotype‐related stratification. MFC+ patients had shorter survival compared to MFC‐ ones, for whom the incidence of progression and/or death was virtually null. Of note, MFC score remained prognostically informative in unadvanced subsets. Furthermore, the integration of MFC and HRM was an independent predictor for outcome, also overcoming WHO‐categories in multivariate analysis for EFS. Our results support the use of MFC analysis in the evaluation of patients with SM, alone and in combination with HRM, for refinement of prognosis assessment.
Ligand‐Promoted RhIII‐Catalyzed Thiolation of Benzamides with a Broad Disulfide Scope
Authors: Kang Yan‐Shang , Zhang Ping , Li Min‐Yan , Chen You‐Ke , Xu Hua‐Jin , Zhao Jing , Sun Wei‐Yin , Yu Jin‐Quan , Lu Yi 
Published: May 2019

AbstractA ligand‐promoted RhIII‐catalyzed C(sp2)−H activation/thiolation of benzamides has been developed. Using bidentate mono‐N‐protected amino acid ligands led to the first example of RhIII‐catalyzed aryl thiolation reactions directed by weakly coordinating directing amide groups. The reaction tolerates a broad range of amides and disulfide reagents.
Asymmetric Synthesis of Chiral 1,4‐Enynes through Organocatalytic Alkenylation of Propargyl Alcohols with Trialkenylboroxines
Authors: Bai Jian‐Fei , Yasumoto Kento , Kano Taichi , Maruoka Keiji 
Published: May 2019

AbstractA highly enantioselective synthesis of 1,4‐enynes is described that proceeds through an organocatalytic reaction between propargyl alcohols and trialkenylboroxines. Our strategy relies on acid‐mediated generation of the carbocationic intermediate from propargyl alcohols followed by enantioselective alkenylation with trialkenylboroxines. A range of chiral 1,4‐enynes were obtained in moderate to good yields with high levels of enantioselectivity. Use of a highly acidic chiral N‐triflyl phosphoramide catalyst, which has two distant Lewis basic oxygen atoms, was found to be crucial for both high reactivity and selectivity in the present reaction.
κ3‐(N^C^C)Gold(III) Carboxylates: Evidence for Decarbonylation Processes
Authors: Beucher Hélène , Merino Estíbaliz , Genoux Alexandre , Fox Thomas , Nevado Cristina 
Published: May 2019

AbstractGold(III) carboxylate species, stabilized by a κ3‐(N^C^C) ligand template, are presented herein. A η1‐AuIII‐C(O)‐OH species has been characterized under cryogenic conditions as a result of the nucleophilic attack of an ammonium hydroxide onto a dinuclear μ‐CO2‐κ3‐(N^C^C)AuIII precursor. Thermal decomposition for these species proceeds by an unusual decarbonylation process, in contrast to typical decarboxylation pathways observed in related metallocarboxylic acids.
A Titanium(IV)‐Based Metal–Organic Framework Featuring Defect‐Rich Ti‐O Sheets as an Oxidative Desulfurization Catalyst
Authors: Smolders Simon , Willhammar Tom , Krajnc Andraž , Sentosun Kadir , Wharmby Michael T. , Lomachenko Kirill A. , Bals Sara , Mali Gregor , Roeffaers Maarten B. J. , De Vos Dirk E. , Bueken Bart 
Published: May 2019

AbstractWhile titanium‐based metal–organic frameworks (MOFs) have been widely studied for their (photo)catalytic potential, only a few TiIV MOFs have been reported owing to the high reactivity of the employed titanium precursors. The synthesis of COK‐47 is now presented, the first Ti carboxylate MOF based on sheets of TiIVO6 octahedra, which can be synthesized with a range of different linkers. COK‐47 can be synthesized as an inherently defective nanoparticulate material, rendering it a highly efficient catalyst for the oxidation of thiophenes. Its structure was determined by continuous rotation electron diffraction and studied in depth by X‐ray total scattering, EXAFS, and solid‐state NMR. Furthermore, its photoactivity was investigated by electron paramagnetic resonance and demonstrated by catalytic photodegradation of rhodamine 6G.
Spectroscopic and single‐crystal X‐ray diffraction studies of enantiomeric copper(II) Schiff base one‐dimensional coordination polymers with 4‐(2‐aminoethyl)benzenesulfonamide appendage: Comprehensive biological evaluation (DNA binding, cleavage, superoxide dismutase mimetic activity, topoisomerase I inhibition and cytotoxicity)
Authors: Afsan Zeenat , Roisnel Thierry , Tabassum Sartaj , Arjmand Farukh 
Published: May 2019

New chiral Cu(II)‐based one‐dimensional coordination polymers [l‐C25H27CuN3O6S] (1a) and [d‐C25H27CuN3O6S] (1b) were designed and synthesized by in situ reaction of Schiff base (o‐vanillin and l‐/d‐phenylalanine) and appended ligand 4‐(2‐aminoethyl)benzenesulfonamide incorporated with Cu(II) ion. The enantiomeric complexes 1a and 1b were fully characterized using various spectroscopic techniques and single‐crystal X‐ray diffraction studies. The enantiomeric analogues 1a and 1b crystallized in chiral monoclinic P21 space group with z = 2 exhibiting a distorted square pyramidal environment around Cu(II) metal centre coordinated to N2O3 donor atoms with apical position occupied by adjacent bridging carboxylate oxygen, resulting in one‐dimensional polymeric chain structures. Comprehensive biological studies of 1a and 1b (DNA binding, superoxide dismutase (SOD), topoisomerase I and cytotoxic activity) were performed which revealed that 1a showed better prospects as a therapeutic drug candidate as compared to 1b as quantified by their comparative DNA binding (Kb, K and Ksv values), SOD mimetic activity (IC50 values of 0.160 and 0.198, respectively) and anticancer properties.