bluuebunny/crossref_metadata_2025_split huggingface dataset:
Structure and Unprecedented Reactivity of a Mononuclear Nonheme Cobalt(III) Iodosylbenzene Complex
Authors: Yang Jindou , Seo Mi Sook , Kim Kyung Ha , Lee Yong‐Min , Fukuzumi Shunichi , Shearer Jason , Nam Wonwoo 
Published: May 2020

AbstractA mononuclear nonheme cobalt(III) iodosylbenzene complex, [CoIII(TQA)(OIPh)(OH)]2+ (1), is synthesized and characterized structurally and spectroscopically. While 1 is a sluggish oxidant in oxidation reactions, it becomes a competent oxidant in oxygen atom transfer reactions, such as olefin epoxidation, in the presence of a small amount of proton. More interestingly, 1 shows a nucleophilic reactivity in aldehyde deformylation reaction, demonstrating that 1 has an amphoteric reactivity. Another interesting observation is that 1 can be used as an oxygen atom donor in the generation of high‐valent metal‐oxo complexes. To our knowledge, we present the first crystal structure of a CoIII iodosylbenzene complex and the unprecedented reactivity of metal‐iodosylarene adduct.
Influence of polymer washing on thermal conductivity enhancement of Cu nanofluids
Authors: Chandan Mohammed R. , Shaik Aabid Hussain , Kumar Hemanth , Rahaman Ariful , Bal Dharmendra K. , Ponnusami Babu A , Imran Mohd 
Published: May 2020

AbstractThis work aims at enhancing the thermal conductivity of base fluids (water and methanol) through successive washing of polymers from the surface of polyvinylpyrollidone (PVP)‐stabilized copper (Cu) nanoparticles. Cu nanofluids were successfully synthesized and characterized using transmission electron microscope and UV–vis spectrophotometer. Thermal conductivity of freshly prepared Cu nanofluid shows ~10% enhancements. The poor enhancement in thermal conductivity is due to the presence of thick polymer coating on the surface of nanoparticles. A new technique has been developed to erode the polymers from the nanoparticle surface by repeated washing and redispersion. After one‐time washing and redispersion, the thermal conductivity of nanofluid has been increased to 0.732 W/mK (~22% enhancements). Greater enhancement (~30.34%) has been achieved after three times continuous washing and redispersion. Finally, the experimental values of thermal conductivity were compared and validated against the existing Maxwell effective model.
Analysis of trap distribution of a red persistent luminescent materials using thermoluminescence
Authors: Singh L. Lovedy , Singh S. Nabadwip , Singh Th. Ranjan , Gopal E. 
Published: May 2020

AbstractTrap distribution plays a crucial role in deciding the applicability of a material. The thermoluminescence (TL) parameter that describes trap distribution is η, which has never been discussed in TL analysis so far. TL analysis of a commercially available red persistent luminescent material (CaSrS:Eu) was performed using computerized glow curve deconvolution (CGCD) in the new general order kinetics. CGCD results showed that the red persistent luminescent material in the temperature range 300–600º K was comprised of nine peaks. Activation energy ranged from 0.66–1.27 eV. Frequency factor was in the range 109 to 1011 sec−1. The major peaks of the red persistent luminescent material had lesser empty traps. The most important information provided by the analysis was that the major peaks of the red persistent luminescent material had 30–60% of the empty traps close to the filled traps, and this accounted for retrapping of thermally released electrons. This finding suggests that the occurrence of 30–60% empty traps close to the filled traps is a necessary requisite for a persistent luminescent material.
Current genetic engineering strategies for the production of antihypertensive ACEI peptides
Authors: Gomes Carolina , Ferreira Diana , Carvalho João P. F. , Barreto Carlos A. V. , Fernandes Joana , Gouveia Marisol , Ribeiro Fernando , Duque Ana S. , Vieira Sandra I. 
Published: May 2020

AbstractHypertension is a major and highly prevalent risk factor for various diseases. Among the most frequently prescribed antihypertensive first‐line drugs are synthetic angiotensin I‐converting enzyme inhibitors (ACEI). However, since their use in hypertension therapy has been linked to various side effects, interest in the application of food‐derived ACEI peptides (ACEIp) as antihypertensive agents is rapidly growing. Although promising, the industrial production of ACEIp through conventional methods such as chemical synthesis or enzymatic hydrolysis of food proteins has been proven troublesome. We here provide an overview of current antihypertensive therapeutics, focusing on ACEI, and illustrate how biotechnology and bioengineering can overcome the limitations of ACEIp large‐scale production. Latest advances in ACEIp research and current genetic engineering‐based strategies for heterologous production of ACEIp (and precursors) are also presented. Cloning approaches include tandem repeats of single ACEIp, ACEIp fusion to proteins/polypeptides, joining multivariate ACEIp into bioactive polypeptides, and producing ACEIp‐containing modified plant storage proteins. Although bacteria have been privileged ACEIp heterologous hosts, particularly when testing for new genetic engineering strategies, plants and microalgae‐based platforms are now emerging. Besides being generally safer, cost‐effective and scalable, these “pharming” platforms can perform therelevant posttranslational modifications and produce (and eventually deliver) biologically active protein/peptide‐based antihypertensive medicines.
Using algorithms to address trade‐offs inherent in predicting recidivism
Authors: Skeem Jennifer , Lowenkamp Christopher 
Published: May 2020

AbstractAlthough risk assessment has increasingly been used as a tool to help reform the criminal justice system, some stakeholders are adamantly opposed to using algorithms. The principal concern is that any benefits achieved by safely reducing rates of incarceration will be offset by costs to racial justice claimed to be inherent in the algorithms themselves. But fairness trade‐offs are inherent to the task of predicting recidivism, whether the prediction is made by an algorithm or human. Based on a matched sample of 67,784 Black and White federal supervisees assessed with the Post Conviction Risk Assessment, we compared how three alternative strategies for “debiasing” algorithms affect these trade‐offs, using arrest for a violent crime as the criterion . These candidate algorithms all strongly predict violent reoffending (areas under the curve = 0.71–72), but vary in their association with race (r = 0.00–0.21) and shift trade‐offs between balance in positive predictive value and false‐positive rates. Providing algorithms with access to race (rather than omitting race or “blinding” its effects) can maximize calibration and minimize imbalanced error rates. Implications for policymakers with value preferences for efficiency versus equity are discussed.
Improved targeting of an anti‐TAG‐72 antibody drug conjugate for the treatment of ovarian cancer
Authors: Minnix Megan , Li Lin , Yazaki Paul , Chea Junie , Poku Erasmus , Colcher David , Shively John E. 
Published: May 2020

AbstractIntroductionOvarian cancer has only a 17% 5‐year survival rate in patients diagnosed with late stage disease. Tumor‐associated glycoprotein‐72 (TAG72), expressed in 88% of all stages of ovarian cancer, is an excellent candidate for antibody‐targeted therapy, as it is not expressed in normal human adult tissues, except in the secretory endometrium.MethodsUsing the clinically relevant anti‐TAG72 murine monoclonal antibody CC49, we evaluated antibody drug conjugates (ADCs) incorporating the highly potent, synthetic antimitotic agent monomethylauristatin E (MMAE). MMAE was conjugated to CC49 via reduced disulfides in the hinge region, using three different types of linker chemistry, vinylsulfone (VS‐MMAE), bromoacetamido (Br‐MMAE), and maleimido (mal‐MMAE).ResultsThe drug antibody ratios (DARs) of the three ADCs were 2.3 for VS‐MMAE, 10 for Br‐MMAE, and 9.5 for mal‐MMAE. All three ADCs exhibited excellent tumor to blood ratios on PET imaging, but the absolute uptake of CC49‐mal‐MMAE (3.3%ID/g) was low compared to CC49‐Br‐MMAE (6.43%ID/g), at 142 hours. Blood clearance at 43 hours was 38% for intact CC49, about 24% for both CC49‐VS‐MMAE and CC49‐Br‐MMAE, and 7% for CC49‐mal‐MMAE. CC49‐VS‐MMAE was not further studied due to its low DAR, while CC49‐mal‐MMAE was ineffective in the OVCAR3 xenograft likely due to its rapid blood clearance. In contrast, CC49‐Br‐MMAE treated mice exhibited an average of a 15.6 day tumor growth delay and a 40% increase in survival vs controls with four doses of 7.5 or 15 mg/kg of CC49‐Br‐MMAE.ConclusionWe conclude that CC49‐Br‐MMAE with a high DAR and stable linker performs well in a difficult to treat solid tumor model.
Click‐Chemistry (CuAAC) Trimerization of an αvβ6 Integrin Targeting Ga‐68‐Peptide: Enhanced Contrast for in‐Vivo PET Imaging of Human Lung Adenocarcinoma Xenografts
Authors: Quigley Neil Gerard , Tomassi Stefano , di Leva Francesco Saverio , Di Maro Salvatore , Richter Frauke , Steiger Katja , Kossatz Susanne , Marinelli Luciana , Notni Johannes 
Published: May 2020

Abstractαvβ6 Integrin is an epithelial transmembrane protein that recognizes latency‐associated peptide (LAP) and primarily activates transforming growth factor beta (TGF‐β). It is overexpressed in carcinomas (most notably, pancreatic) and other conditions associated with αvβ6 integrin‐dependent TGF‐β dysregulation, such as fibrosis. We have designed a trimeric Ga‐68‐labeled TRAP conjugate of the αvβ6‐specific cyclic pentapeptide SDM17 (cyclo[RGD‐Chg‐E]‐CONH2) to enhance αvβ6 integrin affinity as well as target‐specific in‐vivo uptake. Ga‐68‐TRAP(SDM17)3 showed a 28‐fold higher αvβ6 affinity than the corresponding monomer Ga‐68‐NOTA‐SDM17 (IC50 of 0.26 vs. 7.4 nM, respectively), a 13‐fold higher IC50‐based selectivity over the related integrin αvβ8 (factors of 662 vs. 49), and a threefold higher tumor uptake (2.1 vs. 0.66 %ID/g) in biodistribution experiments with H2009 tumor‐bearing SCID mice. The remarkably high tumor/organ ratios (tumor‐to‐blood 11.2; ‐to‐liver 8.7; ‐to‐pancreas 29.7) enabled high‐contrast tumor delineation in PET images. We conclude that Ga‐68‐TRAP(SDM17)3 holds promise for improved clinical PET diagnostics of carcinomas and fibrosis.
Direct Synthesis of Ammonia from N2 and H2O on Different Iron Species Supported on Carbon Nanotubes using a Gas‐Phase Electrocatalytic Flow Reactor
Authors: Chen Shiming , Perathoner Siglinda , Ampelli Claudio , Wei Hua , Abate Salvatore , Zhang Bingsen , Centi Gabriele 
Published: May 2020

AbstractGreen NH3 production by direct electrocatalytic synthesis from N2 and H2O is still a challenging reaction, which requires us to better understand the nature of the active materials. We show here that iron oxide (Fe2O3) nanoparticles (supported over carbon nanotubes, CNTs) become more active than the corresponding samples after reduction to form Fe‐ or Fe2N‐supported nanoparticles, both indicated as active species in the thermal catalytic reduction of N2 to ammonia. Characterization data, however, indicate that even for these Fe‐ and Fe2N−CNT samples, obtained from Fe2O3−CNT by reduction in H2 or NH3 at 500 °C, the active species responsible for N2 reduction reaction (NRR) at low applied potential (−0.5 V vs RHE) are the same, that is, small (<1–2 nm) iron oxide nanoparticles that are not detected by XRD, but evidenced by XPS and which amount could be correlated to the rate of ammonia formation. This species is stable for at least 24 h of electrocatalytic flow tests. However, at higher applied potentials, sintering/transformation of this species occurs, with loss of the electrocatalytic activity, and Fe2N nanoparticles may also be reduced in situ, forming ammonia, but with irreversible deactivation.
Bismuth Oxychloride Dispersed on Nitrogen‐Doped Carbon as Catalyst for the Electrochemical Reduction of CO2 to Formate
Authors: Subramanian Siddhartha , Chukwuike V. I. , Kulandainathan M. Anbu , Barik Rakesh C. 
Published: May 2020

AbstractElectrochemical reduction of CO2 has received significant interest for converting CO2 to value added products and closing the carbon cycle. Recent advances through catalyst development have aided in satisfying the requirements of achieving a high product selectivity, activity and long‐term stability. Among various industrially valuable products, formic acid has found numerous applications such asin fuel cells and textile industry. In this work, we report the synthesis of bismuth oxychloride dispersed on nitrogen‐doped carbon through a facile ion adsorption process using bismuth acetate, hydrochloric acid and urea as precursors, and discuss its performance as an electrocatalyst for the electrochemical reduction of CO2 to formate. The results show that bismuth oxychloride dispersed on nitrogen‐doped carbon has good catalytic activity for CO2 reduction to formate in 0.5 M KHCO3, achieving a maximum faradaic efficiency of 84.3 % at −0.87 V versus RHE. The catalyst is found to be stable for 5 h of continuous operation and achieves a turnover frequency of 146.36 h−1.
Trifluorosulfonylation Cascade in Allenols: Stereocontrolled Synthesis of Bis(triflyl)enones
Authors: Lázaro‐Milla Carlos , Macicior Jon , Yanai Hikaru , Almendros Pedro 
Published: May 2020

AbstractHerein, we report investigations embodying the first example of reversal of the native regioselectivity in the reaction of allenols with electrophiles. The effortlessness of C−C bond formation, mild reaction conditions, neither catalysts nor light irradiation, and exquisite selectivity, both in terms of functional‐group tolerance and chemo‐, site‐, and stereo‐selectivity, converts this trifluorosulfonylation‐rearrangement sequence into an appealing protocol for the preparation of novel functionalized enones. The synthetic utility of this method has been validated by the conversion of the initially prepared bis(triflyl)enones into a variety of bis(triflyl)‐functionalized molecules such as 1,3‐dienes, allylic alcohols, pyrroles, pyrazoles, and chromenes. Besides, DFT calculations have provided a reliable understanding of observed selectivity.
Cobalt‐Catalyzed α‐Arylation of Substituted α‐Bromo α‐Fluoro β‐Lactams with Diaryl Zinc Reagents: Generalization to Functionalized Bromo Derivatives
Authors: Lorion Mélanie M. , Koch Vanessa , Nieger Martin , Chen Hi‐Yung , Lei Aiwen , Bräse Stefan , Cossy Janine 
Published: May 2020

AbstractA cobalt‐catalyzed cross‐coupling of α‐bromo α‐fluoro β‐lactams with diarylzinc or diallylzinc reagents is herein disclosed. The protocol proved to be general, chemoselective and operationally simple allowing the C4 functionalization of β‐lactams. The substrate scope was expanded to α‐bromo lactams and amides, α‐bromo lactones and esters as well as N‐ and O‐containing heterocycles.
A Stable Homoleptic Organometallic Iron(IV) Complex
Authors: Prakash Om , Chábera Pavel , Rosemann Nils W. , Huang Ping , Häggström Lennart , Ericsson Tore , Strand Daniel , Persson Petter , Bendix Jesper , Lomoth Reiner , Wärnmark Kenneth 
Published: May 2020

AbstractA homoleptic organometallic FeIV complex that is stable in both solution and in the solid state at ambient conditions has been synthesized and isolated as [Fe(phtmeimb)2](PF6)2 (phtmeimb=[phenyl(tris(3‐methylimidazolin‐2‐ylidene))borate]−). This FeIV N‐heterocyclic carbene (NHC) complex was characterized by 1H NMR, HR‐MS, elemental analysis, scXRD analysis, electrochemistry, Mößbauer spectroscopy, and magnetic susceptibility. The two latter techniques unequivocally demonstrate that [Fe(phtmeimb)2](PF6)2 is a triplet FeIV low‐spin S=1 complex in the ground state, in agreement with quantum chemical calculations. The electronic absorption spectrum of [Fe(phtmeimb)2](PF6)2 in acetonitrile shows an intense absorption band in the red and near IR, due to LMCT (ligand‐to‐metal charge transfer) excitation. For the first time the excited state dynamics of a FeIV complex was studied and revealed a ≈0.8 ps lifetime of the 3LMCT excited state of [Fe(phtmeimb)2](PF6)2 in acetonitrile.
Palladium(II)‐η3‐Allyl Complexes Bearing N‐Trifluoromethyl N‐Heterocyclic Carbenes: A New Generation of Anticancer Agents that Restrain the Growth of High‐Grade Serous Ovarian Cancer Tumoroids
Authors: Scattolin Thomas , Bortolamiol Enrica , Visentin Fabiano , Palazzolo Stefano , Caligiuri Isabella , Perin Tiziana , Canzonieri Vincenzo , Demitri Nicola , Rizzolio Flavio , Togni Antonio 
Published: May 2020

AbstractThe first palladium organometallic compounds bearing N‐trifluoromethyl N‐heterocyclic carbenes have been synthesized. These η3‐allyl complexes are potent antiproliferative agents against different cancer lines (for the most part, IC50 values fall in the range 0.02–0.5 μm). By choosing 1,3,5‐triaza‐7‐phosphaadamantane (PTA) as co‐ligand, we can improve the selectivity toward tumor cells, whereas the introduction of 2‐methyl substituents generally reduces the antitumor activity slightly. A series of biochemical assays, aimed at defining the cellular targets of these palladium complexes, has shown that mitochondria are damaged before DNA, thus revealing a behavior substantially different from that of cisplatin and its derivatives. We assume that the specific mechanism of action of these organometallic compounds involves nucleophilic attack on the η3‐allyl fragment. The effectiveness of a representative complex, 4 c, was verified on ovarian cancer tumoroids derived from patients. The results are promising: unlike carboplatin, our compound turned out to be very active and showed a low toxicity toward normal liver organoids.
Amphiphilic Organic Cages: Self‐Assembly into Nanotubes and Enhanced Anion‐π Interactions
Authors: Li Zi‐Ying , Li Chuanlong , Li Pan , Zuo Yong , Liu Xiaoning , Xu Shijun , Zou Lingyi , Zhuang Qixin , Gao Shan , Liu Xiaoyun , Zhang Shaodong 
Published: May 2020

AbstractAn amphiphilic organic cage was synthesized and used as self‐assembly synthon for the fabrication of novel functional supramolecular structures in solution. The transmission electron microscopy (TEM) results showed that this amphiphilic cage self‐assembled in aqueous solution into unilamellar nanotubes with a diameter of 29±4 nm at a concentration of 0.05 mg mL−1. Interestingly, the self‐assembly of this cage significantly enhanced the anion‐π interactions as indicated by a remarkable increasement of association constant (Ka) between Cl− and this amphiphilic cage after self‐assembly. In specific, Ka was increased from 223 M−1 for discrete cages in methanol to 6800 M−1 for aggregated cages after self‐assembly in water at the same concentration of 2.26×10−5 M. A mechanism based on a synergistic effect was proposed in order to explain this self‐assembly process through enhanced anion‐π interactions.
Implementation of a separate fluid‐neutral energy equation in SOLPS‐ITER and its impact on the validity range of advanced fluid‐neutral models
Authors: Van Uytven Wim , Blommaert Maarten , Dekeyser Wouter , Horsten Niels , Baelmans Martine 
Published: May 2020

AbstractIn plasma edge transport codes for nuclear fusion devices, fluid‐neutral models offer an interesting alternative to the currently used kinetic Monte Carlo simulations, especially for cases of high ion‐neutral collisionality. In this paper, we elaborate a separate neutral energy equation in the state‐of‐the‐art SOLPS‐ITER code suite, which previously assumed perfect ion‐neutral temperature equilibration. Furthermore, we study the coupled plasma‐neutral solutions for a range of divertor operating regimes, proving the validity of these fluid‐neutral models for high‐recycling and detached regimes.
Renal malakoplakia mimicking a malignancy and diagnosed by fine‐needle aspiration: A case report
Authors: Ho Linh , Mehrotra Sanjana 
Published: May 2020

AbstractMalakoplakia is a rare, granulomatous disease that affects a wide variety of organs and can have a clinical and radiographic presentation resembling that of malignancy. The genitourinary tract is the most commonly involved site. There are scant reported cases presenting as a locally advanced renal mass and even rarer, diagnosed by fine‐needle aspiration (FNA) cytology. We report clinical, imaging, cytologic, and histological findings of an interesting case of malakoplakia initially diagnosed by FNA cytology. We also briefly review the literature and emphasize the importance of recognizing this entity when encountered in an aspirate material, which can help mitigate the diagnostic confusion of malakoplakia for clinicians.
In vivo pharmacokinetic study and oral glucose tolerance test of sulfoxide analogs of GPR40 agonist TAK‐875
Authors: Yan Yugang , Xu Qifu , Zhao Chunlong , Dong Hang , Xu Wenfang , Zhang Yingjie 
Published: May 2020

AbstractTAK‐875 (compound 1) was the only GPR40 agonist with promising oral glucose‐lowering effect, which entered phase III clinical trials. In previous studies, we successfully synthesized the TAK‐875 sulfoxide analog 2, which was further separated to optically pure compounds 3 (S, S, 100.0% de) and 4 (R, S, 100.0% de). In vitro biological evaluation revealed that the sulfoxide analogs 3 and 4 possessed comparable GPR40 agonist activity to TAK‐875. Herein, in order to further evaluate the druglikeness of TAK‐875 sulfoxide analogs, the pharmacokinetic properties of compounds 2, 3, and 4 in rats were investigated and compared with that of TAK‐875. The results showed that sulfoxide (2, 3, and 4) and sulfone (TAK‐875) could be converted into each other in different degrees in vivo. Interestingly, compound 3 showed higher drug exposure calculated by the AUC sum of sulfoxide and sulfone in plasma than TAK‐875, 2 and 4. In order to further investigate the in vivo glucose‐lowering potency of sulfoxide analogs, asymmetric synthesis was carried out and led to two sulfoxides with moderate de values, 5 (S, S, 66.4% de) and 6 (R, S, 71.0% de). The following oral glucose tolerance test (OGTT) in rats showed that 5 (S, S, 66.4% de) had stronger glucose‐lowering effect in vivo than 6 (R, S, 71.0% de) and TAK‐875, which could be partly rationalized by the superior pharmacokinetic property of sulfoxide 3 (the main component of 5) relative to sulfoxide 4 (the main component of 6) and TAK‐875.
In vitro–in vivo evaluation of tetrahydrozoline‐loaded ocular in situ gels on rabbits for allergic conjunctivitis management
Authors: Okur Neslihan Üstündağ , Yozgatli Vildan , Okur Mehmet Evren 
Published: May 2020

AbstractOcular allergy is one of the most common disorders of the eye surface. The conventional eye drops lack of therapeutic efficacy due to low ocular bioavailability and decreased drug residence time on eye surface. Hence, the present research work aimed to formulate, optimize, and evaluate the in situ gel for ophthalmic drug delivery. The prepared in situ gel formulations were evaluated for clarity, pH, gelling capacity, viscosity, osmolality, in vitro release study, and kinetic evaluation. ex vivo corneal permeation/penetration study using goat and in vivo studies on rabbits were also performed. Fourier‐transformed infrared spectroscopy was also applied to study possible interactions between drug and polymers. The formulations found to be stable, nonirritant, and showed sustained release of the drug for a period of up to 24 hr with no ocular damage. The developed in situ gels loaded with tetrahydrozoline are alternative and promising ocular candidates for the treatment of allergic conjunctivitis.