bluuebunny/crossref_metadata_2025 huggingface dataset:
Highly Efficient and Stereoselective Mukaiyama Aldol Reaction with Chiral Aziridine‐2‐carboxaldehyde and Its Synthetic Applications
Authors: Srivastava Nikhil , Ha Hyun‐Joon
Published: October 2021

A straightforward and highly diastereoselective synthesis of β‐(aziridin‐2‐yl)‐β‐hydroxy ketones was achieved by the Mukaiyama aldol reaction of optically pure 1‐(α‐methylbenzyl)‐aziridine‐2‐carboxaldehyde and various enol‐silanes in ZnCl2 via a chelation‐controlled transition state (98 : 2 dr and >82% yields). These β‐(aziridin‐2‐yl)‐β‐hydroxy ketones were applied for the synthesis of various alkaloids including epiallo‐isomuscarine, epi‐enigmol, and epi‐galantinic acid.
Stereodivergent Synthesis of Enantioenriched γ‐Butyrolactones Bearing Two Vicinal Stereocenters Enabled by Synergistic Copper and Iridium Catalysis
Authors: Xiao Lu , Wei Liang , Wang Chun‐Jiang
Published: October 2021

By virtue of a fundamentally new reaction model of azomethine ylide serving as a two‐atom synthon, we present the first example of stereodivergent preparation of γ‐butyrolactones via synergistic Cu/Ir‐catalyzed asymmetric cascade allylation/lactonization, and all four stereoisomers of γ‐butyrolactones bearing two vicinal stereocenters are accessible with excellent diastereoselective and enantioselective control. The chiral IrIII‐π‐allyl intermediate was separated and characterized to understand the origin of the regio‐ and stereoselectivity of the initial C−C bond formation process. Control experiments shed some light on the catalyst/substrate and catalyst/catalyst interactions in this dual catalytic system to rationalize the related kinetic/dynamic kinetic resolution process with different catalyst combinations. The enantioenriched γ‐butyrolactone products were converted into an array of structurally complex chiral molecules and organocatalysts that were otherwise inaccessible.
Optimized Synthesis of Solution‐Processable Crystalline Poly(Triazine Imide) with Minimized Defects for OLED Application
Authors: Burmeister David , Tran Ha Anh , Müller Johannes , Guerrini Michele , Cocchi Caterina , Plaickner Julian , Kochovski Zdravko , List‐Kratochvil Emil J. W. , Bojdys Michael J.
Published: October 2021

Poly(triazine imide) (PTI) is a highly crystalline semiconductor, and though no techniques exist that enable synthesis of macroscopic monolayers of PTI, it is possible to study it in thin layer device applications that are compatible with its polycrystalline, nanoscale morphology. We find that the by‐product of conventional PTI synthesis is a C−C carbon‐rich phase that is detrimental for charge transport and photoluminescence. An optimized synthetic protocol yields a PTI material with an increased quantum yield, enabled photocurrent and electroluminescence. We report that protonation of the PTI structure happens preferentially at the pyridinic N atoms of the triazine rings, is accompanied by exfoliation of PTI layers, and contributes to increases in quantum yield and exciton lifetimes. This study describes structure–property relationships in PTI that link the nature of defects, their formation, and how to avoid them with the optical and electronic performance of PTI. On the basis of our findings, we create an OLED prototype with PTI as the active, metal‐free material.
Streptococcus oralis endocarditis leading to central nervous system infection in pregnancy
Authors: Wydall S. , Durrant F. , Scott J. , Cheesman K.
Published: October 2021

This report describes a challenging obstetric case in which septic emboli from Streptococcus oralis endocarditis subsequently led to central nervous system infection. There were delays in diagnosis as the patient presented with non‐specific symptoms of fever, diarrhoea and vomiting, initially suspected to be due to viral gastroenteritis and later SARS‐CoV‐2 infection. Antibiotics were commenced once gram positive cocci were isolated from a blood culture. The patient made no significant improvement despite antimicrobial therapy and subsequently developed a worsening headache and delirium. This deterioration was not rapidly recognised despite the use of a routine obstetric early warning score. However, a diagnosis of meningitis was made once the potential severity of the patient’s condition was recognised and Streptococcus oralis was identified in cerebrospinal fluid and blood cultures. Bacterial endocarditis was diagnosed following transthoracic echocardiography. The patient improved with optimised antimicrobial therapy and delivered a healthy baby. This example highlights how non‐specific symptoms can be caused by rare and life‐threatening illnesses, and emphasises that early warning scores might not easily identify neurological deterioration in obstetric patients.
Exploring the influence of electron beam crosslinking in SEBS/TPU and SEBS‐g‐MA/TPU thermoplastic elastomer blends
Authors: Anagha M. G. , Chatterjee Tuhin , Picchioni Francesco , Naskar Kinsuk
Published: October 2021

The effects of electron beam (EB) radiation in thermoplastic elastomers based on SEBS/TPU and SEBS‐g‐MA/TPU are evaluated. 60/40 blend of both the systems were subjected to EB using an ILU type industrial accelerator. Radiation dose was varied from 0 to 100 kGy, and the sol–gel content evaluation along with detailed analysis of mechanical, thermal, rheological, and morphological implications was conducted. The interplay between crosslinking and chain scission was quantified using the Charlesby‐Pinner equation. Both the blends showed the presence of a three‐dimensional cross‐linked network in them after the irradiation. The tensile strength of SEBS/TPU was found to deteriorate with an increase in radiation dose, but an opposite trend was observed in SEBS‐g‐MA/TPU. Improvement in interfacial adhesion between SEBS‐g‐MA and TPU was confirmed. The morphological analysis through atomic force microscopy and scanning electron microscopy clearly showed the appearance of rough ridges and pits due to irradiation along with the cross‐linked networks. From differential scanning calorimetry analysis, the changes in glass transitions and melting endotherm were assessed. Thermogravimetric analysis results indicated an improvement in the thermal stability of the blends. The storage modulus and complex viscosity of the samples enhanced as perceived from the rheological measurements. X‐ray diffraction patterns of the blends also showed considerable variation after irradiation.
Dielectric properties of organophosphorus polyurethane ionomers
Authors: Davletbaeva Ilsiya , Sazonov Oleg , Nikitina Elizaveta , Kapralova Victoria , Nizamov Aidar , Akhmetov Ildar , Arkhipov Alexander , Sudar Nicolay
Published: October 2021

The dielectric and physical‐mechanical properties of organophosphorus polyurethane ionomers based on the ethers and aminoethers of ortho‐phosphoric acid have been investigated. The influence of the content of ionogenic groups and polyphosphate structures on the dielectric properties of polyurethanes has been analyzed. It is shown that the values of dielectric permittivity and tangent of dielectric loss in a wide frequency range increase with the content of ionogenic groups in polyurethanes studied. In this case, the increase in conductivity is diffusive in nature and is due to the mobility of protons within the phosphate anion clusters. The compositions of samples with a combination of high dielectric properties and excellent physical‐mechanical and adhesion characteristics have been determined. These are samples in which polyphosphate structures are present in addition to phosphate anions.
Direct bonding and de‐bonding on demand of polystyrene and polyamide surfaces, treated with oxygen plasma
Authors: Günther Roman , Caseri Walter R. , Brändli Christof
Published: October 2021

Smooth polystyrene (PS) and polyamide 12 (PA 12) surfaces were produced via an injection molding process followed by a smoothing process and subsequently treated with O2 plasma to increase the number of polar groups capable of hydrogen bond formation on the surface. The presence of related groups was evident from X‐ray photoelectron spectroscopy (XPS) and contact angle measurements. The sample topographies were investigated by atomic force microscopy (AFM). The plasma treatment allowed the joining of the substrates without adhesive by pressing the substrates together below or around the glass transition temperature. Notably, not only substrates of the same polymer but also PS and PA 12, which are incompatible, were joined with this method. The adhesion between the substrates was determined using a LUMifrac apparatus. The adhesion strength increased with increasing bonding temperature and when both substrates were plasma‐treated, reaching adhesive strengths up to 5.5 ± 1.7 MPa. Remarkably, the joint substrates could be rapidly de‐bonded on demand simply by treatment with water, and the separated substrates could be re‐bonded by renewed plasma treatment.
Identifying mineral decrement with bone injury by quantifying osteocalcin on current‐volt sensor
Authors: Bi Huanjie , Bian Peimin , Gopinath Subash C. B. , Marimuthu Kasi , Lv Genbing , Yin XinHua
Published: October 2021

Osteoporosis, a bone disease is caused by the deterioration of bone and shows an enhanced risk of bone fracture and decreasing bone mineral density. Unfortunately, the available radiological techniques are expensive, and have disadvantages such as radiation intake, need a specialist to handle the instrument, and so forth. This research is focused to develop a point‐of‐care system to identify osteocalcin on current‐volt sensor, which helps to diagnose the bone metabolism and prognostics. Antiosteocalcin antibody was attached on the electrode through the silane‐modified iron material. The antibody‐immobilized sensing surface was utilized to identify the level of osteocalcin and the detection limit of 100 pg/ml reached on linear concentrations of 0.01–3000 ng/ml. Calculations were made by triplicates (n = 3; 3δ) on the determination coefficient ofy = 0.2637x–0.6012;R2= 0.9319. Further, control proteins failed to bind with immobilized antibody, confirmed by the specific osteocalcin detection. This research is to identify the osteoporosis biomarker and to help determine the conditions with osteoporosis.
An electrochemical aptasensor for detection of prostate‐specific antigen using reduced graphene gold nanocomposite and Cu/carbon quantum dots
Authors: Mehdipour Golnaz , Shabani Shayeh Javad , Omidi Meysam , Pour Madadi Mehrab , Yazdian Fatemeh , Tayebi Lobat
Published: October 2021

We report a label‐free electrochemical aptamer‐based biosensor for the detection of human prostate‐specific antigen (PSA). The thiolate DNA aptamer against PSA was conjugated to the reduced graphene oxide/Au (RGO‐Au) nanocomposite through the self‐assembly of Au‐S groups. Owing to the large volume to surface ratio, the RGO‐Au nanocomposite provides a large surface for aptamer loading. The RGO‐Au/aptamer was combined with a Nafion polymer and immobilized on a glassy carbon electrode. The interaction of aptamer with PSA was studied by cyclic voltammetry, square wave voltammetry, and electrochemical impedance spectroscopy. The detection of limit for prepared electrode was obtained about 50 pg/mL at the potential of 0.4 V in potassium hexacyanoferrate [K4Fe(CN)6] medium. To decrease the limit of detection (LOD) and applied potential of the prepared nanoprobe Cu/carbon quantum dots (CuCQD) is introduced as a new redox. The results show that this new electrochemical medium provides better conditions for the detection of PSA. LOD of a nanoprobe in CuCQD media was obtained as 40 pg/mL at the potential of −0.2 V. Under optimal conditions, the aptasensor exhibits a linear response to PSA with a LOD as small as 3 pg/mL. The present aptasensor is highly selective and sensitive and shows satisfactory stability and repeatability.
Estimating the correlation between semi‐competing risk survival endpoints
Authors: Sorrell Lexy , Wei Yinghui , Wojtyś Małgorzata , Rowe Peter
Published: October 2021

Time‐to‐event, bivariate, semi‐competing risk data occur when a terminal event can censor a non‐terminal event, but not vice versa. There are potential correlations between these endpoints as they are measured on the same individual. However, traditional methods to estimate the correlations cannot be used directly due to the censoring of time‐to‐event endpoints. We develop methods using a copula‐based approach to study the dependence structures between the two survival endpoints. We use a variety of copulas to estimate the correlation between endpoints and to acknowledge different dependence structures. The estimated association parameter in the copula function is transformed into Spearman's rank correlation coefficient. We conduct a simulation study to evaluate the estimation from the proposed models along with the effects of misspecification of the copula functions and survival distributions. The proposed methods are applied to two real‐life data sets.
Stability assessment of FDA‐approved ramucirumab monoclonal antibody; validated SE‐HPLC method for degradation pattern evaluation
Authors: Abdelghaffar Sara Hesham , Hegazy Maha Abdelmonem , Eltanany Basma Mohamed
Published: October 2021

Ramucirumab (RAMU) is a recently US Food and Drug Administration‐approved monoclonal antibody that is included in various anticancer protocols. It has a structural complexity and high degradation risk that have a significant effect on its safety and effectiveness. The major aim of this work was to assess the degradation pattern of RAMU based on physicochemical characterization. Mechanical agitation, repeated freeze–thaw cycles, pH and temperature were the selected stress conditions to which RAMU samples were subjected. The SE‐HPLC method was applied and validated to monitor the RAMU monomer along with its aggregates and/or fragments. The purity of the separated peaks together with system suitability parameters were determined through the calculation of percentage purity and percentage drop in RAMU concentration. The results were interpreted by correlating them with those of dynamic light scattering and reducing and non‐reducing sodium dodecyl sulfate–polyacrylamide gel electrophoresis. Samples incubated at pH 2.0–10.0 and 37°C for up to 4 weeks were analysed, recording detection of reversed phase (RP) aggregates and low molecular weight peptide fragments. Similarly, samples under short‐term storage conditions of 4 weeks at different temperatures (−20, 2–8, 25, 37 and 50°C) showed low molecular weight peptide fragments but to a lesser extent. These results highlight the alarming effect on RAMU multidose vial efficacy and safety.
Structure and agency in capabilities‐enhancing homeless services: Housing first, housing quality and consumer choice
Authors: Greenwood Ronni Michelle , Manning Rachel M. , O'Shaughnessy Branagh R. , Vargas‐Moniz Maria J. , Auquier Pascal , Lenzi Michela , Wolf Judith , Bokszczanin Anna , Bernad Roberto , Källmén Håkan , Spinnewijn Freek , Ornelas Jose ,   the Home_EU Consortium
Published: October 2021

The capabilities approach, a framework for understanding and measuring inequality, stipulates that equality is best understood as the freedom to do and be within a particular context. Homelessness has been referred to as a situation of ‘capabilities deprivation’, and the extent to which homeless services restore or enhance capabilities is of increasing interest. As part of a large, eight‐country study of homelessness in Europe, we examined the extent to which adults with histories of homelessness perceived the services they receive as capabilities‐enhancing. We collected data at two time points: baseline (nt1 = 565) and follow‐up (nt2 = 399). Measures included perceived capabilities, choice and housing quality. Participants engaged with Housing First (HF) programmes perceived services as more capabilities‐enhancing than participants engaged with treatment as usual (TAU); this relationship was mediated by consumer choice and perceived housing quality. Implications for social policy, practice and training are discussed.
Chemical Composition and Phytotoxic Activity of Artemisia selengensis Turcz. Volatiles
Authors: Shi Kai , Zhou Shixing , Lei Lijing , Huang Ling , Zhang Chi , Shao Hua
Published: October 2021

The chemical profile and allelopathic action of the volatiles produced by Artemisia selengensis were studied. Artemisia selengensis was found to release volatile chemicals to the environment to influence other plants’ growth, which suppressed the root length of Amaranthus retroflexus and Poa annua by 50.46 % and 87.83 % under 80 g/1.5 L treatment, respectively. GC/MS analysis led to the identification of 41 compounds (by hydrodistillation, HD) and 48 compounds (by headspace solid‐phase microextraction, HS‐SPME), with eucalyptol (15.45 % by HD and 28.09 % by HS‐SPME) being detected as the most abundant constituent. The essential oil (EO) of A. selengensis completely inhibited the seed germination of A. retroflexus and P. annua at 1 mg/mL and 0.5 mg/mL, respectively. However, eucalyptol displayed much weaker activity compared with the EO, indicating that other less abundant constituents might contribute significantly to the EO's activity. Our study is the first report on the phytotoxicity of A. selengensis EO, suggesting that A. selengensis might release allelopathic volatile agents into the environment that negatively affect other plants’ development so as to facilitate its own dominance; the potential value of utilizing A. selengensis EO as an environmentally friendly herbicide is also discussed.
Investigation on the Phytochemical Composition, Antioxidant and Enzyme Inhibition Potential of Polygonum Plebeium R.Br: A Comprehensive Approach to Disclose New Nutraceutical and Functional Food Ingredients
Authors: Saleem Muhammad , Shazmeen Natasha , Nazir Mamona , Riaz Naheed , Zengin Gokhan , Ataullah Hafiz Muhammad , Qurat‐ul‐Ain  , Nisar Farrukh , Mukhtar Mahreen , Tousif Muhammad Imran
Published: October 2021

The present work describes medicinal potential and secondary metabolic picture of the methanol extract (PP‐M) of Polygonum plebeium R.Br. and its fractions; hexane (PP‐H), ethyl acetate (PP‐E) and water (PP‐W). In total bioactive component estimation, highest contents of phenolic (89.38±0.27 mgGAE/g extract) and flavonoid (51.21±0.43 mgQE/g extract) were observed in PP‐E, and the same fraction exhibited the highest antioxidant potential in DPPH (324.80±4.09 mgTE/g extract), ABTS (563.18±11.39 mgTE/g extract), CUPRAC (411.33±15.49 mgTE/g extract) and FRAC (369.54±1.70 mgTE/g extract) assays. In Phosphomolybdenum activity assay, PP‐H and PP‐E showed nearly similar potential, however, PP‐H was the most active (13.54±0.24 mgEDTAE/g extract) in metal chelating activity assay. PP‐W was the stronger inhibitor (4.03±0.05 mgGALAE/g extract) of the enzyme AChE, while PP‐H was potent inhibitor of BChE (5.62±0.27 mg GALAE/g extract). Interestingly, PP‐E was inactive against BChE. Against tyrosinase activity, PP‐E was again the most active fraction with inhibitory value of 71.89±1.44 mg KAE/g extract, followed by the activity of PP‐M and PP‐W. Antidiabetic potential was almost equally distributed among PP‐M, PP‐H and PP‐E. For mapping the chemodiversity of P. plebeium, PP‐M was analyzed through UHPLC/MS, which led to the identification of more than 50 compounds. Flavonoids were the main components derived from isovitexin, kaempferol and luteolin however, gallic acid, protocatechuic acid, gingerols and lyoniresinol 9′‐sulfate were among important bioactive phenols. These findings prompted to conclude that Polygonum plebeium can be a significant source to offer new ingredient for nutraceuticals and functional foods.
Controlling Enzymatic Activity by Modulating the Oligomerization State via Chemical Rescue and Optical Control
Authors: Kropp Cosimo , Bruckmann Astrid , Babinger Patrick
Published: October 2021

Selective switching of enzymatic activity has been a longstanding goal in synthetic biology. Drastic changes in activity upon mutational manipulation of the oligomerization state of enzymes have frequently been reported in the literature, but scarcely exploited for switching. Using geranylgeranylglyceryl phosphate synthase as a model, we demonstrate that catalytic activity can be efficiently controlled by exogenous modulation of the association state. We introduced a lysine‐to‐cysteine mutation, leading to the breakdown of the active hexamer into dimers with impaired catalytic efficiency. Addition of bromoethylamine chemically rescued the enzyme by restoring hexamerization and activity. As an alternative method, we incorporated the photosensitive unnatural amino acid o‐nitrobenzyl‐O‐tyrosine (ONBY) into the hexamerization interface. This again led to inactive dimers, but the hexameric state and activity could be recovered by UV‐light induced cleavage of ONBY. For both approaches, we obtained switching factors greater than 350‐fold, which compares favorably with previously reported activity changes that were caused by site‐directed mutagenesis.
Cutaneous angiosarcoma presenting as band‐shaped erythematous plaques on the neck
Authors: Matsudate Yoshihiro
Published: October 2021

Band‐shaped presentation of cutaneous angiosarcoma has not been reported. Cutaneous angiosarcoma should be included in the differential diagnosis when a persistent erythematous lesion is observed in the head and neck region of an elderly patient without a clear explanation, but skin biopsy is required for an accurate diagnosis.
Controlling the Production of Acid Catalyzed Products of Furfural Hydrogenation by Pd/TiO2
Authors: Tierney George F. , Alijani Shahram , Panchal Monik , Decarolis Donato , de Gutierrez Martha Briceno , Mohammed Khaled M. H. , Callison June , Gibson Emma K. , Thompson Paul B. J. , Collier Paul , Dimitratos Nikolaos , Corbos E. Crina , Pelletier Frederic , Villa Alberto , Wells Peter P.
Published: October 2021

We demonstrate a modified sol‐immobilization procedure using (MeOH)x/(H2O)1‐x solvent mixtures to prepare Pd/TiO2 catalysts that are able to reduce the formation of acid catalyzed products, e. g. ethers, for the hydrogenation of furfural. Transmission electron microscopy found a significant increase in polyvinyl alcohol (PVA) deposition at the metal‐support interface and temperature programmed reduction found a reduced uptake of hydrogen, compared to an established Pd/TiO2 preparation. We propose that the additional PVA hinders hydrogen spillover onto the TiO2 support and limits the formation of Brønsted acid sites, required to produce ethers. Elsewhere, the new preparation route was able to successfully anchor colloidal Pd to the TiO2 surface, without the need for acidification. This work demonstrates the potential for minimizing process steps as well as optimizing catalyst selectivity – both important objectives for sustainable chemistry.
Trace Single‐Atom Iron‐Decorated Nitrogen‐Doped Carbons Enable Highly Efficient Selective Oxidation of Ethyl Benzene
Authors: Wang Shiyi , Qiao Panzhe , Mou Xiaoling , Zhu Hejun , Jiang Zheng , Lin Ronghe , Ding Yunjie
Published: October 2021

The hybridization of abundant transition metals with facile nitrogen‐doped carbons is an effective strategy to fabricate advanced functional materials for targeted applications. Herein, we demonstrate a novel and straightforward synthetic approach of preparing a series of different transition metal‐modified nitrogen‐doped carbons (M/NC, M=Fe, Co, Ni) through the addition of corresponding metal sulfates during the polymerization of aniline, followed by high‐temperature (873–1273 K) pyrolysis treatment. While Fe/NC features predominantly single Fe atoms, nanoparticles of mixed metal oxides and or carbonates are formed on Co/NC and Ni/NC. When employed in the selective oxidation of ethyl benzene by using tert‐butyl hydroperoxide both as the solvent and the oxidant, these materials showed promoted catalytic response with the order of Fe>Co>Ni as compared with the metal‐free analogue. The performance can be further tuned by controlling the pyrolysis temperature, and the best performance can be achieved over Fe/NC‐1273 (0.153 wt.% Fe), affording an unprecedented acetophenone yield of 98 % and excellent cycling performance.
Tunable Linear and Nonlinear Optical Properties from Room Temperature Phosphorescent Cyclic Triimidazole‐Pyrene Bio‐Probe
Authors: Previtali Andrea , He Wei , Forni Alessandra , Malpicci Daniele , Lucenti Elena , Marinotto Daniele , Carlucci Lucia , Mercandelli Pierluigi , Ortenzi Marco Aldo , Terraneo Giancarlo , Botta Chiara , Kwok Ryan Tsz Kin , Lam Jacky Wing Yip , Tang Ben Zhong , Cariati Elena
Published: October 2021

Organic materials with multiple emissions tunable by external stimuli represent a great challenge. TTPyr, crystallizing in different polymorphs, shows a very rich photophyisics comprising excitation‐dependent fluorescence and phosphorescence at ambient conditions, and mechanochromic and thermochromic behavior. Transformation among the different species has been followed by thermal and X‐ray diffraction analyses and the emissive features interpreted through structural results and DFT/TDDFT calculations. Particularly intriguing is the polymorph TTPyr(HT), serendipitously obtained at high temperature but stable also at room temperature, whose non‐centrosymmetric structure guarantees an SHG efficiency 10 times higher than that of standard urea. Its crystal packing, where only the TT units are strongly rigidified by π‐π stacking interactions while the Pyr moieties possess partial conformational freedom, is responsible for the observed dual fluorescence. The potentialities of TTPyr for bioimaging have been successfully established.
Size‐Controlled Synthesis of β(1→4)‐GlcNAc Oligosaccharides Using an Endo‐Glycosynthase
Authors: Rousseau Antoine , Armand Sylvie , Cottaz Sylvain , Fort Sébastien
Published: October 2021

Chitin and peptidoglycan fragments are well recognized as pathogen associated molecular patterns (PAMPs). Long‐chain oligosaccharides of β(1→4)‐linked N‐acetyl‐D‐glucosamine (GlcNAc) units indeed activate plants and mammals innate immune system. However, the mechanisms underlying PAMPs perception by lysine motif (LysM) domain receptors remain largely unknown because of insufficient availability of high‐affinity molecular probes. Here, we report a two‐enzyme cascade to synthesize long‐chain β(1→4)‐linked GlcNAc oligomers. Expression of the D52S mutant of hen egg‐white lysozyme (HEWL) in Pichia pastoris at 52 mg L−1 provided a new glycosynthase catalyzing efficient polymerization of α‐chitintriosyl fluoride. Selective N‐deacetylation at the non‐reducing unit of the glycosyl fluoride donor by Sinorhizobium meliloti NodB chitin‐N‐deacetylase abolished its ability to be polymerized by the glycosynthase but not to be transferred onto an acceptor. Using NodB and D52S HEWL in a one‐pot cascade reaction allowed the synthesis on a milligram scale of chitin hexa‐, hepta‐ and octasaccharides with yields up to 65 % and a perfect control over their size.
Recovery of Phosphoric Acid from Spent Petrochemical Catalysts
Authors: Greb Valentin G. , Bertau Martin , Düker Axel , Geisbauer Andreas , Fröhlich Peter
Published: October 2021

Petrochemical catalysts are widely used in the industry. For the production of cumene, zeolite‐based catalysts containing phosphoric acid are applied. Over the time, coking deactivates the surface, and the catalyst has to be exchanged and disposed of. Different process approaches for recycling the phosphoric acid‐containing catalysts were investigated. Related preliminary investigations have shown that calcination of the used catalyst is necessary prior to reprocessing. By digesting the catalyst with hydrofluoric acid, ∼96 % phosphate was recovered. However, this process is very costly in terms of process technology. More promising is digestion by basic or acidic routes. Several options are possible here, and digestion with H3PO4 proved to be particularly suitable. Here, phosphate yields reached up to 98.8 %, with a positive balance of economic efficiency at the same time. The catalyst can be produced and recycled in the same plant with the same reagents, what constitutes a major breakthrough towards sustainability in industrial catalysis.
Estimated reproduction ratios in the SIR model
Authors: Elliott Sean , Gouriéroux Christian
Published: October 2021

The aim of this article is to understand the extreme variability in estimates of the reproduction ratio R0 observed in practice. For expository purposes, we consider a discrete‐time, stochastic version of the susceptible‐infected‐recovered model and introduce different approximate maximum likelihood estimators of R0. We carefully discuss the properties of these estimators and illustrate, by a Monte Carlo study, the widths of confidence intervals for R0.
Investigation of Basalt Properties as Heterogeneous Catalyst for Fenton Oxidation of Textile Wastewater
Authors: Saleh Mohammed , Yalvac Mutlu , Arslan Hudaverdi , Dizge Nadir
Published: October 2021

In this study, basalt is used as a catalyst for the removal of the dyes malachite green (MG) and crystal violet (CV) from aqueous solution. First, the effect of sintering temperature on Fenton process is optimized using basalt powder. Different analysis techniques such as X‐ray diffraction (XRD), X‐ray fluorescence (XRF), Brunauer‐Emmett‐Teller (BET), and Fourier‐Transform Infrared Spectroscopy (FTIR) are used to characterize basalt powder. It is concluded that Fe2O3 in basalt powder is the main component responsible for the degradation of dyes in the Fenton process. The maximum degradation of the dyes (97.02% for CV and 95.71% for MG) is obtained at 10 mg L−1 dye concentration, solution pH of 6, 1 g L−1 catalyst amount, and 12 mm H2O2 concentration for 2 h. The results are fitted to the second‐order kinetic model. The reusability of the catalyst is explored, and the basalt showed stability in the removal efficiency for repeated five cycles. The degradation of real textile wastewater is also studied. The removal efficiency reached up to 60.33% at optimum conditions of pH 2, basalt amount of 5 g L−1, H2O2 concentration of 400 mm. The results showed that the basalt powder is successfully utilized as a heterogeneous catalyst for textile wastewater treatment.
Consensus Virtual Screening Identified [1,2,4]Triazolo[1,5‐b]isoquinolines As MELK Inhibitor Chemotypes
Authors: Rácz Anita , Palkó Roberta , Csányi Dorottya , Riedl Zsuzsanna , Bajusz Dávid , Keserű György M.
Published: October 2021

Maternal Embryonic Leucine‐zipper Kinase (MELK) is a current oncotarget involved in a diverse range of human cancers, with the usage of MELK inhibitors being explored clinically. Here, we aimed to discover new MELK inhibitor chemotypes from our in‐house compound library with a consensus‐based virtual screening workflow, employing three screening concepts. After careful retrospective validation, prospective screening and in vitro enzyme inhibition testing revealed a series of [1,2,4]triazolo[1,5‐b]isoquinolines as a new structural class of MELK inhibitors, with the lead compound of the series exhibiting a sub‐micromolar inhibitory activity. The structure‐activity relationship of the series was explored by testing further analogs based on a structure‐guided selection process. Importantly, the present work marks the first disclosure of the synthesis and bioactivity of this class of compounds.
A Bivalent Supramolecular GCP Ligand Enables Blocking of the Taspase1/Importin α Interaction
Authors: Höing Alexander , Zimmermann Alexander , Moews Lisa , Killa Matthias , Heimann Marius , Hensel Astrid , Voskuhl Jens , Knauer Shirley K.
Published: October 2021

Taspase1 is a unique protease not only pivotal for embryonic development but also implicated in leukemia as well as solid tumors. As such, it is a promising target in cancer therapy, although only a limited number of Taspase1 inhibitors lacking general applicability are currently available. Here we present a bivalent guanidiniocarbonyl‐pyrrole (GCP)‐containing supramolecular ligand that is capable of disrupting the essential interaction between Taspase1 and its cognate import receptor Importin α in a concentration‐dependent manner in vitro with an IC50 of 35 μM. Here, size of the bivalent vs the monovalent construct as well as its derivation with an aromatic cbz‐group arose as critical determinants for efficient interference of 2GC. This was also evident when we investigated the effects in different tumor cell lines, resulting in comparable EC50 values (∼40–70 μM). Of note, in higher concentrations, 2GC also interfered with Taspase1’s proteolytic activity. We thus believe to set the stage for a novel class of Taspase1 inhibitors targeting a pivotal protein‐protein interaction prerequisite for its cancer‐associated proteolytic function.
Why it is our responsibility to speak out for a universal vaccination mandate
Authors: Sorscher Steven
Published: October 2021

Patients with cancer are among the most likely to suffer life‐threatening complications should they contract coronavirus disease 2019, yet despite encouragement from their oncologists, many continue to refuse to be vaccinated. On behalf of our patients, I believe that oncologists should now exhort our elected government to fulfill its most fundamental responsibility—protecting Americans from existential threats—by enacting either an emergency executive order or universal vaccination legislation and then by helping the rest of the world to vaccinate without delay.
Catalysts for Li−CO2 Batteries: From Heterogeneous to Homogeneous
Authors: Hao Qian Qian , Zhang Zhen , Mao Ya , Wang Kai Xue
Published: October 2021

Li−CO2 batteries attract extensive attention owing to their high energy density, fixation and utilization of CO2. However, the practical application of Li−CO2 batteries is greatly limited by the inferior electrochemical performance. The development of highly efficient electrocatalysts is the key to improve the performance of Li−CO2 batteries. This minireview focuses on both heterogeneous and homogeneous electrocatalysts for Li−CO2 batteries, which are introduced from the aspects of characteristics, mechanisms and design principles. Compared with heterogeneous catalysts, homogeneous catalysts can simplify the reaction interface, promoting the reaction kinetics and consequently resulting in the high electrochemical performance of Li−CO2 batteries. Finally, the issues of Li−CO2 batteries need to be addressed are outlined and corresponding perspectives of Li−CO2 batteries are also prospected.
Lightness perception of structured surfaces
Authors: Muth Felicitas V. , Heilig Michael , Marquardt Dorothea , Mittelberg Linda , Sebald Albrecht , Kunde Wilfried
Published: October 2021

Visual perception of surfaces is of utmost importance in everyday life. Therefore, it comes naturally, that different surface structures evoke different visual impressions in the viewer even if the material underlying these surface structures is the same. This topic is especially virulent for manufacturing processes in which more than one stakeholder is involved, but where the final product needs to meet certain criteria. A common practice to address such slight but perceivable differences in the visual appearance of structured surfaces is that trained evaluators assess the samples and assign a pass or fail. However, this process is both time consuming and cost intensive. Thus, we conducted two studies to analyze the relationship between physical surface structure parameters and participants visual assessment of the samples. With the first experiment, we aimed at uncovering a relationship between physical roughness parameters and visual lightness perception while the second experiment was designed to test participants' discrimination sensitivity across the range of stimuli. Perceived lightness and the measured surface roughness were nonlinearly related to the surface structure. Additionally, we found a linear relationship between the engraving parameter and physical brightness. Surface structure was an ideal predictor for perceived lightness and participants discriminated equally well across the entire range of surface structures.
Leveraging Human Plasma‐Derived Small Extracellular Vesicles as Liquid Biopsy to Study the Induction of Cytochrome P450 3A4 by Modafinil
Authors: Rodrigues A. David , Wood Linda S. , Vourvahis Manoli , Rowland Andrew
Published: October 2021

Preparations of plasma‐derived small extracellular vesicles (sEVs) were deployed as liquid biopsy to study cytochrome P450 (CYP) 3A4 (CYP3A4) induction following modafinil 400 mg once daily × 14 days (young healthy volunteers, N = 10 subjects). Induction was confirmed using the 4β‐hydroxycholesterol‐to‐cholesterol (4βHC/C) ratio, a plasma CYP3A4/5 biomarker, with a mean 2.1‐fold increase (Day 15 vs. Day 1; 90% confidence interval (CI) = 1.8–2.3; P value = 0.0004). Proteomic analysis revealed the induction (mean Day 15 vs. Day 1 fold‐increase (90% CI)) of both liver (1.3 (1.1–1.5), P value = 0.014) and nonliver (1.9 (1.6–2.2), P value = 0.04) sEV CYP3A4 protein expression. In CYP3A5 nonexpresser subjects, the baseline (pre‐dose) 4βHC/C plasma ratio was more highly correlated with liver sEVs (r = 0.937, P value = 0.001) than nonliver sEVs (r = 0.619, P value = 0.101) CYP3A4 protein expression. When CYP3A5 expressers (CYP3A5*1/*3) were included, the correlation with liver sEVs (r = 0.761, P value = 0.011) and nonliver sEVs (r = 0.391, P value = 0.264) CYP3A4 protein was weaker. Although modafinil‐induced changes in plasma 4βHC/C ratio did not correlate with sEVs CYP3A4 protein expression, the individual subject sEVs proteomic data were used successfully to predict victim drug (midazolam, triazolam, dextromethorphan, 17α‐ethinylestradiol, and abemaciclib) area under the plasma concentration‐time curve (AUC) ratios (AUCRs) following modafinil. Based on the AUCR values, modafinil was classified as a weak to moderate CYP3A4 inducer (vs. rifampicin). For the first time, it was possible to deploy plasma‐derived sEVs to study CYP3A4 induction beyond rifampicin, a more potent CYP3A4 inducer.
Big data applications on the Internet of Things: A systematic literature review
Authors: Ahmadova Ulkar , Mustafayev Mustafa , Kiani Kalejahi Behnam , Saeedvand Saeed , Rahmani Amir Masoud
Published: October 2021

The Internet of Things (IoT) is a system of physical objects embedded with various sensors to receive information, software, chips, and other technologies that allow connecting and transferring data to other devices through the Internet without human intervention. As the number of smart devices increase, IoT has started to be applied in many more fields. Therefore, there is a lot of information that should be processed. To manage this amount of data, some researchers proposed the usage of big data techniques. Big data are a collection of structured and unstructured data incoming with a high speed and large amounts. This paper investigates big data applications in IoT to comprehend the different published approaches using the systematic literature review (SLR) technique. This paper systematically studies the latest research methods on big data in IoT approaches published between 2016 and August 2021. A methodical taxonomy is shown for big data in IoT‐related fields consistent with the content of existing articles chosen with the SLR process in this research like healthcare, smart city, algorithms, industry, and general aspects in those environments. The advantages and drawbacks of each paper are presented, with specific proposals for stating their pros and cons open issues and advising possible research challenges in big data implementation in the IoT. The evaluation factors of big data applications in IoT are distributed as follows: security (18%), throughput (17%), cost (17%), energy consumption (15%), reliability (15%), response time (9%), and availability (9%).
Troxerutin regulates HIF‐1α by activating JAK2/STAT3 signaling to inhibit oxidative stress, inflammation, and apoptosis of cardiomyocytes induced by H2O2
Authors: Li Hui , Yang Min , Lou Danfei
Published: October 2021

Heart failure (HF) is greatly threatening human health and affecting morbidity and mortality worldwide. Troxerutin can alleviate myocardial injury induced by ischemia and hypoxia. The present study aimed to investigate the protective effect of troxerutin on H2O2‐induced cardiomyocytes and the underlying molecular mechanism. Primary mouse cardiomyocytes morphology induced by H2O2 in a different duration time was observed by a microscope. After indicated treatment, the viability and apoptosis of cardiomyocytes were detected by CCK‐8 assay and flow cytometry analysis. The expression of inflammatory factors and oxidative stress biomarkers was detected by Reverse transcription‐quantitative polymerase chain reaction (RT‐qPCR) and assay kits. Hypoxia inducible factor‐1a (HIF‐1α) expression was determined by western blot analysis, RT‐qPCR analysis and immunofluorescence staining. The apoptosis‐related protein expression and the phosphorylation level of janus‐activated kinase 2 (JAK2)/signal transducer and activator of transcription 3 (STAT3) were detected by the western blot analysis. As a result, after the H2O2 treatment in a different duration time, the primary mouse cardiomyocytes gradually stopped beating and the morphology of cardiomyocytes treated with H2O2 was changed significantly from fusiform shape to round shape. The viability of cardiomyocytes was decreased after H2O2 induction. The HIF‐1α expression was increased after the H2O2 treatment within 30 min while decreased over 30 min. In addition, troxerutin improved viability and suppressed apoptosis, inflammation and oxidative stress of H2O2‐induced cardiomyocytes, which was reversed by KC7F2 (a HIF‐1α inhibitor) or CHZ868 (a JAK inhibitor). To sum up, troxerutin could regulate HIF‐1α by activating JAK2/STAT3 signaling to inhibit oxidative stress, inflammation, and apoptosis of cardiomyocytes induced by H2O2.
LC‐HRMS/MS study of the prodrug ciclesonide and its active metabolite desisobutyryl‐ciclesonide in plasma after an inhalative administration to horses for doping control purposes
Authors: Trevisiol Stéphane , Moulard Yves , Kaabia Zied , Delcourt Vivian , Loup Benoit , Garcia Patrice , Boyer Sophie , Dauriac Karine , Groseille Guillaume , Rouger Sébastien , Narbe Ruediger , Popot Marie‐Agnès , Bailly‐Chouriberry Ludovic
Published: October 2021

Ciclesonide (CIC) is the first inhaled highly potent corticosteroid that does not cause any cortisol suppression. It has been developed for the treatment of asthma in human and more recently in equine. CIC is the active compound of Aservo® EquiHaler® (Boehringer Ingelheim Vetmedica GmbH), the pre‐filled inhaler generating a medicated mist based on Soft Mist™ technology. This prodrug is rapidly converted to desisobutyryl‐ciclesonide (des‐CIC), the main pharmacologically active compound. Due to its anti‐inflammatory properties, CIC is prohibited for use in horse competitions. To set up an appropriate control, the determination of detection times and screening limits are required. Therefore, a highly sensitive analytical method based on supported liquid extraction (SLE) combined with liquid chromatography–high resolution tandem mass spectrometry (LC‐HRMS/MS) was developed to detect CIC and its active metabolite des‐CIC in plasma. The lower limit of detection of CIC and des‐CIC was approximately 1 pg/ml in plasma. After a pilot study conducted on a single horse at the recommended dose (eight actuations twice daily corresponding to 5.5 mg/day for the first 5 days, followed by 12 actuations once daily corresponding to 4.1 mg/day in the last 5 days), the same protocol was applied in the main study using six horses. In all horses, CIC and des‐CIC levels were less than 5 and 10 pg/ml, respectively, at 36 h after the end of the administration. The outcome of this risk assessment study should be useful to draw any recommendations for horse competitions.
Experimental validation of taxon‐specific mini‐barcode primers for metabarcoding of zooplankton
Authors: Govender Ashrenee , Singh Sohana , Groeneveld Johan , Pillay Sureshnee , Willows‐Munro Sandi
Published: October 2021

Metabarcoding to determine the species composition and diversity of marine zooplankton communities is a fast‐developing field in which the standardization of methods is yet to be fully achieved. The selection of genetic markers and primer choice are particularly important because they substantially influence species detection rates and accuracy. Validation is therefore an important step in the design of metabarcoding protocols. We developed taxon‐specific mini‐barcode primers for the cytochrome c oxidase subunit I (COI) gene region and used an experimental approach to test species detection rates and primer accuracy of the newly designed primers for prawns, shrimps and crabs and published primers for marine lobsters and fish. Artificially assembled mock communities (with known species ratios) and unsorted coastal tow‐net zooplankton samples were sequenced and the detected species were compared with those seeded in mock communities to test detection rates. Taxon‐specific primers increased detection rates of target taxa compared with a universal primer set. Primer cocktails (multiple primer sets) significantly increased species detection rates compared with single primer pairs and could detect up to 100% of underrepresented target taxa in mock communities. Taxon‐specific primers recovered fewer false‐positive or false‐negative results than the universal primer. The methods used to design taxon‐specific mini‐barcodes and the experimental mock community validation protocols shown here can easily be applied to studies on other groups and will allow for a level of standardization among studies undertaken in different ecosystems or geographic locations.
Wilderness areas in a changing landscape: changes in land use, land cover, and climate
Authors: Aycrigg Jocelyn L. , Mccarley T. Ryan , Belote R. Travis , Martinuzzi Sebastian
Published: October 2021

Wilderness areas are not immune to changes in land use, land cover, and/or climate. Future changes will intensify the balancing act of maintaining ecological conditions and untrammeled character within wilderness areas. We assessed the quantitative and spatial changes in land use, land cover, and climate predicted to occur in and around wilderness areas by (1) quantifying projected changes in land use and land cover around wilderness areas; (2) evaluating if public lands surrounding wilderness areas can buffer future land‐use change; (3) quantifying future climate conditions in and around wilderness areas; and (4) identifying wilderness areas expected to experience the most change in land use, land cover, and climate. We used projections of land use (four variables), land cover (five variables), and climate (nine variables) to assess changes for 707 wilderness areas in the contiguous United States by mid‐21st century under two scenarios (medium‐low and high). We ranked all wilderness areas relative to each other by summing and ranking decile values for each land use, land cover, and climate variable and calculating a multivariate metric of future change. All wilderness areas were projected to experience some level of change by mid‐century. The greatest land‐use changes were associated with increases in agriculture, clear cutting, and developed land, while the greatest land cover changes were observed for grassland, forest, and shrubland. In 51.6% and 73.8% of wilderness areas, core area of natural vegetation surrounding wilderness was projected to decrease for the medium‐low and high scenarios, respectfully. Presence of public land did not mitigate the influence of land‐use change around wilderness areas. Geographically, projected changes occurred throughout the contiguous U.S., with areas in the northeast and upper Midwest projected to have the greatest land‐use and climate change and the southwestern U.S. projected to undergo the greatest land cover and climate change. Our results provide insights into potential future threats to wilderness areas and the challenges associated with wilderness stewardship and climate adaptation. Despite the high degree of protection and remoteness of wilderness areas, effective management and preservation of these lands must consider future changes in land use, land cover, and climate.