bluuebunny/crossref_metadata_2025 huggingface dataset:
Clinical characteristics of central compartment atopic disease in Southern China
Authors: Nie Zhiying , Xu Zhaofeng , Fan Yunping , Guo Yuanyuan , Chen Chuxin , Liu Wendong , Li Yueqi , Lai Yinyan , Shi Jianbo , Chen Fenghong
Published: July 2022

Background

Central compartment atopic disease (CCAD) is a newly reported subset of chronic rhinosinusitis. It was considered associated with inhalant antigen. However, CCAD in Chinese population is not fully studied yet.

Design

Prospective cohort study.

Objective

This study aimed to describe the clinical manifestations of CCAD and compared the following two subtypes: sinonasal polyps and concomitant polypoid disease in the central compartment (CRSwNP/CC) and CRSwNP not otherwise specified (CRSwNP NOS). Also, we compared the clinical manifestations of atopy CCAD and non‐atopy CCAD.

Methods

We consecutively enrolled CRSwNP patients without prior sinus surgery, and assessed the nasal endoscopy and computed tomography of the paranasal sinuses. Allergy was confirmed by skin or serum testing. Eosinophilic CRSwNP (ECRS) was considered as tissue eosinophils to total inflammatory cells >10%.

Results

We enrolled a total of 116 patients, including 39 with CCAD, 38 with CRSwNP/CC and 39 with CRSwNP NOS. Atopy was detected in 37.1% of the CCAD group, an incidence showing no significant difference from those in the other two groups (37.1% in the CRSwNP/CC group, 31.0% in the CRSwNP NOS group; p = 0.846). However, the incidence of ECRS in the CCAD group was the highest among the different groups (97.4% in the CCAD group vs. 67.6% in the CRSwNP/CC group vs. 35.1% in the CRSwNP NOS group; p = 0.000). In addition, the incidence of asthma in the CCAD group (33.3%) was significantly higher than that in the CRSwNP NOS group (10.3%), but quite similar to CRSwNP/CC (34.2%). In the subgroup analysis of CCAD, only total serum IgE and sIgE demonstrated significant differences between atopy CCAD and non‐atopy CCAD.

Conclusion

CCAD in Southern China may associate with asthma and significant eosinophilia, with a lower incidence of systemic allergy based on skin and serum testing.
Rapid olfactory decline during aging predicts dementia and GMV loss in AD brain regions
Authors: Pacyna Rachel R. , Han S. Duke , Wroblewski Kristen E. , McClintock Martha K. , Pinto Jayant M.
Published: July 2022

Introduction

Longitudinal multivariable analyses are needed to determine if the rate of olfactory decline during normal cognition predicts subsequent Alzheimer's disease (AD) diagnoses and brain dysmorphology.

Methods

Older adults (n = 515) were assessed annually for odor identification, cognitive function and dementia clinical diagnosis (max follow‐up 18 years). Regional gray matter volumes (GMV) were quantified (3T MRI) in a cross‐sectional subsample (n = 121). Regression models were adjusted for APOE‐ε4 genotype, dementia risk factors and demographics.

Results

Faster olfactory decline during periods of normal cognition predicted higher incidence of subsequent MCI or dementia (OR 1.89, 95% CI: 1.26, 2.90, p < 0.01; comparable to carrying an APOE‐ε4 allele) and smaller GMV in AD and olfactory regions (β = −0.11, 95% CI −0.21, −0.00).

Discussion

Rapid olfactory decline during normal cognition, using repeated olfactory measurement, predicted subsequent cognitive impairment, dementia, and smaller GMVs, highlighting its potential as a simple biomarker for early AD detection.

Highlights

Rate of olfactory decline was calculated from olfactory testing over ≥3 time points.

Rapid olfactory decline predicted impaired cognition and higher risk of dementia.

Neurodegeneration on 3T magnetic resonance imaging was identical in those with olfactory decline and Alzheimer's disease.
Nanographene Metallaprisms: Structure, Stimulated Transformation, and Emission Enhancement
Authors: Chai Ling , Ju Yang‐Yang , Xing Jiang‐Feng , Ma Xiao‐Hui , Zhao Xin‐Jing , Tan Yuan‐Zhi
Published: July 2022

Nanographenes are inclined to assemble into stacked columnar structures that are stabilized by π‐π interactions, whereas other supramolecular structures of nanographenes, such as prisms and cages, are rarely investigated. Herein, a diazananographene was synthesized, and then assembled with a coordination unit, thereby producing a triangular metallaprism. After adding C60 or C70, the triangular metallaprism was transformed into a square tetramer, which encapsulated a pair of C60 or C70 molecules. The formed host‐guest complex demonstrated efficient energy transfer from the diazananographene shell to the C60 cores. The emission intensity of the capsulated C60 was enhanced remarkably, compared with free C60, due to an increased quantum yield and optical absorption coefficient. This work demonstrates the versatility of nanographene‐based supramolecular architectures beyond columnar stacking and their ability to enhance the emission of otherwise non‐emissive fullerene.
Thermally Depolymerizable Polyether Electrolytes for Convenient and Low‐Cost Recycling of LiTFSI
Authors: Li Wei , Ma Le , Liu Sisi , Li Xiaolei , Gao Jian , Hao Shu‐meng , Zhou Weidong
Published: July 2022

Solid polymer electrolytes (SPEs) with LiTFSI (lithium bis(trifluoromethane sulfonimide)) are promising candidates for solid‐state batteries, owing to their good interfacial contact with solid electrodes. Here, three copolymerized polyethers were prepared as SPEs, using the catalysts of SnF2or SnF2‐LiPF6. The thermal depolymerization of these polyethers was observed at elevated temperatures, which limits their operating temperature ranges. Once the catalyst is removed, the thermal degradation temperatures of these SPEs are raised by 30–55 °C, together with improved thermal performance in cells. For SPEs, the high price of LiTFSI is an obstacle for their large‐scale application, and it's recycling is hindered by the strong interaction with polymers. By the thermal depolymerization of polyethers, LiTFSI can be easier reclaimed from above mentioned SPEs and even the commercial PEO(poly(ethylene‐oxide)) based SPE in rates of 70–80 %, providing a low‐cost strategy for the recycling of LiTFSI.
Stereoretentive Regio‐ and Enantioselective Allylation of Isoxazolinones by a Planar Chiral Palladacycle Catalyst
Authors: Yu Xin , Hu Lingfei , Frey Wolfgang , Lu Gang , Peters René
Published: July 2022

The catalytic allylic substitution is one of the most important tools in asymmetric synthesis to form C−C bonds in an enantioselective way. While high efficiency was previously accomplished in terms of enantio‐ and regiocontrol using different catalyst types, a strong general limitation is a very pronounced preference for the formation of allylic substitution products with (E)‐configured C=C double bonds. Herein, we report that with a planar chiral palladacycle catalyst a diastereospecific reaction outcome is achieved using isoxazolinones and allylic imidates as substrates, thus maintaining the C=C double bond geometry of the allylic substrates in the highly enantioenriched products. DFT calculations show that the reactions proceed via an SN2 mechanism and not via π‐allyl Pd complexes. Crucial for the high control is the stabilization of the allylic fragment in the SN2 transition state by π‐interactions with the phenyl substituents of the pentaphenylferrocenyl catalyst core.
Experimental and theoretical studies of new Co(III) complexes of hydrazide derivatives proposed as multi‐target inhibitors of SARS‐CoV‐2
Authors: Parvarinezhad Sakineh , Salehi Mehdi , Kubicki Maciej , Eshaghi Malekshah Rahimeh
Published: July 2022

Cobalt(III) complexes with Schiff base ligands derived from hydrazone, (HL1 = (E)‐N′‐(3,5‐dichloro‐2‐hydroxybenzylidene)‐4‐hydroxybenzohydrazide, HL2 = (E)‐N′‐(3,5‐dichloro‐2‐hydroxybenzylidene)‐4‐hydroxybenzohydrazide (3,5‐dibromo‐2‐hydroxybenzylidene), and HL3 = (E)‐4‐hydroxy‐N′‐(2‐hydroxy‐3‐ethoxybenzylidene)benzohydrazide), were synthesized and characterized by elemental analysis, Fourier transform infrared (FT‐IR) spectroscopy, UV–Vis spectroscopy, and cyclic voltammetry. X‐ray diffraction was used to determine the single crystal structure of the complex (1). Co(III) was formed in a distorted, very regular octahedral coordination in this complex; three pyridine moieties complete this geometry. Schiff base complexes' redox behaviors are represented by irreversible (1), quasi‐reversible (2), and quasi‐reversible (3) voltammograms. A density functional theory (DFT)/B3LYP method was used to optimize cobalt complexes with a base set of 6‐311G. Furthermore, fragments occupying the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were investigated at the same theoretical level. Quantum theory of atoms in molecules (QTAIM) computations were also done to study the coordination bonds and non‐covalent interactions in the investigated structures. Hirshfeld surface analysis was used to investigate the nature and types of intermolecular exchanges in the crystal structure of the complex (1). The capacity of cobalt complexes to bind to the major protease SARS‐CoV‐2 and the molecular targets of human angiotensin‐converting enzyme‐2 (ACE‐2) was investigated using molecular docking. The molecular simulation methods used to assess the probable binding states of cobalt complexes revealed that all three complexes were stabilized in the active envelope of the enzyme by making distinct interactions with critical amino acid residues. Interestingly, compound (2) performed better with both molecular targets and the total energy of the system than the other complexes.
Pyridine‐functionalized N‐heterocyclic carbene gold(I) binuclear complexes as molecular electrocatalysts for oxygen evolution reactions
Authors: Yhobu Zhoveta , Markandeya Geetha Basappa , Małecki Jan Grzegorz , Srinivasa Hosapalya Thimmaiah , Keri Rangappa S. , Nagaraju Doddahalli Hanumantharayudu , Azam Mohammad , Al-Resayes Saud I. , Budagumpi Srinivasa
Published: July 2022

N‐heterocyclic carbene (NHC) complexes of gold(I/III) attained immense interest in catalytic organic transformations and as anticancer agents against several types of human cancers; however, their potential as electrocatalysts is scarce. The electrocatalytic oxygen evolution reaction was performed for the first time using pyridine‐functionalized NHC gold(I) binuclear metallacycles (8 and 9) possessing aptly designed ligand field. Complexes were prepared by the transmetallation of corresponding silver(I) NHC complexes, which were prepared by in situ deprotonation of pyridine and aryl substituted 1,2,4‐triazolium hexafluorophosphate salts (6 and 7) with Ag2O under dark. Both triazolium salts and binuclear gold(I) metallacycles were thoroughly characterised by NMR and ATR‐IR spectral and elemental analyses. A bromide salt 4 and a binuclear gold complex 9 were elucidated for structure by single crystal X‐ray diffraction analysis. Complex 9 possesses distorted linear coordination geometry around the gold atoms by the coordination of carbene carbon and pyridine nitrogen atoms bearing close Au–Au interaction (3.251 Å). The binuclear gold complexes 8 and 9 (along with 10 wt% conductive mesoporous carbon) were investigated as molecular electrocatalysts in oxygen evolution reaction (OER), which evidenced an oxygen evolution overpotential of 2.422 and 2.370 V versus reversible hydrogen electrode (RHE), respectively, to attain a current density of 10 mA.cm−2. The Tafel slope values of 40.9 and 30.4 mV dec−1 for 8 and 9, respectively, indicate the reaction mechanism involved and the suitability of these complexes as apt electrocatalysts for OER. The stability of the prepared molecular electrocatalysts was investigated by cyclic voltammetry and chronoamperometry techniques.
Synthesis of dimethyl‐ and diphenylsilane‐based oligo(azine)s: Thermal, optical, electronic, and morphological properties
Authors: Sobarzo Patricio A. , Jessop Ignacio A. , Pérez Yasmín , Hauyon René A. , Velázquez‐Tundidor María V. , Medina Jean , González Alexis , García Luis E. , González‐Henríquez Carmen M. , Coll Deysma , Ortiz Pablo A. , Tundidor‐Camba Alain , Terraza Claudio A.
Published: July 2022

Four new oligo(azine)s were synthesized from dimethyldiphenylsilane and tetraphenylsilane core‐based dialdehydes and hydrazine by high‐temperature polycondesation and proposed as materials for optoelectronic applications. The oligo(azine)s were characterized by EA, FT‐IR, and NMR. Although most of samples were poorly soluble, TPS‐containing PAZ‐4 was soluble in aprotic polar solvents. According to SEC and FT‐IR studies, the samples were oligomers with up to five repeating units long. TGA showed highly stable samples with TDT10%over 420°C except for PAZ‐1 that contains a DMS core along with phenyl units, and thus, the lowest carbon content in the series. From DSC analysis, the substitution of phenyl groups in PAZ‐1/3 by biphenyl moieties in PAZ‐2/4 allowed to obtain oligo(azine)s with lowerTgvalues. PAZ‐4 showed a UV‐A absorption with optical band‐gap values of 2.91 and 2.65 eV from UV–vis (solution) and DRS (films), respectively. PL analysis showed a violet emission. PAZ‐4 showed resistivity of 29.24 Ω cm, similar to wide‐band gap materials. Their contact angle measurements showed a critical surface tension of 42.29 dynes/cm, revealing its hydrophobicity. AFM analysis indicated that the PAZ‐4 films had homogeneous surfaces. Young's modulus close to 4.46 GPa was established by microindentation for the PAZ‐4 thin‐films.
Interleukin 15 in murine models of colitis
Authors: Kautzman Alicia Molina , Mobulakani Jeanne Masunga Faida , Marrero Cofino Gisela , Quenum Akouavi Julite Irmine , Cayarga Anny Armas , Asselin Claude , Fortier Louis‐Charles , Ilangumaran Subburaj , Menendez Alfredo , Ramanathan Sheela
Published: July 2022

Inflammatory bowel diseases (IBDs) are characterized by abnormal, non‐antigen specific chronic inflammation of unknown etiology. Genome‐wide association studies show that many IBD genetic susceptibility loci map to immune function genes and compelling evidence indicate that environmental factors play a critical role in IBD pathogenesis. Clinical and experimental evidence implicate the pro‐inflammatory cytokine IL‐15 in the pathogenesis of IBD. IL‐15 and IL‐15α expression is increased in the inflamed mucosa of IBD patients. IL‐15 contributes to the maintenance of different cell subsets in the intestinal mucosa. However, very few studies have addressed the role of IL‐15 in pre‐clinical models of colitis. In this study, we use three well‐characterized models of experimental colitis to determine the contribution of IL‐15 to pathological intestinal inflammation.
Amino‐functionalized perylenediimide derivative with dual fluorescence emission for the detection of ascorbic acid in vivo and in vitro
Authors: Zhang Gui‐Qun , Chi Kuan‐Neng , Yao Chao , Yang Tong , Zhang Rui‐Lin , Hu Rong , Yang Yun‐Hui
Published: July 2022

The rapid, sensitive, and selective detection of ascorbic acid (AA) is of significance in medical assays and diagnostics. In this work, a new aminoperylenediimide (APDI) derived ratiometric fluorescent probe based on the specific redox reaction of cobalt oxyhydroxide (CoOOH) and AA was constructed. APDI exhibited dual fluorescence emission peaks at 549 and 596 nm with an excitation wavelength of 494 nm. In the presence of CoOOH, the dual fluorescence could be quenched. The dominant fluorescence quenching mechanism was caused by the inner filter effect. Using the red emission as a reference, the fluorescence intensity ratio (F549/F596) was linearly correlated with the concentration of AA over a range of 0.05 to 1 μM. The limit of detection for AA was found to be 17 nM. Importantly, the probe was successfully used to detect AA in living cells. Therefore, this high sensitivity and selectivity strategy could directly survey the AA levels in real samples.
Anhydride chemistry‐based hexanoylation of polyethylenimine increases transfection efficiency and expression of tagged DNA for therapeutic proteins in cultured cells
Authors: Ulgekar Goutam , Kaur Dilpreet , Ganesan Venkateswaran , Sen Sharma Souvik , Ganguli Nirmalya , Majumdar Subeer S.
Published: July 2022

Transfection of nucleic acid molecules into mammalian cells can be facilitated using viral vectors, electroporation, or biocompatible cationic materials. However, safety issues and the requirement of specialized equipment limits the use of viral vectors and physical methods of transfection like electroporation and microinjection, respectively. Biocompatible cationic lipids and polymers like branched‐polyethyleneimine (bPEI) have a wide transfection range and are user‐friendly in most applications. However, bPEI exhibits low transfection efficiency in most cell types. In the present work, we have crosslinked the hexanoyl group to bPEI using anhydride chemistry to enhance its efficiency as a transfection reagent. The efficient association of hexanoyl group to bPEI was assessed using Fourier‐transform infrared spectroscopy and other physicochemical methods. Hexanoyl‐modified bPEI (FA6‐bPEI) was found to exhibit significantly enhanced transfection efficiency in both cell lines and cultured primary cells, as compared to native bPEI and the commercially available transfection reagent, Lipofectamine 3000. Furthermore, our in vitro studies indicated that FA6‐bPEI can be used for robust transfection for increased production of therapeutic proteins in a cell culture‐based system. These results suggested that hexanoyl‐modified bPEI can serve as an efficient transfection reagent for studies on hard‐to‐transfect cells and for enhanced production of therapeutic proteins in vitro.
Development of prediction model of low anterior resection syndrome for colorectal cancer patients after surgery based on machine‐learning technique
Authors: Huang Ming Jun , Ye Lin , Yu Ke Xin , Liu Jing , Li Ka , Wang Xiao Dong , Li Ji Ping
Published: July 2022

Background

Low anterior resection syndrome (LARS) is a common postoperative complication in patients with colorectal cancer, which seriously affects their postoperative quality of life. At present, the aetiology of LARS is still unclear, but some risk factors have been studied. Accurate prediction and early management of medical intervention are keys to improving the quality of life of such high‐risk patients.

Objectives

Based on machine‐learning methods, this study used the follow‐up results of postoperative patients with colorectal cancer to develop prediction models for LARS and conducted a comparative analysis between the different models.

Methods

A total of 382 patients diagnosed with colorectal cancer and undergoing surgery at West China Hospital from April 2017 to December 2020 were retrospectively selected as the development cohort. Logistic regression, support vector machine, decision tree, random forest and artificial neural network algorithms were used to construct the prediction models of the obtained dataset. The models were internally validated using cross‐validation. The area under the curve and Brier score measures were used to evaluate and compare the differentiation and calibration degrees of the models. The sensitivity, specificity, positive predictive value and negative predictive value of the different models were described for clinical use.

Results

A total of 342 patients were included, the incidence of LARS being 47.4% (162/342) during the six‐month follow‐up. After feature selection, the factors influencing the occurrence of LARS were found to be location, distance, diverting stoma, exsufflation and surgical type. The prediction models based on five machine‐learning methods all showed acceptable performance.

Conclusions

The five models developed based on the machine‐learning methods showed good prediction performance. However, considering the simplicity of clinical use of the model results, the logistic regression model is most recommended. The clinical applicability of these models will also need to be evaluated with external cohort data.
Inferring one's own attitude toward an unknown attribute: The moderating role of complexity in juice tasting
Authors: Alcser‐Isais Alexa N. , Smith Leigh K. , Eastwick Paul W.
Published: July 2022

This study examined how people learn about their own summarized attribute preferences: their overall evaluative summaries of an attribute (e.g., one's liking for “sweetness” or “crispness”). Participants tasted and evaluated 14 juices varying on (a) an unknown attribute “Barinium” (low‐complexity condition), or (b) both Barinium and a second, unrelated attribute (high‐complexity condition). Participants then reported their summarized preference for Barinium as the dependent variable. Results revealed that participants' functional attribute preferences—that is, the extent to which they actually liked the high versus low Barinium juices—predicted their summarized preference for Barinium. This functional‐summarized preference association was stronger when the juices varied on Barinium alone rather than two attributes; that is, complexity caused participants to weigh their actual experiences of liking less when forming summarized preferences. Furthermore, functional and summarized preferences independently and simultaneously predicted participants' choice of juices to take home—especially when each juice sample was labeled with its Barinium content. Implications for attitudes and consumer research are discussed.
Antegrade dissection and re‐entry versus parallel wiring in chronic total occlusion percutaneous coronary intervention: Insights from the PROGRESS‐CTO registry
Authors: Simsek Bahadir , Kostantinis Spyridon , Karacsonyi Judit , Alaswad Khaldoon , Jaffer Farouc A. , Doshi Darshan , Gorgulu Sevket , Goktekin Omer , Kerrigan Jimmy , Haddad Elias , Rinfret Stephane , Jaber Wissam A. , Nicholson William , Abi Rafeh Nidal , Allana Salman , Koutouzis Michalis , Tsiafoutis Yiannis , Brilakis Emmanouil S. ,   PROGRESS‐CTO Investigators
Published: July 2022

Background

The comparative efficacy and safety of parallel wiring versus antegrade dissection and re‐entry (ADR) in chronic total occlusion (CTO) percutaneous coronary intervention (PCI) is controversial.

Methods

We compared the clinical and angiographic characteristics and outcomes of parallel wiring versus ADR after failed antegrade wiring in a large, multicenter CTO PCI registry.

Results

A total of 1725 CTO PCI procedures with failed antegrade wiring with a single wire were approached with parallel wiring (692) or ADR (1033) at the discretion of the operator. ADR patients were older (65 ± 10 vs. 62 ± 10, years, p < 0.001) and had higher prevalence of comorbidities, such as diabetes mellitus (43% vs. 32%, p < 0.001), prior coronary artery bypass graft surgery (31% vs. 19%, p < 0.001), and lower left ventricular ejection fraction (50 ± 14 vs. 53 ± 11%, p < 0.001). The ADR group had higher J‐CTO (2.8 ± 1.1 vs. 2.1 ± 1.3, p < 0.001) and PROGRESS‐CTO (1.6 ± 1.1 vs. 1.2 ± 1.0, p < 0.001) scores. Equipment use including guidewires, balloons, and microcatheters was higher, and the procedures lasted longer in the ADR group. Technical success (78% vs. 75%, p = 0.046) and major adverse cardiovascular events (composite of all‐cause mortality, stroke, acute myocardial infarction, emergency surgery or re‐PCI, and pericardiocentesis) (3.7% vs. 1.9%, p = 0.029) were higher in the ADR group, with similar procedural success (75% vs. 73%, p = 0.166).

Conclusion

In lesions that could not be crossed with antegrade wiring, ADR was associated with higher technical but not procedural success, and also higher MACE compared with parallel wiring.
Early coronary angiography in patients after out‐of‐hospital cardiac arrest without ST‐segment elevation: Meta‐analysis of randomized controlled trials
Authors: Freund Anne , van Royen Niels , Kern Karl B. , Jobs Alexander , Thiele Holger , Lemkes Jorrit S. , Desch Steffen ,   TOMAHAWK, PEARL, and COACT investigators
Published: July 2022

Objectives

To compare early coronary angiography to a delayed or selective approach in out‐of‐hospital cardiac arrest (OHCA) without ST‐segment elevation of possible cardiac cause by means of meta‐analysis of available randomized controlled trials (RCTs).

Methods

We searched MEDLINE and the Cochrane Central Register of Controlled Trials for RCTs comparing early with delayed or selective coronary angiography in OHCA patients of possible cardiac origin without ST‐segment elevation. The primary endpoint was all‐cause short‐term mortality (PROSPERO CRD42021271484).

Results

The search strategy identified three RCTs enrolling a total of 1167 patients. An early invasive approach was not associated with improved short‐term mortality (odds ratio 1.19, 95% confidence interval 0.94–1.52; p = 0.15). Further, no significant differences were shown with respect to the risk of severe neurological deficit, the composite of all‐cause mortality or severe neurological deficit, need for renal replacement therapy due to acute renal failure, and significant bleeding at short‐term follow‐up.

Conclusion

Early coronary angiography in OHCA without ST‐segment elevation is not superior compared to a delayed/selective approach.
Well‐Defined Ni(0) and Ni(II) Complexes of Bicyclic (Alkyl)(Amino)Carbene (MeBICAAC): Catalytic Activity and Mechanistic Insights in Negishi Cross‐Coupling Reaction
Authors: Thakur Sandeep Kumar , Kaur Mandeep , Manar Krishna Kumar , Adhikari Manu , Choudhury Angshuman Roy , Singh Sanjay
Published: July 2022

Negishi cross‐coupling reaction of organozinc compounds as nucleophiles with aryl halides has drawn immense focus for C−C bond formation reactions. In comparison to the well‐established library of Pd complexes, the C−C cross‐coupling of this particular approach is largely primitive with nickel‐complexes. Herein, we describe the syntheses of Ni(II) complexes, [(MeBICAAC)2NiX2] (X=Cl (1), Br (2), and I (3)) by employing the bicyclic (alkyl)(amino)carbene (MeBICAAC) ligand. The reduction of complexes 1–3 using KC8 afforded the two coordinate low valent, Ni(0) complex, [(MeBICAAC)2Ni(0)] (4). Complexes 1–4 have been characterized by spectroscopic techniques and their solid‐state structures were also confirmed by X‐ray crystallography. Furthermore, complexes 1–4 have been applied in a direct and convenient method to catalyze the Negishi cross‐coupling reaction of various aryl halides with 2,6‐difluorophenylzinc bromide or phenylzinc bromide as the coupling partner in the presence of 3 mol % catalyst. Comparatively, among all‐pristine complexes, 1 exhibit high catalytic potential to afford value‐added C−C coupled products without the use of any additive. The UV‐vis studies and HRMS measurements of controlled stochiometric reactions vindicate the involvement of Ni(I)−NI(III) cycle featured with a penta‐coordinated Ni(III)‐aryl species as the key intermediate for 1 whereas Ni(0)/Ni(II) species are potentially involved in the catalytic cycle of 4.
A Logic Gate Based on a Flexible Metal–Organic Framework (JUK‐8) for the Concomitant Detection of Hydrogen and Oxygen
Authors: Roztocki Kornel , Bon Volodymyr , Senkovska Irena , Matoga Dariusz , Kaskel Stefan
Published: July 2022

We present an autonomous, chemical logic gate based on a switchable metal–organic framework (MOF) composite, containing carbon nanoparticles and a Pt catalyst. The switchable MOF composite performs as AND logic gate. Hydrogen and oxygen gas streams serve as binary inputs. Catalytically formed water induces a structural transition (crystal volume expansion) of the MOF, and as a consequence, a detectable drop in conductance of the composite as a ‘true’ output only if both gases come in contact with the composite.
An analytical and numerical approach to the determination of thermal necrosis in cortical bone drilling
Authors: Aydın Kutay , Ökten Korhan , Uğur Levent
Published: July 2022

In the process of repairing fractures in the bone region with orthopedic injuries, the application of supporting and strengthening the bone tissue with screws, wires, rods, and plates is a widely preferred internal fixation method. In this treatment process, it is necessary to drill the bone tissue to fix the screws. Due to the heat generated in the drilling process, mechanical and thermal damage occurs in the bone tissue. In this study, it is focused that the effect of different cutting conditions on the temperature distribution and necrosis zones in the drilling of human cortical bone. In this context, by selecting variable drill geometry (diameter, point angle, and helix angle) and variable cutting parameters (cutting speed and feed rate), temperature distribution and necrosis zones were investigated with finite element analyses and analytical calculations. When the findings were evaluated, it was understood that drill diameter and cutting speed did not have a significant effect on temperatures and necrosis zone at low cutting speeds. At high cutting speeds, it was observed that the feed rate and drill point angle had an indeterminate effect on the temperatures. The lowest temperature values were obtained at cutting speed of 750 rpm and a feed rate of 0.1 mm/rev for low cutting speeds, and cutting speed of 1500 rpm, helix angle of 10° and drill bit diameter of 2 mm for high cutting speeds. The narrowest necrosis zones were obtained at cutting speed of 250 rpm and feed rate of 0.1 mm/rev for both drill diameters. As a result, the effects of different drill geometry and cutting parameters were determined in order to obtain low temperature distribution and narrow necrosis zone in cortical bone drilling.
Self‐improved moth flame for optimal container resource allocation in cloud
Authors: Netaji Vhatkar Kapil , Bhole Girish P.
Published: July 2022

Resource allocation in the cloud is becoming more complicated and challenging due to the rising necessities of cloud services. Effective management of virtual resources in the cloud is of large significance since it has a great impact on both the operational cost and scalability of the cloud environment. Nowadays, containers are becoming more popular in this regard due to their characteristics like reduced overhead and portability. Conventional resource allocation schemes are usually modeled for the migration and allocation of virtual machines (VM), as a result; the question may arise on, “how these strategies can be adapted for the management of a containerized cloud”. This work evolves the solution to this issue by introducing a new fitness oriented moth flame algorithm (F‐MFA) for optimizing the allocation of containers. Further in this work, the optimal allocation relies on certain constraints like balanced cluster use, system failure, total network distance (TND), security and threshold distance, and credibility factor as well. In the end, the supremacy of the presented model is computed to the conventional models in terms of cost and convergence analysis.
The emotional landscape of curriculum making
Authors: Anttila Henrika , Tikkanen Lotta , Soini Tiina , Pietarinen Janne , Pyhältö Kirsi
Published: July 2022

Our aim with this study was to gain a better understanding of the emotional landscape of curriculum making by exploring the variety of emotions embedded in shared sense‐making about the national curriculum reform implementation at the district level. Focus group interview data were collected from 12 curriculum reform steering groups around Finland, that were responsible for orchestrating curriculum reform work at the district level. The data were qualitatively content analysed. The results showed that the local steering group members experienced a wide range of emotions in shared sense‐making. Positive emotions were described slightly more often than negative emotions. The emotional landscape of the sense‐making strategies applied in curriculum reform work varied depending on the strategy applied.
Two‐way chemotaxis‐based communication for biological nanonetworks
Authors: Grammenos Theodoros , Kantelis Konstantinos , Nicopolitidis Petros , Papadimitriou Georgios
Published: July 2022

Chemotaxis has been studied as a means to improve communication performance in the promising field of biological nanonetworks. However, as of today, no protocols for reliable two‐way communications have been proposed in such networks. This work proposes a new protocol for switching between different chemotactic substances as a novel scheme to improve reliability of two‐way communications in biological nanonetworks. Multiple simulations, involving message exchange between stations and chemotactic release, were performed to evaluate the performance of the proposed strategies and achieve a deeper understanding of the behaviour of molecular communication nanonetworks. Furthermore, a novel message sending strategy utilising chemorepellent is presented, which does not involve the release of new molecules into the medium. Simulating chemotactic substance as individual molecules allowed for a more accurate modelling of the system in the boundaries of the chemotactic interface, bringing out the wave‐like behaviour of the latter. The results of the experiments indicate the effectiveness of the proposed controlled release strategy in improving message transmission quality. Furthermore, based on the findings of this work, we propose amendments of existing protocols that incorporate switching between chemotactic substances.
Synthesis, biological evaluation, and in silico studies of indole‐tethered pyrazoline derivatives as anticancer agents targeting topoisomerase IIα
Authors: Haider Kashif , Sharma Shivani , Pokharel Yuba Raj , Das Subham , Joseph Alex , Najmi Abul Kalam , Ahmad Faiz , Yar Mohammad Shahar
Published: July 2022

We herein report a new series of indole‐tethered pyrazoline derivatives as potent anticancer agents. A total of 12 compounds were designed and synthesized by conventional as well as microwave‐irradiated synthesis methods. The latter method results in a significant reduction in the duration of reaction along with improved yields. All synthesized derivatives (7a−7l) were evaluated for their cytotoxic activity against A431, HeLa, and MDAMB‐231 cell lines. Compounds 7a and 7b were found most potent in the series and demonstrated an IC50 value of 3.17 and 5.16 µM against the A431 cell line, respectively, compared to the standard drug doxorubicin. Compounds 7a and 7b significantly suppress colony formation, migration, and S phase cell cycle arrest of A431 cells. Furthermore, compound 7a regulated the expression of apoptotic proteins causing the downregulation of procaspase 3/9, antiapoptotic protein Bcl‐xL, and upregulation of proapoptotic protein Bax in a dose‐dependent manner. Topoisomerase enzyme inhibition assay confirmed that compounds 7a and 7b can significantly inhibit topoisomerase IIα. In vivo oral acute toxicity of compounds 7a and 7b revealed that both compounds are safe compared to doxorubicin; cardiomyopathy studies showed normal architecture of cardiomyocytes and myofibrils. In addition, molecular docking studies revealed the possible interaction of compounds 7a and 7b within the active binding site of the topoisomerase enzyme. The 100 ns molecular dynamic simulation of compounds 7a and 7b proved that both compounds validate all screening parameters.
Building a bridge from solid wastes to solar fuels and chemicals via artificial photosynthesis
Authors: Du Mengmeng , Xing Mengyuan , Kang Sailei , Ma Yingxin , Qiu Bocheng , Chai Yang
Published: July 2022

Photoreforming (PR) is a process that splits water into hydrogen coupled with oxidation of solid waste into value‐added products, which provides a way to mitigate resource depletion of solid waste and accumulation of CO2 in the atmosphere. The realization of solid waste PR by harnessing the redox capabilities of photocatalyst is crucial to address the environmental pollution issue and reduce our reliance on fossil fuels. In this review, we overview the continuous progress from the latest studies in constructing the PR system for upgrading of solid waste. We classify the different kinds of solid wastes and illustrate the PR mechanism. Furthermore, we discuss the advantages for cooperatively coupling of hydrogen production with solid waste valorization. We also highlight some state‐of‐the‐art photocatalysts for valorization of biomass, plastics, and food wastes. Finally, we focus on the development of high‐performance catalysts needed in the PR domain to tackle the future challenges.

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A general Lagrangian tracking methodology for riverine flow and transport
Authors: Nelson Jonathan , Shimizu Yasuyuki , Kyuka Tomoko , Charlton Scott
Published: July 2022

This article presents a new public domain tool for generalized Lagrangian particle tracking in rivers. The approach can be applied with a variety of two‐ and three‐dimensional flow solvers. Particle advection by the flow is incorporated using flow fields from the chosen solver assuming particles follow the Reynolds‐averaged flow, although some other simple passive and active particle behaviors are also treated. Turbulence effects are treated using a random walk algorithm with spatial step lengths randomly chosen from Gaussian distributions characterized by the diffusivity from the flow solver. Our work extends this concept to a general framework that is solver and coordinate system independent to allow easy comparisons between differing flow treatments. To better treat problems where detailed information is required in specific regions, the approach includes novel cloning and colligation algorithms which enhance local resolution at modest computational expense. We also provide tools for computing local concentrations and total exposure over a user‐specified time interval. Several examples of predictions are provided to illustrate applications of the technique, including examination of the role of curvature‐driven secondary flows, storage in lateral separation eddies, treatment of larval drift, treatment of fuel spill dispersion, river‐floodplain connections, and sedimentation in floodplain ponds by tie channel connections. We also demonstrate that the model can reproduce analytically derived concentration profiles for simple diffusivities. These examples show that the Lagrangian particle tracking approach and the extensions proposed here are broadly applicable and viable for treating difficult river problems with multiple temporal and spatial scales. The examples also illustrate the utility of the cloning/colligation extensions and show how these can decrease the computational effort required on problems where high local resolution is required. Enhancement of the tools and even broader applicability can be achieved through the inclusion of multiple particle populations and particle–particle interactions.
Rupture of liver metastasis in high‐volume metastatic prostate cancer patient on androgen deprivation therapy combined with upfront docetaxel chemotherapy
Authors: Hata Kenichi , Tanaka Masatoshi , Takahashi Kazuhiro , Kimura Takahiro
Published: July 2022

Introduction

Recent studies have indicated an improvement in the survival rate of patients using docetaxel in addition to androgen deprivation therapy for high‐volume metastatic hormone‐sensitive prostate cancer. Hepatorrhexis, characterized by the rupture of the liver, is a rare complication associated with chemotherapies. We report a case of hepatic metastases rupture during androgen deprivation therapy combined with upfront docetaxel chemotherapy.

Case presentation

A 77‐year‐old man diagnosed with high‐volume metastatic hormone‐sensitive prostate cancer received an upfront docetaxel treatment combined with androgen deprivation therapy. Hepatic metastases rupture with substantial hemoperitoneum occurred on the 14th day of the fifth cycle of docetaxel chemotherapy. Transcatheter arterial embolization was performed; however, despite receiving optimal supportive care, the patient died.

Conclusion

The addition of upfront docetaxel to androgen deprivation therapy may be effective in patients with high‐volume metastatic hormone‐sensitive prostate cancer; however, strict observation is required to monitor for the occurrence of rare complications, including hepatorrhexis.
Enrollment and outcomes of home visiting for mothers with and without a history of out‐of‐home care
Authors: Nause Katie , Ammerman Robert T. , Folger Alonzo T. , Hall Eric S. , Greiner Mary V. , Beal Sarah
Published: July 2022

Women previously in out‐of‐home care (i.e., foster care) experience poorer health and psychosocial outcomes compared to peers, including higher pregnancy rates and child protective services involvement. Home visiting programs could mitigate risks. Studies examining home visiting enrollment for women with a history of out‐of‐home care are needed. Women previously in out‐of‐home care based on child welfare administrative data between 2012 and 2017 (n = 1375) were compared to a demographically matched sample (n = 1375) never in out‐of‐home care. Vital records data identified live births in the two groups. For those who had given live birth (n = 372), linked administrative data were used to determine and compare rates of referral and enrollment into home visiting, and two indicators of engagement: number of days enrolled, and number of visits received. Women previously in out‐of‐home care were referred for home visiting more often than their peers. There were no differences in rates of enrollment. Women previously in out‐of‐home care remained enrolled for shorter durations and completed fewer home visits than peers. Findings suggest barriers to home visiting enrollment and retention in home visiting programs for women previously in out‐of‐home care. Studies with larger samples and more complete assessments of outcomes are warranted.
Oxygen gradients dictate angiogenesis but not barriergenesis in a 3D brain microvascular model
Authors: Tran Kiet A. , Baldwin‐Leclair Abigail , DeOre Brandon J. , Antisell Morgan , Galie Peter A.
Published: July 2022

A variety of biophysical properties are known to regulate angiogenic sprouting, and in vitro systems can parse the individual effects of these factors in a controlled setting. Here, a three‐dimensional brain microvascular model interrogates how variables including extracellular matrix composition, fluid shear stress, and radius of curvature affect angiogenic sprouting of cerebral endothelial cells. Tracking endothelial migration over several days reveals that application of fluid shear stress and enlarged vessel radius of curvature both attenuate sprouting. Computational modeling informed by oxygen consumption assays suggests that sprouting correlates to reduced oxygen concentration: both fluid shear stress and vessel geometry alter the local oxygen levels dictated by both ambient conditions and cellular respiration. Moreover, increasing cell density and consequently lowering the local oxygen levels yields significantly more sprouting. Further analysis reveals that the magnitude of oxygen concentration is not as important as its spatial concentration gradient: decreasing ambient oxygen concentration causes significantly less sprouting than applying an external oxygen gradient to the vessels. In contrast, barriergenesis is dictated by shear stress independent of local oxygen concentrations, suggesting that different mechanisms mediate angiogenesis and barrier formation and that angiogenic sprouting can occur without compromising the barrier. Overall, these results improve our understanding of how specific biophysical variables regulate the function and activation of cerebral vasculature, and identify spatial oxygen gradients as the driving factor of angiogenesis in the brain.
A low‐input strategy for chromium removal from industrial stormwater using peat sorbent
Authors: Stewart Brandy , Nicholas Sarah , Bone Sharon , Tappero Ryan , Eger Paul , Sheik Cody , Toner Brandy M.
Published: July 2022

Low‐cost and low‐input water treatment systems are important for industrial stormwater remediation. Here we examine a flow‐through reactor treatment installation where water exceeds the allowable maximum concentration for drinking water in multiple metals (e.g., chromium [Cr], cadmium [Cd], zinc [Zn]) prior to treatment. Specifically, we seek to understand why Cr attenuated in the reactors is not leachable by identifying the specific chemical form of Cr and dominant mechanisms promoting sequestration in the reactors. Total solid‐phase Cr concentration in the peat media ranged from 50 to 150 mg/kg after 1 yr of exposure to stormwater to 300 to 900 mg/kg after 3.5 yr. X‐ray fluorescence mapping images show Cr, iron (Fe), and Zn spatially correlated over a scale of 10 μm to 5 mm. Chromium rinds form on the edges of peat particles as Cr accumulates. Chromium and Fe K‐edge X‐ray absorption near edge structure spectroscopy reveal chromium predominately in the 3+ oxidation state with lesser amounts of elemental Cr. We propose the primary means of chromium attenuation in the reactors is precipitation as Cr‐Fe hydroxides combined with trivalent Cr adsorption onto peat surfaces.
The seasonality of nitrate and phosphorus leaching from manure and chemical fertilizer added to a chernozemic soil in Canada
Authors: Kokulan Vivekananthan , Akinremi O. O. , Moulin Alan P.
Published: July 2022

Identifying seasons sensitive to nutrient losses could help farmers and policymakers to formulate effective nutrient loss reduction strategies. This long‐term study monitored water percolation as well as nitrate (NO3–N) and total phosphorus (TP) leaching from liquid swine manure and chemical fertilizer applied to intact core lysimeters in a sandy loam soil in Manitoba, Canada. Water percolation, NO3–N, and TP leaching were monitored from 2005 to 2016. Chemical fertilizer showed greater average annual mean water percolation (p = .01), annual flow‐weighted mean concentration (FWMC) of NO3–N (22 mg L–1; p < .001), and annual NO3–N leaching (36 kg N ha–1; p = .002) compared with the manure treatment (FWMC NO3–N, 15 mg L–1; NO3–N leaching load, 22 kg N ha–1). Average annual mean TP loss did not differ between treatments (p = .86). Spring (April–June) was the most sensitive season, when >75% of annual percolation, >80% of annual NO3–N, and >68% of annual TP leaching losses occurred from both manure and chemical fertilizer. Annual NO3–N and TP leaching increased exponentially with cumulative winter and spring precipitation (control, r2 = .69; manure, r2 = .79; chemical fertilizer, r2 = .63) and decreased with winter and spring air temperatures. The largest spring NO3–N and TP leaching losses were observed in 2013, which followed the dry year of 2012, indicating the potential for nutrient flushing. The findings emphasize the need for environmentally sound N and P management strategies in cold North American regions underlain by coarse‐textured soils, particularly during the spring season.