bluuebunny/crossref_metadata_2025 huggingface dataset:
Bubble size distribution in a bubble column with vertical tube internals: Experiments and CFD‐PBM simulations
Authors: Guan Xiaoping , Yang Ning
Published: May 2022

Knowledge of bubble size distribution (BSD) is critical for controlling mass transfer and reaction in bubble column reactors. Installation of internals further complicates this issue. The effects of internals on BSD were systematically investigated through experiments and computational fluid dynamics‐population balance model simulations. The experiments show a bimodal distribution of the volume‐based BSD except at low superficial gas velocity of 0.01 m/s. Addition of 20% internals increases the small‐bubbles fraction, making the first BSD peak more evident. Correspondingly, the simulation reveals a prominent decrease of turbulent dissipation rate and turbulent kinetic energy. Moreover, while the unresolved turbulent kinetic energy dominates in the empty columns, the resolved portion becomes the major component in the presence of internals. This suggests that internals may redistribute turbulent kinetic energy in each scale, which provides more insights into the complex flow characteristics in the presence of internals and process intensification.
Fluorescent Microswimmers Based on Cross‐β Amyloid Nanotubes and Divergent Cascade Networks
Authors: Chatterjee Ayan , Ghosh Souvik , Ghosh Chandranath , Das Dibyendu
Published: May 2022

Shaped through millions of years of evolution, the spatial localization of multiple enzymes in living cells employs extensive cascade reactions to enable highly coordinated multimodal functions. Herein, by utilizing a complex divergent cascade, we exploit the catalytic potential as well as templating abilities of streamlined cross‐β amyloid nanotubes to yield two orthogonal roles simultaneously. The short peptide based paracrystalline nanotube surfaces demonstrated the generation of fluorescence signals within entangled networks loaded with alcohol dehydrogenase (ADH). The nanotubular morphologies were further used to generate cascade‐driven microscopic motility through surface entrapment of sarcosine oxidase (SOX) and catalase (Cat). Moreover, a divergent cascade network was initiated by upstream catalysis of the substrate molecules through the surface mutation of catalytic moieties. Notably, the resultant downstream products led to the generation of motile fluorescent microswimmers by utilizing the two sets of orthogonal properties and, thus, mimicked the complex cascade‐mediated functionalities of extant biology.
Thionitrite (SNO−) and Perthionitrite (SSNO−) are Simple Synthons for Nitrosylated Iron Sulfur Clusters
Authors: Sherbow Tobias J. , Fu Wen , Tao Lizhi , Zakharov Lev N. , Britt R. David , Pluth Michael D.
Published: May 2022

S/N crosstalk species derived from the interconnected reactivity of H2S and NO facilitate the transport of reactive sulfur and nitrogen species in signaling, transport, and regulatory processes. We report here that simple Fe2+ ions, such as those that are bioavailable in the labile iron pool (LIP), react with thionitrite (SNO−) and perthionitrite (SSNO−) to yield the dinitrosyl iron complex [Fe(NO)2(S5)]−. In the reaction of FeCl2 with SNO− we were able to isolate the unstable intermediate hydrosulfido mononitrosyl iron complex [FeCl2(NO)(SH)]−, which was characterized by X‐ray crystallography. We also show that [Fe(NO)2(S5)]− is a simple synthon for nitrosylated Fe−S clusters via its reduction with PPh3 to yield Roussin's Red Salt ([Fe2S2(NO)4]2−), which highlights the role of S/N crosstalk species in the assembly of fundamental Fe−S motifs.
Oxidative Fluorination of Heteroatoms Enabled by Trichloroisocyanuric Acid and Potassium Fluoride
Authors: Kraemer Yannick , Bergman Emily Nicole , Togni Antonio , Pitts Cody Ross
Published: May 2022

In synthetic method development, the most rewarding path is seldom a straight line. While our initial entry into pentafluorosulfanyl (SF5) chemistry did not go according to plan (due to inaccessibility of reagents such as SF5Cl at the time), a “detour” led us to establish mild and inexpensive oxidative fluorination conditions that made aryl‐SF5compound synthesis more accessible. The method involved the use of potassium fluoride and trichloroisocyanuric acid (TCICA)—a common swimming pool disinfectant—as opposed to previously employed reagents such as F2, XeF2, HF, and Cl2. Thereafter, curiosity led us to explore applications of TCICA/KF as a more general approach to the synthesis of fluorinated Group 15, 16, and 17 heteroatoms in organic scaffolds; this, in turn, prompted SC‐XRD, VT‐NMR, computational, and physical organic studies. Ultimately, it was discovered that TCICA/KF can be used to synthesize SF5Cl, enabling SF5chemistry in an unexpected way.
Transesterification of Non‐Activated Esters Promoted by Small Molecules Mimicking the Active Site of Hydrolases
Authors: Garrido‐González José J. , Sánchez‐Santos Estela , Habib Asmaa , Cuevas Ferreras Ángel V. , Sanz Francisca , Morán Joaquín R. , Fuentes de Arriba Ángel L.
Published: May 2022

The synthesis of small molecules able to mimic the active site of hydrolytic enzymes has been largely pursued in recent decades. The high reaction rates and specificity shown by natural hydrolases present an attractive target, and yet the preparation of suitable small‐molecule mimics remains challenging, requiring activated substrates to achieve productive outcomes. Here we present small synthetic artificial enzymes which mimic the catalytic site and the oxyanion hole of chymotrypsin and N‐terminal hydrolases and are able to perform, for the first time, the transesterification of a non‐activated ester such as ethyl acetate with methanol under mild and neutral reaction conditions.
Family Unit Functioning Questionnaire: Development and Initial Validation
Authors: Collier Carrie E. , Villareal Pedro
Published: May 2022

Despite the importance of Bowen family systems theory in the field of family therapy, there have been few studies examining family unit functioning. To fill this gap, a self‐report instrument, the Family Unit Functioning (FUF) questionnaire has been developed. The FUF questionnaire is a multidimensional measure specifically for adults (aged 25+) about nuclear and family‐of‐origin responses to challenges. Eighty‐six adults who were enrolled in Bowen theory training programs participated in an online questionnaire. The FUF assessment tests five dimensions of family unit functioning developed by Papero (2020). The investigators employed a confirmatory factor analysis, and the following analyses results indicate support for four of the five proposed FUF dimensional constructs: 1. resourcefulness; 2. connectedness and integration; 4. systems thinking; and 5. goal structure. However, the third construct, tension management, requires further validation using a larger data source to generate a more favourable result. The potential contribution of the FUF instrument for testing Bowen theory, use as a family psychotherapy assessment tool, and as an indicator of psychotherapeutic outcomes is discussed.
The dependence of high catalytic performance on the tunable oxygen vacancy in the CZxS/Zn‐HZSM‐5 bifunctional catalyst for alkylation of benzene and syngas
Authors: Safi Naseer Ahmad , Li Yanchun , Yu Bo , Liu Ping , Wang Junwen , Ge Hui , Zhang Kan
Published: May 2022

A bifunctional catalyst (CZxS/Zn‐HZSM‐5) with tunable oxygen vacancy was prepared by coupling ceria–zirconia solid solution (CZxS) and zinc‐modified HZSM‐5 zeolite (Zn‐HZSM‐5). The characterization results indicated that the formation of CZxS by insertion of zirconia (Zr) atoms into cerium oxide (CeO2) could generate more oxygen vacancy due to the structural distortion. With the increasing of Zr content, the oxygen vacancy concentration on the surface of CZxS increased as well, which reached a maximum for a Zr/Ce ratio of 4 and then decreased by further increase of Zr content. The dependence of oxygen vacancy concentration in the CZxS/Zn‐HZSM‐5 bifunctional catalyst on their catalytic performance in the benzene alkylation with syngas was further investigated. The result exhibited that the oxygen vacancy was the site for CO activation, and the more oxygen vacancy, the better catalytic performance. The best catalytic activity, with a CO conversion of 33%, the benzene conversion of 30% and the total toluene and xylene selectivity of 92% was obtained over the bifunctional catalyst CZ4S/Zn‐HZSM‐5 with the highest oxygen vacancy concentration.
Simplified cooperative viscoplasticity theory based on overstress model for nanocomposites
Authors: Bakbak Okan , Colak Ozgen
Published: May 2022

Cooperative‐viscoplasticity theory based on overstress (C‐VBO) theory proposed to cover the total time, temperature, and graphene fraction dependent mechanical behavior of the nanocomposite material is simplified in this work. The previous version of the VBO model for nanocomposites includes the agglomeration effect of nanofiller by dividing the polymer nanocomposite into two parts as “agglomerated” and “effective matrix” phases. In this work, to be able to define the behavior of nanocomposites when nanofiller is evenly distributed into the matrix, the material model is simplified by defining the bulk and shear modulus without agglomerated and effective matrix phases and they are calculated separately using the Mori‐Tanaka homogenization scheme. The capabilities of the modified C‐VBO model for nanocomposites are investigated by simulating rate‐dependent uniaxial compression, creep, and relaxation behaviors for different graphene fractions (0.1 and 0.5 wt.%). In addition, to investigate high strain rate behavior, Split Hopkinson pressure bar tests are performed. The adiabatic heating effect that occurs at high strain rates is taken into account and incorporated into the model. All behaviors mentioned above are simulated well by simplified C‐VBO for nanocomposites. The developed constitutive model is ready to implement into finite element codes to be used in the structural analysis.
Digital body preservation: Technique and applications
Authors: Vandenbossche Vicky , Van de Velde Joris , Avet Stind , Willaert Wouter , Soltvedt Stian , Smit Noeska , Audenaert Emmanuel
Published: May 2022

High‐fidelity anatomical models can be produced with three‐dimensional (3D) scanning techniques and as such be digitally preserved, archived, and subsequently rendered through various media. Here, a novel methodology—digital body preservation—is presented for combining and matching scan geometry with radiographic imaging. The technique encompasses joining layers of 3D surface scans in an anatomical correct spatial relationship. To do so, a computed tomography (CT) volume is used as template to join and merge different surface scan geometries by means of nonrigid registration into a single environment. In addition, the use and applicability of the generated 3D models in digital learning modalities is presented. Finally, as computational expense is usually the main bottleneck in extended 3D applications, the influence of mesh simplification in combination with texture mapping on the quality of 3D models was investigated. The physical fidelity of the simplified meshes was evaluated in relation to their resolution and with respect to key anatomical features. Large‐ and medium‐scale features were well preserved despite extensive 3D mesh simplification. Subtle fine‐scale features, particular in curved areas demonstrated the major limitation to extensive mesh size reduction. Depending on the local topography, workable mesh sizes ranging from 10% to 3% of the original size could be obtained, making them usable in various learning applications and environments.
Interleukin 6/gp130 axis promotes neural invasion in pancreatic cancer
Authors: Suzuki Hidetaka , Mitsunaga Shuichi , Ikeda Masafumi , Aoyama Takao , Yoshizawa Kazumi , Yamaguchi Masayuki , Suzuki Masami , Narita Minoru , Kawasaki Toshikatsu , Ochiai Atsushi
Published: May 2022

Background

Nerve invasion (N‐inv) is an important prognostic factor in pancreatic ductal adenocarcinoma (PDAC). Elucidation of circulating N‐inv stimulators could provide deeper insights and novel perspectives for PDAC therapy. The interleukin (IL)‐6/gp130 axis was evaluated in this study as a candidate N‐inv stimulator.

Methods

A human pancreatic cancer (PC) cell, Capan‐1, was confirmed to have the stimulant activity of IL‐6/gp130 axis through the evaluation of mRNA, cell surface protein and intracellular protein levels and chemotaxis and wound healing assay. The upregulation of IL‐6/gp130 axis was evaluated using tumor‐derived IL‐6 level and intratumoral pSTAT3 expression in N‐inv of murine sciatic nerves by intraneural injection of Capan‐1 cell (N‐inv model) and using resected pancreatic cancer tissue and clinical data from 46 PDAC patients.

Results

mRNA and protein expressions of IL‐6 and IL‐6 receptor were found in whole cell lysate and condition medium from PC cell. Cell surface protein expression of gp130 were clearly detected on PC cell. IL‐6 promoted migration and chemotaxis of PC cell. Serum IL‐6 and tumoral IL‐6 mRNA levels in N‐inv model mice were significantly higher than those in subcutaneous tumor mice (p = 0.004 and p = 0.002, respectively). Silencing of IL‐6 and gp130 on PC cell and administration of an anti‐IL‐6 receptor antibody, tocilizumab, suppressed N‐inv, compared to each control (p = 0.070, p = 0.118 and p = 0.122, respectively). In PDAC patients, the high‐N‐inv group showed poor prognosis (p =0.059) and elevated serum levels of IL‐6 and C‐reactive protein, synthesis of which is promoted by IL‐6, compared to those in the low‐N‐inv group (p = 0.006 and p = 0.075, respectively). Tumoral gp130 expression at N‐inv was higher than that in the primary pancreatic tumor (p = 0.026).

Conclusion

Biological activity of IL‐6/gp130 axis promoted N‐inv in murine model and was upregulated in PDAC patients with severe N‐inv. This study is the first evidence that the IL‐6/gp130 axis offers a potential therapeutic target in PDAC with N‐inv.
New Metabolites, Antifeedant, Insecticidal Activities, and Reciprocal Relationship Between Insect and Fungus from Endophyte Schizophyllum commune
Authors: Wang Cui‐Fang , Yang Xue‐Qiong , Sun Jing , Wang Ting , Cui Han‐Rong , Yang Ya‐Bin , Ding Zhong‐Tao
Published: May 2022

Five new bisabolane sesquiterpenes, a new polyketide, along with seven known compounds, were isolated from endophyte Schizophyllum commune associated with a famous medicinal and edible plant, Gastrodia elata. Most compounds 1–12, and extract indicated antifeedant activities against silkworm with feeding deterrence index (FDI) of 21–85 %, at concentrations of 20 μg/cm2, 40 μg/cm2, respectively. Compound 6 indicated obvious insecticidal activity with fatality rate of 60 %, at the concentration of 20 μg/cm2. Five bisabolane sesquiterpenes, two ergosterols, and a glyceride showed insecticidal synergism by combining with abamectin. Interesting, ergosterol peroxide (13) distributed widely in mushrooms and fungi, was found to have feeding attractant activities on insects and antifungal activity against entomopathogen Beauveria bassiana. The reciprocal relationship should be occurred between S. commune and pests for the fungus produced ergosterol peroxide to attract the pests propagating spore, and its anti‐entomopathogen activity was also benefit for the health of insects.
M379A Mutant Tyrosine Phenol‐lyase from Citrobacter freundii Has Altered Conformational Dynamics
Authors: Phillips Robert S. , Jones Benjamin , Nash Sarah
Published: May 2022

The M379A mutant of Citrobacter freundii tyrosine phenol‐lyase (TPL) has been prepared. M379A TPL is a robust catalyst to prepare a number of tyrosines substituted at the 3‐position with bulky groups that cannot be made with wild type TPL. The three dimensional structures of M379A TPL complexed with L‐methionine and 3‐bromo‐DL‐phenylalanine have been determined by X‐ray crystallography. Methionine is bound as a quinonoid complex in a closed active site in 3 of 4 chains of homotetrameric M379A TPL. M379A TPL reacts with L‐methionine about 8‐fold slower than wild type TPL. The temperature dependence shows that the slower reaction is due to less positive activation entropy. The structure of the M379A TPL complex of 3‐bromo‐DL‐phenylalanine has a quinonoid complex in two subunits, with an open active site conformation. The effects of the M379A mutation on TPL suggest that the mutant enzyme has altered the conformational dynamics of the active site.
Recovery of Hydroxytyrosol from Olive Mill Wastewater Using the Promiscuous Hydrolase/Acyltransferase PestE
Authors: Terholsen Henrik , Kaur Jasmin , Kaloudis Nikolaos , Staudt Amanda , Müller Henrik , Pavlidis Ioannis V. , Bornscheuer Uwe T.
Published: May 2022

Olive mill wastewater (OMWW) is produced annually during olive oil extraction and contains most of the health‐promoting 3‐hydroxytyrosol of the olive fruit. To facilitate its recovery, enzymatic transesterification of hydroxytyrosol (HT) was directly performed in an aqueous system in the presence of ethyl acetate, yielding a 3‐hydroxytyrosol acetate rich extract. For this, the promiscuous acyltransferase from Pyrobaculum calidifontis VA1 (PestE) was engineered by rational design. The best mutant for the acetylation of hydroxytyrosol (PestE_I208A_L209F_N288A) was immobilized on EziG2 beads, resulting in hydroxytyrosol conversions between 82 and 89 % in one hour, for at least ten reaction cycles in a buffered hydroxytyrosol solution. Due to inhibition by other phenols in OMWW the conversions of hydroxytyrosol from this source were between 51 and 62 %. In a preparative scale reaction, 13.8 mg (57 %) of 3‐hydroxytyrosol acetate was extracted from 60 mL OMWW.
MUC21 controls melanoma progression via regulating SLITRK5 and hedgehog signaling pathway
Authors: Liu Xueping , Xiao Yajun , Xiong Xia , Qi Xiaoyi
Published: May 2022

Mucins are heavily glycosylated proteins secreted by various cell types, to protect the epithelial surface of the gastrointestinal tract from damage. Currently, increasing studies provided evidence to suggest that mucins play an essential role in regulating tumor progression. However, the role of mucins and the underpinning mechanism of how mucins drive melanoma progression remains elusive. In this study, we first demonstrated that mucin 21 (MUC21) expression was significantly upregulated in metastatic melanoma tissues, and a higher MUC21 expression resulted in poor overall survival in melanoma patients by The Cancer Genome Atlas database analysis. In vitro, MUC21 overexpression markedly promoted proliferative properties and aggressive behavior of melanoma cell A375 and A875, as assessed by Cell Counting Kit‐8 and transwell assay. In mechanism, we proved that MUC21 suppressed expression of SLITRK5, an integral membrane protein, leading to activation of prosurvival hedgehog pathway and sustained melanoma development. More importantly, we found that combination of hedgehog pathway inhibitor cyclopamine and chemotherapy revealed an improved anticancer effect in MUC21 overexpression xenograft model. Altogether, our study described a novel role of MUC21 in regulating tumor progression, which offers a promising target for melanoma diagnosis and therapy.
The Significant Role of the Atomic Surface Structure of Support in Strong Metal‐Support Interaction
Authors: Tang Min , Wang Yong
Published: May 2022

Supported metal catalysts are important in many industrial reactions. It is reported that support materials are not always inert, and in some cases could even interact with metal nanoparticles (NPs) actively via various ways. In particular, the strong metal‐support interaction (SMSI), referring to metal NPs covered by support materials, affects catalysis at the active sites on the metal NP surface, which can serve as a very effective method in tuning and improving catalytic performance. By tailoring the support materials or controlling the treatment processes, different kinds of SMSI, such as classical SMSI, oxidative SMSI, wet‐chemistry SMSI, and adsorbate‐mediated SMSI, can be achieved. This concept summarizes the general strategies to tune SMSI and discusses the key results. Moreover, a new proposal is presented to tailor SMSI by combining both the exposed facets of the support materials and external environments. Furthermore, the challenges faced at present are discussed and useful insights for future research concerning this topic are provided.
A Catalyst and Solvent Free Route for the Synthesis of N‐Substituted Pyrrolidones from Levulinic Acid
Authors: Dolui Pritam , Tiwari Vikas , Saini Parul , Karmakar Tarak , Makhal Koushik , Goel Harshita , Elias Anil J.
Published: May 2022

An efficient, metal‐free, catalyst‐free and solvent‐free methodology for the reductive amination of levulinic acid with different anilines has been developed using HBpin as the reducing reagent. This protocol offers an excellent method to avoid solvents and added catalysts on the synthesis of different kinds of N‐substituted pyrrolidones under metal free conditions. It is also the first report for the synthesis of different pyrrolidones by solvent‐free as well as catalyst‐free methods. The proposed mechanism for the formation of pyrrolidone has been supported by DFT calculations and control experiments.
Plasma‐Electrolytic Polishing as a Post‐Processing Technology for Additively Manufactured Parts
Authors: Zeidler Henning , Böttger‐Hiller Falko
Published: May 2022

Additive manufacturing (AM) as a key enabling technology provides new options for engineering design of complex parts. Freeform shapes, grid‐like structures and internal cavities enable functional integration, reducing assembly and space requirements and increasing reliability. Metal AM technologies, however, require post‐processing in order to achieve acceptable surface roughness and ‐functionality. Plasma‐electrolytic polishing can, due to its toolless nature and excellent achievable surface properties, be a beneficial option.
Racial disparity in distant recurrence‐free survival in patients with localized breast cancer: A pooled analysis of National Surgical Adjuvant Breast and Bowel Project trials
Authors: Kim Gina , Pastoriza Jessica M. , Qin Jiyue , Lin Juan , Karagiannis George S. , Condeelis John S. , Yothers Greg , Anderson Stewart , Julian Thomas , Entenberg David , Rohan Thomas E. , Xue Xiaonan , Sparano Joseph A. , Oktay Maja H.
Published: May 2022

Background

Black race is associated with worse outcome in patients with breast cancer. The distant relapse‐free survival (DRFS) between Black and White women with localized breast cancer who participated in National Cancer Institute–sponsored clinical trial was evaluated.

Methods

Pooled data were analyzed from 8 National Surgical Adjuvant Breast and Bowel Project (NSABP) trials including 9702 women with localized breast cancer treated with adjuvant chemotherapy (AC, n = 7485) or neoadjuvant chemotherapy (NAC, n = 2217), who self‐reported as Black (n = 1070) or White (n = 8632) race. The association between race and DRFS was analyzed using log‐rank tests and multivariate Cox regression.

Results

After adjustment for covariates including age, tumor size, nodal status, body mass index and taxane use, and treatment (AC vs NAC), Black race was associated with an inferior DRFS in estrogen receptor–positive (ER+; hazard ratio [HR], 1.24; 95% CI, 1.05‐1.46; P = .01), but not in ER– disease (HR, 0.97; 95% CI, 0.83‐1.14; P = .73), and significant interaction between race and ER status was observed (P = .03). There was no racial disparity in DRFS among patients with pathologic complete response (pCR) (log‐rank P = .8). For patients without pCR, Black race was associated with worse DRFS in ER+ (HR, 1.67; 95% CI, 1.14‐2.45; P = .01), but not in ER– disease (HR, 0.91; 95% CI, 0.65‐1.28; P = .59).

Conclusions

Black race was associated with significantly inferior DRFS in ER+ localized breast cancer treated with AC or NAC, but not in ER– disease. In the NAC group, racial disparity was also observed in patients with residual ER+ breast cancer at surgery, but not in those who had pCR.

Lay Summary

Black women with breast cancer have worse outcomes compared with White women.

We investigated if this held true in the context of clinical trials that provide controlled treatment setting.

Black women with cancer expressing estrogen receptors (ERs) had worse outcome than White women. If breast cancers did not express ERs, there was no racial disparity in outcome.

We also observed racial disparity in women who received chemotherapy before their cancer was removed, but only if they had cancer expressing ERs and residual disease on completion of treatment. If the cancer disappeared with presurgical chemotherapy, there was no racial disparity.
Medical concept integrated residual short‐long temporal convolutional networks for predicting clinical events
Authors: Yang Jie , Wang Hong
Published: May 2022

Large collections of electronic clinical data today provide us with a vast source of information on medical practice. However, the utilization of those data for exploratory analysis to support clinical decisions is still limited. It is particularly challenging for extracting useful disease progression patterns from such data because it is longitudinal, incomplete, irregular, and heterogeneous of the patient conditions. In this article, we propose an integrated clinical event prediction model medical concept integrated residual short‐long temporal convolutional networks (SL‐TCN) to address these challenges. Compared to existing models, our model has three‐fold advantages: (1) it learns a compact set of medical concepts as the bridge between the hidden progression process and the observed medical evidence. (2) it learns a continuous‐time progression model from discrete‐time observations with nonequal intervals and high‐dimensional features. (3) We fuse the temporal convolutional network, the long short‐term memory network, and the residual connector so as to capture the local and global dependency of the sequence and make the clinical event predictions more robust. Through extensive experiments on the MIMIC III dataset, we demonstrate that our SL‐TCN achieves higher precision in clinical event prediction and derives some interesting clinical insights.
The Negative Solvatochromism of Reichardt‘s Dye B30 – A Complementary Study
Authors: Spange Stefan , Mayerhöfer Thomas G.
Published: May 2022

The UV/Vis spectra of a hypothetical negative solvatochromic dye in a solvent are theoretically calculated assuming the classical damped harmonic oscillator model and the Lorentz‐Lorenz relation. For the simulations, the oscillator strength of the solvent was varied, while for the solute all oscillator parameters were kept constant. As a result, a simple change of the oscillator strength of the solute can explain the redshift and intensity increase of the UV/Vis band of the solute. Simulated results are compared with measured UV/Vis spectroscopic data of 2,6‐diphenyl‐4‐(2,4,6‐triphenylpyridinium‐1‐yl) phenolate B30 (Reichardt‘s dye) Significant correlations of the absorption energy (1/λmax) with the molar absorption coefficient ϵ as function of solvent polarity are demonstrated for several derivatives of B30. The approach presented is only applicable to negative solvatochromism. Therefore, while the approach is vital to fully understand solvatochromism, it needs to be complemented by other approaches, e. g., to describe the changes of the chemical interactions based on the nature of the solvent, to explain all its various aspects.
Agronomical evaluation of low dormancy alfalfa populations selected by an indoor screening method
Authors: Claessens Annie , Bertrand Annick , Thériault Mireille , Baron Vern , Lajeunesse Julie , Schellenberg Mike , Rocher Solen
Published: May 2022

Fall dormancy is a vital component of alfalfa (Medicago sativa L.) yield in northern climates, but selection for the trait is often done at the expense of winter survival. We performed one cycle of selection to reduce fall dormancy in two winter hardy cultivars (Yellowhead and Peace) using a new indoor screening method. We compared the reduced dormancy populations with their respective initial cultivars for fall dormancy, yield, and winter survival at four sites across Canada. During the establishment and the first production years, plants of the reduced dormancy populations were generally taller in the fall than their respective cultivar, which resulted in a one unit increase of their fall dormancy class. Under field conditions, plants of the reduced dormancy populations had a similar winter survival than those of the initial cultivars. Under simulated winter conditions, freezing tolerance was not affected by selection for reduced dormancy in Peace, whereas a decrease from −24.0 to −21.5 °C was observed in Yellowhead. However, in this cultivar, we noted a 37% yield increase under field conditions and a 40% more vigorous regrowth under simulated winter conditions in the reduced dormancy population. These results showed that the indoor selection method effectively reduced fall dormancy and that indirect responses for yield and winter survival were dependent on the genetic background used as selection material. This selection method could therefore be promising to develop alfalfa cultivars adapted to northern latitudes with high winter hardiness and improved late season yield.
Blood transcriptomics identifies immune signatures indicative of infectious complications in childhood cancer patients with febrile neutropenia
Authors: Haeusler Gabrielle M , Garnham Alexandra L , Li‐Wai‐Suen Connie SN , Clark Julia E , Babl Franz E , Allaway Zoe , Slavin Monica A , Mechinaud Francoise , Smyth Gordon K , Phillips Bob , Thursky Karin A , Pellegrini Marc , Doerflinger Marcel
Published: May 2022

Objectives

Febrile neutropenia (FN) is a major cause of treatment disruption and unplanned hospitalization in childhood cancer patients. This study investigated the transcriptome of peripheral blood mononuclear cells (PBMCs) in children with cancer and FN to identify potential predictors of serious infection.

Methods

Whole‐genome transcriptional profiling was conducted on PBMCs collected during episodes of FN in children with cancer at presentation to the hospital (Day 1;n = 73) and within 8–24 h (Day 2;n = 28) after admission. Differentially expressed genes as well as gene pathways that correlated with clinical outcomes were defined for different infectious outcomes.

Results

Global differences in gene expression associated with specific immune responses in children with FN and documented infection, compared to episodes without documented infection, were identified at admission. These differences resolved over the subsequent 8–24 h. Distinct gene signatures specific for bacteraemia were identified both at admission and on Day 2. Differences in gene signatures between episodes with bacteraemia and episodes with bacterial infection, viral infection and clinically defined infection were also observed. Only subtle differences in gene expression profiles between non‐bloodstream bacterial and viral infections were identified.

Conclusion

Blood transcriptome immune profiling analysis during FN episodes may inform monitoring and aid in defining adequate treatment for different infectious aetiologies in children with cancer.
The association between cardiac involvement and long‐term clinical outcomes in patients with Duchenne muscular dystrophy
Authors: Cha Jung‐Joon , Kim In‐Soo , Kim Jong‐Youn , Choi Eui‐Young , Min Pil‐Ki , Yoon Young Won , Lee Byoung Kwon , Hong Bum‐Kee , Kwon Hyuck Moon , Cho Han Eol , Choi Won Ah , Kang Seong‐Woong , Rim Se‐Joong
Published: May 2022

Aims

Despite advances in contemporary cardiopulmonary therapies, cardiomyopathy remains the leading cause of death in patients with Duchenne muscular dystrophy (DMD). Also, the long‐term clinical outcomes of patients with DMD and cardiomyopathy is unknown. This study investigated long‐term clinical outcomes and their associated factors in patients with late‐stage DMD.

Methods and results

A total of 116 patients with late‐stage DMD (age > 15 years) were enrolled in this retrospective study. All enrolled patients were followed up at a single tertiary referral hospital. LV systolic dysfunction was dichotomously defined as reduced [left ventricular ejection fraction (LVEF) ≤ 40%] vs. preserved [>40%] based on the initial echocardiographic result. The primary endpoint was all‐cause death. The secondary endpoint was a composite event defined as death or unexpected hospitalization due to cardiovascular reasons including chest pain, dyspnoea, and generalized oedema. The patients were divided into preserved (n = 84, 72.4%) and reduced LVEF groups (n = 32, 27.6%). The mean age was 20.8 ± 5.9 years, the mean disease duration, 8.8 ± 3.7 years, and the mean follow‐up duration, 1708 ± 659 days. For primary endpoint, the reduced LVEF group showed a lower rate of overall survival (Reduced LVEF vs. Preserved LVEF; 81.3% vs. 98.8%, log‐rank P = 0.005). In the multivariable Cox regression analysis, brain‐natriuretic peptide (BNP) level (adjusted hazard ratio [HR] 1.088, 95% confidence interval [CI] 1.019–1.162, P = 0.011) and diuretic use (adjusted HR 9.279, 95%CI 1.651–52.148, P = 0.011) were significant predictors of all‐cause death in patients with DMD. For the secondary endpoint, the reduced LVEF group had a lower rate of freedom from composite events than the preserved LVEF group (65.6% vs. 86.9%, log‐rank P = 0.005). In the multivariable Cox regression analysis, BNP level (adjusted HR 1.057, 95%CI 1.005–1.112, P = 0.032) and diuretic use (adjusted HR 4.189, 95% CI 1.704–10.296, P = 0.002) were significant predictors of the composite event in patients with DMD.

Conclusions

Patients with DMD and reduced LVEF had worse clinical outcomes than those with preserved LVEF. BNP level and diuretic use were associated with adverse clinical outcomes in patients with late‐stage DMD, irrespective of LVEF.
Substituent Controlled Synthesis of Dioxidomolybdenum(VI) Complexes of N,N,N’,N’‐Tetrakis(2‐Hydroxyl‐3,5‐Disubstitutedbenzyl)‐1,2‐Diaminoethane, Their Trans‐Metalation to Oxidovanadium(V) Complexes and Biocatalytic Applications
Authors: Maurya Mannar R. , Maurya Shailendra K. , Kumar Naveen , Avecilla Fernando , Gupta Puneet
Published: May 2022

The reaction of [MoVIO2(acac)2] (acac=acetylacetonate anion) with N,N,N’,N’‐tetrakis(2‐hydroxy‐3,5‐disubstitutedbenzyl)‐1,2‐diaminoethane having different 3,5‐disubstituents on the phenyl ring in 1 : 1 molar ratio in MeOH results in the formation of two different types of substituent controlled mononuclear complexes. Ligands having 3,5‐di‐t‐butyl substituents [H4en(3,5‐dtbb)4, I] and 3‐t‐butyl‐5‐methyl substituents [H4en(3‐tb,5‐mb)4, II], result in the formation of complexes, [{MoVIO2(MeOH)}H2en(3,5‐dtbb)4] (1) and [{MoVIO2(MeOH)}H2en(3‐tb,5‐mb)4] (2), respectively. In these complexes ligands behave as a bis(dibasic ONO) donor and coordinate to only one side of the ONO functionalities. On the contrary, ligands having 3,5‐dimethyl substituents [H4en(3,5‐dmb)4, III] and 3,5‐dichloro substituents [H4en(3,5‐dcb)4, IV] facilitate mononuclear α‐cis, symmetric complexes, [{MoVIO2}H2en(3,5‐dmb)4] (3) and [{MoVIO2}H2en(3,5‐dcb)4] (4), respectively. Here ligands behave as a dibasic ONNO tetradentate. Further reaction of complexes 1 and 2 with equimolar amount of [MoVIO2(acac)2] in DMF‐MeOH gives homo‐binuclear complexes, [{MoVIO2(DMF)}2en(3,5‐dtbb)4] (5) and [{MoVIO2(DMF)}2en(3‐tb,5‐mb)4] (6), respectively. Reaction of VVO(OEt)3 with complexes 1–4 in refluxing EtOH caused the displacement of cis‐[MoVIO2] group by [VVO] along with the breaking of one of the arms of ligand and the formation of oxidovanadium(V) complexes, [{VVO}en(3,5‐dtbb)3] (7), [{VVO}en(3‐tb,5‐mb)3] (8), [{VVO}en(3,5‐dmb)3] (9), and [{VVO}en(3,5‐dcb)3] (10). This is an example of trans‐metalation. Complexes [{VVO}Hen(3,5‐dmb)4] (11) and [{VVO}Hen(3,5‐dcb)4] (12) upholding all four arms have also been obtained by direct reaction of ligands III and IV, respectively, with VVO(OEt)3. Biomimetic catalytic activity similar to enzymes haloperoxidases was performed with thymol and other phenol derivatives and all these complexes serve as excellent functional models.
Construction of Pyrrolocoumarin Cores through Double C−H Annulation Cascade
Authors: Michikita Ryudai , Usuki Yoshinosuke , Satoh Tetsuya
Published: May 2022

Rhodium(III)‐catalyzed double C−H annulation of 3‐(acetylamino)coumarins with internal arylacetylenes is reported. The reaction proceeds smoothly accompanied by two C−C and two C−N bond formation to produce 8‐aryl‐6H‐chromeno[4’,3’:4,5]pyrrolo[2,1‐a]isoquinolin‐6‐ones selectively. It also provides a straightforward route to natural product inspired pentacyclic pyrrolocoumarin derivatives from readily available building blocks.
Energy, Exergy, Economic, Exergoeconomic, and Exergoenvironmental (5E) Analyses and Optimization of a Novel Three‐Stage Cascade System Based on Liquefied Natural Gas Cold Energy
Authors: Wu Jingjing , Shang Liyan , Pan Zhen , Zhou Li
Published: May 2022

Herein, a novel three‐stage cascade power/cooling cogeneration system that includes the gas turbine (GT) cycle, supercritical CO2 Brayton cycle (S‐CO2), transcritical CO2 Rankine cycle (T‐CO2), and organic Rankine cycle is proposed. The system is simulated by connecting MATLAB and Aspen HYSYS via Active‐X control. It is indicated in the results that the system exhibits power generation, primary energy utilization, and exergy efficiencies of 59.43%, 81.66%, and 53.94%, respectively. The total product cost and environmental cost per unit exergy are 23.80 and 32.66 $GJ−1, respectively. Monoethanolamine is used to absorb CO2 from the exhaust gas, and cold energy from liquefied natural gas is utilized to capture carbon, with a capture rate of 96%, to realize low‐carbon‐emission characteristics. Additionally, the performance of the established system is verified using three basic cycles for comparison. It is revealed in the results that the designed system exhibits the highest thermodynamic performance and net present value among the investigated cycles. Furthermore, multi‐objective optimization of the systems is performed using the second‐generation non‐dominated sorting genetic algorithm algorithm. Although the GT/S‐CO2/T‐CO2 cycle is found to be more cost‐effective than the proposed system at generation efficiencies less than 55%, the established system is deemed the best option among the cycles at power‐generation efficiencies greater than 55%.
Combination process for dye removal based on photocatalyst and adsorption using low cost waste material adsorbent
Authors: Mohadesi Majid , Gouran Ashkan , Shahbazi Faezeh
Published: May 2022

This study investigated the removal of methylene blue and methyl orange dyes from aqueous solutions containing these dyes. The process of wastewater treatment involved a combination of adsorption processes performed using UV/H2O2/TiO2 and fly‐ash adsorbent prepared from sunflower seed pulp. In this study, first the effect of UV/H2O2/TiO2 process parameters including initial dye concentration (10–30 mg/L), UV lamp power (0–30 W), hydrogen peroxide concentration (100–500 mg/L), and titanium dioxide concentration (10–50 mg/L) were investigated (under a process time of 75 min and adsorbent concentration of 2 g/L). In optimal conditions, the percentage of removal of methylene blue and methyl orange dyes were 96.43% and 83.60%, respectively. After the optimization of the parameters of UV/H2O2/TiO2 process, the processing time and adsorbent concentration were investigated. The results indicated that when performing the process under the process time of 150 min and the adsorbent concentration of 2 g/L, the removal of methylene blue dye exceeded 99%. In addition, the removal of methyl orange dye under the process time of 300 min and the adsorbent concentration of 10 g/L exceeded 99%. At the end of the study, an assessment was carried out using quasifirst‐order and quasisecond‐order kinetic models and the results indicated that both kinetic models had a high level of accuracy for modeling the adsorption of methylene blue and methyl orange dyes on fly‐ash adsorbents prepared from sunflower seed pulp.
A practical methodology for predicting electricity consumption of urban residential buildings
Authors: Yurtsever Özlem
Published: May 2022

It is a challenging task for determining the emissions and energy‐saving options for counties and countries. In order to overcome this issue, two new concepts are introduced in this study. These are residential base electricity consumption and residential base natural gas consumption. A new model that estimates the total energy consumption of urban residential buildings from the available electricity consumption data is developed. The model employs heating degree days (HDD) and cooling degree days (CDD) parameters to predict the energy consumption for heating and cooling purposes. A month with zero or almost zero values of both HDD and CDD is considered as “base month.” These months when there is neither heating nor cooling, plays a key role in this study.

The proposed model is applied to a county with a population of over 62,000 located in Southern Turkey, and the total electricity consumption is calculated with 1.24% accuracy. The validity and accuracy of the model are tested by theoretical electricity calculations, coal, and wood consumption. Accordingly, while annual electrical heating is equal to 2618 kWh/year for an average house of 96 m2, for the coal and wood burning households, the annual energy consumption values are 2190 and 2616 kWh/year, respectively.
A comprehensive analysis on elastic, mechanical, thermodynamic and thermoelectric properties of PbSnO3: A density functional theory study
Authors: Patel Shiv , Srivastava Anshuman , Abraham Jisha Annie , Sharma Ramesh , Dar Sajad Ahmad , Srivastava Vipul
Published: May 2022

The full‐potential linearized augmented plane wave (FP‐LAPW) method was employed in the framework of density functional theory (DFT) and semi‐classical Boltzmann transport theory to compute the electronic, elastic, mechanical, thermal, and thermoelectric characteristics of PbSnO3. The properties are derived using a variety of exchange correlations, that is, local density approximations (LDA), Perdew Burke Ernzerhof generalized gradient approximation (PBE‐GGA), Wu‐Cohen (WC‐GGA), Engel‐Vosko GGA (EV‐GGA) and Perdew Burke‐Ernzerhof generalized gradient approximation improved for solids (PBEsol‐GGA), modified Becke‐Johnson GGA, (mBJ‐GGA), new modified Becke‐Johnson GGA (nmBJ‐GGA), and unmodified Becke‐Johnson GGA, (unmBJ‐GGA). In order to accurately describe the characteristics of the perovskite materials, a new modified Becke Johnson (nmBJ) potential is used. In comparison to other computations, the obtained band gap of nmBJ (3.08 eV) is consistent with the other theoretical and experimental findings. The results of our calculations show that PbSnO3 has a direct band gap. In addition, the bulk modulus, elastic constants, Poisson's ratio, shear modulus, anisotropy, and Young's modulus are calculated. The transport theory based on BoltzTraP code is used to calculate electronic transport characteristics such as electrical conductivity and thermal conductivity, Hall‐coefficient, and so on in the temperature range 100 to 1200 K. Furthermore, the thermal characteristics such as Debye temperature, specific heat capacity, entropy and thermal expansion coefficient have been analyzed with quasi‐harmonic Debye model.
Episodic boundary cells in human medial temporal lobe during the free recall task
Authors: Yoo Hye Bin , Umbach Gray , Lega Bradley
Published: May 2022

A necessary condition for forming episodic memories is the construction of specific episodes demarcated from other episodes in space and time. Evidence from studies of episodic memory formation using rodent models suggest that the medial temporal lobe (MTL) supports the representation of boundary information. Building on recent work using human microelectrode recordings as well, we hypothesized of human MTL neurons with firing rates sensitive to episodic boundary information. We identified 27 episodic boundary neurons out of 736 single neurons recorded across 27 subjects. Firing of these neurons increased at the beginning and end of mnemonically relevant episodes in the free recall task. We distinguish episodic boundary neurons from a population of ramping neurons (n = 58), which are time‐sensitive neurons whose activity provides complementary information during episodic representation. Episodic boundary neurons exhibited a U‐shaped activity pattern demonstrating increased activity after both beginning and end boundaries of encoding and retrieval epochs. We also describe evidence that the firing of boundary neurons within episodic boundaries is organized by hippocampal theta oscillations, using spike‐field coherence metrics.
Predictors of mortality and morbidity in critically ill COVID‐19 patients: An experience from a low mortality country
Authors: Khatib Mohamad Y. , Ananthegowda Dore C. , Elshafei Moustafa S. , El‐Zeer Hani , Abdaljawad Wael I. , Shaheen Muhsen A. , Ibrahim Abdulsalam S. , Abujaber Ahmad A. , Soliman Ahmed A. , Mohamed Ahmed S. , Al‐Wraidat Mohammad , Ahmed Amna , Nashwan Abdulqadir J. , Saad Mohamed O. , Butt Adeel A. , Al‐Maslamani Muna A. , Al‐Mohammed Ahmed
Published: May 2022

Background and Aims

Clinical characteristics and factors associated with mortality in patients admitted to the intensive care unit (ICU) in countries with low case fatality rates (CFR) are unknown. We sought to determine these in a large cohort of critically ill COVID‐19 patients in Qatar and explore the early mortality predictors.

Methods

We retrospectively studied the clinical characteristics and outcomes in patients admitted to the ICU at the national referral hospital for COVID‐19 patients in Qatar. Logistic regression analysis was used to determine factors associated with mortality.

Results

Between March 7 and July 16, 2020, a total of 1079 patients with COVID‐19 were admitted to the ICU. The median (IQR) age of patients was 50 (41–59) years. Diabetes (47.3%) and hypertension (42.6%) were the most common comorbidities. In‐hospital mortality was 12.6% overall and 25.9% among those requiring mechanical ventilation. Factors independently associated with mortality included older age ([OR]; 2.3 [95% CI; 1.92–2.75] for each 10‐year increase in age, p < 0.001), chronic kidney disease (OR; 1.9 [95% CI; 1.02–3.54], p = 0.04), active malignancy (OR; 6.15 [95% CI; 1.79–21.12], p = 0.004), lower platelet count at ICU admission (OR; 1.41 [95% CI; 1.13–1.75] for each 100 × 103/µl decrease, p = 0.002), higher neutrophil‐to‐lymphocyte ratio at admission (OR; 1.01 [95% CI; 1–1.02] for each 1‐ point increase, p = 0.016), higher serum ferritin level at admission (OR; 1.05 [(95% CI; 1.02–1.08] for each 500 µg/L increase, p = 0.002), and higher serum bilirubin level at admission (OR; 1.19 [95% CI; 1.04–1.36] for each 10 μmol/L increase, p = 0.01).

Conclusions

The mortality rate among critically ill COVID‐19 patients is low in Qatar compared to other countries. Older age, chronic kidney disease, active malignancy, higher neutrophil‐to‐lymphocyte ratios, lower platelet counts, higher serum ferritin levels, and higher serum bilirubin levels are independent predictors of in‐hospital mortality.