bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fluorescent Microswimmers Based on Cross‐β Amyloid Nanotubes and Divergent Cascade Networks
Authors: Chatterjee Ayan , Ghosh Souvik , Ghosh Chandranath , Das Dibyendu 
Published: May 2022

AbstractShaped 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

AbstractS/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

AbstractIn 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

AbstractThe 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.
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

AbstractA 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

AbstractCooperative‐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

AbstractHigh‐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

AbstractBackgroundNerve 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.MethodsA 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.ResultsmRNA 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).ConclusionBiological 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

AbstractFive 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

AbstractThe 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

AbstractOlive 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

AbstractMucins 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

AbstractSupported 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

AbstractAn 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

AbstractAdditive 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

BackgroundBlack 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.MethodsPooled 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.ResultsAfter 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).ConclusionsBlack 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

AbstractLarge 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.