bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis and structural characterization of palladium pincer complexes: Sustainable synthesis of benzothiazoles
Authors: Anandaraj Pennamuthiriyan , Saranya Sundar , Ramesh Rengan 
Published: February 2023

An efficient Pd(II)N^N^S pincer type catalysts‐promoted sustainable construction of pharmaceutically important benzothiazole derivatives from primary alcohols and 2‐aminothiophenol via acceptorless dehydrogenative coupling (ADC) method has been described. The newly synthesized ligand L2 and the Pd(II) complexes in addition to L1 and L3 were characterized by analytical and Fourier transform infrared spectroscopy (FT‐IR), UV–visible (UV–vis), and nuclear magnetic resonance (NMR) spectral techniques. Further, the ORTEP views of the complexes 2 and 3 were established by a single crystal XRD study, which evidenced the coordination of the thiosemicarbazone ligands and disclose the square‐planar geometry around the Pd(II) ion. The present homogeneous catalytic system involves synthesizing a range of benzothiazoles via C−S and C−N bond formation with excellent yields up to 93%. The described methodology employs a sustainable, highly abundant, and inexpensive alcohol as starting material using 1 mol% catalyst loading, and water and hydrogen gas are the only by‐products. Furthermore, a plausible mechanism involving in situ aldehyde formation via dehydrogenation of primary alcohols has been proposed. A large‐scale synthesis of 2‐(4‐methoxyphenyl)benzo[d]thiazole illustrates the synthetic utility of the present catalytic protocol.
Improving epoxy adhesion with steel adherends using a tannic acid‐based additive: Impact on resin properties and interfacial bonding
Authors: Babu Noel , Zhang Puxuan , Xian Guijun 
Published: February 2023

AbstractTraditional adherend surface treatment techniques such as grit blasting, acid etching, phosphating and primer treatments alone are often inadequate for maintaining interfacial bond durability of adhesively bonded joints. Therefore, the existing interfacial bonds between epoxy adhesive and the adherend should be strengthened. Tannic acid (TA) is a plant‐based polyphenol that is inexpensive and easily available in nature. Its potential as an additive to improve the interfacial bond durability of epoxy adhesives has not been studied adequately. In the present study, an additive (TA‐AGE) was synthesized by grafting allyl glycidyl ether (AGE) onto phenolic hydroxyl groups of TA. With 1 wt% TA‐AGE additive in the epoxy, the single lap shear strength improved by 37%. Further, accelerated aging studies were performed to understand the impact of water uptake on the mechanical and viscoelastic properties and interfacial bond durability of the epoxy with 1 wt% TA‐AGE additive. TA‐AGE modification can increase hydrophilicity and enhance the water uptake characteristics of epoxy. This can negatively impact its mechanical properties and glass transition temperature (Tg) due to plasticization effects. Nevertheless, Boeing wedge test and single lap shear tests reveal that the strengthened interfacial bonds to steel adherends with the additive were robust and durable.
Artificial scaffolding: Augmenting social cognition by means of robot technology
Authors: Ghiglino Davide , Floris Federica , De Tommaso Davide , Kompatsiari Kyveli , Chevalier Pauline , Priolo Tiziana , Wykowska Agnieszka 
Published: February 2023

AbstractThe concept of scaffolding refers to the support that the environment provides in the acquisition and consolidation of new abilities. Technological advancements allow for support in the acquisition of cognitive capabilities, such as second language acquisition using simple smartphone applications There is, however, one domain of cognition that has been scarcely addressed in the context of technologically assisted scaffolding: social cognition. We explored the possibility of supporting the acquisition of social competencies of a group of children with autism spectrum disorder engaged in a rehabilitation program (age = 5.8 ± 1.14, 10 females, 33 males) by designing two robot‐assisted training protocols tailored to Theory of Mind competencies. One protocol was performed with a humanoid robot and the other (control) with a non‐anthropomorphic robot. We analyzed changes in NEPSY‐II scores before and after the training using mixed effects models. Our results showed that activities with the humanoid significantly improved NEPSY‐II scores on the ToM scale. We claim that the motor repertoire of humanoids makes them ideal platforms for artificial scaffolding of social skills in individuals with autism, as they can evoke similar social mechanisms to those elicited in human‐human interaction, without providing the same social pressure that another human might exert.
Querverschub der 985 m langen Lennetalbrücke
Authors: Lechner Thomas , Neumann Michael , Felgendreher Jan , Casper Hans‐Joachim 
Published: February 2023

AbstractDie Lennetalbrücke gehört zu den großen Talbrücken der A45. Aufgrund des gestiegenen Verkehrsaufkommens und des baulichen Zustands der Bestandsbrücke war die Notwendigkeit eines Ersatzneubaus gegeben. Um den Verkehr während der Bauzeit möglichst wenig einzuschränken, wurde der neue Überbau für eine Fahrtrichtung in Seitenlage hergestellt und im Anschluss durch einen Querverschub an die endgültige Position gebracht. Mit einer Länge von fast 1000 m handelt es sich bei der Lennetalbrücke – bezogen auf die Brückenlänge – um den größten Querverschub, der bisher in Deutschland realisiert wurde. In diesem Beitrag wird auf die Besonderheiten bei Planung und Ausführung des Querverschubs eingegangen.
Bayesian estimation of two‐part joint models for a longitudinal semicontinuous biomarker and a terminal event with INLA: Interests for cancer clinical trial evaluation
Authors: Rustand Denis , van Niekerk Janet , Rue Håvard , Tournigand Christophe , Rondeau Virginie , Briollais Laurent 
Published: February 2023

AbstractTwo‐part joint models for a longitudinal semicontinuous biomarker and a terminal event have been recently introduced based on frequentist estimation. The biomarker distribution is decomposed into a probability of positive value and the expected value among positive values. Shared random effects can represent the association structure between the biomarker and the terminal event. The computational burden increases compared to standard joint models with a single regression model for the biomarker. In this context, the frequentist estimation implemented in the R package frailtypack can be challenging for complex models (i.e., a large number of parameters and dimension of the random effects). As an alternative, we propose a Bayesian estimation of two‐part joint models based on the Integrated Nested Laplace Approximation (INLA) algorithm to alleviate the computational burden and fit more complex models. Our simulation studies confirm that INLA provides accurate approximation of posterior estimates and to reduced computation time and variability of estimates compared to frailtypack in the situations considered. We contrast the Bayesian and frequentist approaches in the analysis of two randomized cancer clinical trials (GERCOR and PRIME studies), where INLA has a reduced variability for the association between the biomarker and the risk of event. Moreover, the Bayesian approach was able to characterize subgroups of patients associated with different responses to treatment in the PRIME study. Our study suggests that the Bayesian approach using the INLA algorithm enables to fit complex joint models that might be of interest in a wide range of clinical applications.
HBcAb positivity increases the risk of postoperative complications after extended hemihepatectomy for hilar cholangiocarcinoma
Authors: Wang Wen‐Qiang , Xu Guang‐Yuan , Li Jian , Liang Bin‐Yong , Li Jiang , Lin Mei‐Long , Chen Xiao‐Ping , Zhang Er‐Lei , Huang Zhi‐Yong 
Published: February 2023

AbstractBackgroundHepatitis B core antibody (HBcAb) positivity is considered a prior hepatitis B virus (HBV) infection. However, little is known about the effect of HBcAb positivity on surgical safety for hilar cholangiocarcinoma (hCCA). The present study aims to investigate the role of HBcAb positivity on postoperative complications of hCCA.MethodsA retrospective analysis was performed on the status of HBcAb positivity, liver fibrosis, perioperative surgical complications, and long‐term outcomes of hCCA patients with Hepatitis B surface antigen (HBsAg) negativity who underwent surgical treatment in Tongji Hospital from April 2012 to September 2019.ResultsHBcAb positivity with negative HBsAg occurs in 137 hCCA patients (63.1%). A total of 99 hCCA patients with negative HBsAg underwent extended hemihepatectomy, of whom 69 (69.7%) and 30 (30.3%) were HBcAb‐positive and HBcAb‐negative, respectively. Significant fibrosis was detected in 63.8% of the patients with HBcAb‐positive, which was markedly higher than those with HBcAb‐negative (36.7%) (p = 0.016). The postoperative complications and 90‐day mortality rates were 37.4% (37/99) and 8.1% (8/99), respectively. The incidence of postoperative complications in HBcAb‐positive patients (44.9%) was significantly higher than that in HBcAb‐negative patients (20.0%) (p = 0.018). All the patients who died within 30‐day after surgery were HBcAb‐positive. Multivariate analysis showed that the independent risk factors for complications were HBcAb positivity, preoperative cholangitis, portal occlusion >15 min, and significant fibrosis. There were no significant differences in recurrence‐free survival (RFS) and overall survival (OS) between HBcAb‐positive and HBcAb‐negative patients (p = 0.642 and p = 0.400, respectively).ConclusionsHBcAb positivity is a common phenomenon in hCCA patients from China, a country with highly prevalent HBcAb positivity. The status of HBcAb‐positive markedly increases the incidence of postoperative complications after extended hemihepatectomy for hCCA patients.
CD169+ sinus macrophages in regional lymph nodes do not predict mismatch‐repair status of patients with colorectal cancer
Authors: Saito Yoichi , Fujiwara Yukio , Miyamoto Yuji , Ohnishi Koji , Nakashima Yuta , Tabata Yasuhiko , Baba Hideo , Komohara Yoshihiro 
Published: February 2023

AbstractAimsMismatch‐repair deficiency and microsatellite instability‐high (dMMR/MSI‐H) colorectal cancer (CRC) is treated with programmed death (PD)‐1 antibody regardless of PD‐ligand (L)1 expression in tumor cells. We previously found that abundant CD169+ macrophages in regional lymph node (RLN) sinuses and CD8+ tumor‐infiltrating lymphocytes (TILs) positively correlated in CRC and were associated with a favorable prognosis. However, associations between dMMR/MSI‐H CRC and CD8+ TILs or prognoses vary among studies. In this study, we attempted to compare the association between MMR status, CD169+ macrophages in RLNs, CD8+ TILs, PD‐L1 scores, and prognoses in CRC.Methods and ResultsWe immunostained 83 surgically resected CRC tumors that we previously analyzed for MMR proteins, and identified 9 that were dMMR. The number of CD169+ macrophages in RLNs and CD8+ TILs significantly correlated with overall survival, whereas MMR status did not. The number of cells positive for the TIL markers CD3, CD4, CD8, and TIA‐1, and macrophage markers CD68 and CD169 in RLNs did not significantly differ between groups according to MMR status. Furthermore, combined positive scores (CPS) for PD‐L1 expression in five of nine dMMR CRCs were all <1. We found that dMMR in CRC did not correlate with numbers of CD169+ macrophages in RLNs or CD8+ TILs.ConclusionsCRC with CD169+ macrophages in RLNs and abundant CD8+ TILs indicates a better prognosis and it should be immunologically classified as a different antitumor group from dMMR CRC.
Zinc‐Catalyzed Hydrocyanation of Ynamides and Photoisomerization, a General and Selective Access to E and Z Trisubstituted α‐Enamidonitriles
Authors: Hansjacob Pierre , Leroux Frédéric R. , Donnard Morgan 
Published: February 2023

AbstractThe fully regio‐ and stereoselective Zn‐catalyzed hydrocyanation of ynamides is reported and represents a general access to various trisubstituted E‐α‐enamidonitriles. The catalyst‐free photoisomerization selectively yields the energetically comparable Z‐stereoisomer. Finally, the synthetic potential of these new α‐enamidonitriles was evaluated through the synthesis of original heterocycles.
Small Molecule Activation on a Base‐stabilized Phosphinidene
Authors: Baradzenka Aliona G. , Pilkington Melanie , Dmitrienko Anton , Nikonov Georgii I. 
Published: February 2023

AbstractReduction of (NP)PCl2 (NP=phosphinoamidinate [PhC(NAr)(=NPPri2)]−) with KC8 affords the phosphinoamidinato‐supported phosphinidene (NP)P (9). Reaction of 9 with a N‐heterocyclic carbene (MeC(NMe))2C: results in the NHC‐adduct NHC→P−P(Pri2)=NC(Ph)=NAr featuring an iminophosphinyl group. Reactions of 9 with HBpin and H3SiPh led to the metathesis products (NP)Bpin and (NP)SiH2Ph, respectively, whereas with HPPh2 a base‐stabilized phosphido‐phosphinidene, the product of N−P and H−P bond metathesis, was obtained. Reaction of 9 with tetrachlorobenzaquinone results in oxidation of P(I) to P(III), accompanied by oxidation of the amidophosphine ligand into P(V). Addition of benzaldehyde to 9 results in a phospha‐Wittig reaction affording a product of P=P and C=O bond metathesis. Related reaction with phenylisocyanate results in a product of N−P(=O)Pri2 addition to the C=N bond of an intermediate iminophosphaalkene to produce a phosphinidene intramolecularly stabilized by a diaminocarbene.
Comparative physiological, transcriptome, and qRT‐PCR analysis provide insights into osmotic adjustment in the licorice species Glycyrrhiza inflata under salt stress
Authors: Cai Mei‐Mei , He Zi‐Hua , Lin Zi‐Ru , Nie Gui‐Bin , Li Xiao‐Yu , Liu Hai‐Shuang , Ma Qing 
Published: February 2023

AbstractLicorice (Glycyrrhiza spp.) is a versatile industrial and fodder crop with important medicinal, economic, and forage values. However, little is known about their salt tolerance mechanisms. Here, to investigate the osmotic adjustment mechanism of Glycyrrhiza inflata, a licorice species with excellent adaptation to the severe saline habitat, we compared the growth, the contributions of major osmolytes to osmotic potential, and the expression of genes associated with the accumulation of major osmolytes under salt stress between G. inflata and Glycyrrhiza uralensis, another licorice species mainly grown in mild salinized regions. The results showed that G. inflata displayed stronger salt tolerance than G. uralensis. Compared with G. uralensis, G. inflata accumulated higher contents of proline, betaine, and soluble sugars, as well as Na+ and NO3− in roots, and meanwhile, accumulated higher concentrations of K+ and Cl− in leaves for osmotic adjustment under salt stress. Analysis combining transcriptome and quantitative reverse transcription polymerase chain reaction indicated that compared with that in G. uralensis, the expression of key genes responsible for the biosynthesis of above organic osmolytes, the uptake of NO3−, and the xylem unloading and vacuolar compartmentation of Na+ and NO3− were upregulated in roots of G. inflata under salt stress; meanwhile, higher expression levels of key genes function in xylem loading of K+ and Cl− in roots and vacuolar K+ and Cl− compartmentation in leaves were observed in G. inflata under salt stress. The identified key genes associated with the strong osmotic adjustment capacity of G. inflata could facilitate the genetic improvement of stress tolerance in crops.
A 256 × 256 CMOS image sensor with differential readout and data converter circuits
Authors: Karamzadeh Khadijeh , Teymouri Masood , Dousti Massoud , Torkzadeh Pooya 
Published: February 2023

SummaryIn this paper, a 256 × 256 CMOS image sensor is introduced in which the pixel signals are read and converted into digital data in a completely differential mode. This technique helps to obtain pixel signals with higher linearity and accuracy compared with conventional methods. Improving the linearity and accuracy of the image sensor has a direct impact on increasing the quality of the generated images. The simulation results of the proposed pixel readout circuit show that the THD, SINAD, SNR, and SFDR are 0.45%, 47 dB, 66 dB, and 46 dB, respectively. The voltage gain of the proposed readout circuit is about 1, causing it to read the photodetector signals more accurately than the conventional methods. A full differential single‐slope ADC with a working frequency of 50 Mhz has the task of converting the pixel signal to 10 bits of digital data. The total power consumption of a column of sensors is about 80 μW. All the circuits are designed and implemented using 0.18‐μm CMOS technology in Virtuoso and simulated by the SPECTRE.
LC‐MS/(MS) confirmatory doping control analysis of intact phase II metabolites of methenolone and mesterolone after Girard's Reagent T derivatization
Authors: Angelis Yiannis S. , Fragkaki Argyro G. , Kiousi Polyxeni , Sakellariou Panagiotis , Christophoridis Christophoros 
Published: February 2023

AbstractIn the present study, the application and evaluation of Girard's Reagent T (GRT) derivatization for the simultaneous detection and significantly important identification of different phase II methenolone and mesterolone metabolites by LC‐MS/(MS) are presented. For the LC‐MS analysis of target analytes two complementary isolation methods were developed; a derivatization and shoot method in which native urine is diluted with derivatization reagent and is injected directly to LC‐MS and a liquid–liquid extraction method, using ethyl acetate at pH 4.5, for the effective isolation of both sulfate and glucuronide metabolites of the named steroids as well as of their free counterparts. For the evaluation of the proposed protocols, urine samples from methenolone and mesterolone excretion studies were analyzed against at least one sample from a different excretion study. Retention times, along with product ion ratios, were evaluated according to the WADA TD2021IDCR requirements, in order to determine maximum detection and identification time windows for each metabolite. Established identification windows obtained after LC‐MS/(MS) analysis were further compared with those obtained after GC‐MS/(MS) analysis of the same samples from the same excretion studies, for the most common analytes monitored by GC‐MS/(MS). Full validation was performed for the developed derivatization and shoot method for the identification of methenolone metabolite, 3α‐hydroxy‐1‐methylen‐5α‐androstan‐17‐one‐3‐glucuronide (mth3). Overall, the GRT derivatization presented herein offers a tool for the simultaneous sensitive detection of free, intact glucuronide and sulfate metabolites by LC‐MS/(MS) that enhance significantly the detection and identification time windows of specific methenolone and mesterolone metabolites for doping control analysis.
Estimating number of European eel (Anguilla anguilla) individuals using environmental DNA and haplotype count in small rivers
Authors: Halvorsen Silje , Korslund Lars , Mattingsdal Morten , Slettan Audun 
Published: February 2023

AbstractKnowledge about population genetic data is important for effective conservation management. Genetic research traditionally requires sampling directly from the organism, for example tissue, which can be challenging, time‐consuming, and harmful to the animal. Environmental DNA (eDNA) approaches offer a way to sample genetic material noninvasively. In attempts to estimate population size of aquatic species using eDNA, researchers have found positive correlations between biomass and eDNA concentrations, but the approach is debated because of variations in the production and degrading of DNA in water. Recently, a more accurate eDNA‐approach has emerged, focusing on the genomic differences between individuals. In this study, we used eDNA from water samples to estimate the number of European eel (Anguilla anguilla) individuals by examining haplotypes in the mitochondrial D‐loop region, both in a closed aquatic environment with 10 eels of known haplotypes and in three rivers. The results revealed that it was possible to find every eel haplotype in the eDNA sample collected from the closed environment. We also found 13 unique haplotypes in the eDNA samples from the three rivers, which probably represent 13 eel individuals. This means that it is possible to obtain genomic information from European eel eDNA in water; however, more research is needed to develop the approach into a possible future tool for population quantification.
Novel functional monomer for the electrochemical synthesis of highly affine epitope‐imprinted polymers
Authors: Bognár Zsófia , Kozma József , Kovács Norbert , Gyurcsányi Róbert E. 
Published: February 2023

AbstractTo address the lack of functional monomer diversity for the electrosynthesis of protein‐selective molecularly imprinted polymers (MIPs), we introduce a new concept able to lead to a new class of functional monomers. This is based on conjugating an electropolymerizable monomer unit (umbelliferone) to an amino acid for closer mimicking of protein‐based natural affinity ligands such as antibodies. As the first representative of this class of monomers an aspartate‐umbelliferone (Asp‐UMB) conjugate was synthesized and here we provide the proof for its suitability to generate highly affine MIPs for proteins by epitope imprinting. As model we used a heptapeptide (GFNCYFP) stemming from the receptor binding domain (RBD) of the SARS‐CoV‐2 spike protein to generate epitope‐imprinted polymers able to recognize the parent RBD protein. For rapid optimization and assessment of the binding kinetics we prepared MIP microarrays on surface plasmon resonance imaging (SPRi) chips. First the peptides were microspotted on the bare gold surface of the chips followed by the electropolymerization of Asp‐UMB. This resulted in ca. 2 nm thick, highly uniform, and electrically insulating polymer film, well suited both for hierarchical epitope imprinting and SPRi read‐out. Taking advantage also of the on‐chip optimization enabled by the microarray format the increased functional diversity of the new monomer resulted in highly affine MIPs with equilibrium dissociation constants in the lower picomolar range.
Impact of gel concentration on filter fluxes in microfiltration of Hanford tank wastes and simulants
Authors: Westesen A. M. , Geeting J. G. H. , Brooks K. P. , Shimskey R. W. , Edwards M. K. , Peterson R. A. 
Published: February 2023

AbstractTreatment processes have been proposed that will utilize crossflow filtration to concentrate sludge waste streams at the Department of Energy's Hanford Site. Challenges associated with solid–liquid separation of the waste streams drive a necessary evaluation of available Hanford high level waste (HLW) filtration data. Limiting flux conditions during crossflow filtration are elucidated with the formation of a cake layer on the membrane surface. A mass transfer coefficient between the gel and bulk concentrations plays a critical role in determining filter flux. A correlation between the gel concentration and mass transfer coefficient is made to assist in determining filter performance of select HLW streams. As a process alternative to crossflow filtration, gravity settling of waste streams may be deployed as a solid–liquid separation technique. However, this results in a contrasting performance with the centrifuged solids concentration. A method was developed to estimate expected filtration and settling performance based on physical characterization data for Hanford tank waste samples. By assessing the estimated processing performance of HLW, technical support can be provided during flowsheet planning.