bluuebunny/crossref_metadata_2025_split huggingface dataset:
Recent Status and Developments of Vacancies Modulation in the ABO3 Perovskites for Catalytic Applications
Authors: Mi Jinxing , Chen Jianjun , Chen Xiaoping , Liu Xiaoqing , Li Junhua 
Published: October 2022

AbstractPerovskite oxides (ABO3) have attracted comprehensive interest for wide range of functional applications (especially for chemical catalysis) due to their high design flexibility, controllable vacancies sites creation, abundant chemical properties, and stable crystal structure. Herein, the previous research and potential development of ABO3 through adjusting the vacancy at different sites (A‐site, B‐site, and O‐site) to enhance catalytic performance are systematically analyzed and generalized. Briefly, the ABO3 with different vacancies sites prepared by multifarious direct and indirect methods, accompanied with the improved physical‐chemical properties, endow them with distinct and intensified development of catalysis application. In addition, the impressive optimization proved by the vacancies sites adjustment over the ABO3 is studied to continuously facilitate the advance in some common catalysis reactions, further expanding to other optimized functional applications. At last, the constructive suggestions for fine regulation and analysis of vacancies sites over ABO3 are also put forward.
Propeller, Linear, Cruciform and Stellate Spiro‐bicarbazolium Salts
Authors: Lu Mengsi , Xu Jun , Baldridge Kim K. , Siegel Jay S. 
Published: October 2022

AbstractA general synthetic approach to halogenated tetraaryl‐ammonium salts has been developed and illustrated crystallographically. Bromide ammonium salts used as common synthetic intermediates together with Suzuki coupling of these bromides to a family of boronic acids provided a simplified strategy for arylation. Resolution of the C2 subset of spiro‐bicarbazolium derivatives led to the first examples of enantiopure spiro‐bicarbazoliums and the assignment of their absolute configuration by comparison of computational and experimental electronic circular dichroism (ECD) spectra. An ECD comparison with Prelog's spirobifluorenes is provided. The absolute configuration of the meta‐bromide spiro‐bicarbazolium salt was confirmed by anomalous scattering. Cruciform and stellate tetra‐substituted salts provide a test of the limits of the methodology, and their structures suggest them to be candidates for MOF building blocks.
Anion‐Driven Programmable Chiral Self‐Sorting in Metal‐Organic Cages and Structural Transformations between Heterochiral and Homochiral Cages
Authors: Ghorai Sandipan , Natarajan Ramalingam 
Published: October 2022

AbstractWhen a racemic mixture of chiral building blocks self‐assembles to form discrete molecular or supramolecular cages, the system can adopt either social or narcissistic chiral self‐sorting. However, control over such chiral self‐sorting is hard to achieve with a desired choice of outcome. Herein, we report anion templated high‐fidelity chiral self‐sorting during the coordination‐driven self‐assembly of [Pd2L4] metal‐organic cages, with a racemic mixture of an axially chiral ligand. Upon varying the counter‐anions, the outcome of the choice of chiral self‐sorting, whether social or narcissistic, leading to kinetically favored heterochiral or thermodynamically favored homochiral cages, can be controlled through specific anion encapsulation. Non‐encapsulating anion afforded a mixture of all possible diastereomers. Anion exchange enabled structural transformations between the diastereomers and the conversion of the mixture of diastereomers into homochiral diastereomers.
Xylitol production by different yeasts: Kinetic study and biosynthesis from cashew apple bagasse hydrolysate
Authors: de Albuquerque Tiago Lima , Lucindo Gomes Sandy Danielle , da Silva Junior Ivanildo José , Gonçalves Luciana Rocha Barros , Rocha Maria Valderez Ponte 
Published: October 2022

AbstractXylitol is a polyol with sweetening and anti‐cariogenic properties and is highly relevant to the food and pharmaceutical industries. This work evaluates xylitol production by three yeasts (Candida tropicalis, Kluyveromyces marxianus CCA510, and Kluyveromyces marxianus ATCC 36907) from different carbon sources: D‐xylose (medium xylose [MX]) and D‐xylose plus D‐glucose (medium xylose and glucose [MXG]). The potential of xylitol production from hemicellulose hydrolysate of cashew bagasse was evaluated. In MX medium, K. marxianus CCA510 was the strain that produced higher xylitol concentration (17.04 g · L−1). However, K. marxianus ATCC 36907 and C. tropicalis produced 13.22 and 9.54 g · L−1, respectively. On the other hand, in MXG medium, probably due to the presence of glucose as a carbon source, lower xylitol production was observed for all microorganisms: the CCA510 strain produced 13.30 g · L−1 of xylitol, while C. tropicalis and ATCC 36907 produced 11.42 and 0.64 g · L−1, respectively. Additionally, the production of ethanol as a secondary product was also noted. According to the results of the kinetic study, xylitol formation is associated with the growth and consumption of substrate (xylose), which is a typical behaviour of a primary metabolite for the three yeasts. Furthermore, the strain K. marxianus CCA510 was able to produce xylitol from cashew apple bagasse hydrolysate (CABH), evidencing its potential for use in bioprocesses related to biorefinery. In view of the results reported here, it was possible to clarify in detail the kinetics of xylitol production by the yeast strains evaluated, which had the ability to produce xylitol from CABH, providing added value to this agro‐industrial residue.
In silico designing and expression of novel recombinant construct containing the variable part of CD44 extracellular domain for prediagnostic breast cancer
Authors: Gheybi Elaheh , Asoodeh Ahmad , Amani Jafar 
Published: October 2022

AbstractBackgroundCD44, as a tumor‐associated marker, can be used to detect stem cells in breast cancer. While CD44 is expressed in normal epithelial cells, carcinoma cells overexpress CD44.AimsIn the current study, we designed a recombinant protein that included the variable component of the CD44 (CD44v) extracellular domain to apply in clinical diagnosis of breast cancer.MethodsA total of 100 CD44v amino‐acid residues were determined, and the structure was examined using bioinformatics tools. The construct was inserted into the PET28a vector and transformed in E. coli BL21(DE3). A nearly 12 kDa fusion protein was obtained by Ni‐NTA affinity metal chromatography. Recombinant CD44v was examined by Western blotting, ELISA, and immunohistochemistry (IHC) assays.ResultsThe findings revealed that the structure of rCD44v was stable, and its antigenic domain was exposed. The recombinant CD44v was confirmed by western blotting, and the presence of antibodies against recombinant CD44v protein in the patient's serum was detected by the ELISA. Our data demonstrated a link between CD44v serum levels and the prevalence of breast cancer.ConclusionAssessments of antiCD44v antibodies with rCD44v could be a useful tool for identifying breast cancer in its early stages, which can lead to better outcomes.
Safety, Pharmacokinetics, and Biomarkers of an Amorphous Solid Dispersion of Genistein, a Radioprotectant, in Healthy Volunteers
Authors: Serebrenik Artur A. , Verduyn Carin W. , Kaytor Michael D. 
Published: October 2022

AbstractA pharmaceutical formulation of genistein, produced as an amorphous solid dispersion by hot melt extrusion (genistein HME), has been developed that can be administered prophylactically to improve outcomes and survival following radiation exposure. Here, genistein HME was evaluated in a phase 1, open‐label, single ascending dose (SAD) and multiple single dose (MSD) study enrolling 34 healthy volunteers. In the SAD study, participants were administered a single dose (500, 1000, 2000, or 3000 mg) and in the MSD study, participants were administered a single daily dose for six consecutive days (3000 mg/day). The overall adverse event profile and pharmacokinetics of genistein HME were determined. Additionally, biomarkers of genistein HME were evaluated by profiling whole blood for changes in gene expression by RNA sequencing. Genistein HME was found to be safe at doses up to 3000 mg. Most toxicities were mild to moderate gastrointestinal events, and no dose‐limiting toxicities were reported. The maximum tolerated dose was not determined and the no observable adverse effect level was 500 mg. Genistein HME bioavailability greatly increased between the 2000 mg and 3000 mg doses. RNA sequencing analysis revealed that the majority of drug‐related changes in gene expression occurred 8–12 hours after the sixth dose in the MSD study. Based on these results, the putative effective dose in humans is 3000 mg.
Rotation‐Inversion Isomerization of Tertiary Carbamates: Potential Energy Surface Analysis of Multi‐Paths Isomerization Using Boltzmann Statistics
Authors: Jameson Brian , Glaser Rainer 
Published: October 2022

AbstractPotential energy surface (PES) analyses at the SMD[MP2/6–311++G(d,p)] level and higher‐level energies up to MP4(fc,SDTQ) are reported for the fluorinated tertiary carbamate N‐ethyl‐N‐(2,2,2‐trifluoroethyl) methyl carbamate (VII) and its parent system N,N‐dimethyl methyl carbamate (VI). Emphasis is placed on the analysis of the rotational barrier about the CN carbamate bond and its interplay with the hybridization of the N‐lone pair (NLP). All rotational transition state (TS) structures were found by computation of 1D relaxed rotational profiles but only 2D PES scans revealed the rotation‐inversion paths in a compelling fashion. We found four unique chiral minima of VII, one pair each of E‐ and Z‐rotamers, and we determined the eight unique rotational TS structures associated with every possible E/Z‐isomerization path. It is a significant finding that all TS structures feature N‐pyramidalization whereas the minima essentially contain sp2‐hybridized nitrogen. We will show that the TS stabilities are affected by the synergetic interplay between NLP/CO2 repulsion minimization, NLP→σ*(CO) negative hyperconjugation, and two modes of intramolecular through‐space electrostatic stabilization. We demonstrate how Boltzmann statistics must be applied to determine the predicted experimental rotational barrier based on the energetics of all eight rotamerization pathways. The computed barrier for VII is in complete agreement with the experimentally measured barrier of the very similar fluorinated carbamate N‐Boc‐N‐(2,2,2‐trifluoroethyl)‐4‐aminobutan‐1‐ol II. NMR properties of VII were calculated with a variety of density functional/basis set combinations and Boltzmann averaging over the E‐ and Z‐rotamers at our best theoretical level results in good agreement with experimental chemical shifts δ(13C) and J(13C,19F) coupling constants of II (within 6 %).
Circ_0002099 is a novel molecular therapeutic target for bladder cancer
Authors: Fang Ping , Jiang Qingling , Liu Sizhong , Gu Jun , Hu Kai , Wang Zishu 
Published: October 2022

AbstractBladder cancer (BLCA) acts as one of the most common malignant tumors in the urinary system without ideal therapy. We performed the present study to explore the role and mechanism of Circ_0002099 in BLCA progression. RNase R treatment assay and actinomycin D treatment assay were used to confirm the circular structure of Circ_0002099. Nuclear‐cytoplasmic fractionation assay and fluorescence in situ hybridization (FISH) were used to indicate the subcellular localization of Circ_0002099. The CCK‐8 assay, colony formation assay, wound‐healing assay, Transwell assay, and animal experiment were used to reveal the facilitative effect of Circ_0002099 on BLCA both in vitro and in vivo. Furthermore, bioinformatic analysis, western blot analysis, FISH, and dual‐luciferase reporter assay were conducted to demonstrate the role of Circ_0002099 in BLCA progression. The results indicated that Circ_0002099 was significantly upregulated in BLCA and could enhance the progression of BLCA in vivo and in vitro. Furthermore, dual‐luciferase reporter assay and FISH assay revealed that Circ_0002099 could regulate miR‐217‐5p/miR‐103a‐3p/Kirsten RAS (KRAS) axis in BLCA. In addition, rescue experiments confirmed that miR‐217‐5p/miR‐103a‐3p could rescue the facilitative effect of Circ_0002099 on BLCA progression. Moreover, FUS (FUSed in sarcoma) was identified to regulate the Circ_0002099‐miR‐217‐5p/miR‐103a‐3p/KRAS axis in BLCA progression. The present study suggested that FUS‐medicated Circ_0002099 could promote the epithelial–mesenchymal transition process in BLCA progression via miR‐217‐5p/miR‐103a‐3p/KRAS axis‐WNT/β‐catenin axis. It could be a promising prognostic biomarker and therapeutic target for BLCA.
Botulax and the US development
Authors: Bravo Monica , Vogel Kelly , Sternfels Whitney , Touchet Natalie , Turegano Mamina 
Published: October 2022

AbstractBackground: LetibotulinumtoxinA (LeBA; Hugel Inc.) is a novel botulinum toxin derived from the Clostridium botulinum strain CBFC26. It is marketed as Botulax with cosmetic and neuromuscular indications.Materials and Methods: This review article summarizes the current literature regarding the key efficacy and safety studies regarding LeBA. It also highlights unique features of LeBA regarding its physical properties, onset with use, duration of effect, and immunogenicity.Results: LeBA's cosmetic use shows efficacy in decreasing glabellar lines and crow's feet. It has also shown efficacy in treating post‐stroke upper limb spasticity, blepharospasm, and dynamic equinus foot deformities in children with cerebral palsy.Discussion: LeBA is a novel BoNT type A that is currently indicated for treatment of both neuromuscular disease and for cosemetic purposes. LeBA has displayed equivocal efficacy and a similar safety profile when compared to other botulinum neurotoxin preparations.
Measuring repeatability of compositional diet estimates: An example using quantitative fatty acid signature analysis
Authors: Stewart Connie , Lang Shelley L. C. , Iverson Sara , Bowen W. Don 
Published: October 2022

AbstractBy measuring the temporal consistency, or repeatability, in the diets of predators, we can gain a better understanding of the degree of individual specialization in resource utilization and implications for predator–prey interactions, population dynamics, and food web structure. To measure repeatability, we require repeated diet estimates of individuals over time, such as those derived from quantitative fatty acid signature analysis (QFASA), a popular diet estimation technique. However, diet estimates are often lengthy compositional vectors with many zeros, as some prey will not be consumed by all individuals, precluding the use of previously proposed measures of repeatability. In this paper, we propose a novel approach for inferring repeatability for multivariate data and, in particular, compositional diet estimates. We extend the commonly used measure of repeatability for univariate data to the multivariate compositional setting by utilizing the mean squares obtained from a nonparametric multivariate analysis of variance, and an appropriate choice of statistical distance. Our measure and its extension are compatible with both balanced and unbalanced data sets. Associated confidence intervals via nonparametric bootstrapping are also developed for the case of QFASA diet estimates that incorporate both sampling error and measurement error, where the latter error arises because the diets of predators are estimated. Simulation study results suggest that for practical levels of repeatability, our methods yield confidence intervals with the desired coverage probability even when the sample size relative to the dimension of the data (i.e., number of prey species eaten) is small. We tested our methods using QFASA diet estimates for free‐ranging Northwest Atlantic grey seals. Given the importance of understanding how predator diets vary over time and space, our method may find broad application to other compositional diet estimates, including those derived from the stomach or fecal contents, and stable isotope analyses.
Amino acid profiling to predict prognosis in patients with heart failure: an expert review
Authors: Hiraiwa Hiroaki , Okumura Takahiro , Murohara Toyoaki 
Published: October 2022

AbstractHeart failure is a complex disease with a poor prognosis. A number of widely used prognostic tools have limitations, so efforts to identify novel predictive markers and measures are important. As a metabolomics tool, amino acid profiling has shown promise in predicting heart failure prognosis; however, the evidence has not yet been sufficiently evaluated. We describe the utilization of amino acids in the healthy heart and in heart failure before reviewing the literature on amino acid profiling for prognostic prediction. We expertly interpret the findings and provide suggestions for future research to advance the understanding of the prognostic potential of amino acid profiling in heart failure. Our analysis revealed correlations between amino acid biomarkers and traditional prognostic factors, the additional prognostic value of amino acid biomarkers over traditional prognostic factors, and the successful use of amino acid biomarkers to distinguish heart failure aetiology. Although certain amino acid biomarkers have demonstrated additional prognostic value over traditional measures, such as New York Heart Association functional class, these measures are deeply rooted in clinical practice; thus, amino acid biomarkers may be best placed as additional prognostic tools to improve current risk stratification rather than as surrogate tools. Once the metabolic profiles of different heart failure aetiologies have been clearly delineated, the amino acid biomarkers with the most value in prognostic prediction should be determined. Amino acid profiling could be useful to evaluate the pathophysiology and metabolic status of different heart failure cohorts, distinguish heart failure aetiologies, and improve risk stratification and prognostic prediction.
Diboration of Alkynes Accelerated by Synergistic Effects of Ruthenium Complexes and Phenoxides
Authors: Murakami Suguru , Matsubara Ryosuke , Hayashi Masahiko 
Published: October 2022

AbstractAlkynes react with bis(pinacolato)diboron (B2pin2) in the presence of 5–10 mol % [Cp*RuCl2]n to afford the corresponding (Z)‐1,2‐diboryl alkenes. The addition of 30 mol % NaOC6H4(4‐tBu) and 2–5 equiv. of methanol was essential for the reaction to proceed with high product yield. Various alkynes were employed in the reaction, and the obtained 1,2‐diboryl alkenes were used as precursors for tetrasubstituted alkenes.
In Situ Generated DBU⋅HF Acts as a Fluorinating Agent in a Hexafluoroisobutylation Tandem Reaction: An Effective Route to 5,5,5,5’,5’,5’‐Hexafluoroleucine
Authors: Naulet Guillaume , Delamare Aline , Guichard Gilles , Compain Guillaume 
Published: October 2022

AbstractWe report the direct incorporation of the hexafluoroisobutyl group on a chiral glycine Schiff base complex mediated by 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU). The fluoroalkylation involves 2‐(bromomethyl)‐1,1,1,3,3,3‐hexafluoropropane reagent, which generates in situ hexafluoroisobutylene (HFIB), and reacts then with the enolate through a tandem allylic shift/hydrofluorination process. We showed that the use of neutral organic base DBU generates in situ an original DBU⋅HF salt, which preserves the fluoride nucleophilicity and acts as a fluorinating agent. This fluoride salt promotes the hydrofluorination of the pentafluorinated alkene overcoming the usual fluoride β‐elimination observed with α‐CF3‐vinyl reagents. With alkali metal bases, by contrast, the hydrofluorination is disfavored and the pentafluorinated alkene intermediate is obtained predominantly. This study highlights the critical role of the fluoride counter ion to preserve its nucleophilicity. The protocol is amenable to multidecagram scale synthesis of enantiopure (S)‐ and (R)‐5,5,5,5’,5’,5’‐hexafluoroleucine and their N‐Fmoc or N‐Boc derivatives in good overall yield.
Astrocytic Yin Yang 1 is critical for murine brain development and protection against apoptosis, oxidative stress, and inflammation
Authors: Pajarillo Edward , Nyarko‐Danquah Ivan , Digman Alexis , Vied Cynthia , Son Deok‐Soo , Lee Jayden , Aschner Michael , Lee Eunsook 
Published: October 2022

AbstractThe transcription factor Yin Yang 1 (YY1) is ubiquitously expressed in mammalian cells, regulating the expression of a variety of genes involved in proliferation, differentiation, and apoptosis in a context‐dependent manner. While it is well‐established that global YY1 knockout (KO) leads to embryonic death in mice and that YY1 deletion in neurons or oligodendrocytes induces impaired brain function, the role of astrocytic YY1 in the brain remains unknown. We investigated the role of astrocytic YY1 in the brain using a glial fibrillary acidic protein (GFAP)‐specific YY1 conditional KO (YY1 cKO) mouse model to delete astrocytic YY1. Astrocytic YY1 cKO mice were tested for behavioral phenotypes, such as locomotor activity, coordination, and cognition, followed by an assessment of relevant biological pathways using RNA‐sequencing analysis, immunoblotting, and immunohistochemistry in the cortex, midbrain, and cerebellum. YY1 cKO mice showed abnormal phenotypes, movement deficits, and cognitive dysfunction. At the molecular level, astrocytic YY1 deletion altered the expression of genes associated with proliferation and differentiation, p53/caspase apoptotic pathways, oxidative stress response, and inflammatory signaling including NF‐κB, STAT, and IRF in all regions. Astrocytic YY1 deletion significantly increased the expression of GFAP as astrocytic activation and Iba1 as microglial activation, indicating astrocytic YY1 deletion activated microglia as well. Accordingly, multiple inflammatory cytokines and chemokines including TNF‐α and CXCL10 were elevated. Combined, these novel findings suggest that astrocytic YY1 is a critical transcription factor for normal brain development and locomotor activity, motor coordination, and cognition. Astrocytic YY1 is also essential in preventing pathological oxidative stress, apoptosis, and inflammation.
The epidemiology and clinical features of personality disorders in later life; a study of secondary care data
Authors: Treagust Natasha , Sidhom Emad , Lewis Jonathan , Denman Chess , Knutson Olivia , Underwood Benjamin R. 
Published: October 2022

AbstractObjectivesPersonality disorders (PDs) are often conceptualised as impacting individuals throughout their life. However, there has been limited study of the disorders in those over the age of 65. We have used the psychiatric secondary care medical records of 21,971 individuals over the age of 65 from Cambridgeshire, UK, who received care between 2014 and 2021 to characterise older patients with a PD diagnosis.MethodsThe data from all patients >65 with a diagnosis of personality disorder (PD) was extracted (n = 217) along with two comparison groups (n = 2170); patients <65 with a diagnosis of PD and patients >65 with a psychiatric diagnosis other than PD or dementia.ResultsCompared to younger patients with PD, older patients were more likely to be male, married, suffering from a mixed PD and live in less deprived areas. Compared to patients >65 with diagnoses other than PD, older patients were more likely to be female, single or divorced and had a higher level of social deprivation. Our most striking finding was that older patients with PDs were more likely to experience polypharmacy. A mean of 18.48 different drugs had been prescribed over their lifetime, compared to 9.51 for patients >65 with other mental health diagnoses.ConclusionHere we present the largest ever description of this group of patients and provide insights that could inform clinical practice and future research.