bluuebunny/crossref_metadata_2025_split huggingface dataset:
Impact of pubertal timing and socioeconomic status on adult height and body proportions in Igbo ethnicity
Authors: Sunday Obaje Godwin , Elsie Ada Obi 
Published: June 2023

AbstractObjectivesAge at menarche is a marker of pubertal timing that may influence adult height and body proportions. Previous studies have shown that socioeconomic status can affect age at menarche and growth patterns in different populations. This study aims to examine the associations between age at menarche, socioeconomic status, height, and leg length in a sample of Igbo ethnicity.MethodsThe study used data from questionnaires and anthropometric measurements of 300 female students aged 18–25 years. Study tested the hypotheses that earlier menarche is associated with shorter stature and shorter leg length, and that these associations are modified by socioeconomic status using nonparametric analysis.ResultsMean age at menarche was fluctuating around 12.84 ± 1.40 and 13.59 ± 1.41 years with school girls and grew 3.0 cm taller per year birth cohort. The study also found that girls with earlier menarche were shorter adult height (162.51 ± 6.00) compared with girls who have menarche at a later age. The linear regression coefficients (bs) ranged from 0.37–0.49 in later year birth cohort and 0.37–0.44 in early year birth cohort for height. The effect of age at menarche on leg length was similar to the relation between age at menarche and birth cohort height.ConclusionThe study will contribute to the understanding of how pubertal timing and socioeconomic status interact to shape adult health outcomes in a transitioning population.
Biallelic variants in NUDCD2 associated with a multiple malformation syndrome with cholestasis and renal failure
Authors: Scheuerle Angela E. , Ni Min , Ahmad Aaliya A. , Timmons Charles F. , Rakheja Dinesh , Gordon Erin E. , Boothe Megan 
Published: June 2023

AbstractNudC‐like protein 2 (NUDCD2) is a 4‐exon protein‐coding gene at 5q34. The protein appears to act in concert with other genes regulating cell migration and microtubule extension. Early studies in model organisms show associations with LIS1, HERC2, and cohesin subunits via a co‐chaperone function with Heat shock protein 90 (Hsp90). It is a candidate gene for human pathology. We present two unrelated patients with biallelic variants in NUDCD2. Their phenotypes comprise similar dysmorphic facies, midline brain hypoplasia, hypothyroidism, pulmonary and aortic valve stenosis, severe dysfunction of the liver and kidneys, profound hypotonia, and early death. The cellular analysis demonstrates the absence of the NUDCD2 protein in fibroblasts of one patient with biallelic loss‐of‐function variants. The data suggest that NUDCD2 deficiency causes this recognizable syndrome that has features of a ciliopathy with additional complications.
Chitin‐ and Streptavidin‐Mediated Affinity Purification Systems: A Screening Platform for Enzyme Discovery
Authors: Kato Shunsuke , Takeuchi Koki , Iwaki Motonao , Miyazaki Kentaro , Honda Kohsuke , Hayashi Takashi 
Published: June 2023

AbstractAffinity purification of recombinant proteins is an essential technique in biotechnology. However, current affinity purification methods are very cost‐intensive, and this imposes limits on versatile use of affinity purification for obtaining purified proteins for a variety of applications. To overcome this problem, we developed a new affinity purification system which we call CSAP (chitin‐ and streptavidin‐mediated affinity purification) for low‐cost purification of Strep‐tag II fusion proteins. The CSAP system is designed to utilize commercially available chitin powder as a chromatography matrix, thereby significantly improving the cost‐efficiency of protein affinity purification. We investigated the CSAP system for protein screening in 96‐well format as a demonstration. Through the screening of 96 types of purified hemoproteins, several proteins capable of the catalytic diastereodivergent synthesis of cyclopropanes were identified as candidates for an abiotic carbene transfer reaction.
Preparation and Reactivity Study of a Versatile Trifluoromethylthiolating Agent: S‐Trifluoromethyl Trifluoromethanesulfonothioate (TTST)
Authors: Yang Yuhao , Miraghaee Seyedesahar , Pace Renee , Umemoto Teruo , Hammond Gerald B. 
Published: June 2023

AbstractA novel, air and thermally stable, yet highly reactive trifluoromethylthiolating reagent, CF3SO2SCF3 (1), was prepared easily in one step from commercially inexpensive CF3SO2Na and Tf2O. 1 is a highly versatile and atom‐efficient reagent that can generate one equivalent of CF3S+, two equivalents of CF3S−, or a combination of CF3S⋅/CF3⋅ species. Many high‐yielding CF3S reactions of C, O, S, and N‐nucleophiles were achieved, including the simple‐step preparations of many reported CF3S reagents. 1 delivered a hitherto hard‐to‐synthesize ArOSCF3 that was followed by a novel CF3SII‐rearrangement. Through Cu or TDAE/Ph3P combinations, 1 generated two equivalents of CF3S anion species, and the photo‐catalyzed reactions of alkenes with 1 provided CF3/CF3S‐containing products in high atom‐efficiency.
X‐Ray‐Induced Drug Release for Cancer Therapy
Authors: Liu Hui , Zhao Jun , Xue Yufei , Zhang Jiaxin , Bai Hua , Pan Sijun , Peng Bo , Li Lin , Voelcker Nicolas H. 
Published: June 2023

AbstractDrug delivery systems (DDSs) are designed to deliver therapeutic agents to specific target sites while minimizing systemic toxicity. Recent developments in drug‐loaded DDSs have demonstrated promising characteristics and paved new pathways for cancer treatment. Light, a prevalent external stimulus, is widely utilized to trigger drug release. However, conventional light sources primarily concentrate on the ultraviolet (UV) and visible light regions, which suffer from limited biological tissue penetration. This limitation hinders applications for deep‐tissue tumor drug release. Given their deep tissue penetration and well‐established application technology, X‐rays have recently received attention for the pursuit of controlled drug release. With precise spatiotemporal and dosage controllability, X‐rays stand as an ideal stimulus for achieving controlled drug release in deep‐tissue cancer therapy. This article explores the recent advancements in using X‐rays for stimulus‐triggered drug release in DDSs and delves into their action mechanisms.
Dynamical Equilibrium between Brønsted and Lewis Sites in Zeolites: Framework‐Associated Octahedral Aluminum
Authors: Jin Mengting , Ravi Manoj , Lei Chen , Heard Christopher J. , Brivio Federico , Tošner Zdeněk , Grajciar Lukáš , van Bokhoven Jeroen A. , Nachtigall Petr 
Published: June 2023

AbstractWhile the structures of Brønsted acid sites (BAS) in zeolites are well understood, those of Lewis acid sites (LAS) remain an active area of investigation. Under hydrated conditions, the reversible formation of framework‐associated octahedral aluminum has been observed in zeolites in the acidic form. However, the structure and formation mechanisms are currently unknown. In this work, combined experimental 27Al NMR spectroscopy and computational data reveal for the first time the details of the zeolite framework‐associated octahedral aluminium. The octahedral LAS site becomes kinetically allowed and thermodynamically stable under wet conditions in the presence of multiple nearby BAS sites. The critical condition for the existence of such octahedral LAS appears to be the availability of three protons: at lower proton concentration, either by increasing the Si/Al or by ion‐exchange to non‐acidic form, the tetrahedral BAS becomes thermodynamically more stable. This work resolves the question about the nature and reversibility of framework‐associated octahedral aluminium in zeolites.
Adenophorone, An Unprecedented Sesquiterpene from Eupatorium adenophorum: Structural Elucidation, Bioinspired Total Synthesis and Neuroprotective Activity Evaluation
Authors: Yin Bo , Li Xiaohuan , Li Zi‐Xiang , Zhu Xiao‐Xin , Zhang Lan , Zhou Xian‐Li , Xu Jin‐Bu , Chen Feng‐Zheng , Tang Pei , Gao Feng 
Published: June 2023

Abstract(−)‐Adenophorone (1), a caged polycyclic sesquiterpene featuring an unprecedented tricyclo[4.3.1.05,9]decane skeleton, was isolated from Eupatorium adenopharum Spreng. The structure of 1 was unambiguously established by a combination of spectroscopic analysis, X‐ray crystallography, and bioinspired total synthesis. Key synthetic features include a sequential Reformatsky/oxidation/regio‐ and stereoselective hydrogenation, and subsequent merged MBH–Tsuji–Trost cyclization. The concise synthetic sequence efficiently constructs the bicyclic skeleton of cadinene sesquiterpene (+)‐euptox A (2) in 8 steps from commercially available monoterpene (−)‐carvone (6), with outstanding performance on diastereocontrol. The bioinspired synthesis of 1 was achieved from 2, a plausible biogenetic precursor, via transannular Michael addition. This work provides experimental evidence of our proposed biosynthetic hypothesis of 1. Additionally, compound 1 showed potent neuroprotective activity in H2O2‐treated SH‐SY5Y and PC12 cells.
Rechargeable Biomass Battery for Electricity Storage/generation and Concurrent Valuable Chemicals Production
Authors: Li Jing , Ji Kaiyue , Li Boyang , Xu Ming , Wang Ye , Zhou Hua , Shi Qiujin , Duan Haohong 
Published: June 2023

AbstractThe development of a rechargeable battery that can produce valuable chemicals in both electricity storage and generation processes holds great promise for increasing the electron economy and economic value. However, this battery has yet to be explored. Herein, we report a biomass flow battery that generates electricity while producing furoic acid, and store electricity while yielding furfuryl alcohol. The battery is composed of a rhodium‐copper (Rh1Cu) single‐atom alloy as anode, a cobalt‐doped nickel hydroxide (Co0.2Ni0.8(OH)2) as cathode, and furfural‐containing anolyte. In a full battery evaluation, this battery displays an open circuit voltage (OCV) of 1.29 V and a peak power density up to 107 mW cm−2, surpassing most catalysis‐battery hybrid systems. As a proof‐of‐concept, we demonstrate that this battery produces 1 kg furoic acid with 0.78 kWh electricity output, and yields 0.62 kg furfuryl alcohol when 1 kWh electricity is stored. This work may shed light on the design of rechargeable batteries with value‐added functionality such as chemicals production.
σ‐Cyclopropyl to π‐Allyl Rearrangement at AuIII
Authors: Holmsen Marte S. M. , Vesseur David , García‐Rodeja Yago , Miqueu Karinne , Bourissou Didier 
Published: June 2023

AbstractThe possibility for AuIII σ‐cyclopropyl complexes to undergo ring‐opening and give π‐allyl complexes was interrogated. The transformation was first evidenced within (P,C)‐cyclometalated complexes, it occurs within hours at −50 °C. It was then generalized to other ancillary ligands. With (N,C)‐cyclometalated complexes, the rearrangement occurs at room temperature while it proceeds already at −80 °C with a dicationic (P,N)‐chelated complex. Density Functional Theory (DFT) calculations shed light on the mechanism of the transformation, a disrotatory electrocyclic ring‐opening. Intrinsic Bond Orbital (IBO) analysis along the reaction profile shows the cleavage of the distal σ(CC) bond to give a π‐bonded allyl moiety. Careful inspection of the structure and bonding of cationic σ‐cyclopropyl complexes support the possible existence of C−C agostic interactions at AuIII.
Quantifying Degradation Parameters of Single‐Crystalline Ni‐Rich Cathodes in Lithium‐Ion Batteries
Authors: Zhao Wengao , Wang Kuan , Fan Xinming , Ren Fucheng , Xu Xieyu , Liu Yangyang , Xiong Shizhao , Liu Xiangsi , Zhang Zhengfeng , Si Mayan , Zhang Ruizhuo , van den Bergh Wessel , Yan Pengfei , Battaglia Corsin , Brezesinski Torsten , Yang Yong 
Published: June 2023

AbstractSingle‐crystal LiNixCoyMnzO2 (SC‐NCM, x+y+z=1) cathodes are renowned for their high structural stability and reduced accumulation of adverse side products during long‐term cycling. While advances have been made using SC‐NCM cathode materials, careful studies of cathode degradation mechanisms are scarce. Herein, we employed quasi single‐crystalline LiNi0.65Co0.15Mn0.20O2 (SC‐NCM65) to test the relationship between cycling performance and material degradation for different charge cutoff potentials. The Li/SC‐NCM65 cells showed >77 % capacity retention below 4.6 V vs. Li+/Li after 400 cycles and revealed a significant decay to 56 % for 4.7 V cutoff. We demonstrate that the SC‐NCM65 degradation is due to accumulation of rock‐salt (NiO) species at the particle surface rather than intragranular cracking or side reactions with the electrolyte. The NiO‐type layer formation is also responsible for the strongly increased impedance and transition‐metal dissolution. Notably, the capacity loss is found to have a linear relationship with the thickness of the rock‐salt surface layer. Density functional theory and COMSOL Multiphysics modeling analysis further indicate that the charge‐transfer kinetics is decisive, as the lower lithium diffusivity of the NiO phase hinders charge transport from the surface to the bulk.
Ribozyme‐Catalyzed Late‐Stage Functionalization and Fluorogenic Labeling of RNA
Authors: Scheitl Carolin P. M. , Okuda Takumi , Adelmann Juliane , Höbartner Claudia 
Published: June 2023

AbstractSite‐specific introduction of bioorthogonal handles into RNAs is in high demand for decorating RNAs with fluorophores, affinity labels or other modifications. Aldehydes represent attractive functional groups for post‐synthetic bioconjugation reactions. Here, we report a ribozyme‐based method for the synthesis of aldehyde‐functionalized RNA by directly converting a purine nucleobase. Using the methyltransferase ribozyme MTR1 as an alkyltransferase, the reaction is initiated by site‐specific N1 benzylation of purine, followed by nucleophilic ring opening and spontaneous hydrolysis under mild conditions to yield a 5‐amino‐4‐formylimidazole residue in good yields. The modified nucleotide is accessible to aldehyde‐reactive probes, as demonstrated by the conjugation of biotin or fluorescent dyes to short synthetic RNAs and tRNA transcripts. Upon fluorogenic condensation with a 2,3,3‐trimethylindole, a novel hemicyanine chromophore was generated directly on the RNA. This work expands the MTR1 ribozyme's area of application from a methyltransferase to a tool for site‐specific late‐stage functionalization of RNA.
Two‐Dimensional Conjugated Metal‐Organic Frameworks with Large Pore Apertures and High Surface Areas for NO2 Selective Chemiresistive Sensing
Authors: Chen Pei , Su Xi , Wang Chuanzhe , Zhang Guang , Zhang Ting , Xu Gang , Chen Long 
Published: June 2023

AbstractThe emergence of two‐dimensional conjugated metal–organic frameworks (2D c‐MOFs) with pronounced electrical properties (e.g., high conductivity) has provided a novel platform for efficient energy storage, sensing, and electrocatalysis. Nevertheless, the limited availability of suitable ligands restricts the number of available types of 2D c‐MOFs, especially those with large pore apertures and high surface areas are rare. Herein, we develop two new 2D c‐MOFs (HIOTP‐M, M=Ni, Cu) employing a large p‐π conjugated ligand of hexaamino‐triphenyleno[2,3‐b:6,7‐b′:10,11‐b′′]tris[1,4]benzodioxin (HAOTP). Among the reported 2D c‐MOFs, HIOTP‐Ni exhibits the largest pore size of 3.3 nm and one of the highest surface areas (up to 1300 m2 g−1). As an exemplary application, HIOTP‐Ni has been used as a chemiresistive sensing material and displays high selective response (405 %) and a rapid response (1.69 min) towards 10 ppm NO2 gas. This work demonstrates significant correlation linking the pore aperture of 2D c‐MOFs to their sensing performance.
Transformation of Type III to Type II Porous Liquids by Tuning Surface Rigidity of Rhodium(II)‐Based Metal‐Organic Polyhedra for CO2 Cycloaddition
Authors: Dinker Manish Kumar , Li Meng‐Meng , Zhao Kan , Zuo Mingrui , Ding Lifeng , Liu Xiao‐Qin , Sun Lin‐Bing 
Published: June 2023

AbstractPorous liquids (PLs), a summation of porous hosts and bulky solvents bestowing permanent cavities, are the prominent emerging materials. Despite great efforts, exploration of porous hosts and bulky solvents is still needed to develop new PL systems. Metal‐organic polyhedra (MOPs) with discrete molecular architectures can be considered as porous hosts; however, many of them are insoluble entities. Here we report the transformation of type III PL to type II PLs by tuning the surface rigidity of insoluble MOP, Rh24L24, in a bulky ionic liquid (IL). Functionalization of N‐donor molecules on Rh−Rh axial sites ensue their solubilization in bulky IL which confer type II PLs. Experimental and theoretical studies reveal the bulkiness of IL as per the cage apertures, and the cause of their dissolution as well. The obtained PLs, capturing more CO2 than neat solvent, have depicted higher catalytic activity for CO2 cycloaddition compared to individual MOPs and IL.
Ligand‐Free Ultrasmall Recyclable Iridium(0) Nanoparticles for Regioselective Aromatic Hydrogenation of Phosphine Oxide Scaffolds: An Easy Access to New Phosphine Ligands
Authors: Hedouin Gaspard , Sharma Sudripet , Kaur Karanjeet , Choudhary Ramesh Hiralal , Jasinski Jacek B. , Gallou Fabrice , Handa Sachin 
Published: June 2023

AbstractHerein, we developed the recyclable ligand‐free iridium (Ir)‐hydride based Ir0 nanoparticles (NPs) for the first regioselective partial hydrogenation of PV‐substituted naphthalenes. Both the isolated and in situ generated NPs are catalytically active. A control nuclear magnetic resonance (NMR) study revealed the presence of metal‐surface‐bound hydrides, most likely formed from Ir0 species. A control NMR study confirmed that hexafluoroisopropanol as a solvent was accountable for substrate activation via hydrogen bonding. High‐resolution transmission electron microscopy of the catalyst supports the formation of ultrasmall NPs, and X‐ray photoelectron spectroscopy confirmed the dominance of Ir0 in the NPs. The catalytic activity of NPs is broad as showcased by highly regioselective aromatic ring reduction in various phosphine oxides or phosphonates. The study also showcased a novel pathway toward preparing bis(diphenylphosphino)‐5,5′,6,6′,7,7′,8,8′‐octahydro‐1,1′‐binaphthyl (H8‐BINAP) and its derivatives without losing enantioselectivity during catalytic events.
Multiple Heteroatom‐Hydrogen Bonds Bridging Electron Transport in Covalent Organic Framework‐Based Supramolecular System for Photoreduction of CO2
Authors: He Yajun , Zhao Yun , Wang Xiaofeng , Liu Zheyuan , Yu Yan , Li Liuyi 
Published: June 2023

AbstractSupramolecular systems consisting of covalent organic frameworks (COFs) and Ni complex are designed for robust photocatalytic reduction of CO2. Multiple heteroatom‐hydrogen bonding between the COF and Ni complex is identified to play a decisive role in the photoexcited electron transfer across the liquid‐solid interface. The diminution of steric groups on COF or metal complex can optimize catalytic performance, which is more attributable to the enhanced hydrogen‐bond interaction rather than their intrinsic activity. The photosystem with relatively strong strength of hydrogen bonds exhibits remarkable photocatalytic CO2‐to‐CO conversion, far superior to photosystems with supported atomic Ni or metal complex alone in the absence of hydrogen‐bond effect. Such heteroatom‐hydrogen bonds bridging electron transport pathway confers supramolecular system with high photocatalytic performance, providing an avenue to rationally design efficient and steadily available photosystems.
Dual Photosensitizer Coupled Three‐Dimensional Metal‐Covalent Organic Frameworks for Efficient Photocatalytic Reactions
Authors: Lu Meng , Zhang Shuai‐Bing , Yang Ming‐Yi , Liu Yu‐Fei , Liao Jia‐Peng , Huang Pei , Zhang Mi , Li Shun‐Li , Su Zhong‐Min , Lan Ya‐Qian 
Published: June 2023

AbstractIn this work, we innovatively assembled two types of traditional photosensitizers, that is pyridine ruthenium/ferrum (Ru(bpy)32+/Fe(bpy)32+) and porphyrin/metalloporphyrin complex (2HPor/ZnPor) by covalent linkage to get a series of dual photosensitizer‐based three‐dimensional metal‐covalent organic frameworks (3D MCOFs), which behaved strong visible light‐absorbing ability, efficient electron transfer and suitable band gap for highly efficient photocatalytic hydrogen (H2) evolution. Rubpy‐ZnPor COF achieved the highest H2 yield (30 338 μmol g−1 h−1) with apparent quantum efficiency (AQE) of 9.68 %@420 nm, which showed one of the best performances among all reported COF based photocatalysts. Furthermore, the in situ produced H2 was successfully tandem used in the alkyne hydrogenation with ≈99.9 % conversion efficiency. Theoretical calculations reveal that both the two photosensitizer units in MCOFs can be photoexcited and thus contribute optimal photocatalytic activity. This work develops a general strategy and shows the great potential of using multiple photosensitive materials in the field of photocatalysis.
Lyophilized mixed micelles of exemestane: A novel paradigm to improve its absorption and anticancer activity
Authors: Singh Gurdeep , Kaur Prabhjot , Singh Davinder , Tiwary Ashok K. , Arora Saroj , Bedi Neena 
Published: June 2023

AbstractThe objective of the present investigation was to prepare and optimize lyophilized mixed micelles (Lyp‐EXE‐MMs) of exemestane (EXE) with improved solubility, bioavailability, in vivo anticancer activity, and physical stability, by using various cryoprotectants. The prepared lyophilized mixed micelles were characterized by various techniques, including dynamic light scattering, zeta potential, powdered X‐ray diffraction, differential scanning calorimetry (DSC), nuclear magnetic resonance (1H NMR), transmission electron microscopy (TEM), and so on. Thereafter, the lyophilized micelles were evaluated for ex vivo permeation, in vitro drug release and gene/protein expression (RT‐PCR and Western blot analysis) in MCF‐7 breast cancer cells. The developed formulation was also investigated for its in vivo anticancer study in BALB/c mice with induced breast cancer. The use of trehalose (10% w/w) was proven to be a suitable cryoprotectant for these micelles. Lyp‐EXE‐MMs were spherical, with a particle size of 42.9 ± 3.8 nm and a polydispersity index of 0.307 ± 0.122. Furthermore, % drug loading and % entrapment efficiency were found to be 5.8 ± 1.4 and 89.1 ± 1.1, respectively. Lyp‐EXE‐MMs showed sustained release behavior as compared to EXE‐suspensions in SGF/SIF (pH 1.2 and 6.8) and phosphate buffer saline (pH 7.4). The micelles induced apoptosis through the regulation of BAX, BCL2, Caspase‐3, p53, and CYP19A1 in MCF‐7 cells, which was correlated to enhanced ex vivo drug permeation. Animals receiving EXE micelle formulations showed reduced tumor volume and improved survivability and pharmacokinetic parameters as compared to pure EXE. Lyp‐EXE‐MMs were found to withstand simulated harsh conditions of SGF/SIF during stability studies. The fabricated EXE micellar preparations hold a promising approach for breast cancer treatment.