bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modular Construction of Unnatural α‐Tertiary Amino Acid Derivatives by Multicomponent Radical Cross‐Couplings
Authors: Li Yujun , Yang Jie , Geng Xinxin , Tao Pan , Shen Yanling , Su Zhishan , Zheng Ke 
Published: October 2022

AbstractAlthough the synthesis of α‐tertiary amino acids (ATAAs) has been extensively studied, the development of an inexpensive and facile methodology to incorporate multifunctionality on ATAAs remains challenging. In this article, we present a single‐step radical approach for the modular synthesis of functionally diverse ATAAs. This synthesis takes place under mild conditions with an absence of metals, photocatalysts, and all other additives. We demonstrate the broad applications of this approach on a variety of aliphatic and aromatic carboxylic acids, alkenes, 1,3‐enynes, and oxazolones. The results prove that our method provides excellent functional group tolerance and late‐stage applicability, as well as gram‐scale synthesis via flow chemistry. Additionally, we include mechanistic studies which reveal that the excited state of oxazolone enolate upon light excitation is a key intermediate that acts as a radical precursor and an efficient reductant.
Glycan Modulation of Insulin‐like Growth Factor‐1 Receptor
Authors: Boothello Rio S. , Sankaranarayanan Nehru Viji , Sistla Jyothi C. , Nagarajan Balaji , Sharon Chetna , Chittum John E. , Niyaz Rabiya Y. , Roy Swarnali , Nandi Aditi , O'Hara Connor P. , Gangji Rahaman Navaz , Afosah Daniel K. , Ongolu Ravikumar , Patel Bhaumik B. , Desai Umesh R. 
Published: October 2022

AbstractThe insulin‐like growth factor‐1 receptor (IGF‐1R) is a receptor tyrosine kinase (RTK) that plays critical roles in cancer. Microarray, computational, thermodynamic, and cellular imaging studies reveal that activation of IGF‐1R by its cognate ligand IGF1 is inhibited by shorter, soluble heparan sulfate (HS) sequences (e.g., HS06), whereas longer polymeric chains do not inhibit the RTK, a phenomenon directly opposed to the traditional relationship known for GAG‐protein systems. The inhibition arises from smaller oligosaccharides binding in a unique pocket in the IGF‐1R ectodomain, which competes with the natural cognate ligand IGF1. This work presents a highly interesting observation on preferential and competing inhibition of IGF‐1R by smaller sequences, whereas polysaccharides are devoid of this function. These insights will be of major value to glycobiologists and anti‐cancer drug discoverers.
Room‐Temperature Ring‐Opening Polymerization of δ‐Valerolactone and ϵ‐Caprolactone Caused by Uptake into Porous Pillar[5]arene Crystals
Authors: Kato Kenichi , Maeda Koki , Mizuno Motohiro , Nishina Yuta , Fa Shixin , Ohtani Shunsuke , Ogoshi Tomoki 
Published: October 2022

AbstractConfined space provides a reaction platform with altered reaction rate and selectivity compared with a homogeneous solution. In this work, porous phenolic pillar[5]arene crystals were used as a reaction space to promote and perturb equilibrium between lactones and their corresponding polyesters. Immersion of porous pillar[5]arene crystals in liquid lactones induced ring‐opening polymerization of δ‐valerolactone and ϵ‐caprolactone at room temperature because the phenolic hydroxy groups have catalytic activity via hydrogen bonds and the pillar[5]arene cavities prefer linear guests. After the reaction, pillar[5]arene and polyesters formed pseudo‐polyrotaxanes.
Enantioselective Synthesis of Spirosilabicyclohexenes by Asymmetric Dual Ring Expansion of Spirosilabicyclobutane with Alkynes
Authors: Chen Hua , Peng Ju , Pang Qinjiao , Du Huimin , Huang Liying , Gao Lu , Lan Yu , Yang Cheng , Song Zhenlei 
Published: October 2022

AbstractSilaspiranes have attracted particular attention due to their chiral spiro‐silicon center, which serves as an ideal carbon isostere and can endow spiro‐analogs with distinct properties. Distinct from previously reported cyclization or cycloaddition strategies to form 5/5‐silaspiranes, we report herein the asymmetric dual ring expansion of spirosilabicyclobutanes with alkynes to synthesize axially chiral spirosilabicyclohexenes bearing a novel 6/6‐silaspirane framework. DFT (density functional theory) calculations provide the deep insight into the origin of the high enantioselectivity controlled by the sterically demanding binaphthyl phosphoramidite ligand. Preliminary studies of chiroptical properties indicate that one of the spirosilabicyclohexene analogs exhibit fluorescence emission, Cotton effects and CPL (circularly polarized luminescence) activity.
Boron‐Cluster Embedded Necklace‐Shaped Nanohoops
Authors: Zhu Miao , Zhou Qin , Cheng He , Sha Ye , Bregadze Vladimir I. , Yan Hong , Sun Zhe , Li Xiang 
Published: October 2022

AbstractThe combination of carbon‐based nanohoops with other functional organic molecular structures should lead to the design of new molecular configurations with interesting properties. Here, necklace‐like nanohoops embedded with carborane were synthesized for the first time. The unique deboronization of o‐carborane has led to the facile preparation of ionic nanohoop compounds. Nanohoops functionalized by nido‐o‐carborane show excellent fluorescence emission, with a solution quantum yield of up to 90.0 % in THF and a solid‐state quantum efficiency of 87.3 %, which opens an avenue for the applications of the nanohoops in OLEDs and bioimaging.
Oxidative Cleavage of Alkenes by Photosensitized Nitroarenes
Authors: Patra Tuhin , Wirth Thomas 
Published: October 2022

AbstractOxidative cleavage of alkenes into carbonyl molecules mainly relies on either ozonolysis or Lemieux‐Johnson oxidation involving high valent transition metal oxides. Safety, technical concerns and highly oxidizing conditions of both these procedures limited their adoption in streamlined synthesis. Like ozone, photosensitized nitroarenes can deliver similar types of [3+2] cycloaddition products with alkenes through biradical formation and the resulting “N‐doped” ozonides can safely be converted to the corresponding carbonyl compounds through hydrolysis. The high prevalence of nitroarenes with diverse electronic and steric profiles combined with the mild oxidizing power allow to modulate site‐selectivity and tolerate highly sensitive functional groups ideal for application in complex molecular setup.
Deep‐Blue Electroluminescence from Phosphine‐Stabilized Au3 Triangles and Au3Ag Pyramids
Authors: Ni Jiteng , Zhong Chunlei , Li Liyuan , Su Mengxue , Wang Xinran , Sun Jianan , Chen Shuo , Duan Chunbo , Han Chunmiao , Xu Hui 
Published: October 2022

AbstractThe optoelectronic applications of clusters emerged rapidly. Cluster light‐emitting diodes (CLED) as representative hold promise as a new generation of displays and lightings. However, as one of the main challenges in electroluminescence (EL) field, until present, no deep‐blue CLEDs were reported, due to the strict requirements on excited‐state characteristics of clusters. Herein, two phosphine‐stabilized Au3 triangle and Au3Ag pyramid named [O(Audppy)3]BF4 and [O(Audppy)3Ag](BF4)2 were chosen to demonstrate efficient deep‐blue CLEDs. The ligand‐incorporated charge transfer transitions of the clusters contribute to both singlet and triplet excited states of the clusters, giving rise to phosphorescence at 460 nm and EL emissions at 436 nm. Based on device engineering, the maximum luminescence beyond 8000 nits and the chromatic coordinates with y <0.1 in deep‐blue region verify the competence of CLEDs for high‐resolution displays.
Boosting Ethane/Ethylene Separation by MOFs through the Amino‐Functionalization of Pores
Authors: Wang Gang‐Ding , Krishna Rajamani , Li Yong‐Zhi , Shi Wen‐Juan , Hou Lei , Wang Yao‐Yu , Zhu Zhonghua 
Published: October 2022

AbstractAdsorption technology based on ethane‐selective materials is a promising alternative to energy‐intensive cryogenic distillation for separating ethane (C2H6) and ethylene (C2H4). We employed a pore engineering strategy to tune the pore environment of a metal–organic framework (MOF) through organic functional groups and boosted the C2H6/C2H4separation of the MOF. Introduction of amino (−NH2) groups into Tb‐MOF‐76 not only decreased pore sizes but also facilitated multiple guest‐host interactions in confined pores. The NH2‐functionalized Tb‐MOF‐76(NH2) has increased C2H6and C2H4uptakes and C2H6/C2H4selectivity. The results of experimental and simulated transient breakthroughs reveal that Tb‐MOF‐76(NH2) has significantly improved one‐step separation performance for C2H6/C2H4mixtures with a high C2H4(>99.95 %) productivity of 17.66 L kg−1compared to 7.53 L kg−1by Tb‐MOF‐76, resulting from the suitable pore confinement and accessible −NH2groups on pore surfaces.
A Dislocated Twin‐Locking Acceptor‐Donor‐Acceptor Configuration for Efficient Delayed Fluorescence with Multiple Through‐Space Charge Transfer
Authors: Xie Feng‐Ming , Li Hao‐Ze , Zhang Kai , Shen Yang , Zhao Xin , Li Yan‐Qing , Tang Jian‐Xin 
Published: October 2022

AbstractOrganic materials featuring intramolecular through‐space charge transfer (TSCT) excited states are advantageous for efficient thermally activated delayed fluorescence (TADF), although the realization of multiple TSCT systems remains challenging. Herein, a rigid molecule with a three‐dimensional dislocated sandwich acceptor‐donor‐acceptor configuration has been developed by a linking biphenazine (2PXZ) donor and 2,4,6‐triphenyl‐1,3,5‐triazine (TRZ) acceptor through the twin‐locking of two spiro‐fluorene bridges. The twin‐locking construction with multiple TSCT effects suppresses the intramolecular rotations of various segments in 2PXZ‐2TRZ, leading to a small singlet‐triplet energy difference, a fast reverse intersystem crossing process, and high photoluminescence quantum yield. This material simultaneously possesses the capabilities of TADF and aggregation‐induced emission. The device employing 2PXZ‐2TRZ as a dopant displays an optimal external quantum efficiency of 27.1 % and a low efficiency roll‐off.
Synthesis and properties of PAM/PLA composite degradable particle temporary plugging agent
Authors: Li Daqi , Li Fan , Liu Jinhua , Liu Chong , Su Gaoshen , Yang Huan , Yu Xiaorong 
Published: October 2022

AbstractUsing acrylamide (AM) and polylactic acid (PLA) as raw materials, polyacrylamide (PAM)/PLA composite temporary plugging agent TZDJ (TZDJ is a synthetic self‐degrading stopper) was synthesized by inverse suspension polymerization. The chemical structure, chemical composition, microscopic morphology, and thermal stability of TZDJ were characterized by Fourier infrared spectral analysis (FT‐IR), carbon nuclear magnetic resonance spectroscopy (13C NMR), scanning electron microscope (SEM), and thermogravimetric analysis (TGA). The degradation and plugging properties of TZDJ were studied by laboratory experiments, and the self‐degradation mechanism of TZDJ was proposed. The results show that TZDJ has good temperature and salt resistance, and it is completely degraded by hydrolysis at 180°C for 120 h. The fracture core displacement experiment shows that TZDJ has good plugging and core permeability recovery performance, and its temporary plugging rate and core permeability recovery rate are all above 90%. The FT‐IR and SEM analysis showed that the degradation process of TZDJ was divided into three stages: degradation of shell PAM, core PLA, and degradation product small molecules.
The effect of polyhedral oligomeric silsesquioxane fillers in non‐isocyanate polyurethane hybrid resins
Authors: MacInnis Carlee M. , Younes Georges R. , Marić Milan 
Published: October 2022

AbstractPolyhedral oligomeric silsesquioxane (POSS) is added to poly(hydroxyurethane) (PHU) prepolymers to create hybrid PHUs (HPHUs) with enhanced mechanical and thermal properties. These hybrid materials were then further functionalized with 3‐Isocyanatopropyl(trimethoxy) silane (IPTMS) via the pendent hydroxyl bonds within the backbone of the polymers to obtain a final cured film comparable to conventional polyurethanes (PU), using less isocyanate‐functional material. The incorporation of POSS into PHU prepolymers to obtain HPHUs was supported by gel permeation chromatography, fourier tranform infrared spectroscopy (FTIR) and nuclear magnetic resonance analysis. Furthermore, the thermal degradation of the HPHUs was significantly improved with increasing POSS concentration compared to their PHU counterparts as the degradation temperatures at 50% weight loss increased from 263°C for the PHU to 341°C for the HPHU. Gel content tests in tetrahydrofuran (THF), water, and toluene were performed and gel contents of 87%–99% in THF were observed for the cured films. Water swelling, and contact angle tests confirmed that the POSS‐modified films exhibited hydrophobic behavior. Finally, mechanical properties of the cured films were investigated. The Young's modulus and tensile strength were improved with increasing POSS concentration (from 2.0 to 3.1 MPa and from 0.82 to 1.32 MPa, respectively) and elongations at break up to 41.6% were observed. When compared to a conventional PU sealant, the HPHU achieved a tensile strength that was two‐fold greater and a comparable elongation at break (increasing from 24.8% to as high as 41.6%).
The suspending appearance of poly(acrylic acid)‐based rheology modifier in high‐content surfactant: The effect of polymer structure and molecular weight on the rheological properties of the complex systems
Authors: Xie Zhengyun , Li Kai , Tang Wei , Yang Shulan , Sun Yanlin 
Published: October 2022

AbstractThe “all in one” multifunctional and concentrated daily chemical products are required by the market, such as the long‐term release of anti‐bacterial, medical, or perfume agents. These functions mainly rely on the microcapsules, which could encapsulate these functional and unstable molecules, and then release them in the long term. To stabilize these functional solid particles in a high‐content surfactant, it is necessary to add a suspending rheological modifier. The poly(acrylic acid) (PAA)‐based rheology modifier is one of the most common additives in the industry of daily chemicals, for thickening or suspending. In this paper, linear PAA, and branched PAA polymers (Carbomer 941 and Carbomer 940) were selected to study the suspending ability of PAA‐based rheology modifier in high‐content surfactant and to investigate the effect of PAA polymer structure and Mw on the complex solution's rheological properties. The yield and viscosity test of the complex solutions of linear PAA and high‐content surfactant revealed that the addition of linear PAA could lead to lower yield stress and viscosity, and failed to suspend the polystyrene (PS) model microspheres due to its smaller mean square radius of gyration. The branched PAA polymer, Carbomer 940 and Carbomer 941 were more stable than the linear PAA in these two kinds of surfactant. More specifically, Carbomer 940 with a higher Mw, would exhibit higher yield stress and viscosity than Carbomer 941 with a lower Mw in nonionic surfactant alcohol polyoxyethylene ether (AEO) solvent with content less than 5 wt%. When the content was higher than 5 wt%, Carbomer 941 presented higher yield stress and viscosity than Carbomer 940, and successfully suspended PS microspheres in the 20 wt% AEO solution. This could depend on the polymer chain's elongation state of these two PAA‐based branched rheology modifiers. The same trend happened in the appearance of Carbomer 940 and Carbomer 941 in alcohol ether sulphate (AES) solution. However, the electrostatic repulsive force between the AES and PAA‐based rheology modifier could further make the polymer chain curl up and restrain the suspending ability in a lower content surfactant solution. Therefore, this fundamental research could guide the application of the anionic polyelectrolytes in the concentrated daily chemical product for stable suspending particles.
Characterization of the complete mitochondrial genome of Cryptotermes domesticus (Blattodea: Kalotermitidae): Genome description and phylogenetic implications
Authors: Yu Guangyu , Cao Yufeng , He Peishan , Li Weijun , Wang Jianguo 
Published: October 2022

AbstractThe complete mitochondrial genome of Cryptotermes domesticus (Haviland) was sequenced and annotated to study its characteristics and the phylogenetic relationship of C. domesticus to other termite species. The mitogenome of C. domesticus is a circular, close, and double‐stranded molecule with a length of 15,655 bp. The sequenced mitogenome contains 37 typical genes, which are highly conserved in gene size, organization, and codon usage. Transfer RNA genes (tRNAs) also have typical secondary structures. All of the 13 protein‐coding genes (PCGs) start with an ATN codon, except for nad4, which starts with GTG and terminates with the terminal codon TAA and TAG or the incomplete form T‐‐ (cox2 and nad5). Most tRNAs have a typical cloverleaf structure, except for trnS1, in which this form is replaced by a simple loop and lacks the dihydrouridine (DHU) arm. The nucleotide diversity (Pi) and nonsynonymous (Ka)/synonymous (Ks) mutation rate ratios indicate that nad1, cox1, and cox3 are the most conserved genes, and that cox1 has the lowest rate of evolution. In addition, an 89 bp repeated sequence was found in the A + T‐rich region. Phylogenetic analysis was performed using Bayesian inference (BI) and maximum likelihood (ML) methods based on 13 PCGs, and the monophyly of Kalotermitidae was supported.
Identifying archaeological parenchyma in three dimensions: Diagnostic assessment of five important food plant species in the Indo‐Pacific region
Authors: Barron Aleese , Pritchard Jeni , Denham Tim 
Published: October 2022

AbstractArchaeobotanical evidence for the exploitation of vegetatively propagated underground storage organs (USOs) in the tropical regions of Australia, Southeast Asia and the Pacific is currently limited. Although there have been several key studies of archaeological parenchyma published in the past two decades, systematic application of identification methods for vegetatively propagated crop species utilising charred, desiccated or waterlogged remains of parenchymatous tissue is not undertaken on a regular basis. Here, microCT imaging technology is used to compile a three‐dimensional virtual reference collection of parenchymatous tissues for five key USO species known to have been extensively cultivated by people in these regions. The five species are Dioscorea alata, Dioscorea esculenta, Colocasia esculenta, Alocasia macrorrhiza and Ipomoea batatas. These reference samples are used to illustrate the character of the virtual, microCT derived reference collection, and they also capture inter‐species differentiation and intra‐species morphological variation characteristic of many tuberous root crops.
Quantifying scientific breakthroughs by a novel disruption indicator based on knowledge entities
Authors: Wang Shiyun , Ma Yaxue , Mao Jin , Bai Yun , Liang Zhentao , Li Gang 
Published: October 2022

AbstractCompared to previous studies that generally detect scientific breakthroughs based on citation patterns, this article proposes a knowledge entity‐based disruption indicator by quantifying the change of knowledge directly created and inspired by scientific breakthroughs to their evolutionary trajectories. Two groups of analytic units, including MeSH terms and their co‐occurrences, are employed independently by the indicator to measure the change of knowledge. The effectiveness of the proposed indicators was evaluated against the four datasets of scientific breakthroughs derived from four recognition trials. In terms of identifying scientific breakthroughs, the proposed disruption indicator based on MeSH co‐occurrences outperforms that based on MeSH terms and three earlier citation‐based disruption indicators. It is also shown that in our indicator, measuring the change of knowledge inspired by the focal paper in its evolutionary trajectory is a larger contributor than measuring the change created by the focal paper. Our study not only offers empirical insights into conceptual understanding of scientific breakthroughs but also provides practical disruption indicator for scientists and science management agencies searching for valuable research.
Non‐π‐Allyl Mechanism for the 1,4‐cis‐Butadiene Polymerization: Theoretical Study of Polymerization via Insertion of Butadiene into Al−C Bond with Cationic Gadolinium Metallocene.
Authors: Fukushima Rika , Tardif Olivier , Kaita Shojiro , Wakatsuki Yasuo , Kojima Yukihiro , Koga Nobuaki 
Published: October 2022

AbstractThis paper reports a computational study on the specific 1,4‐cis polymerization of butadiene catalyzed by the cationic gadolinium metallocene [(C5Me5)2Gd][B(C6F5)4] combined with excess amount of Al(iBu)3. Because this reaction system has no initial Gd–alkyl bond, a mechanism with conventional coordinative chain transfer polymerization (CCTP) is not feasible. Density functional theory (DFT) analyses indicate a novel mechanism in which the cationic Gd plays a crucial role by assisting butadiene insertion into one of the Al−C bond of Al(iBu)3. The proposed butadiene polymerization mechanism can account for the specific 1,4‐cis selectivity of this catalyst system.
The impact of cardiopulmonary exercise testing (CPET) and Charlson comorbidity index (CCI) in a large contemporary cohort of patients undergoing robot‐assisted radical cystectomy and intracorporeal urinary diversion (RARC‐ICUD)
Authors: McPhee Arthur , Ridgway Alexander , Bird Thomas , Pal Raj , Rowe Edward W. , Koupparis Anthony J. , Aning Jonathan J. 
Published: October 2022

AbstractObjectiveThe aim of this study was to investigate whether pre‐operative comorbidity status measured by the Charlson comorbidity index (CCI) or cardiopulmonary exercise testing (CPET) is associated with postoperative complications and length of stay (LOS) in patients undergoing robot‐assisted radical cystectomy and intracorporeal urinary diversion (RARC‐ICUD).Patients and methodsWe conducted a retrospective study of a prospectively maintained database of 428 consecutive patients who underwent RARC‐ICUD at a tertiary referral centre between 2011 and 2019. CCI was correlated with peri‐operative outcomes including postoperative LOS, Clavien–Dindo (CD) complications and survival. A planned subgroup analysis was performed to evaluate the relationship between pre‐operative CPET, and the same outcomes utilising the threshold of anaerobic threshold (AT) ≥ 11/ <11 ml/kg/min were analysed.ResultsOf the total cohort, 350 patients undergoing RARC‐ICUD with complete data were included in the final analysis. A CCI score ≥5 was associated with a higher rate of CD III–V complications at 30‐day incidence rate ratio (IRR) = 3.033, (p = 0.02) and at 90‐day IRR 2.495, (p = 0.04) postsurgery. LOS was not associated with CCI; the strongest association with LOS was a CD complication of any grading. CCI did not predict readmission or mortality rates after surgery. Subanalyses of patients who underwent pre‐operative CPET found that CPET <11 ml/kg/min did not predict for LOS, CD complications or death within 1 year of surgery.ConclusionsCCI score is a simple, reliable and cost‐effective way of identifying patients at increased risk of complication after RARC‐ICUD. Surgeons performing radical cystectomy should consider utilising CCI to augment pre‐operative patient counselling prior to RARC‐ICUD.