bluuebunny/crossref_metadata_2025_split huggingface dataset:
Role of Jundi-Shapur in Streamlining of ILM-E-TIBB (Medicine)
Authors: I. Munshi Younis , Ansari Masihuzzaman 
Published: October 2021

People have always felt the need to seek the knowledge from time immemorial. Be it the knowledge of religion or science or philosophy or astronomy. The knowledge of medicine was confined to cultures till 4th century AD. Every subcontinent and every civilization was having its own traditions to treat the diseases, e.g. Ayurved in India, Egyptian traditional medicine in Egypt, Chinese traditional medicine in China, Iranian Traditional medicine in Iran etc etc.
It was during the 5th century AD when Roman Empire cracked down on its seminaries and the intellectuals were forced to leave the country. Those intellectuals were given refuge by Persian Empire where in a city was established with ultimate autonomy under Khusro, Jundi-Shapur became a prosperous metropolis, refuge, and melting pot for intellectuals from many regions. Shapur II (309-379 A.D.) is credited for conceiving and establishing the nucleus of the university in the latter part of the fourth century. The closing of the Athenian school by the Byzantine Emperor Justinian (AD 539) also drove many leaned Greek physicians to Jundi-Shapur. This was the start of the integration of different traditional medicine of different civilizations. This formed the basis of what we see today as modern medicine. In this way JundiShapur has important role in the development of Medical knowledge and it remained in the leading role until 9th Century AD.
Bacterial Materials: Applications of Natural and Modified Biofilms
Authors: Hayta Elif N. , Ertelt Marvin J. , Kretschmer Martin , Lieleg Oliver 
Published: October 2021

AbstractOver millennia, bacteria have developed clever strategies to build biopolymer‐based communities in which they can survive even extremely challenging conditions. Such bacterial biofilms come with a broad range of fascinating material properties that—in settings such as medicine, food production, or other areas of industry—make it difficult to remove or inactivate them: they can stick to many surfaces, repel water and oils, and can even transport electrons. Inspired by the outstanding versatility and sturdiness of such bacterial biofilms, material scientists have set out to harness those properties and to create bacterial materials for different applications. However, as the range of technological applications employing biofilms keeps expanding, improved material properties or broader functionalities are desired. Here, such attempts where materials with improved properties were created by making use of either natural or modified bacterial biofilms are reviewed. The areas in which those bacterial materials may be used range from agriculture and (environmental) biotechnology over biomedical and electrical engineering to construction engineering.
Probing Ultrafast Dynamics of Ferroelectrics by Time‐Resolved Pump‐Probe Spectroscopy
Authors: Zhang Yuan , Dai Junfeng , Zhong Xiangli , Zhang Dongwen , Zhong Gaokuo , Li Jiangyu 
Published: October 2021

AbstractFerroelectric materials have been a key research topic owing to their wide variety of modern electronic and photonic applications. For the quick exploration of higher operating speed, smaller size, and superior efficiencies of novel ferroelectric devices, the ultrafast dynamics of ferroelectrics that directly reflect their respond time and lifetimes have drawn considerable attention. Driven by time‐resolved pump‐probe spectroscopy that allows for probing, controlling, and modulating dynamic processes of ferroelectrics in real‐time, much research efforts have been made to understand and exploit the ultrafast dynamics of ferroelectric. Herein, the current state of ultrafast dynamic features of ferroelectrics tracked by time‐resolved pump‐probe spectroscopy is reviewed, which includes ferroelectrics order parameters of polarization, lattice, spin, electronic excitation, and their coupling. Several potential perspectives and possible further applications combining ultrafast pump‐probe spectroscopy and ferroelectrics are also presented. This review offers a clear guidance of ultrafast dynamics of ferroelectric orders, which may promote the rapid development of next‐generation devices.
Insight into Carbocation‐Induced Noncovalent Interactions in the Methanol‐to‐Olefins Reaction over ZSM‐5 Zeolite by Solid‐State NMR Spectroscopy
Authors: Wang Chao , Chu Yueying , Hu Min , Cai Wenjin , Wang Qiang , Qi Guodong , Li Shenhui , Xu Jun , Deng Feng 
Published: October 2021

AbstractCarbocations such as cyclic carbenium ions are important intermediates in the zeolite‐catalyzed methanol‐to‐olefins (MTO) reaction. The MTO reaction propagates through a complex hydrocarbon pool process. Understanding the carbocation‐involved hydrocarbon pool reaction on a molecular level still remains challenging. Here we show that electron‐deficient cyclopentenyl cations stabilized in ZSM‐5 zeolite are able to capture the alkanes, methanol, and olefins produced during MTO reaction via noncovalent interactions. Intermolecular spatial proximities/interactions are identified by using two‐dimensional 13C–13C correlation solid‐state NMR spectroscopy. Combined NMR experiments and theoretical analysis suggests that in addition to the dispersion and CH/π interactions, the multiple functional groups in the cyclopentenyl cations produce strong attractive force via cation‐induced dipole, cation–dipole and cation–π interactions. These carbocation‐induced noncovalent interactions modulate the product selectivity of hydrocarbon pool reaction.
Sterically Wrapped Multiple Resonance Fluorophors for Suppression of Concentration Quenching and Spectrum Broadening
Authors: Zhang Yuewei , Wei Jinbei , Zhang Dongdong , Yin Chen , Li Guomeng , Liu Ziyang , Jia Xiaoqin , Qiao Juan , Duan Lian 
Published: October 2021

AbstractMultiple resonance (MR) emitters are promising for highly efficient organic light‐emitting diodes (OLEDs) with narrowband emission; however, they still face intractable challenges with concentration‐caused emission quenching, exciton annihilation, and spectral broadening. In this study, sterically wrapped MR dopants with a fluorescent MR core sandwiched by bulk substituents were developed to address the intractable challenges by reducing intermolecular interactions. Consequently, high photo‐luminance quantum yields of ≥90 % and small full width at half maximums (FWHMs) of ≤25 nm over a wide range of dopant concentrations (1–20 wt %) were recorded. In addition, we demonstrated that the sandwiched MR emitter can effectively suppress Dexter interaction when doped in a thermally activated delayed fluorescence sensitizer, eliminating exciton loss through dopant triplet. Within the above dopant concentration range, the optimal emitter realizes remarkably high maximum external quantum efficiencies of 36.3–37.2 %, identical small FWHMs of 24 nm, and alleviated efficiency roll‐offs in OLEDs.
Carboxylation of a Palladacycle Formed via C(sp3)−H Activation: Theory‐Driven Reaction Design
Authors: Kanna Wataru , Harabuchi Yu , Takano Hideaki , Hayashi Hiroki , Maeda Satoshi , Mita Tsuyoshi 
Published: October 2021

AbstractTheory‐driven organic synthesis is a powerful tool for developing new organic transformations. A palladacycle(II), generated from 8‐methylquinoline via C(sp3)−H activation, is frequently featured in the scientific literature, albeit that the reactivity toward CO2, an abundant, inexpensive, and non‐toxic chemical, remains elusive. We have theoretically discovered potential carboxylation pathways using the artificial force induced reaction (AFIR) method, a density‐functional‐theory (DFT)‐based automated reaction path search method. The thus obtained results suggest that the reduction of Pd(II) to Pd(I) is key to promote the insertion of CO2. Based on these computational findings, we employed various one‐electron reductants, such as Cp*2Co, a photoredox catalyst under blue LED irradiation, and reductive electrolysis ((+)Mg/(−)Pt), which afforded the desired carboxylated products in high yields. After screening phosphine ligands under photoredox conditions, we discovered that bidentate ligands such as dppe promoted this carboxylation efficiently, which was rationally interpreted in terms of the redox potential of the Pd(II)‐dppe complex as well as on the grounds of DFT calculations. We are convinced that these results could serve as future guidelines for the development of Pd(II)‐catalyzed C(sp3)−H carboxylation reactions with CO2.
A Free Radical Cyclization Catalyzed by Ruthenium Hydride Species
Authors: Kim Rira , Kwon Kuktae , Lee Hee‐Yoon 
Published: October 2021

AbstractA photolytically generated ruthenium hydride species catalyzing a free radical cyclization reaction was developed. As the new methodology ensures reproducibility of the free radical reaction of trialkyltin hydrides and a fast hydrogen transfer to the radical intermediates, the methodology provides fast quenching of radical intermediates and thus suppresses rearrangement of radical intermediates before the hydride quench. By offering new reactivity and selectivity to the trialkyltin hydride mediated free radical cyclization reactions, the methodology will find wide range of applications in organic synthesis.
Controllable Modulation of Defects for Layered Double Hydroxide Nanosheets by Altering Intercalation Anions for Efficient Electrooxidation Catalysis
Authors: Lai Tianyi , Wang Jikang , Sun Xiaoliang , Zhao Yufei , Song Yu‐Fei 
Published: October 2021

AbstractHydrazine (N2H4) is considered as one of the most potential energy storage materials in liquid fuel cells, as it contains high energy and power density, and the high‐efficiency oxidation of N2H4 in fuel cells has drawn great attention. However, the most used catalysts are expensive noble metal catalysts, thus the development of highly efficient non‐noble metal catalysts is crucial to reduce the cost of hydrazine oxidation in practical industry. Herein, we synthesized a series of CoFe‐layered double hydroxides (CoFe‐LDHs) intercalated with different anions via a simple one‐step co‐precipitation method for the electrooxidation of hydrazine. Through altering the intercalated anions of CoFe‐LDHs, the defects and the electronic structure can be well controlled, and the catalytic performance for the electrooxidation of hydrazine were well promoted by using NO3− intercalated into CoFe‐LDH compared with other anions (like Cl−, BO33−, CO32−). This work developed a series of hydrazine electrooxidation catalysts and established the relationship between the intercalated anions, the fine structure of the catalyst and the electrocatalytic performance.
Antisense Oligonucleotide Modified with Disulfide Units Induces Efficient Exon Skipping in mdx Myotubes through Enhanced Membrane Permeability and Nucleus Internalization
Authors: Hiraoka Haruka , Shu Zhaoma , Tri Le Bao , Masuda Keiko , Nakamoto Kosuke , Fangjie Lyu , Abe Naoko , Hashiya Fumitaka , Kimura Yasuaki , Shimizu Yoshihiro , Veedu Rakesh N. , Abe Hiroshi 
Published: October 2021

AbstractWe have found that antisense oligonucleotides and siRNA molecules modified with repeat structures of disulfide units can be directly introduced into the cytoplasm and exhibit a suppressive effect on gene expression. In this study, we analyzed the mechanism of cellular uptake of these membrane‐permeable oligonucleotides (MPONs). Time‐course analysis by confocal microscopy showed that the uptake of MPONs from the plasma membrane to the cytoplasm reached 50 % of the total uptake in about 5 min. In addition, analysis of the plasma membrane proteins to which MPONs bind, identified several proteins, including voltage‐dependent anion channel. Next, we analyzed the behavior of MPONs in the cell and found them to be abundant in the nucleus as early as 24 h after addition with the amount increasing further after 48 and 72 h. The amount of MPONs was 2.5‐fold higher than that of unmodified oligonucleotides in the nucleus after 72 h. We also designed antisense oligonucleotides and evaluated the effect of MPONs on mRNA exon skipping using DMD model cells; MPONs caused exon skipping with 69 % efficiency after 72 h, which was three times higher than the rate of the control. In summary, the high capacity for intracytoplasmic and nuclear translocation of MPONs is expected to be useful for therapeutic strategies targeting exon skipping.
Reconstruction of Hyper‐Thermostable Ancestral L‐Amino Acid Oxidase to Perform Deracemization to D‐Amino Acids
Authors: Ishida Chiharu , Miyata Ryo , Hasebe Fumihito , Miyata Azusa , Kumazawa Shigenori , Ito Sohei , Nakano Shogo 
Published: October 2021

AbstractL‐amino acid oxidases (LAAOs) with broad substrate specificity can be used in the deracemization of D,L‐amino acids (D,L‐AAs) to their D‐enantiomers. Hyper‐thermostable LAAO (HTAncLAAO) was designed through a combination of manual sequence data mining and ancestral sequence reconstruction. Soluble expression of HTAncLAAO (>50 mg/L) can be achieved using an E. coli system. HTAncLAAO, which recognizes seven L‐AAs as substrates, exhibits extremely high thermal stability and long‐term stability; the t1/2 value was 95 °C and <5% activity loss after incubation of the enzyme at 30 °C for 1 week. Deracemization could be achieved at 40 °C with a small amount of enzymes compared to previously reported LAAOs. A total of 0.4 mg (2 U) of HTAncLAAO is enough to deracemize three D,L‐AAs at a preparative scale with high enantiomeric excess (>99 % ee, D‐enantiomer). These results suggest that HTAncLAAO is an excellent biocatalyst to perform this deracemization.
Diastereoselective [2+2+1] Hydrative Annulation of Phenol‐Linked 1,6‐Enynes with Acetylenes Through Rhodium Catalysis: A Rapid Access to Cyclopenta[b]benzofuranols
Authors: Nagireddy Attunuri , Dattatri  , Babu Nanubolu Jagadeesh , Sridhar Reddy Maddi 
Published: October 2021

AbstractAn unprecedented [2+2+1] hydrative annulation of 1,6‐enynes with terminal alkynes is achieved using catalytic cationic Rh(I). Thus, a modular assembly of cyclopenta[b]benzofuranols with two consecutive quarternary stereocenters is achieved from readily available alkynes. The reaction is proposed to go through a sequence of 5‐membered rhoda‐cycle formation, regioselective acetylene insertion, 1,5 H‐shift, substrate controlled stereoselective addition of water molecule followed by 1,2‐rhodium migration gave contracted rhoda‐cycle D and reductive elimination. Necessary control/labelling experiments were conducted to gain insight in to the mechanism.
Reactivity of the Bicyclic Amido‐Substituted Silicon(I) Ring Compound Si4{N(SiMe3)Mes}4 with FLP‐Type Character
Authors: Schwedtmann Kevin , Quest Michael , Guddorf Benedikt J. , Keuter Jan , Hepp Alexander , Feldt Milica , Droste Jörn , Hansen Michael Ryan , Lips Felicitas 
Published: October 2021

AbstractThe bicyclic amido‐substituted silicon(I) ring compound Si4{N(SiMe3)Mes}4 2 (Mes=Mesityl=2,4,6‐Me3C6H2) features enhanced zwitterionic character and different reactivity from the analogous compound Si4{N(SiMe3)Dipp}4 1 (Dipp=2,6‐iPr2C6H3) due to the smaller mesityl substituents. In a reaction with the N‐heterocyclic carbene NHC
(1,3,4,5‐tetramethyl‐imidazol‐2‐ylidene), we observe adduct formation to give Si4{N(SiMe3)Mes}4 ⋅ NHC
(3). This adduct reacts further with the Lewis acid BH3 to yield the Lewis acid–base complex Si4{N(SiMe3)Mes}4 ⋅ NHC
⋅ BH3 (4). Coordination of AlBr3 to 2 leads to the adduct 5. Calculated proton affinities and fluoride ion affinities reveal highly Lewis basic and very weak Lewis acidic character of the low‐valent silicon atoms in 1 and 2. This is confirmed by protonation of 1 and 2 with Brookharts acid yielding 6 and 7. Reaction with diphenylacetylene only occurs at 111 °C with 2 in toluene and is accompanied by fragmentation of 2 to afford the silacyclopropene 8 and the trisilanorbornadiene species 9.
Thermotriggered Domino‐like Single‐Crystal‐to‐Single‐Crystal Phase Transition from Face‐to‐Edge to Face‐to‐Face Packing of Anthracenes
Authors: Hino Yuto , Hayashi Shotaro 
Published: October 2021

AbstractStimuli‐triggered crystal‐to‐crystal and single‐crystal‐to‐single‐crystal (SCSC) transformations have received significant attention in the scientific community. To visualize such phenomenon, controlling the optical properties and the thermodynamic stability of the molecular crystals is a very important research subject. In this report, the selective growth of photoluminescent (PL) 1,8‐bisphenylanthracene polymorphic (cI and cII) and 1,2‐dichloroethane‐inclusion crystals (iC) under various optimized conditions is described. These crystals exhibited unique mechano‐ and thermoresponsive disordering, crystal‐to‐crystal phase transition, and SCSC phase transition. In particular, rapid thermostimulus SCSC occurred from blue‐PL cI into greenish‐blue‐PL cII. Interestingly, the SCSC phase transition of cI into cII was triggered by thermal stimuli and propagated spontaneously. Thermotriggered domino‐like SCSC phase transition was observed on a fully visible timescale (ca. 125 μm min−1).
Photochemical Hydrogen Evolution at Metal Centers Probed with Hydrated Aluminium Cations, Al+(H2O)n, n=1–10
Authors: Heller Jakob , Pascher Tobias F. , van der Linde Christian , Ončák Milan , Beyer Martin K. 
Published: October 2021

AbstractHydrated aluminium cations have been investigated as a photochemical model system with up to ten water molecules by UV action spectroscopy in a Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometer. Intense photodissociation was observed starting at 4.5 eV for two to eight water molecules with loss of atomic hydrogen, molecular hydrogen and water molecules. Quantum chemical calculations for n=2 reveal that solvation shifts the intense 3s–3p excitations of Al+ into the investigated photon energy range below 5.5 eV. During the photochemical relaxation, internal conversion from S1 to T2 takes place, and photochemical hydrogen formation starts on the T2 surface, which passes through a conical intersection, changing to T1. On this triplet surface, the electron that was excited to the Al 3p orbital is transferred to a coordinated water molecule, which dissociates into a hydroxide ion and a hydrogen atom. If the system remains in the triplet state, this hydrogen radical is lost directly. If the system returns to singlet multiplicity, the reaction may be reversed, with recombination with the hydroxide moiety and electron transfer back to aluminium, resulting in water evaporation. Alternatively, the hydrogen radical can attack the intact water molecule, forming molecular hydrogen and aluminium dihydroxide. Photodissociation is observed for up to n=8. Clusters with n=9 or 10 occur exclusively as HAlOH+(H2O)n‐1 and are transparent in the investigated energy range. For n=4–8, a mixture of Al+(H2O)n and HAlOH+(H2O)n‐1 is present in the experiment.
Development of astrocyte morphology and function in mouse visual thalamus
Authors: Somaiya Rachana D. , Huebschman Natalie A. , Chaunsali Lata , Sabbagh Ubadah , Carrillo Gabriela L. , Tewari Bhanu P. , Fox Michael A. 
Published: October 2021

AbstractThe rodent visual thalamus has served as a powerful model to elucidate the cellular and molecular mechanisms that underlie sensory circuit formation and function. Despite significant advances in our understanding of the role of axon‐target interactions and neural activity in orchestrating circuit formation in visual thalamus, the role of non‐neuronal cells, such as astrocytes, is less clear. In fact, we know little about the transcriptional identity and development of astrocytes in mouse visual thalamus. To address this gap in knowledge, we studied the expression of canonical astrocyte molecules in visual thalamus using immunostaining, in situ hybridization, and reporter lines. While our data suggests some level of heterogeneity of astrocytes in different nuclei of the visual thalamus, the majority of thalamic astrocytes appeared to be labeled in Aldh1l1‐EGFP mice. This led us to use this transgenic line to characterize the neonatal and postnatal development of these cells in visual thalamus. Our data show that not only have the entire cohort of astrocytes migrated into visual thalamus by eye‐opening but they also have acquired their adult‐like morphology, even while retinogeniculate synapses are still maturing. Furthermore, ultrastructural, immunohistochemical, and functional approaches revealed that by eye‐opening, thalamic astrocytes ensheathe retinogeniculate synapses and are capable of efficient uptake of glutamate. Taken together, our results reveal that the morphological, anatomical, and functional development of astrocytes in visual thalamus occurs prior to eye‐opening and the emergence of experience‐dependent visual activity.
Thermal Fluctuations in Conjugation and their Effect on Calculated Excitation Energies: A Case Study on the Astaxanthin Carotenoid
Authors: Wang Jun , Durbeej Bo 
Published: October 2021

AbstractA popular approach to the calculation of molecular excitation energies is to consider only equilibrium geometries and neglect the effects of thermal motion. Although this static approach is sensible for molecules with distinct potential‐energy minima, its adequacy relative to dynamical approaches appears not to have been thoroughly tested. Here, we report a case study investigating how thermal motion accounted for by molecular dynamics simulations influences the optically bright state of astaxanthin, a carotenoid of broad photobiological interest that features 13 conjugated double bonds. Employing several different density functional methods, it is shown that thermal fluctuations in the conjugation result in the Boltzmann‐weighted average excitation energies for this state being shifted by up to 0.05 eV relative to those obtained from purely static calculations. Accordingly, it is concluded that the effects of thermal motion on excitation energies of conjugated systems can be quite large even for molecules with distinct potential‐energy minima.
Ditch the low flow: Agricultural impacts on flow regimes and consequences for aquatic ecosystem functions
Authors: Rideout Natalie K. , Lapen David R. , Peters Daniel L. , Baird Donald J. 
Published: October 2021

AbstractLarge‐scale, intensive agriculture is a critical activity supporting global food production, yet it has taken a significant toll on the equally critical ecosystem services supplied by global biodiversity. This is particularly true for the planet's most threatened ecosystems: freshwaters. As one of the world's largest agricultural producers, Canada is also home to much of the world's freshwater. As Canada's agricultural capacity expands under climate warming into more northerly latitudes—and in some cases regions with large carbon sinks—it is imperative that this sectoral shift is accompanied by careful management to avoid exacerbating ecosystem service losses. Across Canada, agricultural practices vary in terms of their impact on freshwater ecosystems. Agricultural water extraction, storage behind dams, diversions, dredging and clearing of riparian vegetation can impact more naturalized flow regimes. This review explores the influence of managed low flows on ecosystem functioning in man‐made drainage/irrigation ditch systems. We examine how low flows in these systems can impact ecosystem functions in agricultural watersheds with fragmented natural capital. We provide management options to protect ecosystem functions under a changing climate, recognizing that in agro‐ecosystems, drainage/irrigation ditch systems provide a critical remnant habitat to support biodiversity in otherwise depauperate landscapes.