bluuebunny/crossref_metadata_2025 huggingface dataset:
Palladium‐Catalyzed Annulative Allylic Functionalization Reactions
Authors: Ansari Arshad J. , Singh Bara , Ramasastry S. S. V.
Published: October 2022

The development of efficient synthetic methods incorporating novel catalytic paradigms is of significant interest to organic chemists. The recent advancements in catalysis have manifested the tremendous potential of transition metal‐catalyzed processes in advancing organic synthesis to a new height. Especially, palladium‐catalyzed transformations provide simple solutions to several synthetic challenges and generate diverse and complex scaffolds with atom‐, pot‐, and step‐economy. This article discusses the advancements in the “Pd‐catalyzed intramolecular allylic alkylation reactions” during the last 20 years. The chosen examples highlight the relevance of CH functionalization reactions in the total synthesis and underscore their future potential in chemical synthesis.
Pd‐Catalyzed CH Olefination Reactions
Authors: Riente Paola , Jia Wen‐Liang , FernÁndez‐IbÁñez M. Ángeles
Published: October 2022

Alkenes are valuable synthetic intermediates present in natural products, bioactive compounds, and materials. Palladium‐catalyzed CH olefination reactions have become an attractive alternative to the commonly used Pd‐catalyzed Mizoroki–Heck cross‐coupling since no prefunctionalization of the starting materials is required. Major efforts have been devoted to developing selective, efficient, and general palladium‐catalyzed CH olefination reactions employing directing groups and ligands. Nowadays, the toolbox of palladium‐catalyzed CH olefination reactions is enormous, permitting the olefination of a wide range of substrates at different positions. In this article, we will offer an overview of the most important palladium‐catalyzed CH olefination reactions of arenes and alkanes.
Oxidative CH Bond Functionalization Mediated by Organopalladium(II) Complexes with Oxygen as Terminal Oxidant
Authors: Vedernikov Andrei N.
Published: October 2022

A rapidly growing area of oxidative CH bond functionalization reactions utilizing O
2
as terminal oxidant and palladium complexes as catalysts is reviewed. First, the most general mechanisms of the key steps involved in such reactions are briefly considered, (i) CH bond activation at a Pd(II) center and (ii) oxidative functionalization of the resulting Pd(II)C bond. The later step remains the least explored but the growing understanding of the underlying reaction mechanisms can drive the future development of this area of catalysis. In particular, the use of carefully chosen ligands can translate to a significant acceleration of aerobic oxidative CH functionalization reactions. Next, a review is presented of the current scope of the reaction. This section is organized according to the type of CH bond broken, C(sp
3
)H, or C(sp
2
)H, as well as the type of a new CX bond formed (X = O, N, C, B, S) and the functional group installed. In each particular example, a comment is provided on the proposed reaction mechanism.
Palladium‐Pincer Complexes in CH Bond Activation
Authors: Paul Sabarni , Paik Aniruddha , Das Rahul , Rana Sujoy
Published: October 2022

Palladium‐pincer complexes containing monoanionic, tridentate pincer ligand have evolved as a privileged synthetic tool that can be applied in different fields of research including material science and synthetic organic chemistry such as cross‐coupling, hydrophosphination, and allylation reaction. Among them, CH bond activation is one of the most efficient, convenient, and greener approach due to its ability to perform corresponding functionalization from easily available and naturally abundant feedstock. However, number of the reports solely highlighting the application of Pd‐pincer complexes in CH activation is very less. In this article, we have discussed the synthesis of Pd‐pincer complexes via CH bond activation followed by their useful application in the field of CH bond activation.
Rhodium‐Catalyzed CH Functionalization with Photoredox Catalysis
Authors: Liu Ruixing , Wei Yin , Shi Min
Published: October 2022

Rhodium‐catalyzed CH bond activation and visible‐light‐induced photocatalysis are amongst the most rapidly expanding fields in organic chemistry and these approaches display complementary characteristics and applications. Innovative reactions for CH functionalization through combining rhodium catalysis and visible‐light‐induced photocatalysis strategies are reported in recent years. Such synergistic dual catalysis gives a promise of devising previously inaccessible transformations and the synthesis of coupling products, which is difficult to access via a traditional CH activation strategy. Although this approach seems particularly tempting, the reported examples of such protocols remain rarely. Further development in this field is highly demanded.
Ruthenium‐Catalyzed Multiple Functionalization of Arene CH Bonds
Authors: Mukherjee Kallol , Shankar Majji , Sahoo Akhila K.
Published: October 2022

Multiple functionalization of environmentally different C(arene)H bonds with distinct functional groups is synthetically important. This process introduces various functionalities in the molecule, making the easily accessible less‐functionalized compounds to structurally complex molecular scaffolds. Although symmetrical multiple functionalizations of C(arene)H bonds are largely well explored, the unsymmetrical multiple functionalization of C(arene)H bonds is often nonselective, uncontrolled, and unproductive. This article briefly discusses the conceptual growth in ruthenium (Ru)‐catalyzed symmetrical and unsymmetrical multifold functionalizations of C(arene)H bonds, which is exceedingly appealing and highly important.
Electrochemical CH Activation Catalyzed by Cobalt and Copper: Synthetic Strategies and Mechanistic Illustration
Authors: Ghosh Munmun , Mallick Samrat , De Sarkar Suman
Published: October 2022

Transition metal‐catalyzed CH activation has gained immense attention in modern age organic synthesis by means of its widespread applicability associated with the advantages of the atom‐ and step economy, reduced waste generation, and overall sustainability. In order to minimize the use of sacrificial oxidants in the course of transition metal‐catalyzed CH activation, electrosynthesis emerged as a potential greener alternative, thereby providing a viable way toward catalytic activation of CH bonds using electrons as environmental friendly oxidants. In this article, we present a systematic description of electrochemical CH functionalization catalyzed by two cost‐efficient and earth‐abundant 3d transition metals, cobalt, and copper. Besides their other prominent features, the uniqueness of these two metals lies in their versatile modes of action and adaptability to various oxidation states, when used under electrochemical conditions.
Late‐Stage CH Activation–Functionalization of Drugs, Natural Products, and Biomolecules: In View of Molecular Property and Mechanistic Pathway
Authors: Guchhait Sankar K. , Rao Vajja Krishna , Acharya Ayan
Published: October 2022

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The CH activation‐based late‐stage functionalization (LSF) has emerged as a powerful strategy in the synthetic organic chemistry. The strategy has definitely transformed the way synthetic chemists think for CC and C–Heteroatom bond‐forming structural diversification. It has made significant advances in functionalization of a diverse range of structurally complex molecules, including drugs, natural products, peptides, nucleosides, nucleic acids, and polysaccharides, which provides highly efficient access to chemical space of biologically/functionally important derivatives or analogs with functionalization at previously inaccessible and otherwise inert CH bonds. These LSF chemistry facets reported in recent years have been illustrated in this article. They have been categorized into classes of molecules and subdivided into aspects of the mechanistic pathway combining with molecular properties. This pool of information will be useful for designing a new strategy of CH activation and application toward the rapid exploration of extended space of complex molecular architectures that are inaccessible by conventional synthesis.
CH Arylation of Saturated
N
‐Heterocycles
Authors: Haldar Surajit , Mandal Sumana , Jana Chandan K.
Published: October 2022

Saturated
N
‐heterocycles having an aryl group are core structures of numerous natural products, pharmaceuticals, chiral catalysts, etc. Therefore, different strategies have been developed for the synthesis of arylated
N
‐heterocycles. In contrast to multistep synthesis, the development of direct arylation of saturated
N
‐heterocycles has become increasingly popular in recent years. This article summarizes the methods for the synthesis of arylated
N
‐heterocycles through direct CH arylation of alicyclic amines.
Iron‐Catalyzed Enantioselective CH Functionalization
Authors: Asako Sobi , Ilies Laurean
Published: October 2022

Because of the combined attractive features of iron as a sustainable catalyst and of CH functionalization, over the past several decades the chemistry of iron‐catalyzed CH functionalization has attracted much attention and is growing rapidly. This article briefly introduces the recent emergence of iron‐catalyzed enantioselective CH functionalization reactions that have been achieved by controlling the reactivity and coordination environment of active iron species by chiral ligands.
Nickel‐Catalyzed Benzylic CH Functionalization
Authors: Sharma Dipesh M. , Punji Benudhar
Published: October 2022

Nickel‐catalyzed CH functionalization has emerged as a powerful tool for the sustainable synthesis of strategic organic molecules. While many efforts have focused on the functionalization of C(sp2)H bond on arenes and heteroarenes in past decades, much less research has been devoted to the activation and functionalization of challenging benzylic C(sp3)H bonds. This article highlights the development in the area of benzylic C(sp3)H functionalization, with a particular emphasis on reaction development, scope, and reaction mechanism.
CH Functionalization Methods in Flow Conditions
Authors: Ferlin Francesco , Carpisassi Luigi , Brufani Giulia , Vaccaro Luigi
Published: October 2022

This article will discuss the adoption of flow conditions in CH functionalization processes highlighting the possible benefits in terms of reactivity, reaction time, and/or safety of the procedure and where possible, results obtained in flow will be compared to those in batch conditions. Main features of the reactor systems will be discussed and the use of tailor‐made customized or commercially available flow system will be compared. Most recent key examples utilizing flow systems in CH functionalization reactions will be discussed including the most relevant report present in the literature until July 2021.
Understanding Methane Activation at Pt Centers from the Perspective of Microscopic Reversibility
Authors: Pal Shrinwantu
Published: October 2022

Despite 50 years since Shilov's seminal discovery, till date no practical systems for catalytic methane functionalization, one of the grandest challenges of chemistry, exist. Approaches to tackle this can be segregated into two, but often overlapping, themes –
synthetic efforts
focusing on the development of new metal–ligand platforms and
mechanistic efforts
focusing on step‐wise delineation of the intended catalytic cycle. This article discusses the mechanism of methane activation from the perspective of microscopic reversibility as inferred through kinetic isotope effects and observation of isotope scrambling.
Inhibiting the Growth of 1D Intermediates in Quasi‐2D Ruddlesden−Popper Perovskites
Authors: Zhang Weichuan , Wu Xianxin , Cheng Qian , Wang Boxin , Zafar Saud Uz , Han Bing , Zhang Jianqi , Zhang Hong , Liu Xinfeng , Zhang Yuan , Zhou Huiqiong
Published: October 2022

Quasi‐2D perovskite solar cells have recently emerged as a highly prospective and inexpensive solution for sustainable energy due to their intrinsic optoelectronic properties and stability. The qualities of these promising quasi‐2D perovskite cells are generally affected by different intermediates derived from the precursor solution during film fabrication processing. However, efficient solutions to inhibit intermediates remain insufficient to date. Here, an effective strategy is prsented to inhibit the growth of 1D solvate intermediate during the fabricating process of quasi‐2D perovskite films by introducing a guanidinium thiocyanate (GUASCN) inhibitor. Theoretical calculations reveal that the SCN− anions spontaneously replace the iodide ions in the inorganic framework [PbI6]3− and induce the decomposition of the solvate intermediate. The resulted perovskite solar cells exhibit a significant improvement in power conversion efficiency (PCE), benefiting from the reduced trap‐state density and enhanced carrier mobilities. The unencapsulated devices retain 91% and 95% of the original PCEs under 45 ± 10% humidity in air or under continuous light irradiation at 100 mW cm−2 and 45 °C in a nitrogen atmosphere for 1000 h. Particularly, devices without electron‐transporting layers maintain 85% of the peak PCE under maximum power point tracking at 45 °C for 1000 h.
Recent Advances in Upgrading of Low‐Cost Oxidants to Value‐Added Products by Electrocatalytic Reduction Reaction
Authors: Li Rui , Xiang Kun , Liu Zhongyi , Peng Zhikun , Zou Yuqin , Wang Shuangyin
Published: October 2022

Recently, the efficient upgrading of abundant and cheap substances (H2O, CO2, N2, and NOxn) into valuable products by reduction and/or hydrogenation has attracted much attention. However, the traditional transformation processes of these oxidants generally suffer high‐energy input, complicated reactors, and rigorous reaction conditions due to their high thermodynamic stability and kinetic inertness. Recently, electrocatalytic reduction reactions (ERRs) for upgrading low‐grade substances have been perceived as promising for sustainable energy conversion due to the ambient condition, high selectivity, and atom economic feasibility. In this review, value‐added fuels and chemicals generation from low‐cost oxidants ERRs are systematically summarized. Specifically, H2 generation from ERR is introduced from water and seawater electrolysis; carbon‐containing compound generation from electrocatalytic COx reduction is classified into C1, and C2 and/or C2+ acquisition; valuable NH3 production is divided into nitrogen reduction reaction (NRR) and NOxn species reduction reaction (NOxnRR); and other valuable chemicals generation from multi‐substance reduction to CC bonds and CN bonds are also reviewed. This review aims to provide a comprehensive overview of high‐valued product generation from ERRs. Besides, an in‐depth understanding of such ERRs to valuable products has been presented, and current challenges and further prospects are also proposed.
Tailoring Electrode Surface Charge to Achieve Discrimination and Quantification of Chemically Similar Small Molecules with Electrochemical Aptamers
Authors: Kesler Vladimir , Fu Kaiyu , Chen Yihang , Park Chan Ho , Eisenstein Michael , Murmann Boris , Soh H. Tom
Published: October 2022

Electrochemical biosensors based on structure‐switching aptamers offer many advantages because they can operate directly in complex samples and offer the potential to integrate with miniaturized electronics. Unfortunately, these biosensors often suffer from cross‐reactivity problems when measuring a target in samples containing other chemically similar molecules, such as precursors or metabolites. While some progress has been made in selecting highly specific aptamers, the discovery of these reagents remains slow and costly. In this work, a novel strategy is demonstrated to distinguish molecules with miniscule difference in chemical composition (such as a single hydroxyl group)—with cross reactive aptamer probes—by tuning the charge state of the surface on which the aptamer probes are immobilized. As an exemplar, it is shown that the strategy can distinguish between DOX and many structurally similar analytes, including its primary metabolite doxorubicinol (DOXol). Then the ability to accurately quantify mixtures of these two molecules based on their differential response to sensors with different surface‐charge properties is demonstrated. It is believed that this methodology is general and can be extended to a broad range of applications.
Advanced Epitaxial Lift‐Off and Transfer Procedure for the Fabrication of High‐Quality Functional Oxide Membranes
Authors: Bouaziz Jordan , Cancellieri Claudia , Rheingans Bastian , Jeurgens Lars P. H. , La Mattina Fabio
Published: October 2022

In the past 5 years, the transfer of epitaxial oxide thin films has drawn a renewed interest in the scientific community. The major challenge in this technology is to minimize the appearance of extended bulk defects such as plastic deformations, cracks, and delamination, which are induced by the transfer process to a new host substrate. In this work, a procedure for the transfer of epitaxial oxide films where a rigid bond to the final host holder is obtained via a metallic Au/Ag bonding layer is presented. Here, the transfer of SrRuO3 (SRO) and SrRuO3/SrTiO3 (STO) epitaxial films grown on a water‐soluble Sr3Al2O6 sacrificial layer is reported. These epitaxial films are grown on a STO substrate and transferred onto a Si host substrate. Roughness values lower than 1nm are observed for the transferred SRO membranes. Cross‐section analysis shows straight interfaces without plastic deformation of the membranes. X‐ray diffraction rocking‐curve analysis evidences that mechanical damage is minimized and the membranes remain close to their initial quality. This procedure represents an important step forward in the development of advanced technologies for membrane transfer of epitaxial oxides and superstructures.
Radiation‐Tolerant Electronic Devices Using Wide Bandgap Semiconductors
Authors: Muhammad Zahir , Wang Yan , Zhang Yue , Vallobra Pierre , Peng Shouzhong , Yu Songyan , Lv Ziyu , Cheng Houyi , Zhao Weisheng
Published: October 2022

The aspiration of electronic technologies that are resistant to high‐energy cosmic radiation is essential for current harsh radiation environment exploration. Integrated circuits mostly require post‐processing after designing, making their structures more complex than the standard systems. Thus, unique designs and strategies are developed to enable the high tolerance of space electronics to radiation in nuclear and avionic applications. The wide bandgap semiconductor (WBG) materials with excellent electronic/optical properties and structural stability are appealing options for radiation‐immune applications. Here, in this article, the development and fabrication of various electronic devices have been reviewed using different wide bandgap materials for radiation‐hardened applications. Detailed investigations are discussed, from the fundamental wide bandgap materials withstanding limited irradiation to the development processes of the electronic devices used in harsh environments. Furthermore, the challenges and future perspectives of the WBG‐based radiation harsh electronic devices are also highlighted in this review with commercial application in space stations and aircraft.
Graphene‐Assisted Epitaxy of High‐Quality GaN Films on GaN Templates
Authors: Feng Tao , Zhang Shuo , Yang Kailai , Chen Qi , Liang Meng , Yan Jianchang , Yi Xiaoyan , Wang Junxi , Li Jinmin , Liu Zhiqiang
Published: October 2022

Graphene (Gr)‐assisted epitaxy of semiconductors has been demonstrated as a revolutionary strategy for the fabrication of nitride materials and flexible devices. However, till now, most of the GaN epitaxy assisted by Gr is performed on thermally stable foreign substrates because Gr suffers obvious deterioration due to the decomposition of GaN substrate. Thus, large lattice and thermal mismatches still exist and inevitably lead to a high density of dislocations in nitrides. To address this issue, here, the Gr‐assisted epitaxy of high‐quality GaN films on GaN templates is demonstrated by constructing specially designed self‐organized defective (SOD) Gr as a buffer layer. The SOD Gr allows for the spontaneous relaxation of strain in GaN epilayers by weakening the interfacial interactions; and thus, blocks the upward spread of threading dislocations in GaN templates. Therefore, screw and edge dislocation densities in GaN epilayers show reductions of 51% and 62%, respectively, compared to that in homoepitaxy. Based on the GaN film grown on SOD Gr, the as‐fabricated blue light‐emitting diode exhibits a 17% enhancement of light output power and a better emission wavelength stability than that without Gr. This work opens a practical pathway for the growth of high‐quality nitrides and manufacturing of high‐performance nitride‐based devices.
Aging‐Driven Composition and Distribution Changes of Electrolyte and Graphite Anode in 18650‐Type Li‐Ion Batteries
Authors: Petz Dominik , Baran Volodymyr , Peschel Christoph , Winter Martin , Nowak Sascha , Hofmann Michael , Kostecki Robert , Niewa Rainer , Bauer Michael , Müller‐Buschbaum Peter , Senyshyn Anatoliy
Published: October 2022

A series of low‐temperature studies on LiNi0.80Co0.15Al0.05O2 18650‐type batteries of high‐energy type with different stabilized states of fatigue is carried out using spatially resolved neutron powder diffraction, infrared/thermal imaging, and quasi‐adiabatic calorimetry. In‐plane distribution of lithium in the graphite anode and frozen electrolyte in fully charged state is determined non‐destructively with neutron diffraction and correlated to the introduced state of fatigue. An independent electrolyte characterization is performed via calorimetry studies on variously aged 18650‐type lithium‐ion batteries, where the shape of the thermodynamic signal is evolving with the state of fatigue of the cells. Analyzing the liquid electrolyte extracted/harvested from the studied cells reveals the decomposition of conducting salt to be the main driving factor for fatigue in the electrolyte degradation.
Cationic Additive with a Rigid Solvation Shell for High‐Performance Zinc Ion Batteries
Authors: Kim Minkwan , Shin Seung‐Jae , Lee Jimin , Park Youngbin , Kim Yangmoon , Kim Hyungjun , Choi Jang Wook
Published: October 2022

Despite substantial progresses, in aqueous zinc ion batteries (AZIBs), developing zinc metal anodes with long‐term reliable cycling capabilities is nontrivial because of dendritic growth and related parasitic reactions on the zinc surface. Here, we exploit the tip‐blocking effect of a scandium (Sc3+) additive in the electrolyte to induce uniform zinc deposition. Additional to the tri‐valency of Sc3+, the rigidity of its hydration shell effectively prevents zinc ions from concentrating at the surface tips, enabling highly stable cycling under challenging conditions. The shell rigidity, quantified by the rate constant of the exchange reaction (kex), is established as a key descriptor for evaluating the tip‐blocking effect of redox‐inactive cations, explaining inconsistent results when only the valence state is considered. Moreover, the tip‐blocking effect of Sc3+ is maintained in blends with organic solvents, allowing the zinc anode to cycle reliably even at −40 °C without corrosion.
Surface Degradation of Single‐crystalline Ni‐rich Cathode and Regulation Mechanism by Atomic Layer Deposition in Solid‐State Lithium Batteries
Authors: Guo Hui‐Juan , Sun Yipeng , Zhao Yang , Liu Gui‐Xian , Song Yue‐Xian , Wan Jing , Jiang Ke‐Cheng , Guo Yu‐Guo , Sun Xueliang , Wen Rui
Published: October 2022

Single‐crystalline Ni‐rich cathode (SC‐NCM) has attracted increasing interest owing to its greater capacity retention in advanced solid‐state lithium batteries (SSLBs), while suffers from severe interfacial instability during cycling. Here, via atomic layer deposition, Li3PO4 is introduced to coat SC‐NCM (L‐NCM), to suppress undesired side reaction and enhance interfacial stability. The dynamic degradation and surface regulation of SC‐NCM are investigated inside a working SSLB by in situ atomic force microscopy (AFM). We directly observe the uneven cathode electrolyte interphase (CEI) and surface defects on pristine SC‐NCM particle. Remarkably, the formed amorphous LiF‐rich CEI on L‐NCM maintains its initial structure upon cycling, and thus endows the battery with improved cycling stability and excellent rate capability. Such on‐site tracking provides deep insights into surface mechanism and structure–reactivity correlation of SC‐NCM, and thus benefits the optimizations of SSLBs.
Efficient Splitting of Alkane Isomers by a Bismuth‐Based Metal‐Organic Framework with Auxetic Reentrant Pore Structures
Authors: Zhang Zhaoqiang , Peh Shing Bo , Kang Chengjun , Yu Kexin , Zhao Dan
Published: October 2022

The isolation of di‐branched alkanes from their isomers is vital in gasoline upgrading to achieve high octane numbers but is significantly challenging and energy‐intensive. Here, we report the highly efficient separation of hexane isomers by combing molecular recognition and size‐sieving in a bismuth‐based MOF, UU‐200. The unique auxetic structure with reentrant honeycomb‐like pore cavities connected by narrow pore windows endows UU‐200 with a complete rejection of di‐branched alkanes and high capacities for linear and mono‐branched isomers. The molecular sieving effect, unprecedented separation selectivities, and excellent efficiencies are proved via adsorption isotherms and breakthrough experiments with high research octane numbers obtained (>96), indicating a benchmark for alkane separation under ambient conditions. The molecular recognition mechanism was unveiled by theoretical simulation and in situ Fourier‐transform infrared spectroscopy.
Localized Lattice Expansion of FAPbBr3 to Design a 3D Hybrid Perovskite for Sensitive Near‐Infrared Photodetection
Authors: Ji Chengmin , Zhu Tingting , Fan Yipeng , Li Zhou , Liu Xitao , Li Lina , Sun Zhihua , Luo Junhua
Published: October 2022

A mixed‐cation 3D lead bromide hybrid perovskite (NMDAP)2FAPb4Br13 (1, NMDAP2+ = N‐methyl‐1,3‐diaminopropanium, FA+ = formamidinium) is tailored by incorporating the large NMDAP2+ cation with the small FA+ ion into 3D FAPbBr3. Structurally, the small FA+ ions occupy the prototypical cavities formed by distorted corner‐sharing PbBr6 octahedra as in FAPbBr3, while the bulky NMDAP2+ ions are confined to the expanded lattice which is defined by a new structural motif composed of eight corner‐sharing PbBr6 octahedra and four edge‐sharing octahedra. This localized lattice expansion from FAPbBr3 creates a new branch of the intriguing 3D hybrid perovskite family, breaking the limits of the conventional Goldschmidt tolerance factor rule. Moreover, a high two‐photon absorption (2AP) coefficient of 60.8 cm MW−1 was demonstrated to near‐infrared (NIR) 800 nm illumination, enabling sensitive NIR photoresponses with large on/off ratio (≈104) as well as favorable stability.
Co‐delivery of tauroursodeoxycholic acid and dexamethasone using electrospun ultrafine fibers to induce early coupled angiogenesis and osteogenic differentiation
Authors: Liu Junyu , Tan Ziwei , Jia Yongliang , Shi Xiaotong , Hou Ruxia , Liu Jiajia , Luo Dongmei , Fu Xinyu , Yang Tingting , Wang Xiangyu
Published: October 2022

In the complicated process of bone regeneration, osteogenic differentiation and angiogenesis are crucial. In this study, a novel dual small molecule composite electrospun scaffold was prepared using polycaprolactone embedded with angiogenic factor tauro‐ursodeoxycholic acid and osteogenic factor dexamethasone to promote early angiogenesis and osteogenesis. Additionally, the related properties, angiogenic activity, and osteogenic activity analyses were conducted for the scaffold. The results demonstrated that the composite scaffold possessed proper mechanical properties and hydrophilicity. During the initial drug release, the release rate of the hydrophilic drug tauro‐ursodeoxycholic acid was higher compared to the hydrophobic drug dexamethasonethe. The drugs were slowly sustained released for more than 528 h. The composite scaffold boosted cell proliferation and accelerated osteogenic differentiation up to 21 days. The alkaline phosphatase activity and mineral deposition were comparatively higher on dual drug‐releasing fibers compared to control scaffolds. Wound healing migration assay and tube formation assay for further in vitro revealed that the composite scaffold exhibited higher efficiency in promoting cell migration and the angiogenesis ductive. Hence, the composite scaffold had a high potential for promoting bone regeneration by enhancing angiogenesis.
Fabrication of LLDPE based biodegradable composite incorporated with leather shavings and buffing dust: An approach for waste management
Authors: Noyon Md. Ashikur Rahaman , Dey Thuhin Kumar , Jamal Mamun , Rathanasamy Rajasekar , Chinnasamy Moganapriya , Uddin Md. Elias
Published: October 2022

The aim of this study is to fabricate biodegradable composite films from leather shavings (LS) and leather buffing (LB) blended with linear low density polyethylene (LLDPE) by twin‐screw extrusion process with blow molding mechanism. Various quantities of leather fiber is used to fabricate the composite films and as prepared films were characterized by FTIR, TGA, DSC, SEM, OTR, biodegradability, water absorption, and mechanical properties respectively. FTIR analysis is performed to validate the chemical bonding between LB/LLDPE and LS/LLDPE. TGA and DSC studies are used to determine the thermal stability whereas SEM analysis is used to examine the surface morphology of fabricated composite films. Oxygen gas barrier properties of LB/LLDPE and LS/LLDPE composite films are enhanced by 11.32% and 15.17% respectively compared to pure LLDPE film. Tensile strengths (TS) of the composite materials are augmented by 228.75% and 313.73% while elongation at break is decreased by 57.85% and 50.09% for LB/LLDPE and LS/LLDPE respectively compared with pure LLDPE film. Water absorption capacity is increased by 4.54% and 3.36% whereas weight loss percentage is improved 7 and 5 times respectively for LB/LLDPE and LS/LLDPE composite. Hence, the fabricated composite films can be used as cost‐effective, biodegradable, and flexible composite films for packaging and interior partitioning.
UAV magnetometer survey in low‐level flight for archaeology: Case study of a Second World War airfield at Ganacker (Lower Bavaria, Germany)
Authors: Stele Andreas , Linck Roland , Schikorra Markus , Fassbinder Jörg W. E.
Published: October 2022

Unmanned aerial vehicle (UAV)‐based magnetometer systems became more and more attractive for large‐scale archaeological prospection in recent years. Although their sensors exhibit the same sensitivity than the ground‐based prospecting systems, UAV prospecting is seriously handicapped by the magnetic and mechanical disturbances of the drone and by limitations of a low‐level flight. To minimize these disturbances, scalar magnetometers are attached only on a tether 2.5–10 m beneath the drone to be flown as close as possible above the ground. First, test measurements with UAV‐fixed fluxgate magnetometers provide more accurate results than the scalar magnetometers in any configuration but have to overcome disturbance by vibrations. Here, we present a case study choosing the compact set‐up of the Sensys MagDrone R4. The high sampling rate of 200 Hz of the three axis fluxgate sensors of the R4 allows sufficient filtering of the interferences generated by the UAV and external disturbances. High‐precision flight control of the drone allows operating the sensors by radar‐controlled flight height ∼1 m above the ground, which is a fundamental and indispensable prerequisite for archaeological prospecting. For our test, we choose the site Ganacker (southern Bavaria), where we expected a large range of archaeological structures and features with high magnetic contrast. We compare and verify the magnetogram with historical and recent geodata. Our results show that the R4 system offers an outstanding step forward regarding a successful application for archaeological prospection. Already now, the system is well suited for the fast mapping of large areas and archaeological sites with intense magnetic anomalies.
A GH42 β‐galactosidase from Bifidobacterium thermophilum: Biochemical characterization and synthesis of galactosyl glycerol by reverse hydrolysis
Authors: Duan Jun , Jia Xiangfei , Cao Kun , Gao Zhen
Published: October 2022

In this study, a β‐galactosidase gene (btgal42) was first cloned from Bifidobacterium thermophilum and successfully expressed in Escherichia coli. The molecular weight of the purified BtGal42 was estimated to be 78 kDa by the sodium dodecyl sulfate‐polyacrylamide gel electrophoresis and 225 kDa by the size‐exclusion chromatography, indicating that the native BtGal42 was a homotrimer. BtGal42 belonged to the glycosidase hydrolase family 42, exhibiting the maximum activity at pH of 7 and at temperature of 50°C. The enzyme displayed a strictly specific activity toward substrates with β‐galactosyl linkages at the nonreducing ends, of which the activity on 4‐nitrophenyl‐β‐d‐galactopyranoside was the highest, followed by 2‐nitrophenyl‐β‐d‐galactopyranoside and lactose. Among the tested metals and reagents, BtGal42 showed tolerance in the presence of various organic solvents. Importantly, BtGal42 exhibited a high reverse hydrolysis activity when using galactose as the donor and the di‐alcohol ethylene glycol and the trialcohol glycerol as the acceptors. Under unoptimized reaction conditions, the galactosyl glycerol yield reached 62.2 g/L (galactose conversion rate, 41.2%). This study might provide a feasible method for the biosynthesis of galactosyl glycerol from low‐cost glycerol and galactose, which was associated with high conversion efficiency and few byproducts.
Glycosides and Vascular Complications of Diabetes
Authors: Yeram Pranali B. , Kulkarni Yogesh A.
Published: October 2022

Diabetes is linked with various microvascular and macrovascular complications. Nephropathy, neuropathy and retinopathy are important microvascular complications of diabetes. Different types of secondary metabolites including glycosides have been studied for their effects in diabetic complications. Various glycosides such as flavanoid glycosides and saponin glycosides are reported for their beneficial effects in diabetic nephropathy, neuropathy, retinopathy and cardiomyopathy by action on various pathways involved in the progression of these complications. Coumarin glycosides and cryanogenic glycosides have been studied for their effective role in diabetic nephropathy. Phenolic glycosides and anthraquinone glycosides also have beneficial role in diabetic neuropathy. The present review focuses on various classes of glycosides and their role in the prevention and treatment of vascular complications of diabetes.
Probing Cell‐Surface Interactions in Fungal Cell Walls by High‐Resolution 1H‐Detected Solid‐State NMR Spectroscopy
Authors: Safeer Adil , Kleijburg Fleur , Bahri Salima , Beriashvili David , Veldhuizen Edwin J. A. , van Neer Jacq , Tegelaar Martin , de Cock Hans , Wösten Han A. B. , Baldus Marc
Published: October 2022

Solid‐state NMR (ssNMR) spectroscopy facilitates the non‐destructive characterization of structurally heterogeneous biomolecules in their native setting, for example, comprising proteins, lipids and polysaccharides. Here we demonstrate the utility of high and ultra‐high field 1H‐detected fast MAS ssNMR spectroscopy, which exhibits increased sensitivity and spectral resolution, to further elucidate the atomic‐level composition and structural arrangement of the cell wall of Schizophyllum commune, a mushroom‐forming fungus from the Basidiomycota phylum. These advancements allowed us to reveal that Cu(II) ions and the antifungal peptide Cathelicidin‐2 mainly bind to cell wall proteins at low concentrations while glucans are targeted at high metal ion concentrations. In addition, our data suggest the presence of polysaccharides containing N‐acetyl galactosamine (GalNAc) and proteins, including the hydrophobin proteins SC3, shedding more light on the molecular make‐up of cells wall as well as the positioning of the polypeptide layer. Obtaining such information may be of critical relevance for future research into fungi in material science and biomedical contexts.
Imatinib dose optimization based on therapeutic drug monitoring in Chinese patients with chronic‐phase chronic myeloid leukemia
Authors: Cheng Fang , Zeng Fang , Li Qiang , Cui Zheng , Chen Yilin , Li Weiming , Zhang Yu
Published: October 2022

Background

Imatinib treatment often produces various adverse reactions in patients with chronic myeloid leukemia (CML), and increasing patients are pursuing dose optimization. In this study, the authors aimed to explore imatinib dose optimization based on therapeutic drug monitoring (TDM) in CML patients.

Methods

The relationship between imatinib concentration and clinical response and adverse reactions was evaluated, then the dose‐reduction data in 110 Chinese CML patients was also explored.

Results

Patients with a major molecular response (MMR) had higher imatinib plasma concentration compared with those not achieving MMR (1473.70 ± 419.13 vs. 985.8 ± 213.32 ng/ml) when receiving 400 mg daily. Imatinib concentration >1000 ng/ml predicted improved event‐free survival and failure‐free survival. In addition, imatinib concentration was significantly correlated with leukopenia or neutropenia, diarrhea, edema, and rash. Patients receiving imatinib concentration >1685 ng/ml were more susceptible to diarrhea and those with levels >1575 ng/ml were more susceptible to periorbital and limb edema. Thirty‐nine (35.5%) patients underwent low‐dose therapy and seven (6.4%) patients received discontinuation therapy. Patients with a higher imatinib concentration were more likely to maintain MMR or deep molecular response after dose reduction. No significant difference in molecular relapse‐free survival rate was observed between the low‐dose and standard‐dose groups over 1 year and 2 years. Furthermore, most adverse reactions significantly improved after dose reduction.

Conclusions

Imatinib concentration was closely associated with clinical response and adverse reactions, suggesting that dose optimization based on TDM might achieve beneficial clinical outcomes. Dose reduction based on TDM is feasible and safe for patients exhibiting optimal response, which could improve adverse reactions.
A novel machine learning‐based framework for detecting fake Instagram profiles
Authors: Kaushik Keshav , Bhardwaj Akashdeep , Kumar Manoj , Gupta Sachin Kumar , Gupta Abhishek
Published: October 2022

Recently, there has been a massive rise in the popularity of Instagram, which connects individuals globally and allows videos and images to be uploaded and exchanged, and communicated over social media. Instagram is also an online playground of deceit. The use of filters, lighting, and cunning angles transforms the mundane into something spectacular. Automated spam accounts and fake profiles use this to their malicious advantage for executing attacks targeting high‐profile executives. Creating fake Instagram identities is easy to reproduce the idea of being accepted by many fans on social media. Fake accounts are used in the marketing of fake services and products. This research focused on designing and training a unique neural network model and proposed a new algorithm for detecting automated spam and fake Instagram account profiles. The precision and accuracy of the proposed method were achieved at 93% and 91%, respectively.
RideNN‐OptDRN: Heart disease detection using RideNN based feature fusion and optimized deep residual network
Authors: Merugula Suneetha , Padmaja Buddi , Veerubommu Ragavi
Published: October 2022

Heart disease detection through early‐stage syndrome remains as a main confront in present world situation. If it is not detected appropriate time, then this turns out to be the major cause of death. Several existing heart disease detection techniques are developed with lower detection performance and therefore it is very significant to introduce a novel heart disease detection model that poses the potential to detect heart disease from input data. A novel detection approach named, social water cycle algorithm‐based deep residual network (SWCA‐based DRN) is proposed for classification of heart disease. The developed SWCA algorithm is a newly designed by the hybridization of social optimization algorithm and water cycle algorithm. Here, an input data is initially preprocessed and the feature fusion procedure is carried out RV coefficient enabled rider optimization algorithm‐based neural network. With the fused feature result, heart disease classification is performed utilizing a DRN classifier where training procedure of DRN is done by proposed optimization algorithm, named SWCA. Furthermore, developed SWCA‐enabled DRN technique outperformed different other present heart disease detection approaches and attained superior performance concerning the performance measures, like testing accuracy, sensitivity, and specificity with highest values of 0.941, 0.954, and 0.925.
Nanoarchitectonics of Indocyanine Green/Doxorubicin‐Loaded Hydroxyl Boron Nitride Nanosheets for Chemophotothermal Therapy
Authors: Liu Ming , Sun Chiyu , Wu Shuangyan , Zhu Mingchang , Zhang Ying
Published: October 2022

Biocompatible hydroxylated boron nitride nanosheets were effectively loaded with indocyanine green and doxorubicin using successive assembly. The indocyanine green/doxorubicin‐loaded hydroxyl boron nitride nanosheets (ICG/DOX@OH‐BNNS) integrated photothermal therapy and chemotherapy into a single nano vehicle. It had been confirmed that ICG/DOX@OH‐BNNS could produce reactive oxygen species and exhibit excellent photothermal effects and light‐triggered faster DOX release with NIR laser irradiation. On the other hand, the fluorescence of DOX in ICG/DOX@OH‐BNNS was also used for visualizing subcellular location. Compared with individual chemotherapy and photothermal therapy, the combined treatment of ICG/DOX@OH‐BNNS could synergistically induce the apoptosis and death of A549 cells and suppress S180 tumor growth in vivo.
Influence of Laser Pulse Welding Power on Welding Joints of Zr‐Based Amorphous Alloys
Authors: Wumeng Liu , Chun Guo , Suisong Wu , Yun Li , Meng Ying , Taiyu Kang
Published: October 2022

A Zr‐based amorphous alloy (thickness = 2 mm) is welded by laser welding. The phase composition and microstructure of the welding joints under different laser powers are analyzed by optical microscopy, X‐ray diffraction, and scanning electron microscopy. Mechanical properties of the welded joints under different laser powers are examined using microhardness and tensile testers. The glass forming ability and thermal stability of the welded joints are investigated using differential scanning calorimetry. With an increase in laser power, the degree of crystallization of welded joints increases, their microhardness is in the range 502.3–546.9 HV0.2, and tensile strength is up to 583 MPa (75% of that of the Zr‐based amorphous alloy). Through the research of the article, it can be found that when the laser power increases, the crystallization degree of the welded joint first increases rapidly and then tends to be stable. The lower laser power should be used as far as possible in the case of penetration.
Identification of etazene (etodesnitazene) metabolites in human urine by LC‐HRMS
Authors: Verougstraete Nick , Verhaeghe Annick , Germonpré Jan , Lebbinck Herve , Verstraete Alain G.
Published: October 2022

Etazene (or etodesnitazene) is a novel and highly active synthetic opioid belonging to the rapidly evolving and emerging group of “nitazenes.” Etazene metabolites were identified through analysis of a human urine sample. The sample was obtained from a 25‐year‐old man who attempted suicide by taking a new psychoactive substances (NPS) cocktail purchased online and was analyzed by ultrahigh performance liquid chromatography‐high‐resolution mass spectrometry (UHPLC‐HRMS). Etazene metabolites were predicted with BioTransformer 3.0, and the exact masses were added to the inclusion list. Eight possible metabolites were identified in the urine sample. N‐ and O‐deethylation were identified as the predominant metabolism routes, resulting in M1 (O‐deethylated etazene; most abundant metabolite based on the peak area), M2 (N‐deethylated etazene), and M3 (N,O‐dideethylated etazene) metabolites. Less abundant hydroxylated products of these deethylated metabolites and etazene were also found. Additionally, in the analysis without β‐glucuronidase treatment, M1‐ and M3‐glucuronide phase II metabolites were found. As N‐ and O‐deethylated products seem to be the predominant urinary metabolites, the detection of these metabolites in urine can be useful to demonstrate etazene exposure.
Vegetation responses to past volcanic disturbances at the Araucaria araucana forest‐steppe ecotone in northern Patagonia
Authors: Moreno‐Gonzalez Ricardo
Published: October 2022

Volcanic eruptions play an important role in vegetation dynamics and its historical range of variability. However, large events are infrequent and eruptions with a significant imprint in today's vegetation occurred far in the past, limiting our understanding of ecological processes. Volcanoes in southern Andes have been active during the last 10 ka and support unique ecosystems such as the Araucaria–Nothofagus forest. Araucaria is an endangered species, with a fragmented distribution and well‐adapted to fire and volcanic disturbances. Yet, it was suggested that volcanism might have increased the fragmentation. Through the use of pollen and tephra analysis from a sedimentary record, this paleoecological study aims to provide an insight into the vegetation responses to past volcanic disturbances, to assess the role of volcanic disturbance on the vegetation dynamics and to determine if the current fragmentation has been caused by volcanism. Results show that during the last 9 kyr, 39 tephra falls buried the vegetation around Lake Relem, more frequently between 4 and 2 ka. The pollen percentage indicates that the vegetation changed after small tephra fall but seldom caused significant changes. However, the large eruption of Sollipulli volcano (~3 ka) changed the environmental conditions affecting severely the vegetation. Ephedra dominated the early successional stage, perhaps facilitating Nothofagus recovering after ~500 years. Slight increase of Araucaria and Nothofagus obliqua‐type pollen percentages suggests that forest resisted without permanent changes and recovered relatively fast after the large eruption, perhaps because of sparse biological legacies distributed in the landscape. In the study area, the relative stability of Araucaria pollen after several tephra fall suggests no change in its past distribution at the current forest‐steppe ecotone, thus not affecting its current conservation status. Perhaps, random factors, the colonization patterns of the high elevations in the Andes after deglaciation and topography might play a more important role than previously thought.