bluuebunny/crossref_metadata_2025 huggingface dataset:
Origin of the Ethiosemitic Verb hlw ‘to be present’
Authors: Suchard Benjamin D.
Published: October 2022

The Ethiosemitic verb hlw ‘to be present’ is strange in three regards: it shows an unusual alternation between -o and -awa in Classical Ethiopic; it is formally Perfect, but used in the present tense; and it has no verbal cognates in other branches of Semitic. This is because it is originally not a Perfect, but a presentative particle, to be connected with other Semitic presentatives reflecting *hallaw. Due to the leveling of the second-person object suffixes to the Perfect endings in Ethiosemitic, suffixed presentative forms like hallo-ka could be reanalyzed as consisting of a verbal stem hallo- and a subject ending -ka. Other forms of the paradigm, including the 3M.SG Perfect hallaw-a, were then created by analogy with III-w 02-stem verbs like fannawa ‘to send’.
Front Matter
Authors: Editors
Published: October 2022

Front matter
Jiankang Empire in Chinese and World History. By Andrew Chittick
Authors: Janousch Andreas
Published: October 2022

The Jiankang Empire in Chinese and World History. By Andrew Chittick. New York: Oxford University Press, 2020. Pp. xi + 411. $85.
Muhammad and the Empires of Faith: The Making of the Prophet of Islam. By Sean William Anthony
Authors: Grasso Valentina A.
Published: October 2022

Muhammad and the Empires of Faith: The Making of the Prophet of Islam. By Sean William Anthony. Oakland, CA: University of California Press, 2020. Pp. xiv + 287. $32.95, £26.
How Sacred Prostitution Is Faring in Academic Publications
Authors: Budin Stephanie Lynn
Published: October 2022

This article looks at the current state of sacred prostitution studies in both ancient Near Eastern and Classical Studies through the review of two books published in 2019. Both books reveal that the current trend is to dismiss the existence of sacred prostitution in antiquity, one by attempting (not entirely successfully) to agree with that assessment, and one by condemning that dismissal altogether. All things considered, it does now appear that there has been a marked change of opinion in the academy, and that Aphrodite’s and Ištar’s cult brothels are making their way to the dustpan of historiography.
Comparison of the Effect of Pretreatment with Cisatracurium and Rocuronium on Succinylcholine Induced Fasciculation for Patients undergoing Surgery under General Anaesthesia: A Randomised Clinical Study
Authors: Gupta Saptadeepa , Hembrom Bani Parvati Magda , Mallick Suchismita , Choudhury Arpita , Ghosh Sarmila
Published: October 2022

Introduction: Succinylcholine is the best agent for providing ideal intubating condition. Muscle fasciculation is common after succinylcholine administration and causes postoperative myalgia. Pretreatment with non depolarising muscle relaxant decreases fasciculation and myalgia after succinylcholine administration. Aim: To compare the efficacy between cisatracurium and rocuronium in preventing succinylcholine induced fasciculation in patients undergoing general anaesthesia and determining association between fasciculation and myalgia after succinylcholine use. Materials and Methods: The present study was a hospitalbased, randomised, double-blinded clinical study conducted from January 2020 to July 2020. The study included 64 patients of American Society of Anaesthesiologists (ASA) grade I and II undergoing surgery under general anaesthesia which were randomly allocated in two groups. Group 1 (N=32) received intravenous (i.v.) cisatracurium (0.01 mg/kg) and Group 2 (N=32) received i.v. rocuronium (0.06 mg/kg) as precurarising agent, three minutes before i.v. succinylcholine (1.5 mg/kg) administration. Incidence and intensity of fasciculation after succinylcholine injection were observed using a 4 point scale. Haemodynamic parameters were compared by measuring Mean Arterial Pressure (MAP) and Heart Rate (HR) before and after intubation. Patients were followed-up in Post Anesthesia Care Unit (PACU) on postoperative day 1 (POD1) for myalgia. Observations in two groups were analysed using standard statistical test. Results: Fasciculation was significantly lower in Group 2 (mean 0.2187±0.4200) than Group 1 (mean 1.125±0.833, p<0.001). A significant association was found between fasciculation after succinylcholine injection and postoperative myalgia (p-value=0.007). Group 2 had less incidence of myalgia than Group 1. However, the difference was not statistically significant. Conclusion: Rocuronium was more efficacious than cisatracurium in preventing succinylcholine induced fasciculation and rocuronium was more effective in preventing succinylcholine-related postoperative myalgia.
ЕСТЬ ЛИ ЖИЗНЬ БЕЗ GPS, "Энергия: экономика, техника, экология"
Authors: Агеев В.
Published: October 2022

В марте этого года гендиректор государственной корпорации “Роскосмос” Дмитрий Рогозин отметил, что в качестве одной из антироссийских санкций власти Соединенных Штатов рассматривают возможность отключения Российской Федерации от американской навигационной системы GPS. Что это могло бы значить для нашей страны
В БОРЬБЕ С ПАНДЕМИЕЙ КОРОНАВИРУСА НАСТАЛА ОЧЕРЕДЬ ЛЕКАРСТВ, "Энергия: экономика, техника, экология"
Authors: Чарушин В.Н.
Published: October 2022

11 февраля 2022 года вице-премьер правительства РФ Юрий Борисов заявил о необходимости поддерживать мало- и среднетоннажную химию и обеспечить технологический суверенитет России. В ситуации пандемии нового коронавируса это становится особенно актуальным для химико-фармацевтической отрасли страны. О перспективах создания отечественных лекарств против COVID 19 рассказывает вице-президент РАН, директор Института органического синтеза имени И.Я. Постовского Уральского отделения РАН, профессор Уральского федерального университета имени первого президента России Б.Н. Ельцина, председатель Уральского отделения РАН Валерий Чарушин.
Impact of National Clinical Practice Guidelines on Exchange Transfusion for Severe Neonatal Hyperbilirubinemia in Singapore
Authors: Ng W. D. , Jeyanthi C. J. , Rajadurai V. S.
Published: October 2022

Aims: To review the incidence of double volume exchange transfusion for severe neonatal hyperbilirubinemia in infants ≥35 weeks’ gestational age before and after implementation of National Clinical Practice Guidelines (NCPGNJ), analyze etiologies for severe hyperbilirubinemia, readmission rates for phototherapy and neurodevelopmental outcomes up to 2 years.

Study Design:  Retrospective study

Place and Duration of Study: KK Women’s and Children’s Hospital, Singapore, between January 2016 and December 2021.

Methodology: National Clinical Practice Guidelines on Evaluation and Management of Neonatal Jaundice (NCPGNJ) was implemented in January 2019. We retrospectively reviewed the medical records of neonates in our center who underwent double volume exchange transfusion for severe neonatal hyperbilirubinemia before and after implementation of the national clinical practice guidelines.

Results: Overall, 56 infants underwent double volume exchange transfusion for severe hyperbilirubinemia during the study period. There was a decline in the incidence of exchange transfusion from 107 per 100 000 live births in epoch 1 (2016-2018) to 61 per 100 000 live births in epoch 2 (2019-2021). There was a steady decline in overall phototherapy rates (p=0.06), readmission rates for phototherapy (p=0.04) and number of neonates needing exchange transfusion (p=0.25). ABO-hemolytic disease of the newborn was the most common etiology. One infant had delayed presentation of severe hyperbilirubinemia and eventually developed cerebral palsy. The rest of the infants had normal neurodevelopmental and audiological assessments at follow-up.

Conclusion: The evidence-based National Clinical Practice Guidelines (NCPGNJ) has reduced the incidence of exchange transfusion. It provides a unified framework for all healthcare professionals who manage neonates with hyperbilirubinemia in different healthcare settings.
Studies on the Root Architecture with Nodulation of the Chickpea (Cicer arietinum L.) as Influence by Different Moisture Management Practices along with Seed Inoculation and Level of Zinc
Authors: Kumar Kishan , Pyare Ram , Niwas Ram , Tiwari Kamal , Sachan Ravindra , Pal Ravikesh Kumar , Patel Vinay Kumar , Ranjan Abhishek Raj
Published: October 2022

The current field experiment was carried out during Rabi season of 2020-21 and 2021-22 at the Student's Instructional Farm of Chandra Shekhar Azad University of Agriculture and Technology, Kanpur, Uttar Pradesh to assess the Studies on the root architecture with nodulation of the chickpea (Cicer arietinum L.) as influence by different moisture management practices along with seed inoculation and level of zinc. The experiment was laid out in split-split plot design with 27 treatment combination comprising three moisture conservation practices namely, flat bed with 2.5 t/ha crop residue, narrow bed and furrow with 2.5 t/ha crop residue, broad bed and furrow with 2.5 t/ha crop residue in main plot and three seed inoculation (control, rhizobium and PSB) in sub-plots and three zinc level (control, 2.5 kg zinc/ha and 5.0 kg zinc/ha) in sub- sub plot with three replication. Results showed that among the different moisture management practices, used of broad bed and furrow with 2.5 t/ha crop residue were significantly enhanced root architecture, nodulation and grain yield, over the flat bed with 2.5 t/ha crop residue, respectively. Among the different Biofertilizers treatments seed inoculation with Rhizobium had significantly improved the root architecture, nodulation and yield, over control. Application of increasing levels of zinc up to 5.0 kg Zn/ha has significant influences on root architecture, nodulation and yield, over control. The combined application broad bed and furrow with 2.5 t/ha crop residue with Rhizobium and 5.0 kg/ha zinc resulted in significantly higher root architecture, nodulation and seed yield of chickpea during both the years of experimentation.
Effectiveness of Monetary Policy Instruments on Bank Liquidity Management
Authors: Bala-Keffi Ladi R. , Tawose Joseph O. B. , Tajudeen Olufunmilayo S. , Hamza Abdul-Aziz , James Emmanuel O.
Published: October 2022

Recognising the importance of monetary and price stability for sustainable growth, many countries’ Central Banks often set certain liquidity targets to be achieved using various monetary policy instruments. This study fills the gap in the literature by employing the ARDL Bounds test to examine the relative effectiveness of a combination of quantity- and price-based policy instruments used by the Central Bank of Nigeria to regulate the level of bank liquidity. Also, the likelihood ratio test is used to determine whether monetary policy instruments work better as a complement (or substitute) concerning liquidity management. Using quarterly data covering 2008/Q1-2020/Q2, we found that, price-based instruments mostly impact liquidity levels in the short- and long-run. The quantity-based instrument shows a significant impact at second lag. However, the impacts of some policy instruments were inconsistent which is partly due to their low usage as short-run measures. We found all the six monetary instruments considered in this study to be complementary for liquidity management. By implication, the combination of monetary instruments for liquidity management is in order. While MPR remains crucial in determining liquidity, a continuous review of its operationality to identify and reduce possible distortions will be beneficial. Also, there is a need for CBN to reassess the disbursement of interventions and their implications on liquidity.
Palladium Nanoparticles in CH Functionalization Reactions
Authors: Shekhar Chander , Kishore Dakoju Ravi , Satyanarayana Gedu
Published: October 2022

The usage of palladium nanoparticles to functionalize the inert CH bond with various functional groups or substituents to organic motifs is briefly described. Significantly, the utilization of nanoparticles as a heterogeneous catalyst holds some advantages like improving atom economy and catalytic activity by increasing surface area and selectivity while lowering reaction costs. In addition, the change in the size of the nanoparticles would switch their electronic and catalytic properties. Remarkably, numerous literature reports showed that nanoparticles are formed in situ manner and catalyze reactions in a heterogeneous way, although supported nanoparticles are synthesized using 1D, 2D, and 3D nanoparticle stabilizers. Hence, in this article, it is being deliberated briefly the synthesis and characterization of palladium nanoparticles and their applications toward the various CH functionalization reactions.
Transition Metal‐Catalyzed C(sp
3
)H Bond Functionalization Adjacent to Heterocycles
Authors: Kumar Jogendra , Gupta Aniket , Rahaman Ajijur , Bhadra Sukalyan
Published: October 2022

Within the last two decades, transition metal‐catalyzed CH bond functionalization of organic substrates has become a powerful tool to access relatively complex frameworks of general synthetic interest. However, significant challenges remain in developing a catalyst system that efficiently functionalizes a specific CH bond in the presence of other chemically equivalent CH bonds. Among various genre of CH bonds, those adjacent to a heteroaromatic system are distinctly special in terms of their reactivity, which is influenced by not only coordinating the heteroatom to a transition metal catalyst but also the electronic impacts of the ring during the CH bond cleavage event. This article depicts an up‐to‐date account on the functionalization reactions of methyl and/or methylene CH bonds adjacent to a heteroaromatic ring by various late and earth‐abundant transition metals, in which the heterocyclic nucleus takes part actively or passively to accelerate the required functionalization process. Of note, this article does not cover examples, wherein transition metals serve as a Lewis acid catalyst in promoting the nucleophilic attack of a methyl/methylene‐CH bond of alkylheteroarenes to an electrophilic coupling partner.
Mechanistic Understanding of Ru‐Catalyzed CH Functionalization Reactions
Authors: Kumar Pravin , Kapur Manmohan
Published: October 2022

Over the past few decades, Ru‐catalyzed CH bond functionalization has emerged as an extensive area of research, and in this regard, tremendous progress has been made toward the construction of new CC and CX bonds. The systematic study of the mechanistic pathways of these ruthenium‐catalyzed CH bond activation–functionalization sequences is crucial, which provides a basis for developing better and novel catalytic systems and exploring their potential applications. We demonstrate here a mechanistic view of those reactions, proposed by either an experimental exploration or theoretical studies. This article provides a detailed mechanistic overview of Ru‐catalyzed CH functionalization reactions, and three general activation modes, namely, oxidative addition, metathesis, and base‐assisted deprotonation, have been discussed. We hope that this mechanistic overview of Ru‐catalyzed CH functionalization reactions would provide a better understanding of the mechanism involved therein and promote the development of novel ruthenium‐based catalytic systems, leading to the discovery of new concepts.
Iron‐Catalyzed CH Functionalization of Heterocycles
Authors: Ghosh Tubai , Chanda Rupsa , Chakraborty Baitan , Jana Umasish
Published: October 2022

Transition metal‐catalyzed CH functionalization/CH bond activation is established as a standard protocol for the construction of new CC and C–heteroatom bonds, both in industries and in academia. But most of the methods are associated with the use of toxic and costly metals along with the generation of hazardous chemical as by‐products. Thus, in need of environmentally benign and sustainable methodology, iron‐catalyzed CH bond functionalization has gained much attention in recent times. Therefore, selective functionalization of heterocycles could be an easy method to access heterocyclic compounds which have applications in the fine chemical industry, medicinal chemistry, etc. In this article, we focused on the recent developments in CH bond functionalization of heterocycles using earth‐abundant iron salts toward the construction of carbon–carbon and carbon–heteroatom bonds.
Photoinduced CH Carboxylation
Authors: Masuda Yusuke
Published: October 2022

It is highly desired to develop a sustainable method to fix carbon dioxide (CO
2
) into readily available feedstocks, in particular hydrocarbons. However, direct carboxylation of thermodynamically stable CH bond with CO
2
is one of the most challenging issue in organic synthesis. These issues have so far been addressed by using transition metal catalysts. On the other hand, a novel approach to carboxylation of CH bonds with CO
2
by using light energy has recently become popular. This approach has demonstrated selectivity and reactivity different from conventional activation methods and has even achieved the conversion of hydrocarbons such as alkenes and aromatic compounds. In the present article, a comprehensive summary of photoinduced CH bond carboxylation reactions is provided.
Visible‐Light‐Mediated CH Functionalizations: CC Formation Enabled by Intermolecular Cleavage of Unactivated CH Bonds
Authors: Shu Wei
Published: October 2022

CH bond is one of the most inert and massive chemical bonds in organic molecules. Thus, the direct conversion of various inert CH bonds to functionalized molecules via carbon–carbon or carbon–heteroatom bond formation represents one of the most ideal and straightforward means to build molecular complexity and is an important theme in organic chemistry, pharmaceutical chemistry, and material sciences. The direct functionalization of CH bond is step‐ and atom‐economic, circumventing the prefunctionalization of molecules, thus attractive and highly desirable for organic synthesis. Due to the inertness of CH bonds and other associated issues, direct transformations from CH bonds remain challenging and attract great effort from the chemistry community. Among the strategies for the direct functionalizations of CH bonds, visible‐light‐mediated CH functionalizations have gained much attention from the community and have emerged as a promising tool for transforming CH bonds to other chemical bonds. This article summarizes the recent progress on the visible‐light‐mediated CH functionalization reactions enabled CC bond‐forming processes, including representative examples of transforming H and H bonds into various carbon–carbon bonds.
Nonspectator Feature of Redox Noninnocent Ligands: CC/CH Functionalization
Authors: Panda Sanjib , Dhara Suman , Lahiri Goutam K.
Published: October 2022

Redox noninnocent ligands, capable of participating in electron transfer processes have gained profound attention toward small molecule activation, catalysis, function of selective metalloenzymes as well as for their fascinating ligand centered reactivity. This article is therefore highlighted the terms “redox noninnocence” and “chemical noninnocence” of the ligands in the context of their chemical ramification at the ligand backbone. Two main types of reactivity by the redox noninnocent ligands have been illustrated here: (i) redox‐induced CC coupling phenomenon via reductive or oxidative pathway and (ii) dioxygen fixation into the ligand backbone to furnish oxygenated or ring cleavage product. Further, potential application of the redox noninnocent ligands in the catalytic transformation by virtue of their multielectron reservoir capability has been briefly introduced.
Directing Group‐Assisted CH Functionalization of Ferrocene and CpCo(C
4
Ph
4
) Derivatives
Authors: Dolui Pritam , Verma Ashutosh , Elias Anil J.
Published: October 2022

Directing group‐assisted CH bond functionalization of metal‐sandwich compounds is an emerging area of research to introduce functional groups on metal‐sandwich compounds, and the method offers significant advantages over traditional textbook methods. In this article, we have highlighted the beginning and growth of the directing group‐assisted CH bond functionalization of metal‐sandwich compounds over the past decade. Several mono‐ and bidentate directing groups have been introduced on the metallocene backbone to selectively functionalize the cyclopentadienyl rings of the metal‐sandwich compounds. The scope of these directing groups and the diversity of the functional groups introduced using them under different reaction conditions have been detailed under different subsections. The article ends with a discussion on the future scope which enlists the type of reactions yet to be carried out on metal‐sandwich compounds in comparison with the recent developments on conventional aromatic substrates.
Transition Metal‐Catalyzed CH Carboxylation/Carbonylation of (Hetero)arenes with CO
2
Authors: Fu Lei , Li Shangda , Li Gang
Published: October 2022

Although carbon dioxide (CO
2
) is known as the primary greenhouse gas, it is also considered by chemists as the ideal one‐carbon (C1) feedstock for producing valuable fine chemicals due to its abundant, inexpensive, nontoxic, and renewable properties. Nevertheless, the use of CO
2
in transition metal‐catalyzed CH carboxylation of arenes is a double challenge due to the inertness of both CO
2
and aryl CH bond. Herein, important achievements until September of 2021 in the field of transition metal‐catalyzed CH carboxylation of (hetero)arenes with CO
2
will be briefly discussed.
Platinum‐Catalyzed CC Bond Formation Through CH Functionalization
Authors: Huo Shouquan , Li Yumin
Published: October 2022

Platinum has played an important role in the discovery, understanding, and development of transition metal‐catalyzed CH activation and functionalization reactions. In this article, the platinum‐catalyzed CC bond formation through CH functionalization is discussed, which includes platinum‐catalyzed hydroarylation of alkynes and alkenes (sp
2
CH functionalization), hydrovinylation of alkynes and alkenes (sp
2
CH functionalization), hydroalkylation of alkynes (sp
3
CH functionalization), directing group‐assisted CH acylation (sp
2
CH functionalization), and aryl–aryl coupling (sp
2
CH functionalization) are reviewed. The mechanisms of these catalytic CH functionalizations are discussed. The synthetic utility of the methods developed based on these catalytic CH functionalization reactions has been demonstrated.
Transition Metal‐Catalyzed CH Functionalization of 2‐Pyridones, 2‐Pyrones, and Their Benzo‐Fused Congeners
Authors: Yamamoto Yoshihiko
Published: October 2022

2‐Pyridone, 2‐pyrone, and their benzo‐fused congeners are privileged heterocyclic scaffolds that are widely found in natural products and drug molecules. The late‐stage functionalization of CH bonds in these heterocyclic scaffolds has been an important research area in synthetic organic chemistry as they provide straightforward and easy access to valuable bioactive derivatives. This article outlines transition metal‐catalyzed CH functionalizations of 2‐pyridones, 2‐pyrones, and their benzo‐fused congeners. It can be classified into several major categories in terms of the methodologies involved: (i) intermolecular CH functionalization without the directing groups, (ii) intermolecular CH functionalization using directing groups, and (iii) intramolecular CH functionalization.
Rhodium‐Catalyzed Heterocycle Synthesis by CH Functionalization
Authors: Cao Yujie , Kou Kevin G. M.
Published: October 2022

Rhodium complexes of +1, +2, and +3 oxidation states are adept at functionalizing CH bonds and do so via distinct mechanistic pathways. These modes of activation have been harnessed into cascade processes that lead to a wide variety of heterocycles, including isoquinolines, isoquinolones, pyridines, pyridones, indoles, lactones, and their fused polycyclic derivatives. As such, this article will focus on the chemistry that enables de novo synthesis of heterocycles rather than those that only functionalize existing heterocycles.

This article is organized into three parts, starting with Part A, Rhodium(III) catalysis, which makes up the largest subfield of rhodium‐catalyzed heterocycle synthesis, and is further divided into the chemistry of alkynes, alkenes, carbenes, and nitrenes. Part B details rhodium(I) catalysis in the contexts of hydroalkenylation (e.g. alkynes), hydroarylation (e.g. alkynes), and hydroacylation (e.g. alkynes, alkenes, and ketones). The article closes with Part C, a brief discussion on the use of rhodium(II) catalysis in constructing heterocycles.
Development of Synthetic Approaches to Biaryl Sultams via CH Functionalization
Authors: Gupta Pankaj , Laha Joydev K.
Published: October 2022

Biaryl sultams represent a privileged molecular scaffold in drug discovery owing to their potential as a clinical candidate. Various developments toward the synthesis of diverse biaryl sultams including metal‐catalyzed and metal‐free CH functionalization involving CC/CN bond formation or annulative cyclization have been advanced in recent time. However, a transition metal‐catalyzed direct CH functionalization approach remains a powerful variant and has been utilized tremendously for the past several decades. The postsynthetic transformations of biaryl sultams to drug‐like molecules offer a tremendous possibility in drug discovery. In this article, we aim to provide an overview of various developments made in the synthetic approaches to biaryl sultams via CH functionalization, with a futuristic emphasis on their postsynthetic utility in accessing (hetero)biaryls containing an
ortho
‐sulfonamide or amine functionality, a promising and potentially useful molecular scaffold in therapeutic discovery. The current challenges and a future perspective are also discussed briefly.
CH Functionalization via Asymmetric Nitrene Transfer
Authors: Zerull Emily , Trinh Tuan Anh , Kim Jed , Schomaker Jennifer M.
Published: October 2022

The prevalence of amines in natural products and pharmaceuticals has stimulated interest in efficient, asymmetric methods to transform CH to CN bonds. Transition metal‐supported nitrene intermediates can undergo ready insertion into a variety of CH bonds via nitrene transfer (NT), provided the chemo‐, site‐, and enantioselectivity can be controlled in a predictive manner. In recent years, the field of transition metal‐catalyzed asymmetric nitrene transfer has grown rapidly with the design of new ligand scaffolds and the addition of a host of biocatalysts to the catalog of catalysts able to furnish diverse enantioenriched amine products. This article focuses on the recent advances in the arena of both intra‐ and intermolecular asymmetric CH aminations. The key differences between the types of catalysts utilized in asymmetric CH functionalization via NT will be highlighted, both in terms of the metal identity and ligand design. The article is organized by metal identity and concludes with a discussion of areas where opportunities and challenges still remain in the field.
CH Functionalization Utilizing CO Surrogates
Authors: Sheetal XXXXXXX , Das Parthasarathi , Das Pralay
Published: October 2022

Carbonyl group is one of the most imperative moieties in synthetic organic chemistry, it has found significant applications in pharmaceuticals, agrochemicals as well as polymer chemistry. The CO gas‐mediated carbonylation via direct CH bond functionalization renders a powerful technique to afford a range of carbonyl compounds in a highly expedient manner. However, the inflammable nature of colorless, odorless, and toxic CO gas along with difficulties associated with its storage and transportation limits the practical utility of these approaches. Hence, the thrust to devise CO gas‐free carbonylative approaches congregate the attention of the scientific community toward the development and application of sustainable CO surrogates from green chemistry viewpoint. The use of these CO surrogates instead of toxic CO gas contributes to enhanced practicality, efficiency as well as safety of the reaction performed. Hence, the direct CO gas‐free carbonylative CH bond functionalization emerged as an atom efficient as well as step‐economical protocol toward the sustainable development of carbonylation chemistry. Herein, we will discuss recent ameliorations realized in carbonylative CH functionalization reactions utilizing different CO surrogates.
CH Oxidative Functionalization Enabled Transformations of the Alkenes
Authors: Li Yang , Han Ya‐Fei , Li Jin‐Heng
Published: October 2022

Both the CH bonds and alkenes are abundant, readily available feedstocks, and have attracted much ongoing attention on the development of efficient methods for their ideal transformations. Methods that merge their transformations in a single reaction are particularly appealing due to their highest atom‐/step‐economy for constructing complex molecules. Here, recent advances in the CH oxidative functionalization enabled transformations of the alkenes are summarized. To date, a variety of CH bonds, including C(sp
3
)H and C(sp
2
)H bonds, underwent the functionalization across the CC bonds in alkene to enable the transformation of alkenes, such as difunctionalization of alkenes and alkylation/arylation of alkenes. These transformations of alkenes are achieved using two strategies, including the radical‐mediated oxidative strategy or transition‐metal oxidative catalysis.
Hypervalent Iodine and Sulfur‐Mediated CH Functionalization
Authors: Xu Zhenchuang , Cai Yanyao , Zhao Yanchuan
Published: October 2022

Hypervalent main group nonmetallic elements, such as iodine and sulfur, have attracted increasing attention owing to their unique reactivities. The facilely interconvertible valencies sometimes render these nonmetallic elements chemical behaviors analogs to transition metals, allowing diverse CH functionalizations to proceed in a green manner. Since their discovery, hypervalent iodine reagents have played a pivotal role in synthetic organic chemistry. Besides their usage as selective oxidants, hypervalent iodine reagents readily participate in single‐electron transfer processes to produce radical cation intermediates, enabling a variety of oxidative carbon–carbon and carbon–heteroatom bond formations. Direct CH functionalization of arenes, alkenes, and alkynes gives rapid access to aryl iodonium salts, which are easily transformed into other functionalities. Similarly, site‐selective CH thianthrenation proceeds smoothly upon suitable activation of sulfoxide reagents. The superior leaving ability and redox properties make the thianthrene moiety an ideal synthetic handle for structural diversifications via transition‐metal and photoredox catalysis. In this article, we focus on the hypervalent iodine and sulfur‐mediated CH functionalizations and describe their applications in carbon–carbon and carbon–heteroatom bond‐forming reactions. The rearrangement‐based CH functionalization will be briefly introduced where possible.
Sequential CH Functionalization in Complex Molecular Synthesis
Authors: Ma Hao‐Ran , Tang Can , Peng Xiao‐Shui
Published: October 2022

CH functionalization is a fundamentally important topic in organic synthesis. Sequentially, application of CH functionalization protocols in the complex molecular synthesis has already been proved to be a practical strategy. In this article, selected significant synthesis of complex molecules involving sequential CH functionalization approaches will be presented and classified into sp2and sp3carbon systems, demonstrating the advantages of the sequential CH functionalization protocol.
Manganese‐Catalyzed CH Bond Activation and Functionalization, From Mechanism to Applications
Authors: Burden Thomas J. , Eastwood Jonathan B. , Fairlamb Ian J.S. , Lynam Jason M.
Published: October 2022

Stoichiometric Mn(I) CH activation and functionalization reactions have seen a steady growth over the last 50 years, with particular interest in catalytic breakthroughs seen in the last 10 years. CH bond functionalization can take place in suitably activated unsaturated aromatic/heteroaromatic ring systems, containing a directing group for Mn(I), with activation typically occurring proximal (ortho) to the directing group. A range of Mn(I) carbonyl complexes can be used as precatalysts for a raft of transformations involving cyclomanganted intermediates and appropriate acceptor molecules, which brings about the formation of a plethora of organic and organometallic products. One of the limitations in Mn(I) carbonyl catalysis is the requirement for typically high catalyst loadings (10 mol% being common). Thus we have focused on mechanistic work that might help solve this problem, particularly if the promising reported synthetic chemistry of Mn(I) carbonyls is to be used more widely, particularly in industry. Finally, we showcase how time‐resolved IR spectroscopic methods are particularly useful for probing the mechanistic steps involved in CH bond activation catalysis, from picosecond to second timescale. The approaches used might be amenable to the study of other metal‐catalyzed processes.
CH Activation for the Synthesis of Organic Redox‐Active Compounds
Authors: Joo Jung Min
Published: October 2022

Organic redox‐active materials are used in several electrochemical applications; however, their application has expanded from conventional optoelectronic devices to new energy storage systems in recent years. Therefore, the design and synthesis of redox‐active organic compounds are critical for modulating their redox potentials, stability, solubility, and related properties to achieve optimal performance. Through a variety of CH functionalization reactions, the CH bonds of representative redox‐active cores, such as quinones, diimides, and ferrocenes, can be directly replaced to form new CC and C–heteroatom bonds. In addition to increasing the atom‐ and step‐economy, this late‐stage modification strategy allows for the preparation of structural analogs that are not readily accessible by conventional methods. This article reviews the position and type of substituents that can be added to these redox‐active cores, thus providing a perspective on CH functionalization and molecular engineering strategies that can be applied to fine‐tune redox‐active compounds.
Photocatalytic Hydrogen Atom Transfer Enabled Ni‐ and Cu‐Catalyzed C(sp
3
)H Functionalization
Authors: Zhu Shengqing , Qin Jian , Huo Liping , Zhang Yanyan , Chu Lingling
Published: October 2022

Transition metal‐catalyzed CH functionalization represents one of the most viably pursuing research areas in modern synthetic chemistry. Significant attention has been drawn to addressing the challenging functionalization of C(sp
3
)H bonds, particularly un‐activated C(sp
3
)H bonds. Among various strategies, hydrogen atom transfer (HAT) represents a distinct yet attractive approach for the direct and selective functionalization of C(sp
3
)H bonds. This article highlights the recent development of photochemical HAT‐enabled nickel and copper‐catalyzed selective functionalization of C(sp
3
)H bonds, with a particular emphasis on reaction development and mechanistic discussions.
CH Functionalization by Weak Interactions
Authors: Bera Shyamal K. , Bose Anima , Mal Prasenjit
Published: October 2022

Transition metal‐catalyzed CH functionalization or activation reactions of organic compounds have witnessed a broad avenue in the synthesis. However, the metal‐free CH functionalization reactions are relatively less explored. In addition, the research area to control the chemical reactions by various cooperative noncovalent or weak interactions has also appeared to be one of the widespread research topics in supramolecular catalysis. In this article, attempts have been made to collect the literature which utilizes hydrogen bonding (H‐bonding) and halogen bonding (XB) interactions toward CH functionalization reactions.
CS Bonds via CH Functionalization
Authors: Pramanik Milan , Mal Prasenjit
Published: October 2022

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The development of CS bonds‐making methodology is mainly explored by condensing metal thiolate with prefunctionalized organic substrates. However, the synthesis of CS bonds via CH functionalization reactions has a significant impact on organic chemistry. Herein, we have collected the literature based on various CS bond formation reactions via CH functionalizations. This article has been subdivided into four categories: (i) metal‐catalysis, (ii) metal‐free reagent, (iii) photoredox catalysis, and (iv) electrochemical‐based.
Recent Advances in Multicomponent Reaction Through CH Bond Functionalization
Authors: Nanda Tanmayee , Mohanty Smruti R. , Ravikumar Ponneri C.
Published: October 2022

Multicomponent reactions (MCRs) serve as a strategic tool for the synthesis of complex molecular architecture in just one step, and hence, it has been an attractive area of research for the synthetic community. In recent years, transition metal‐catalyzed CH bond activation/functionalization has taken the center stage of organic synthesis on account of step and atom economy. The combination of these two enabling methodologies provides a wide opportunity to diversify and enrich the known molecular library. In this regard, MCRs involving transition metal‐catalyzed CH bond activation strategy have been studied in the past few years, which led to many pathbreaking discoveries. This article aims to provide comprehensive knowledge to the reader about MCRs involving the CH bond activation strategy as a key threshold step.
Heterogenous Palladium‐Catalyzed CH Functionalization Reactions
Authors: Liu Dan , Bao Yong‐Sheng
Published: October 2022

Direct CH bond functionalization to construct carbon–carbon bonds has been known as a chemical economic strategy for sustainable syntheses. Especially, palladium‐catalyzed CH functionalization has been extensively studied and proved to be the most efficient and powerful protocol to assemble complex compounds, but this approach was limited by the high price and heavy metal pollution of homogeneous Pd catalysts. To improve the chemical economic and environmentally benign Pd‐catalyzed CH functionalization, heterogeneous Pd nanoparticles were used as catalysts, which can be recovered and reused. This article presented the advances in the heterogeneous Pd nanoparticles with a variety of supporting materials that was applied to catalyze CH functionalization reaction. The common characteristics of the heterogeneous Pd catalyst are recommended, after which methods of Pd nanoparticle catalyst preparation and reactions catalyzed by them are also described.
Inkjet‐Printed, Large‐Area, Flexible Photodetector Array Based on Electrochemical Exfoliated MoS2 Film for Photoimaging
Authors: Kong Lingxian , Li Guangliang , Su Qi , Zhang Xuning , Liu Zhiyong , Liao Guanglan , Sun Bo , Shi Tielin
Published: October 2022

Although a variety of MoS2‐based photodetectors have been reported over the last few years, the controlled fabrication of large‐area photodetector array for photoimaging remains a major challenge due to the low yield and poor quality of MoS2 film. Herein, a high‐performance inkjet‐printed flexible photodetector array based on stacked MoS2 nanosheets is demonstrated for the first time. The 2H phase MoS2 nanosheets is obtained by intercalating quaternary ammonium cation into MoS2 bulk. The inkjet‐printed photodetector achieves excellent performance with a highest responsivity of 552.5 A W−1, detectivity of 1.19 × 1012 Jones, and fast response and recovery time of 23 and 26 ms, respectively, at room temperature. Furthermore, a photodetector array with 85 pixels per inch is successfully constructed, and the letter of “T” is clearly recognized. These results indicate that electrochemical exfoliation coupled with inkjet printing has great prospect for application in high‐performance photodetector array. Besides, the electrochemical exfoliation is also successfully applied to obtain the ink of In2Se3, black phosphorus (BP), and MoTe2. It is believed that this work paves the way for various potential printable optoelectronics based on 2D materials.
Multimaterial 3D Printing Technique for Electronic Circuitry Using Photopolymer and Selective Metallization
Authors: Ryspayeva Assel , Zhakeyev Adilet , Desmulliez Marc P. Y. , Marques-Hueso Jose
Published: October 2022

Herein, a 3D printing technique to enable the manufacturing of selectively plated polymer objects by photopolymer printing and copper metallization is presented. Metallized plastic has become popular in a number of industries due to its lightweight, flexibility of design, and cost‐effective fabrication. Common metallization techniques require multiple pretreatment steps, such as surface etching, sensitization/activation, and acceleration. The proposed method, by eliminating the sensitization step, allows selective metallization of 3D‐printed samples by direct plating. The method relies on the inclusion of silver seeds into a mixture of acrylate‐ and methacrylate‐based monomers and oligomers, which enables direct electroless copper metallization following 3D printing. Ag(I) ions act as catalytic sites for copper deposition. Copper films grown with embedded 2 and 4 wt% Ag(I) seeds reach thicknesses of 5.7 ± 1.2 and 7.7 ± 1.3 μm, respectively. Furthermore, printing with pristine and silver‐modified resins on the same sample allows selective plating: only the modified resin is plated leaving the pristine resin unaffected. A proof‐of‐concept temperature sensor is manufactured to demonstrate the performance of the printed interconnects.
Design and Synthesis of Carbazole‐Cyclopentathiophene Alternating Copolymers for Inhibiting Phase Separation of Cs0.15FA0.85PbI3
Authors: Tan Yulin , Wan Li , Zhao Yang , Lou Lingyun , Wang Zhong‐Sheng
Published: October 2022

To inhibit phase separation of CsxFA1−xPbI3 perovskite into optically inactive δ‐CsPbI3 and δ‐FAPbI3 under high humidity and light conditions, herein two polymers, poly[3‐methyl‐6‐(2‐methylspiro[cyclopenta[1,2‐b:5,4‐b′]dithiophene‐4,2′‐[1,3]dithiolan]‐6‐yl)‐9‐octyl‐9H‐carbazole] (TM3) and poly[3‐methyl‐6‐(2‐methylspiro[cyclopenta[1,2‐b:5,4‐b′]dithiophene‐4,2′‐[1,3]dioxolan]‐6‐yl)‐9‐octyl‐9H‐carbazole] (TM4), are designed and synthesized to dope the Cs0.15FA0.85PbI3 perovskite film for perovskite solar cells (PSCs). The results of X‐ray photoelectron spectroscopy and nuclear magnetic resonance confirm the existence of coordination and hydrogen bonds between the polymer and Cs0.15FA0.85PbI3 perovskite. Ion migration in the perovskite film is thus markedly suppressed by the TM doping, as verified by the electrical poling measurement. Benefiting from these interactions, the TM doping is able to inhibit phase separation of Cs0.15FA0.85PbI3 markedly at a relative humidity of 55–65% and under light. Furthermore, the TM doping has other positive effects such as enhancing perovskite crystallinity, improving crystal growth orientation, reducing trap density, increasing hole extraction, and suppressing charge recombination. Consequently, the TM3‐ and TM4‐doped PSCs achieve a power conversion efficiency of 21.96% and 20.01%, respectively, against 17.82% for the undoped PSC. The humidity, environmental, illumination, and thermal stabilities of unencapsulated devices are also improved significantly by the TM3‐ and TM4‐doping, respectively. By comparison, TM3 with the S substitution shows abetter effect than TM4 with the O substation on photovoltaic performance and device stability.
Engineering Interfacial Effects in Electron and Phonon Transport of Sb2Te3/MoS2 Multilayer for Thermoelectric ZT Above 2.0
Authors: Ahmad Mujeeb , Agarwal Khushboo , Munoz Sergio Gonzalez , Ghosh Abhishek , Kodan Nisha , Kolosov Oleg Victor , Mehta Bodh Raj
Published: October 2022

Efficient thermoelectric (TE) conversion of waste heat to usable energy is a holy grail promising to address major societal issues related to energy crisis and global heat management. For these to be economical, synthesis of a solid‐state material with a high figure‐of‐merit (ZT) values is the key, with characterization methods quantifying TE and heat transport properties being indispensable for guiding the development of such materials. In the present study, a large enhancement of the TE power factor in Sb2Te3/MoS2 multilayer structures is reported. A new approach is used to simultaneously experimentally determine the values of in‐plane (kxy) and out‐of‐pane (kz) thermal conductivities for multilayer samples with characteristic layer thickness of few nanometres, essential for the quantification of the ZT, the key parameter for the TE material. Combining simultaneous enhancement in the value of in‐plane power factor (to (4.9 ± 0.4) × mWm−1 K−2) and reduction of the in‐plane value of the thermal conductivity (to 0.7 ± 0.1 Wm−1 K−1) for Sb2Te3/MoS2 multilayer sample led to high values of ZT of 2.08 ± 0.37 at room temperature. The present study, therefore, sets the foundation for a new methodology of exploiting the properties of 2D/3D interfaces for the development of novel fully viable thermoelectric materials.
Solution Plasma Processing Single‐Atom Au1 on CeO2 Nanosheet for Low Temperature Photo‐Enhanced Mars–van Krevelen CO Oxidation
Authors: Xing Yanmei , Wang Changhua , Li Dashuai , Wang Rui , Liang Shuang , Li Yuanyuan , Liu Yichun , Zhang Xintong
Published: October 2022

Creating oxygen vacancies in metal oxide support holds promise in anchoring and stabilizing single atom metals, activating the lattice oxygen of metal oxide and accelerating Mars–van Krevelen (MvK) catalytic oxidation. However, it is challenging to achieve nearly 100% trapping of single atom metal in solution by oxygen vacancy typed metal oxide, resulting from the difficulty in synchronized formation of oxygen vacancies and capture of the single atom metal. In this study, a solution plasma process (SPP) is developed, enabling ≈99% trapping of single atom Au by using oxygen vacancy typed CeO2 nanosheet in 2 min. Owing to the large number of electrons and free radicals present in the plasma region, the SPP can simultaneously reduce HAuCl4 to single‐atom Au and bring oxygen vacancies as anchoring sites onto CeO2. The catalytic test of CO oxidation assisted by solar light can reach a conversion of 91.7% with a high turnover frequency of 1.3 s−1 at room temperature, far exceeding the requirements for the “150 °C challenge.” A photo‐enhanced MvK pathway is proposed for the superior performance of Au1/CeO2. This study not only explores a novel solution approach to prepare single‐atom metal catalysts, but also provides an effective strategy for efficient low‐temperature catalytic oxidation.
Self‐Passivated Metal Klein Edge of 1T‐Phase Transition Metal Dichalcogenides and the Induced High‐Efficient Hydrogen Evolution Reaction Activity
Authors: Liu Yue , Li Da , Cui Tian
Published: October 2022

The pristine edge of a 2D material generally undergoes an edge self‐passivation into its ground‐state configuration. To date, several self‐passivated edges of 1H‐phase transition metal dichalcogenides (TMDCs) have been reported in theories and experiments. However, no self‐passivated edges of its sister material 1T‐phase TMDCs are found. Here, taking 1T‐VS2 as an example, a self‐passivated V2 dimer‐like metal Klein (DM‐Klein) edge of 1T‐TMDCs is reported. It exhibits high thermodynamic stability and can spontaneously form at V‐rich chemical potential conditions. Unexpected intermetallic d–d orbital interaction of edge metal atoms results in metal dimerization. This edge self‐passivation mode is universal in group IV and V 1T‐TMDCs. Furthermore, strong intermetallic interaction and appropriate edge sulfur saturation make DM‐Klein edges of 1T‐TMDCs show excellent catalytic activity in the hydrogen evolution reaction compared to that of well‐known Pt(111) surface. This study provides opportunities for the further practical application of 1T‐TMDCs in catalysts.