bluuebunny/crossref_metadata_2025 huggingface dataset:
Parental Defenses in Interactions with the Police
Authors: Gashi Liridona
Published: May 2024

Decades of stigma research has shown that people draw on different coping strategies to manage stigma in their daily lives. Yet, scholar have paid less attention to how people deal with and manage feelings of stigma as they arise in ongoing interactions. Drawing on observations of police‐parent interactions, in this study I identify four common ways that parents of young offenders respond to police interventions: compliance, passivity, minimization of severity, and defensive attacks. I discuss how these parental responses shape and change the interactional dynamics between police and parents, and how they simultaneously may help the parents protect and regulate their sense of parental identity in interaction. Finally, although the stigma defenses I identify are based on police‐parent interactions, I conclude that the same responses may be found in other relatable fields and interactions.
Conceptual contamination: Investigating the impact of misinformation on conceptual change and inoculation strategies
Authors: Danielson Robert W. , Heddy Benjamin C. , Ramazan Onur , Jin Gan , Gill Kanvarbir S. , Berry Danielle N.
Published: May 2024

Misinformation has been extensively studied as both maliciously intended propaganda and accidentally experienced incorrect assumptions. We contend that “conceptual contamination” is the process by which the learning of incorrect information interferes, pollutes, or otherwise disrupts the learning of correct information. This is similar to a medical model of disease transmission wherein misinformation travels from person to person via multiple methods. And just as we can inoculate the public against diseases like smallpox or measles, we suggest this same approach (providing refutations to misconceptions that individuals may not have read yet) can inoculate the public from misconceptions. We sought to examine whether we could inoculate against misconceptions, and if so, would a refutation text outperform a more traditional expository text. We also sought to examine the role of emotions and attitudes. We randomly assigned 152 undergraduate students to one of four experimental conditions comparing both text type (refutation vs. expository) and text order (misconception first or second) on their ability to overcome misconceptions. Our findings indicate that reading refutation texts led to significantly fewer misconceptions and reduced negative emotions. We also illustrate that the prevailing approach to countering misinformation—providing expository support after exposure to misinformation—performed the worst overall. Our findings suggest that refutation texts continue to provide significant reductions in misconceptions, and that overall misconceptions can be reduced regardless of text type, if the correct information can precede misinformation.
Physiological, molecular, and environmental insights into plant nitrogen uptake, and metabolism under abiotic stresses
Authors: Akhtar Kashif , Ain Noor ul , Prasad P. V. Vara , Naz Misbah , Aslam Mehtab Muhammad , Djalovic Ivica , Riaz Muhammad , Ahmad Shakeel , Varshney Rajeev K. , He Bing , Wen Ronghui
Published: May 2024

Nitrogen (N) as an inorganic macronutrient is inevitable for plant growth, development, and biomass production. Many external factors and stresses, such as acidity, alkalinity, salinity, temperature, oxygen, and rainfall, affect N uptake and metabolism in plants. The uptake of ammonium (NH4+) and nitrate (NO3−) in plants mainly depends on soil properties. Under the sufficient availability of NO3− (>1 mM), low‐affinity transport system is activated by gene network NRT1, and under low NO3− availability (<1 mM), high‐affinity transport system starts functioning encoded by NRT2 family of genes. Further, under limited N supply due to edaphic and climatic factors, higher expression of the AtNRT2.4 and AtNRT2.5T genes of the NRT2 family occur and are considered as N remobilizing genes. The NH4+ ion is the final form of N assimilated by cells mediated through the key enzymes glutamine synthetase and glutamate synthase. The WRKY1 is a major transcription factor of the N regulation network in plants. However, the transcriptome and metabolite profiles show variations in N assimilation metabolites, including glycine, glutamine, and aspartate, under abiotic stresses. The overexpression of NO3− transporters (OsNRT2.3a and OsNRT1.1b) can significantly improve the biomass and yield of various crops. Altering the expression levels of genes could be a valuable tool to improve N metabolism under the challenging conditions of soil and environment, such as unfavorable temperature, drought, salinity, heavy metals, and nutrient stress.
Tumour or haemorrhage?: Differential diagnosis of an unknown mass within the brain of a budgerigar (Melopsittacus undulatus) using a novel imaging pipeline
Authors: Vasquez Tatiana , Gignac Paul M. , Brewer Peter , Gold Maria Eugenia Leone
Published: May 2024

We report on a previously healthy zoo specimen of an adult budgerigar (Melopsittacus undulatus, obtained with permission from Southwick's Zoo) found deceased in its enclosure. To assess cause of death and ensure the absence of an infectious neoplasia, we used an integrated multiscale brain‐imaging workflow, previously only used on mammals. The specimen was imaged with microcomputed tomography before and after enhancing soft‐tissue contrast with diffusible iodine‐based contrast‐enhanced microcomputed tomography. Scans revealed an orbital blowout fracture and an unidentified large mass across majority of the diencephalon, striatum and midbrain caudal to the right orbit. After destaining, neural pathohistology confirmed the mass as a brain haemorrhage with no evidence of neoplasia or inflammation. We conclude that this specimen died of head trauma, likely from a head‐on collision within its enclosure. This multiscale imaging workflow (diffusible iodine‐based contrast‐enhanced microcomputed tomography followed by destaining and pathohistology) can improve our evaluation of differential diagnoses in avian specimens.
Computed tomography angiographic findings following gradual occlusion of the dorsal sagittal sinus for definitive excision of a caudal calvarial multilobular tumour of bone in a dog
Authors: Moore Vaughan W. , Lam Richard , Bennett Tristram
Published: May 2024

Multilobular tumour of bone is a rare, slow growing, locally aggressive malignancy in dogs. Surgical resection of the primary tumour is currently the recommended treatment for local disease control. Wide or definitive extent excision to obtain a histologically complete excision is ideal when possible; however, wide excision can be challenging for caudally located calvarial tumours in which the excision will include removal of the confluence of the two transverse sinuses and dorsal sagittal sinus. Acute sacrifice to the dorsal sagittal sinus has the potential for fatal cerebral oedema. To manage this risk, gradual occlusion of the dorsal sagittal sinus before wide excision of caudally located multilobular tumour of bones has been successfully reported in two patients. The current case report documents another successfully managed case with this technique, and includes the computed tomography angiographic findings during the gradual occlusion process.
The fallacies of globalization: Development or underdevelopment in India?
Authors: Lahiry Sujit
Published: May 2024

Globalization heralded the world economy in the 1980s, even though its policy prescriptions were laid out more broadly by neoliberal theorists in the 1960s and 1970s. Globalization endorsed the neoliberal policies of free trade and the free market economy as a counter‐narrative to the growing resurgence of the models of “social democracy” in the post‐Second World War period. This article seeks to unravel the inequalities and inequities brought in by the policies of globalization through the prisms of the Indian experience. Through a thorough analysis of the human development index (HDI) indicators, we can only agree with dependency theorists like Andre Gunder Frank and Immanuel Wallerstein that globalization has accentuated the miseries and underdevelopment of a developing country like India. It has exacerbated the class differences between the rich and the poor and deepened poverty, inequality, and unemployment in India.
Drivers, changes, and impacts of hydrological extremes in India: A review
Authors: Mishra Vimal , Nanditha J. S. , Dangar Swarup , Chuphal Dipesh Singh , Vegad Urmin
Published: May 2024

The frequency of hydrological extremes (droughts and floods) has increased in recent years in India. A dense population, intensive agriculture, and rapidly developing physical infrastructure put India under the risk of hydrological extremes. However, a comprehensive overview of the drivers, changes, and impacts associated with hydrological extremes in India has been lacking. We examine the key processes and the role of climate and human interventions on hydrological extremes in India. We discuss the observed and projected changes in hydrological extremes along with their impacts. While the Indian summer monsoon is the primary driver of the hydrological extremes in India, human interventions (irrigation, reservoir storage, and groundwater pumping) play a crucial role in the changes and variability of hydrological extremes. The relative role of climate change and direct human interventions on changing the intensity and impacts of hydrological extremes need to be considered for future adaptation planning under climate change. The observed increase in the frequency and intensity of hydrological extremes will continue in the future with compound and cascading impacts due to the warming climate. We need to strengthen the observational network, improve hydrological modeling, reduce climate uncertainty, and develop robust early warning systems to adapt and mitigate hydrological extremes in India.

This article is categorized under:

Science of Water > Hydrological Processes

Science of Water > Water Extremes

Science of Water > Water and Environmental Change
Effects of transcutaneous electrical nerve stimulation on recovery of gastrointestinal motility after laparotomy: A randomized controlled trial
Authors: Karthik N. , Lodha Mahendra , Baksi Aditya , Dutt Akshat , Banerjee Niladri , Swathi M. , Choudhary Indra Singh , Meena Satya Prakash , Sharma Naveen , Puranik Ashok Kumar
Published: May 2024

Introduction

Postoperative Ileus (POI) negatively impacts patient outcomes and increases healthcare costs. Transcutaneous electrical nerve stimulation (TENS) has been found to improve gastrointestinal (GI) motility following abdominal surgery. However, its effectiveness in this context is not well‐established. This study was designed to evaluate the role of TENS on the recovery of GI motility after exploratory laparotomy.

Methods

Patients undergoing exploratory laparotomy were randomized in a 1:1 ratio into control (standard treatment alone) and experimental (standard treatment + TENS) arms. TENS was terminated after 6 days or after the passage of stool or stoma movement. The primary outcome was time for the first passage of stool/functioning stoma. Non‐passage of stool or nonfunctioning stoma beyond 6 days was labeled as prolonged POI. Patients were monitored until discharge.

Results

Median (interquartile range) time to first passage of stool/functioning stoma was 82.6 (49–115) hours in the standard treatment group and 50 (22–70.6) hours in the TENS group [p < 0.001]. Prolonged POI was noted in 11 patients in the standard treatment group (35.5%) and one in the TENS group (3.2%) [p = 0.003]. Postoperative hospital stay was similar in the two groups.

Conclusion

TENS resulted in early recovery of GI motility by shortening the duration of POI without any improvement in postoperative hospital stay.

Trial Registration Number

CTRI/2021/10/037054.
What’s So Special About Private Parts? How Anthropology Questions the Public–Private Dichotomy
Authors: Hawkins Simon
Published: May 2024

Following the anthropological model, this chapter examines the concept of privacy from a cross-cultural perspective, showing how its meaning and experience varies enormously. Privacy is not an objective, consistent quality of an activity or situation, because privacy is always rooted in the specific socio-economic structures of each society. It is not a case of societies and groups being more private than others, but having contrasting views on what is private. The category of private is not independent, but always exists in comparison to what is public. Drawing on examples from western and middle eastern societies, this chapter illustrates how that ideological pair is in turn linked to other ideological pairs, such as male/female and modern/traditional. More than simply arguing that differing understandings of privacy are due to cultural relativism, this chapter shows that even within a society, shifting contexts drive categorization. Within a culture, any given setting may manifest as either private or public. When people define it as one or the other, they highlight elements of that setting, asserting that those are the most relevant.
Privacy in the Digital Age: Navigating the Risks and Benefits of Cybersecurity Measures
Authors: Farnell Christopher , Huff Philip , Cox William
Published: May 2024

This chapter provides an overview of privacy and cybersecurity, classifies, and describes various attack vectors, presents best practices to mitigate potential attacks, discusses relevant standards, and offers concluding remarks. Privacy differs from cybersecurity because individuals control the policy. The dynamic protections apply through user consent, data labeling, and contextual access management. We explore how systems align privacy controls into their cybersecurity plans using the privacy control catalog in NIST 800-53 revision 5 and examine the future of privacy controls in a system security setting.
Web2 Versus Web3 Information Privacy: An Information Systems Discipline Perspective
Authors: Lacity Mary C. , Carmel Erran
Published: May 2024

This chapter has two purposes. First, we describe how information system (IS) scholars approach privacy research and summarize major findings. IS scholars are concerned withinformation privacyand have discovered that individuals have serious information privacy concerns. These concerns, however, do not prevent individuals from disclosing personal identifiable information (PII) with centralized platform providers, a phenomenon called theprivacy paradox. We highlight four common explanations for the privacy paradox: privacy calculus, privacy fatigue, trust, and lack of choice. Most IS research investigated Web2 applications. Web2 is the foundation for today’s global economy. With Web2, users rely on centralized platforms for online searching, shopping, banking, data storage, social media, and other services. Second, we introduce readers to the new paradigm of Web3. Privacy protection has been the paramount logic behind the grand design of Web3 applications. Web3 is the era of the Internet that is based on decentralized infrastructures and applications, like Bitcoin and Ethereum. Web3 applications enhance information privacy compared to Web2 because individuals can access services without disclosing PII to a central authority. The privacy objective is achieved technically through a combination of digital wallets, cryptography, and distributed ledgers (a.k.a blockchain). While Web3 is still in its early days, education is an important driver of adoption.
Multi-party Computation: Privacy in Coopetition
Authors: Conway Daniel , Garimella Kiran K.
Published: May 2024

While it may not always be possible to choose who follows you on social media or who gains access to your search history, Multi-Party Computation (MPC) empowers users to select their friends. Privacy environments often approach privacy as a binary property, but MPC offers more privacy granularity, a choice of when to participate, and the ability to initiate a session with a selection of peers. Also, privacy protection occurs at a transaction level and can change with every engagement. MPC offers a way to obtain specific information from friends while preserving the privacy of the data and/or the connection of data to the owner.
An Architect’s View of Privacy
Authors: Blackwell Marlon , Coon Lynda , Lacity Mary C.
Published: May 2024

Marlon Blackwell is the E. Fay Jones Chair in Architecture and a Distinguished Professor in the Fay Jones School of Architecture and Design at the University of Arkansas in Fayetteville. He’s earned many awards, including the 2020 AIA Gold Medal, which is the highest honor awarded by the American Institute of Architects (AIA). In addition to being a full-time faculty member, he is also the founder and the principal at Marlon Blackwell Architects (MBA), based in Fayetteville Arkansas. His lecture on “architectural privacy” was the most popular in the University of Arkansas Honors course on privacy. We interviewed him in June of 2023 to capture his design philosophy in relation to privacy. The conversation focused on four architectural privacy themes: (1) the relationship between privacy and comfort, and the roles of (2) primary, secondary, and tertiary spaces, (2) light, and (3) sounds in creating private moments in public spaces. A fifth theme encapsulates the essence of his design philosophy: “ennobling the prosaic.”
Music as a Vehicle for Climate Change Communication: The ClimateMusic Project
Authors: Dixon Catherine Emma , Goldman Laurie S. , Crawford Stephan , Lease Phoebe Camille
Published: May 2024

Climate change is often communicated in a scientific manner that fails to capture lay audiences emotionally, resulting in a lack of motivation to take action. Studies show that narrative is an effective strategy for engaging the emotional response to scientific information that is necessary to encourage community participation and action. Music can reliably express, modulate, and induce emotional states, and, as a temporal art form, may be a particularly effective vehicle for conveying narrative. This chapter reviews the evidence for music-based approaches to emotional engagement, information delivery, psychological well-being and social cohesion, and their application in climate change communication. The authors discuss the methodologies used in The ClimateMusic Projects compositions and performances, as well as their outreach projects and partnerships. Lastly, the authors examine future opportunities in climate communication, including potential funding sources.
Telling the Story of Climate Change through Food
Authors: Eiseman Danielle L. , Hoffmann Michael P.
Published: May 2024

The impacts of climate change continue to magnify, having devastating effects on populations across the world. Despite the mounting evidence that climate change will continue to intensify and it is due to human activities, humanity is slow to act. To encourage wider action among the public, this chapter discusses the use of food to tell the story of climate change, a growing yet underexplored area of research. The chapter first discusses the current state of food and climate change as an engagement tool. Next, the chapter describes how both food storytelling can overcome some of the challenges within the field of climate change communication. Lastly, the chapter provides examples of how food storytelling techniques can enhance engagement with climate change solutions and shift eating patterns.
Instructional Strategies for Climate Education in the Classroom: Storytelling about Our Place in the Earth System
Authors: Bean Jessica R.
Published: May 2024

It is essential that we prepare tomorrow’s scientists, engineers, and communities to respond to the ongoing climate and environmental crises to plan for a sustainable future. Successfully addressing these needs requires contextualizing learning and using student-centered teaching practices that help learners construct an understanding of the world around them. For this reason, local phenomena can successfully anchor instructional storylines—coherent sequences of lessons that connect to students’ lives and engage them in synthesizing various scientific concepts to explain how the world works and why it changes through time. Students should reflect on how they are a part of the Earth system, and how individual and collective actions can address climate and environmental problems. These shifts in teaching practices are supported by tools developed by the Understanding Global Change (UGC) Project at the University of California Museum of Paleontology to investigate the causes, consequences, and solutions to the climate crisis.
The Power of Locally Driven Narratives to Support and Sustain Climate Action
Authors: Brown Neemesha 
Published: May 2024

This chapter will explore the value of entertainment-education applications that center narratives that originate from the local context. The discussion will examine how centering narratives informed by local points of view have the potential to create the conditions for climate solutions to be optimally contextualized in the socio-cultural context of intended audiences. This optimal contextualization can lead to deeper engagement with the entertainment-education application and greater impact. The chapter will illustrate these concepts through two examples, the Sustainable and Thriving Environments for West Africa Regional Development (STEWARD) Program administered by the US Forest Service—International Programs Department, West Africa Biodiversity and Climate Change (WA BiCC) Program funded by and administered by USAID. Using these examples, the chapter will demonstrate how PCI Media’s My Community methodology allows local actors to authentically engage in a participatory approach to the narrative development process as part of an entertainment-education program.
Positively Life-Changing Stories Today, Intergenerational Climate Benefits Tomorrow
Authors: Bish Joseph J.
Published: May 2024

Today, popular entertainment is purposefully creating a more sustainable world. Locally produced radio and video series, created from applied theories of social learning and social cognition, feature relatable characters, familiar communities, and dramatically unfolding plots. Constructed to improve human health and human rights, these stories also offer audiences liberating information, alternative perspectives, and confidence to enact meaningful change in their own lives. Unrestricted access to family planning and universal girls’ education is instrumental in realizing the full human rights of women and girls around the world. Moreover, by destigmatizing voluntary family planning, correcting misinformation about the safety and efficacy of modern contraception, and strengthening social acceptance and support of girls’ education, the long arc of human population size is influenced toward a smaller, more sustainably scaled civilization in the future. This relatively smaller human presence on the planet offers many potential alleviations of human-induced environmental stress, including scaling down the basic human need for, and propensity to emit, greenhouse gas emissions in the future.
Let’s Go! Let’s Know! N*Gen as an EE Tool for Climate Education and Agency
Authors: Falzone Paul , Kiano Joy , Lukomska Gosia
Published: May 2024

Sub-Saharan Africa is incredibly vulnerable to the increasing impacts of climate crisis. With a median age of 19 years old, it is also home to the largest youth population in the world. How this population understands their relationship to science and nature can have incredible impacts moving forward. The case study in this chapter is N*Gen, the first cross-African science TV show for kids. Filmed across Kenya, Nigeria, Tanzania, South Africa, Uganda and Zambia, its goals are to elevate girls and women in STEM, increase trust in science and scientists, and help give people the critical thinking tools to fight misinformation by exploring a range of topics, including ocean conservation, ecosystem change, zoology, vaccines, and human–wildlife interactions. This chapter also details broader aspects of the media landscape in Sub-Saharan Africa, existing science education efforts, and opportunities to use media to change knowledge, attitude, and behavior related to the climate crisis.
Rewrite the Future: Helping Hollywood Accelerate Climate Solutions through Storytelling
Authors: Hinerfeld Daniel , Slean Cheryl , Jacobs Katy
Published: May 2024

Rewrite the Future is an initiative of NRDC (the Natural Resources Defense Council) launched in 2020 to help Hollywood tell stories about climate change. Our team assessed the social impact entertainment landscape and interviewed over 50 entertainment professionals. We determined that concerted advocacy, outreach, and education were needed to position climate entertainment as a powerful strategy for social change. We developed a program offering climate storytelling events, workshops, consultations, publications, and diverse partnerships. The centerpiece of Rewrite the Future is climate story consulting to help entertainment-makers engage creatively with a range of topics that best pertain to their show or film. Consultations are customized to interact with each story on its own terms and defer to storytellers’ expertise in entertainment. Early outcomes of Rewrite the Future’s programs will be reported including successful story placements and evidence of a growing community of climate story practitioners in the entertainment sector.
Overcoming Stigma: The Human Side of Monkeypox Virus
Authors: Umar Tungki Pratama , Jain Nityanand , Sayad Reem , Tandarto Kevin , Jain Shivani , Reinis Aigars
Published: May 2024

Monkeypox (Mpox) virus is a zoonotic disease that was recently declared a public health emergency of international concern (PHEIC) by the World HealthOrganization (WHO). Symptoms of Mpox include fever, headache, muscle pain, and a rash which starts on the face and spreads to the rest of the body. The stigma surrounding the Mpox virus has been one of the greatest challenges in dealing with the disease. People with Mpox have been often shunned by their communities, and many are afraid to seek medical care for fear of ostracism. For those affected by the virus, this stigma can significantly impact their mental health and quality of life. It is further fueled by misinformation and societal norms. Hence, a multifaceted approach that includes education, awareness campaigns, and community engagement is needed to overcome the stigma associated with Mpox. Effective communication strategies are critical to the dispelling of rumors and the reduction of fear. Interventional measures need to be shaped according to the needs of those affected.
Rational Executives and Selfish Politicians: The Cultural Repertoires of Legal Experts
Authors: Trombini Maria Eugenia , Valarini Elizangela
Published: May 2024

Grand corruption affairs, and the arrest of politicians and high-ranking executives, has ignited the debate about the strategic action of law enforcers and the effects produced on democracy and political institutions. Other authors have already focused on the political uses of Law and the consequences of the fight against corruption in Brazil. But after all, what do legal professionals, working inside and outside the administration of justice, think about the people labeled white-collar criminals in the cases they sentence, accuse, and defend? The objective of this work is to advance the research agenda on the point of convergence between Law and Politics by shedding light on the action orientation of members of the justice system.
Moro’s Opinions: A Quantitative Analysis of Sentencing in Operation Car Wash
Authors: Da Ros Luciano , da Fontoura Luísa Zanini , Junior Sérgio Simoni , Taylor Matthew M.
Published: May 2024

Despite growing numbers of cases around the globe, the literature on judicial decision-making in corruption prosecutions remains underdeveloped. Why do judges convict some defendants in corruption cases and not others? Why do judges apply harsher sentences to some defendants than others? In sum, what explains variation in the severity with which the judicial system judges public figures and private citizens accused of corruption? This chapter draws on the experience of Brazil’s Operation Car Wash (Lava Jato, in Portuguese) to begin to address these questions.
Businessmen, Political Financing, and Corruption: Odebrecht in Operation Car Wash
Authors: Costa Paulo Roberto Neves , Ferreira Silvana Zulmira , de Campos Marta Pontes
Published: May 2024

This chapter presents the results of the testimony analysis of Odebrecht businessmen who were involved in Operation Car Wash, specifically concerning illegal political financing. This approach was made through the analytical category of representation, and it allowed us to verify a specific and little-explored dimension of the political culture and the political action of the businessmen: the practice of corruption, that is recognised as an illegal action. The analysed statements indicate a certain homogeneity in the characterisation of the company’s political illicit practice and the relationship with the political system as something that was given and that could not be done differently. Thus, both concerning the legal and illegal scope of the company’s political actions, there was an allegation of impotence in the face of how the relationship between businesspeople and politicians in Brazil took place, which shows an essential aspect of the way influential Brazilian businesspeople thought and how they acted in the face of politics and democracy.
A Journey to the Total Synthesis of Brasilicardins
Authors: Itoh Ryusei , Tanino Keiji , Yoshimura Fumihiko
Published: May 2024

C(sp3)-rich natural products with quaternary carbon stereocenters have recently received increasing attention as formidable synthetic targets and higher lead and drug compounds. Among them, brasilicardins, which are terpenoids–amino acids–saccharide(s) hybrids, share a unique and highly strained anti-syn-anti-fused 6,6,6-tricyclic terpenoid skeleton containing two adjacent quaternary carbon stereocenters and have attracted attention as promising immunosuppressive drug lead compounds. Herein, we describe our endeavor toward a unified total synthesis of brasilicardins A–D, focusing on overcoming various synthetic challenges. In addition, we discuss several key lessons learned from our journey.
Overcoming Difficulties in Total Synthesis of (+)-Cotylenin A
Authors: Uwamori Masahiro , Osada Ryunosuke , Sugiyama Ryoji , Nagatani Kotaro , Tezuka Haruka , Hoshino Yunosuke , Minami Atsushi , Nakada Masahisa
Published: May 2024

The total synthesis of the natural product cotelynin A, which exhibits promising anti-cancer activity, is urgently required, as its source, Cladosporium sp. 501-7W, has lost its proliferative ability. Herein, we report the first total synthesis of cotelynin A. Contiguous asymmetric carbons at the C8 and C9 positions in the B-ring of the aglycon moiety of cotylenin A are difficult to construct after the formation of the B-ring via pinacol coupling. The revised synthesis of the aglycon moiety involved the alkenylation of a methyl ketone to construct the B-ring; for this convergent synthesis, one fragment was prepared using our catalytic asymmetric intramolecular cyclopropanation, and the other fragment was obtained via the acyl radical cyclization of a known aldehyde, which was prepared by sharpless asymmetric epoxidation of geraniol and subsequent rearrangement. Radical generation using a copper catalyst and TBHP was effective for an acyl radical cyclization. The two prepared fragments were then assembled via Utimoto coupling. The α-hydroxyketone at the C8-C9 position was stereoselectively reduced with Me4NBH(O2CiPr)3, which was newly prepared in this study, and led to the successful construction of the C8-C9 1,2-diol. A structurally unprecedented sugar moiety was synthesized for the first time by terminating successive reversible acetalizations with an irreversible epoxide ring-opening reaction. Although the glycosylation of the synthesized fragments proceeded with difficulty owing to steric hindrance around the C9 hydroxy group of the aglycone, the desired product was successfully obtained under the reaction conditions reported by Wan et al.
Unified Total Synthesis of Madangamine Alkaloids
Authors: Sato Takaaki
Published: May 2024

Development of a unified total synthesis of madangamine alkaloids is described. The synthesis consists of three parts: (1) construction of the central ABC-ring, (2) installation of the skipped diene bearing a trisubstituted olefin, and (3) the synthesis of various D-rings from a tetracyclic ABCE-common intermediate. The ABC-tricyclic framework is successfully assembled by intramolecular allenylation. The most significant issue in this synthesis is the stereoselective installation of the skipped diene. This challenge is ultimately overcome by development of a stereodivergent approach using hydroboration of allenes and Migita-Kosugi-Stille coupling. The hydroboration is especially useful because the reaction of 1,1-disubstituted allenes with either 9-BBN or (Sia)2BH gives (E)- or (Z)-allylic alcohols, respectively. The key to the success of our unified total synthesis is macrocyclic alkylation to form a wide variety of D-rings from the tetracyclic ABCE-common intermediate. Our collective synthesis of madangamine alkaloids revealed structure–activity relationship of D-rings in their cytotoxicity against human cancer cell lines.
Total Syntheses of (+)-Aquatolide and Related Humulanolides
Authors: Ogura Akihiro , Takao Ken-ichi
Published: May 2024

Herein, the total syntheses of (+)-aquatolide, a humulane-derived sesquiterpenoid lactone, and five other related humulanolides are described. The key reactions in these syntheses are a cascade metathesis reaction of cyclobutenecarboxylate to construct a γ-butenolide with an unsaturated aldehyde side chain, an intramolecular Nozaki–Hiyama–Takai–Kishi reaction to form an all-trans-humulene lactone skeleton, and a biosynthesis-inspired [2 + 2] photocycloaddition to provide a bridged 5/5/4/8-ring system. A cycloaddition giving a 5/4/4/7-ring system was also found. In addition, biological studies were conducted using the synthesized samples.
Complex Oligosaccharides Synthesis—Challenges and Tactics
Authors: Takahashi Daisuke , Toshima Kazunobu
Published: May 2024

1,2-cis glycoside structures exist as constituents of biologically active natural products, pharmaceuticals, and functional materials. Therefore, there is a pressing need for the development of novel and efficient 1,2-cis-glycosylation methods to understand their specific roles and to create new lead compounds for pharmaceutical and functional materials by derivatization of these glycosides. In this context, we have developed a conceptually new glycosylation method called boron-mediated aglycon delivery (BMAD), which utilizes organoboron catalysis for simultaneously controlling the 1,2-cis stereoselectivity of the glycosidic bond formed and regioselectivity of the reaction site in the glycosyl acceptor. The method has been applied to synthesize useful glycosides including complex oligosaccharides found in pathogenic bacteria. We recently extended the BMAD method to the reaction of partially protected and unprotected glycosides for the late-stage modification of natural glycosides with interesting biological activities, and synthesized complex oligosaccharides using minimal protecting groups. Furthermore, we developed a diastereoselective desymmetric BMAD reaction of meso-diols as a new synthetic tactic for complex glycosides. Herein, we discuss the abovementioned BMAD methods and their use in the synthesis of useful glycosides.
Pursuing Step Economy in Total Synthesis of Complex Marine Macrolide Natural Products
Authors: Fuwa Haruhiko
Published: May 2024

Here I describe our first-, second-, and third-generation synthesis of (+)-neopeltolide, which is a Jamaican marine macrolide that shows potent antiproliferative and antifungal activities. The third-generation synthesis enabled an expedient access to (+)-neopeltolide in 11 linear and 23 total steps, which is so far the shortest synthesis of this natural product. Convergent synthesis planning by taking advantage of chemoselective transformations, cross-coupling reactions, and tandem reactions was the key for increasing step economy.
Nonbiomimetic Total Synthesis of Polycyclic Alkaloids
Authors: Ohno Hiroaki , Arichi Norihito , Inuki Shinsuke
Published: May 2024

In nonbiomimetic natural product synthesis, there are no restrictions on the design of synthetic routes; however, the feasibility of the planned routes is often completely unknown. To discover more efficient and creative syntheses of natural products, and to identify bioactive natural product derivatives that have never been synthesized in nature, our group is engaged in the nonbiomimetic total synthesis of indole alkaloids. In this chapter, we describe our nonbiomimetic total syntheses of quinocarcin, dictyodendrins A–F, and zephycarinatines C and D, by employing alkyne-based approaches and reductive radical spirocyclization. We also describe our efforts in the identification of bioactive alkaloid derivatives.
Sequential Site-Selective Functionalization: A Strategy for Total Synthesis of Natural Glycosides
Authors: Ueda Yoshihiro , Kawabata Takeo
Published: May 2024

Total synthesis of several ellagitannins, strictinin (1), pterocarinin C (2), cercidinin A (3), and tellimagrandin II (19), is described. The key issues for the synthetic strategy rely on the catalyst-controlled site-selective acylation and stereoselective glycosylation with unprotected glucose. Total synthesis of punicafolin (5) with a glucose core in 1C4 (chair) conformation and macaranganin (30) with a glucose core in 5S1 (skew boat) conformation was also accomplished based on a similar unconventional retrosynthetic route. For success in the synthesis of 5 and 30, the flipping behavior of the pyranose ring from the stable 4C1 conformer to the unstable axial-rich 1C4 conformer is the key. Because no protective groups for glucose were employed throughout the synthesis of these natural glycosides, the total synthesis was achieved in extremely short overall steps.
Synthetic Study of Bio-functional Glycans
Authors: Fukase Koichi , Shimoyama Atsushi , Manabe Yoshiyuki
Published: May 2024

The molecular structures responsible for the immune functions of complex glycans were unraveled by synthetic studies. We focused on developing efficient methods for synthesizing glycans and conducting diverse chemical syntheses of these compounds, to identify the molecular structures responsible for activating or modulating innate immunity. Many natural glycans contain multiple active structures, potentially leading to emergent higher-order functions through their synergistic interactions. Therefore, by employing a conjugation-based approach, we successfully created immune-regulating complex glycoconjugates.
Total Synthesis of a Marine Bromotriterpenoid Isodehydrothyrsiferol
Authors: Nishikawa Keisuke , Morimoto Yoshiki
Published: May 2024

The thyrsiferol family natural products are marine triterpene polyethers biogenetically derived from squalene and structurally characterized by a bromine atom and some six- and five-membered ethereal rings. Their stereostructures cannot easily be determined by modern spectroscopic analysis, because there are acyclic tetrasubstituted chiral centers and the remote stereoclusters. In these cases, asymmetric total synthesis demonstrates its power. Herein, to determine the entire stereostructure of the thyrsiferol family member isodehydrothyrsiferol, isolated from the red alga Laurencia viridis, the asymmetric total synthesis has been performed. The key steps are the convergent and effective synthetic strategy using a Suzuki–Miyaura cross-coupling, a one-pot construction of the tetrahydropyranyl C ring via a stoichiometric Katsuki-Sharpless asymmetric epoxidation and 6-exo oxacyclization in situ promoted by Ti chelation, and 6-endo bromoetherification for the A ring formation. Through the enantioselective total synthesis, we have accomplished complete assignment of the entire stereostructure for isodehydrothyrsiferol and found the absolute configuration of the ABC ring system is opposite to that common to the other congeners from the same red algae. In addition, such enantiodivergency also occurred between dehydrothyrsiferol and isodehydrothyrsiferol originating from the identical red alga Laurencia viridis. There are no these findings without asymmetric total synthesis.
Utilizing the pKa Concept to Address Unfavorable Equilibrium Reactions in the Total Synthesis of Palau’amine
Authors: Ohashi Eisaku , Takeuchi Kohei , Tanino Keiji , Namba Kosuke
Published: May 2024

Herein, we introduce the pKa concept as a strategy for proceeding with unfavorable reactions in the total synthesis of palau’amine. The cascade reaction aimed at constructing palau’amine’s ABDE tetracyclic ring core initially encountered poor reproducibility due to an unfavorable equilibrium reaction. However, the addition of 1.0 equivalent of AcOH enabled the progression of the unfavorable equilibrium reaction. In the second-generation synthesis, the improved cascade reaction to construct CDE ring core also initially did not proceed due to an unfavorable equilibrium reaction, but using Ph2NLi as a base was later found to enable the reaction to proceed smoothly. The conjugate acid of Ph2NLi proved to be a suitable acid in the unfavorable equilibrium mixture. These investigations of the cascade reactions revealed that the coexistence of an appropriate acid played an important role in allowing the unfavorable equilibrium reaction to proceed. The authors propose a general equation for proceeding with an unfavorable equilibrium reaction.
Total Synthesis of (+)-Siladenoserinol A
Authors: Yoshida Masahito , Saito Koya , Doi Takayuki
Published: May 2024

The total synthesis of (+)-siladenoserinol A (1) was accomplished. The bicyclic acetal core, a 6,8-dioxabicyclo[3.2.1]octane skeleton, was constructed by Au(III)-catalyzed cycloisomerization of 6,7-dihydroxy-2-alkynoate. A serinol side chain was introduced by the Julia–Kocienski olefination and the other side chain was efficiently introduced by the Horner–Wadsworth–Emmons reaction with glycerophosphocholine-containing phosphonoacetate, and selective sulfamation of the serinol moiety yielded (+)-1. The synthetic (+)-1 exhibited potent inhibitory activity against p53–Hdm2 interaction comparable to that of the natural product. In contrast, the desulfamate derivative did not show the inhibitory activity. Notably, its benzoyl analog exhibited more potent activity than (+)-1.
The Asymmetric Total Synthesis of Discorhabdin B, H, K, and Aleutianamine
Authors: Sakata Juri , Shimomura Masashi , Tokuyama Hidetoshi
Published: May 2024

This review article summarizes the general introduction of discorhabdin marine alkaloids and the synthetic efforts in developing congeners with a hexacyclic N, S-acetal structure, which are major constituents of discorhabdin. Our total synthesis of (+)-discorhabdin B is discussed in detail following the introduction of the biosynthetic pathway and early synthetic studies, which include the landmark first total synthesis of discorhabdin A. Furthermore, previous synthetic studies on more structurally complex congeners with C6–N15 bonds are introduced, followed by the first total synthesis of (–)-discorhabdin H and (+)-discorhabdin K, which are achieved by our research group. Finally, the isolation, structure determination, and proposed biosynthesis of the structurally intriguing congener aleutianamine are summarized. Then, the first total synthesis of aleutianamine, which involves an unprecedented reductive skeletal rearrangement of N-Ts-(+)-discorhabdin B to N-Ts-aleutianamine, is discussed.
Fluoroarene Strategy in Total Synthesis of Natural Flavonoids
Authors: Ohmori Ken , Suzuki Keisuke
Published: May 2024

Vicenin-2, a naturally occurring bis-C-glucosyl flavonoid, was synthesized by exploiting a sequential C-glycoside formation and aromatic nucleophilic substitution (SNAr reaction) of the fluoroarene derivative, i.e., 1,3,5-trifluorobenzene, converting fluorine atoms to oxygen function.
Collective Total Synthesis of Secologanin-Related Natural Products
Authors: Sakamoto Jukiya , Ishikawa Hayato
Published: May 2024

We have been interested in the reactivity of secologanin, which is transformed into more than 3000 natural products in nature and have been working on the bioinspired synthesis of several natural products using secologanin derivatives. In this chapter, we describe the total synthesis of secologanin using an organocatalytic reaction and the collective and divergent total synthesis of glycosylated monoterpenoid indole alkaloids and hetero-oligomeric iridoid glycosides through biogenetically inspired transformations from secologanin derivatives.
Colonial Nostalgia and Postcolonial Longings
Authors: Chow Yiu Fai , de Kloet Jeroen , Schmidt Leonie
Published: May 2024

This chapter continues our theoretical discussion on popular music and politics with a specific remit: its intersection with postcolonial studies and its deliberations on home, identity, and power contestations. The insertion of an inquiry over Tat Ming Pair and Hong Kong here serves two purposes. The first is, quite generally, the lack of research on music and postcoloniality in the Asian experience in English language scholarship—save for some notable exceptions music. Second, and more fundamentally, we see Tat Ming Pair and its politics as an “anomaly”—as much as the decolonisation of Hong Kong itself. Put simply, Hong Kong’s decolonisation proceeds in tandem with its renationalisation. While the former colonies in postcolonial studies became nations in their own right, Hong Kong became part of China after its sovereignty was handed from London to Beijing in 1997. Drawing primarily from the interviews with Anthony Wong and Tats Lau, Chapter 2 tracks and analyses the emergence and development of the duo in the larger geopolitical and geocultural context. Their musical engagements with a host of issues including sexual autonomy, gender equality, freedom of thoughts and speech, and Sino-Hong Kong relationships will be highlighted to prelude the more detailed analyses in the following two chapters. At the same time, Chapter 2 aims at mapping out a history of Hong Kong in its colonial entanglements with the British administration, and its postcolonial struggles with the Chinese regime. It will also seek to retell a concomitant history of Hong Kong popular music that is not dictated by the “Golden Era” logic, that is from its popularity zenith as the “global cool” to its alleged post-Handover decline or even death; rather the history we write will be informed and inspired by the vitality and complexity of Tat Ming Pair’s music and politics. Chapter 2 will converse with existing scholarship on Cantopop, as well as on Tat Ming Pair.