Modern Synthesis Research Articles

The environment: An ambiguous concept in Waddington's biology

Waddington is usually acknowledged as a biologist who proposed a more subtle concept of environment than the one generally in currency during the rise of the Modern Synthesis. As such, he was among the few scientists in the mid-twentieth century to develop an elaborated concept of the environment that would fully embrace its constructive role both in development and evolution. Yet, on close inspection, there is an inconsistency in Waddington's theoretical positioning. On the one hand, as a critic of population genetics, Waddington never stopped claiming that natural selection acts on phenotypes and that the phenotype is the outcome of both the genome and the environment. On the other, however, the topology of his famous epigenetic landscape was anchored only in the genome, and the variation of the environment was treated as an external perturbation. In other words, the genes and the environment were sometimes considered as symmetric agents in the epigenetic system, and sometimes not.My aim is to shed light on the significance of this tension in Waddington's theoretical framework. I show that Waddington's biology is best characterized as an asymmetric understanding of the causal role of genes and environment both in development and evolution. His model of genetic assimilation was based on the idea of differential levels of hereditary responsiveness to environmental variations, giving the genome a leading role and paving the way for critics of his conceptions. In the final section, I argue that eventually Waddington was trapped by his diagram of the epigenetic landscape, which might also have been an obstacle to achieving a proper conception of the creativity of embryogenesis.

Enantioselective Synthesis of Acyclic Stereotriads Featuring Fluorinated Tetrasubstituted Stereocenters.

Elaboration of enantioenriched complex acyclic stereotriads represents a challenge for modern synthesis even more when fluorinated tetrasubstituted stereocenters are targeted. We have been able to develop a simple strategy in a sequence of two unprecedented steps combining a diastereoselective aldol-Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution. The aldol-Tishchenko reaction directly generates a large panel of acyclic 1,3-diols possessing a fluorinated tetrasubstituted stereocenter by condensation of fluorinated ketones with aldehydes under very mild basic conditions. The anti 1,3-diols featuring three contiguous stereogenic centers are generated with excellent diastereocontrol (typically >99 : 1 dr). Depending upon the precursors both diastereomers of stereotriads are accessible through this flexible reaction. Furthermore, from the obtained racemic scaffolds, development of an organocatalyzed kinetic resolution enabled to generate the desired enantioenriched stereotriads with excellent selectivity (typically er >95 : 5).

MEDIA ART IN MODERN SYNTHESIS OF ARTS IN ARCHITECTURE

The article substantiates the problem of synthesis of media art in the modern synthesis of arts in architecture, provides a definition of the term " Media Art" as a higher form of artistic development. Attention is paid to the analysis of recent research and publications devoted to the study of the artistic component of interactive design in the synthesis of the arts of architectural space, the influence of media technologies on the formation of the architectural image of art centers, describing trends in media technology in architecture. The purpose of the article is to consider the forms of media art, their role in the synthesis of arts in architecture. The article emphasizes the objects created and embodied in Ukraine, describes the synthesis of arts from the angle of influence of media art on human perception and outlines the prospects for development. The history of the synthesis of arts in architecture from ancient times, the development of the synthesis of arts in the Art Nouveau style, the preconditions for the emergence of media art are briefly described. The synthesis of media art and architecture, interaction with other arts, namely painting, sculpture, music and others is considered on the example of the multimedia center Atelier des Lumières – "Workshop of the World" in Paris, which specializes in digital art exhibitions; Ukraine WOW exhibition in Kyiv, which is equipped with various forms of media art; media facades in Kyiv; media cube on the facade of Chicago Central House, which is the first media sculpture in Europe. The definition of "media facades" is also given and the influence of media technologies on the emotional and psychological state of a person is considered. Examples of interaction of various forms of media art with architecture are given. The conclusions determine the role of media art in architecture, the impact of media technology on human psychology, outline the prospects for the development of media art in the modern synthesis of arts in architecture.

Tandem Nickel-Catalyzed Dimerization/(4+2) Cycloaddition of Terminal Alkynes with Four-Membered Ring Ketones

AbstractControlling the behavior of terminal alkynes in metal-catalyzed intermolecular tandem reactions is a formidable challenge despite the potential advantage offered by these strategies in modern synthesis. Herein, we describe that a nickel catalyst enables a tandem process involving the rapid dimerization of terminal alkynes into 1,3-enynes and the cycloaddition of these intermediates with an azetidinone, an oxetanone or benzocyclobutenones. Significantly, the slow or sequential addition of reagents and catalysts is not required to orchestrate their reactivity. These results are in stark contrast with previous cycloadditions of terminal alkynes with strained four-membered ring substrates, which previously led to oligomerization or cyclotrimerization, except in the case of tert-butylacetylene.

C\u2013H activation by immobilized heterogeneous photocatalysts

During the last decades, the merger of photocatalysis with transition metal chemistry has been surfaced as a sustainable tool in modern molecular syntheses. This Account highlights major advances in synergistic photo-enabled C‒H activations. Inspired by our homogenous ruthenium- and copper-catalyzed C‒H activations in the absence of an exogenous photosensitizer, this Account describes the recent progress on heterogeneous photo-induced C‒H activation enabled by immobilized hybrid catalysts until September 2021, with a topical focus on recyclability as well as robustness of the heterogeneous photocatalyst.

Sculpting the Plasmonic Responses of Nanoparticles by Directed Electron Beam Irradiation.

Spatial confinement of matter in functional nanostructures has propelled these systems to the forefront of nanoscience, both as a playground for exotic physics and quantum phenomena and in multiple applications including plasmonics, optoelectronics, and sensing. In parallel, the emergence of monochromated electron energy loss spectroscopy (EELS) has enabled exploration of local nanoplasmonic functionalities within single nanoparticles and the collective response of nanoparticle assemblies, providing deep insight into associated mechanisms. However, modern synthesis processes for plasmonic nanostructures are often limited in the types of accessible geometry, and materials and are limited to spatial precisions on the order of tens of nm, precluding the direct exploration of critical aspects of the structure-property relationships. Here, the atomic-sized probe of the scanning transmission electron microscope is used to perform precise sculpting and design nanoparticle configurations. Using low-loss EELS, dynamic analyses of the evolution of the plasmonic response are provided. It is shown that within self-assembled systems of nanoparticles, individual nanoparticles can be selectively removed, reshaped, or patterned with nanometer-level resolution, effectively modifying the plasmonic response in both space and energy. This process significantly increases the scope for design possibilities and presents opportunities for unique structure development, which are ultimately the key for nanophotonic design.

Further illusions: On key evolutionary mechanisms that could never fit with Modern Synthesis

In light of illusions of the Modern Synthesis (MS) listed by Noble (2021a), MS's key concept, that gradual accumulation of gene mutations within microevolution leads to macroevolution, requires reexamination too. In this article, additional illusions of the MS are identified therein caused by the absence of system information and correct history. First, the MS lacks distinction among the two basic types of information: genome-defined system and gene-defined parts-information, as its treatment was based mostly on gene information. In contrast, it is argued here that system information is maintained by species-specific karyotype code, and macroevolution is based on the whole genome information package rather than on specific genes. Linking the origin of species with system information shows that the creation and accumulation of the latter in evolution is the fundamental question omitted from the MS. Second, modern evidence eliminates the MS's preferred theory that present evolutionary events can be linearly extrapolated to the past to reconstruct Life's history, wrongly assuming that most of the fossil record supports the gradual change while ignoring the true karyotype/genome patterns. Furthermore, stasis, as the most prominent pattern of the deep history of Life, remains a puzzle to the MS, but can be explained by the mechanism of karyotype-preservation-via-sex. Consequently, the concept of system-information is smoothly integrated into the two-phased evolutionary model that paleontology requires (Eldredge and Gould, 1972). Finally, research on genome-level causation of evolution, which does not fit the MS, is summarized. The availability of alternative concepts further illustrates that it is time to depart from the MS.

1,4-Azaborines: Origin, Modern Synthesis, and Applications as Optoelectronic Materials

AbstractThis short review summarizes the origins and recent progress in 1,4-azaborine research, focusing on synthetic methodologies. Academic laboratories have made significant efforts to generate boron-nitrogen-containing heteroaromatic compounds that mimic arenes. 1,2-, 1,3-, and 1,4-Azaborine motifs have provided breakthrough molecules in applications ranging from medicines to materials. Owing to recent advances in polyaromatic 1,4-azaborine synthesis and applications in industry, the research field is currently undergoing a renaissance. Photo- and electroluminescent properties driven by distinct structural variations are key components in the design of novel 1,4-azaborine structures. In this review, seminal reports on the synthesis of simple 1,4-azaborines to complex π-extended structures are briefly highlighted together along with key optoelectronic properties.1 Introduction2 Non-Fused 1,4-Azaborines3 Monobenzo-Fused 1,4-Azaborines4 Dibenzo-Fused 1,4-Azaborines and Their Derivatives5 Ladder-Type 1,4-Azaborines6 Complex 1,4-Azaborines7 Optoelectronic Properties of Key 1,4-Azaborines8 Conclusion and Outlook

A Dual Role for Behavior in Evolution and Shaping Organismal Selective Environments

The hypothesis that evolved behaviors play a determining role in facilitating and impeding the evolution of other traits has been discussed for more than 100 years with little consensus beyond an agreement that the ideas are theoretically plausible in accord with the Modern Synthesis. Many recent reviews of the genomic, epigenetic, and developmental mechanisms underpinning major behavioral transitions show how facultative expression of novel behaviors can lead to the evolution of obligate behaviors and structures that enhance behavioral function. Phylogenetic and genomic studies indicate that behavioral traits are generally evolutionarily more labile than other traits and that they help shape selective environments on the latter traits. Adaptive decision-making to encounter resources and avoid stress sources requires specific sensory inputs, which behaviorally shape selective environments by determining those features of the external world that are biologically relevant. These recent findings support the hypothesis of a dual role for behavior in evolution and are consistent with current evolutionary theory.

Role of environmentally induced epigenetic transgenerational inheritance in evolutionary biology: Unified Evolution Theory.

The current evolutionary biology theory primarily involves genetic alterations and random DNA sequence mutations to generate the phenotypic variation required for Darwinian natural selection to act. This neo-Darwinian evolution is termed the Modern Evolution Synthesis and has been the primary paradigm for nearly 100 years. Although environmental factors have a role in neo-Darwinian natural selection, Modern Evolution Synthesis does not consider environment to impact the basic molecular processes involved in evolution. An Extended Evolutionary Synthesis has recently developed that extends the modern synthesis to consider non-genetic processes. Over the past few decades, environmental epigenetics research has been demonstrated to regulate genetic processes and directly generate phenotypic variation independent of genetic sequence alterations. Therefore, the environment can on a molecular level through non-genetic (i.e. epigenetic) mechanisms directly influence phenotypic variation, genetic variation, inheritance and adaptation. This direct action of the environment to alter phenotype that is heritable is a neo-Lamarckian concept that can facilitate neo-Darwinian (i.e. Modern Synthesis) evolution. The integration of genetics, epigenetics, Darwinian theory, Lamarckian concepts, environment, and epigenetic inheritance provides a paradigm shift in evolution theory. The role of environmental-induced epigenetic transgenerational inheritance in evolution is presented to describe a more unified theory of evolutionary biology.

Functional Group Interconversion Reactions in Continuous Flow Reactors

: An overview of the current uptake of continuous flow techniques for various functional group interconversion reactions is presented. Besides highlighting a variety of prominent examples and their main features, this review provides insights into specific reaction classes, such as oxidations, reductions, rearrangements as well as different C-H functionalization processes. While this review can only include key examples from the last decade, the reader will find a solid foundation of important transformations along with further references to inform and appreciate the opportunities arising from modern synthesis technologies such as flow synthesis.

UNDER THE SAME ROOF: RECONCILIATION OF THE OPPOSITE ENDS IN E. M. FORSTER S HOWARDS END

The twentieth century marks the beginning of a new period in England during which the norms and the traditions pertaining to the Victorian age start to be questioned. While the echoes of this change have been audible from the 1890s onwards, they reach their climax with the death of Queen Victoria in 1901 because it announces not only the physical death of the Queen but also the symbolic death of the Victorian mindset. With the reign of King Edward VII, therefore, the literary texts of the period illustrate a liberal outlook that questions the outdated ideals of the previous era. Within this context, this article examines E. M. Forster’s Howards End (1910) by foregrounding and analysing the clash between the ideals of the past and those of the present, which in the wider perspective demonstrates Forster’s modernist agenda to go beyond the strict dualities and to introduce a totally fresh synthesis. Epitomising the cultural inheritance of the country, Howards End is more than a house; it represents the future of England. Thus, it is important that Howards End should function as a unifying force that will bring these opposite ends together – as represented through different socio-economic classes embodied through three families whose lives get connected to one another at the end of the novel. Thereby, Forster aptly weaves the stories of the Schlegels, the Wilcoxes, and the Bast family by counterbalancing the intellectual and the material; the spiritual and the physical; the feminine and the masculine; the past and the present, and he presents a modern synthesis that, he believes, will shape England in the future.

The evolution of evolutionary processes in organismal and cancer evolution

The evolution of early life and of contemporary viruses has been driven in significant part by random genetic mutations, while modern unicellular and organismal evolution primarily leverages evolved, efficient and active cell biology processes for adaptive changes prior to selection. Random mutations are often buffered by cell homeostasis, or they have a negative role, e.g., by causing death or monogenic diseases, or by triggering real-time cancer evolution. Accordingly, the Modern Synthesis theory no longer adequately describes the efficient, often punctuated and at times directionally adaptive natural genetic engineering (NGE) processes deduced from the DNA record of evolution.Similarly, the somatic mutation theory (SMT) of cancer describes driver mutations that can trigger oncogenesis, and passenger mutations characteristic of periods of genetic microevolution in cancer. At the precancerous stage, most somatic mutations are repaired or buffered in the cell, aberrant cells are removed, or organismal bioelectric tissue signals or other physiological functional networks maintain control of rogue, mutated cells. However, the SMT is not sufficient to describe the observed punctuated macroevolution of cancer-cell genes, chromosomes, karyotypes and epigenomes, nor of expressed cancer-cell transcriptomes, proteomes and epiproteomes, which include non-DNA-templated post-translational modifications, protein-protein interactions and metabolites. Moreover, punctuated cancer cell macroevolution often culminates in macro-effects, which include epithelial-mesenchymal transitions (EMT), cancer cell polyploidies and even giant multinucleated cancer cells that drive cancer progression, therapy resistance and metastasis. All of this cancer-cell evolution competes in a molecular and cellular arms race with host immune cells and antibodies, as well as with the host tumor microenvironment.Empirically observed punctuated, multilevel and multiclonal cancer macroevolution, and the concomitant, rapid co-development of the host immune system and tumor microenvironment, can occur with the efficiency, speed and lethality of cancer that is enabled by evolved, active natural genetic engineering (NGE) mechanisms. NGE affects both vertical cancer-cell genomic inheritance and evolution towards therapy resistance and metastasis, as well as viral or cancer-cell exosome vector-driven horizontal gene transfers that contributes to cancer cell cooperation, or to transforming previously non-cancerous somatic cells into destabilized cancer cells during metastasis.In addition, externally driven, irreversible and transferable (EDIT) adaptations are exemplified by mitotically heritable, non-templated cancer cell epigenetics, and by mitotically heritable cancer-cell surface protein and lipid glycosylation, as important examples of fast time-scale molecular evolution mechanisms in which genes are followers, similar to evo-devo processes in organismal evolution.

Morphogenesis – “The Riddles of Form” in Twenty-First Century Science

Morphogenesis – “The Riddles of Form” in Twenty-First Century Science

Eclipsing the Eclipse?: A Neo-Darwinian Historiography Revisited.

Julian Huxley's eclipse of Darwinism narrative has cast a long shadow over the historiography of evolutionary theory around the turn of the nineteenth century. It has done so by limiting who could be thought of as Darwinian. Peter Bowler used the eclipse to draw attention to previously understudied alternatives to Darwinism, but maintained the same flaw. In his research on the Non-Darwinian Revolution, he extended this problematic element even further back in time. This paper explores how late nineteenth-century neo-Darwinian conceptualizations of Darwinism were later utilized by several advocates and detractors of the Modern Synthesis. John Beatty has shown how this continuity hinges at least partly on the perceived importance of the creativity of natural selection. The paper provides a more thorough look at Darwin's two conflicting accounts of variation, ascribed to struggles in explaining quantitative versus qualitative characters. In doing so, it suggests that other forms of Darwinism persisted, in both the non-Darwinian revolution and eclipse periods, because of tension between contingency and creativity in Darwin's own work. This tension is traced out from Darwin's conceptions of variation into the work of Alfred Russel Wallace, Hugo de Vries, and Thomas Henry Huxley. Based on this, the eclipse narrative is criticized for not considering the meaning of Darwinism in different geographical locations. Britain and the United States showed few signs of an eclipse. Rather, the rise of German debates about Haeckel's vision of Darwinism have been mistaken for a universal decline in support.

The information continuum model of evolution

Most biologists agree that evolution is contingent on inherited information shaped by natural selection. This apparent consensus could be taken to indicate agreement on the forces shaping evolution, but vivid discussions reveal divergences on how evolution is perceived. The predominant Modern Synthesis (MS) paradigm holds the position that evolution occurs through random changes acting on genomic inheritance. However, studies from recent decades have revealed that evolutionary inheritance also includes DNA-methylation, RNA, symbionts, and culture, among other factors. This has fueled a demand of a broader evolutionary perspective, for example from the proponents of the Extended Evolutionary Synthesis (EES). Despite fundamental disagreements the different views agree that natural selection happens through dissimilar perpetuation of inheritable information. Yet, neither the MS, nor the ESS dwell extensively on the nature of hereditary information. We do - and conclude that information in and of itself is immaterial. We then argue that the quality upon which natural selection acts henceforth is also immaterial. Based on these notions, we arrive at the information-centric Information Continuum Model (ICM) of evolution. The ICM asserts that hereditary information is embedded in diverse physical forms (DNA, RNA, symbionts etc.) representing a continuum of evolutionary qualities, and that information may migrate between these physical forms. The ICM leaves theoretical exploration of evolution unrestricted by the limitations imposed by the individual physical forms wherein the hereditary information is embedded (e.g. genomes). ICM bestows us with a simple heuristic model that adds explanatory dimensions to be considered in the evolution of biological systems.

Polyacetylene Revisited: A Computational Study of the Molecular Engineering of N-type Polyacetylene.

The development of stable and highly conductive polymers, particularly n-type materials, remains an outstanding challenge in organic electronics. N-doped polyacetylene has long been studied as a highly conductive organic n-type material but suffers from extremely poor stability. Herein, we use DFT to model a series of n-doped polyacetylene derivatives, which have been functionalized with a range of electron-withdrawing substituents, with the goal of identifying attractive candidates for synthesis. We analyze the predicted molecular orbital energies, polymer planarity, and delocalization of charge carriers along the polymer backbone. In so doing, we develop key insights about the ideal substituents for both stable and highly conductive polyacetylene derivatives. This work will inform the modern synthesis and development of new polyacetylene derivatives. Beyond this, the work identifies a variety of new materials that have not yet been synthesized and should be good candidates for emerging optoelectronic applications including soft thermoelectrics, bioelectronics, and flexible device technologies.

Visible Light Induced Cu-Catalyzed Asymmetric C(sp3)-H Alkylation.

The asymmetric functionalization of C-H is one of the most attractive strategies in asymmetric synthesis. In the past decades, catalytic enantioselective C(sp3)-H functionalization has been intensively studied and successfully applied in various asymmetric bond formations, whereas asymmetric C(sp3)-H alkylation was not well developed. Photoredox catalysis has recently emerged as an efficient way to synthesize organic compounds under mild conditions. Despite many photoinduced stereoselective reactions that have been achieved, the related enantioselective C(sp3)-C(sp3) coupling is challenging, especially of the photocatalytic asymmetric C(sp3)-H radical alkylation. Here, we report a visible light induced Cu catalyzed asymmetric sp3 C-H alkylation, which is effective for coupling with unbiased primary, secondary, and tertiary alkyl fragments in high enantioselectivities. This reaction would provide a new approach for the synthesis of important molecules such as unnatural α-amino acids and late-stage functionalization of bioactive compounds, and will be useful for modern peptide synthesis and drug discovery.

Recent advance of new sample preparation materials in the analysis and detection of environmental pollutants

针对复杂样品的分析和痕量目标物的检测,样品前处理是必不可少的,高效的样品前处理技术不仅可以去除或减小样品基质干扰而且能够实现分析物的富集,提高分析检测的准确性和灵敏度。近年来,固相萃取、磁分散固相萃取、枪头固相萃取、搅拌棒萃取、固相微萃取等高效的样品前处理技术已在环境污染物分析检测中获得广泛关注,萃取效率主要取决于萃取材料,所以新型的高效萃取材料一直是样品前处理研究领域的重要发展方向。该文总结和讨论了近年来新型样品前处理材料在环境污染物分析检测中的研究进展,主要聚焦在石墨烯、氧化石墨烯、碳纳米管、无机气凝胶、有机气凝胶、三嗪基功能材料、三嗪基聚合物、分子印迹聚合物、共价有机框架材料、金属有机框架材料以及它们的功能化萃取材料等。这些材料已经被应用于环境样品中不同类别污染物的萃取富集,如重金属离子、多环芳烃、塑化剂、烷烃、苯酚、氯酚、氯苯、多溴联苯醚、全氟磺酸、全氟羧酸、雌激素、药物残留、农药残留等。这些样品前处理材料具有高的表面积、大量的吸附位点,并涉及多种萃取机理如π-π、静电、疏水、亲水、氢键、卤键等相互作用。基于这些萃取材料的多种样品前处理技术与各类检测方法如色谱、质谱、原子吸收光谱、荧光光谱、离子迁移谱等相结合,已广泛应用于环境污染物的高灵敏分析检测。最后,该文总结了样品前处理发展中存在的问题,并展望了其未来在环境分析中的发展趋势。

A Semiotic Modern Synthesis: Conducting Quantitative Studies in Zoosemiotics and Interpreting Existing Ethological Studies through a Semiotic Framework

In this paper, I present an argument that quantitative behavioural analysis can be used in zoosemiotic studies to advance the field of biosemiotics. The premise is that signs and signals form patterns in space and time, which can be measured and analysed mathematically. Whole organism sign processing is an important component of the semiosphere, with individual organisms in their Umwelten deriving signs from, and contributing to, the semiosphere, and vice versa. Moreover, there is a wealth of data available in the traditional ethology literature which can be reinterpreted semiotically and drawn together to make a cohesive biosemiotic whole. For example, isolated signals, such as structural elements of birdsong, are attributed meaning by an interpreter, thus generating new ideas and hypotheses in both biology and semiotics. Furthermore, animal behaviour science has developed numerous test paradigms that with careful adaptation, could be suitable for use within a Peircean tripartite model, and thus give valuable insights into Umwelten of other species. In my conclusion, I suggest that by bringing together traditional ethology and biosemiotics, it is possible to use the Modern Synthesis to provide context to biosemiosis, thus pragmatic meaning to animal signals. On this basis, I propose updating the Modern Synthesis to a Semiotic Modern Synthesis, which focuses on whole-organism signals and their contexts, the latter being derived from neo-Darwinian theory and the ‘Umwelt’. Thus, there need be no dichotomy; the Modern Synthesis can successfully be integrated with biosemiotics.