Baldwin Effect Research Articles

Recent advances of 5-endo-trig radical cyclization: promoting strategies and applications.

5-endo-trig radical cyclization has long been recognized as one of the most straightforward ways for the construction of densely functionalized five-membered rings. Nevertheless, according to Baldwin's rules, the 5-endo-trig radical cyclization is kinetically disfavored due to stereoelectronic effects and thus usually proceeds via a slow rate, which renders its application a challenging task. In recent years, with the emergence of efficient radical generation methods and effective cyclization strategies, 5-endo-trig radical cyclization has been successfully accelerated to a synthetically useful rate and has been utilized in the access of diverse five-membered carbo- and heterocyclic compounds. This review comprehensively summarizes the methodologies involving the 5-endo-trig radical cyclization process, with particular emphasis on the elucidation of the promoting strategies, which include the polar effect, geometrical constraints, spin delocalization effect, and persistent radical effect. Each of these strategies is discussed in detail, with illustrative examples from recent literature studies to highlight their practical applications and effectiveness. It is anticipated that the in-depth understanding of the 5-endo-trig radical cyclization provided by this review would inspire further innovation of this privileged reaction mode and expand its applications. Moreover, the potent ring-closure-promoting strategies revealed herein would also contribute to achieving other challenges of cyclizations with particular significance for organic synthesis.

Quasars as standard candles

A sample of quasars has been recently assembled to investigate the non-linear relation between their monochromatic luminosities at 2500 Å and 2 keV and to exploit quasars as a new class of ‘standardized candles’. The use of this technique for cosmological purposes relies on the non-evolution with redshift of the UV-optical spectral properties of quasars, as well as on the absence of possible contaminants such as dust extinction and host galaxy contribution. We address these possible issues by analysing the spectral properties of our cosmological quasar sample. We produced composite spectra in different bins of redshift and accretion parameters (black hole mass, bolometric luminosity), to investigate any possible evolution of the spectral properties of the continuum of the composites with these parameters. We found a remarkable similarity amongst the various stacked spectra. Apart from the well known evolution of the emission lines with luminosity (i.e. the Baldwin effect) and black hole mass (i.e. the virial relation), the overall shape of the continuum, produced by the accretion disc, does not show any statistically significant trend with black-hole mass (MBH), bolometric luminosity (Lbol), or redshift (z). The composite spectrum of our quasar sample is consistent with negligible levels of both intrinsic reddening (with a colour excess E(B − V)≲0.01) and host galaxy emission (less than 10%) in the optical. We tested whether unaccounted dust extinction could explain the discrepancy between our cosmographic fit of the Hubble–Lemaître diagram and the concordance ΛCDM model. The average colour excess required to solve the tension should increase with redshift up to unphysically high values (E(B − V)≃0.1 at z > 3) that would imply that the intrinsic emission of quasars is much bluer and more luminous than ever reported in observed spectra. The similarity of quasar spectra across the parameter space excludes a significant evolution of the average continuum properties with any of the explored parameters, confirming the reliability of our sample for cosmological applications. Lastly, dust reddening cannot account for the observed tension between the Hubble–Lemaître diagram of quasars and the ΛCDM model.

Use of a Cyclic α-Alkylidene-β-Diketone as a Cleavable Linker Strategy for Antibody-Drug Conjugates.

In the fast-evolving landscape of targeted cancer therapies, the revolutionary class of biotherapeutics known as antibody-drug conjugates (ADCs) are taking center stage. Most clinically approved ADCs utilize cleavable linkers to temporarily attach potent cytotoxic payloads to antibodies, allowing selective payload release under tumor-specific conditions. In this study, we explored the utilization of 1-(4,4-dimethyl-2,6-dioxocyclohexylidene)ethyl (Dde), a cyclic β-diketone featuring an active alkylidene group, to develop a novel chemically labile linker. This linker was designed to exploit the difference in reduction potential between the intracellular compartment and plasma. Upon reduction of an azido trigger strategically installed neighboring the cyclic β-diketone, the resulting nucleophilic primary amine reacts with the alkylidene group facilitated by a favorable ring closure reaction in accordance with Baldwin's rules. Consequently, this reaction enables the simultaneous release of the attached cytotoxic payload. The therapeutic utility of this novel linker strategy was demonstrated by separate conjugation of the linker to two epidermal growth factor receptor (EGFR)-targeting ligands to afford a peptide-drug conjugate and an ADC. This work comprises a significant contribution to the bioconjugation field by introducing the alkylidene cyclic β-diketone as a tunable scaffold used for the temporary conjugation of therapeutic agents to peptides and proteins.

Studies on the Biomimetic Synthesis of Marine Ladder Polyethers via Endo‐Selective Epoxide‐to‐Epoxonium Ring‐Opening Cascades

AbstractMarine ladder polyethers have attracted the attention of chemists and biologists because of their potent biological activities. Synthetic chemists have attempted to construct their polyether frameworks by epoxide ring‐opening cascades, as Nakanishi hypothesis describes. However, Baldwin's rules of ring closure state that exo‐selective intramolecular cyclization of epoxy alcohols is preferred over endo‐selective cyclization. Herein, we investigated epoxide ring‐opening cascades of polyepoxy alcohols in [EMIM]BF4/PFTB (1‐ethyl‐3‐methylimidazolium tetrafluoroborate /perfluoro‐tert‐butyl alcohol) and found that all‐endo products were formed via epoxide‐to‐epoxonium ring‐opening cyclizations (not restricted by Baldwin's rules, which only apply to intramolecular hydroxyl‐to‐epoxide cyclizations). We determined that the key factor enabling polyepoxy alcohols to undergo a high proportion of all‐endo‐selective cyclization was inhibition of exo‐selective hydroxyl‐to‐epoxide cyclization starting from the terminal hydroxyl group of a polyepoxy alcohol. By introducing a slow‐release protecting group to the terminal hydroxyl group, we could markedly increase the cyclization yields of polyether fragments with hydrogen atoms at the ring junctions. For the first time, we constructed consecutively fused six‐membered‐ring and fused seven‐, eight‐, and nine‐membered‐ring polyether fragments by epoxide‐to‐epoxonium ring‐opening cyclizations through the addition of a suitable Lewis acid. We also suggest that the biosynthesis of marine ladder polyethers may proceed via epoxide‐to‐epoxonium ring‐opening cyclization of polyepoxide.

Studies on the Biomimetic Synthesis of Marine Ladder Polyethers via Endo-Selective Epoxide-to-Epoxonium Ring-Opening Cascades.

Marine ladder polyethers have attracted the attention of chemists and biologists because of their potent biological activities. Synthetic chemists have attempted to construct their polyether frameworks by epoxide ring-opening cascades, as Nakanishi hypothesis describes. However, Baldwin's rules of ring closure state that exo-selective intramolecular cyclization of epoxy alcohols is preferred over endo-selective cyclization. Herein, we investigated epoxide ring-opening cascades of polyepoxy alcohols in [EMIM]BF4/PFTB (1-ethyl-3-methylimidazolium tetrafluoroborate /perfluoro-tert-butyl alcohol) and found that all-endo products were formed via epoxide-to-epoxonium ring-opening cyclizations (not restricted by Baldwin's rules, which only apply to intramolecular hydroxyl-to-epoxide cyclizations). We determined that the key factor enabling polyepoxy alcohols to undergo a high proportion of all-endo-selective cyclization was inhibition of exo-selective hydroxyl-to-epoxide cyclization starting from the terminal hydroxyl group of a polyepoxy alcohol. By introducing a slow-release protecting group to the terminal hydroxyl group, we could markedly increase the cyclization yields of polyether fragments with hydrogen atoms at the ring junctions. For the first time, we constructed consecutively fused six-membered-ring and fused seven-, eight-, and nine-membered-ring polyether fragments by epoxide-to-epoxonium ring-opening cyclizations through the addition of a suitable Lewis acid. We also suggest that the biosynthesis of marine ladder polyethers may proceed via epoxide-to-epoxonium ring-opening cyclization of polyepoxide.

Extreme Variability Quasars in Their Various States. II. Spectral Variation Revealed with Multiepoch Spectra

We previously built a sample of 14,012 extremely variable quasars (EVQs) based on Sloan Digital Sky Survey (SDSS) and Pan-STARRS1 photometric observations. In this work we present the spectral fitting to their SDSS spectra and study the spectral variation in 1259 EVQs with multiepoch SDSS spectra (after prudently excluding spectra with potentially unreliable spectroscopic photometry). We find a clear “bluer-when-brighter” trend in EVQs, consistent with previous findings of normal quasars and active galactic nuclei. We detect significant intrinsic Baldwin effect (iBeff, i.e., smaller line equivalent width at higher continuum flux in individual active galactic nuclei) in the broad Mg ii and C iv lines of EVQs. Meanwhile, no systematical iBeff is found for the broad Hβ line, which could be attributed to strong host contamination at longer wavelengths. Remarkably, by comparing the iBeff slope of EVQs with archived changing-look quasars, we show that the changing-look quasars identified in the literature are most likely a biased (due to its definition) subpopulation of EVQs, rather than a distinct population of quasars. We also found no significant broad line breathing of Hβ, Mg ii, or C iv, suggesting the broad line breathing in quasars may disappear at longer timescales (∼3000 days).

The Minimum Protein Staple? - Towards 'bio'-Baldwin's rules via inter-phosphosite linking in the MEK1 activation loop.

In small molecule organic chemistry, the heuristic insight into ring-forming processes that was enabled by Baldwin's rules some 50 years ago proved a step-change in the role of mechanistically guided synthesis. It created a lens upon and marker of fundamental stereoelectronic and conformation-guided chemical processes. However, despite the widespread role of stereoelectronics and conformational control in Biology, no equivalent coherent exploitation of trapped, ring-forming processes yet exists in biomolecules. In the development of a minimal ring-closing process in intact proteins that might prove suitable in a coherent rule-set, we have tested endo-trig ring-closing conjugate thioether lanthionine (Lan) -CH2-S-CH2- formation as a limiting cyclization. Spontaneous Lan formation in proteins is rare if not non-existent and when found in natural product cyclic peptides it requires the mediation of corresponding biosynthetic enzymes as well as productive reactive conformations to guide it. Here, we show that within a conformationally flexible and functionally important protein loop - the MAPK kinase phosphorylation-targeted activation loop - Lan ring-closing is possible. Ring-closing proves to be critically dependent on the location of a trig electrophilic site in just one of two regioisomeric potential precursors to allow phosphosite-to-phosphosite 'stapling'. This first example of spontaneous protein thioether ring-closing/'stapling' and its accessibility from just one precursor (despite the potential for both to form an identical 'staple') now reveals the potential for Lan formation not only as an accessible form of minimal stapling in proteins but also as an exquisitely sensitive probe of associated protein geometries. We suggest that the use of this (as well as the development of other such, intramolecular protein traps that are dependent on inherent protein-controlled reactivity rather than forced crosslinking) may allow the broader trapping and mapping of relevant, even minor, protein states. In this way, protein ring formation may enable a form of extended 'bio-Baldwin's rules' that help to delineate relevant protein conformational space.

The Sloan Digital Sky Survey Reverberation Mapping Project: Investigation of Continuum Lag Dependence on Broad-line Contamination and Quasar Properties

This work studies the relationship between accretion-disk size and quasar properties, using a sample of 95 quasars from the Sloan Digital Sky Survey Reverberation Mapping Project with measured lags between the g and i photometric bands. Our sample includes disk lags that are both longer and shorter than predicted by the Shakura and Sunyaev model, requiring explanations that satisfy both cases. Although our quasars each have one lag measurement, we explore the wavelength-dependent effects of diffuse broad-line region (BLR) contamination through our sample’s broad redshift range, 0.1 < z < 1.2. We do not find significant evidence of variable diffuse Fe ii and Balmer nebular emission in the rms spectra, nor from Anderson–Darling tests of quasars in redshift ranges with and without diffuse nebular emission falling in the observed-frame filters. Contrary to previous work, we do not detect a significant correlation between the measured continuum and BLR lags in our luminous quasar sample, similarly suggesting that our continuum lags are not dominated by diffuse nebular emission. Similar to other studies, we find that quasars with larger-than-expected continuum lags have lower 3000 Å luminosities, and we additionally find longer continuum lags with lower X-ray luminosities and black hole masses. Our lack of evidence for diffuse BLR contribution to the lags indicates that the anticorrelation between continuum lag and luminosity is not likely to be due to the Baldwin effect. Instead, these anticorrelations favor models in which the continuum lag increases in lower-luminosity active galactic nuclei, including scenarios featuring magnetic coupling between the accretion disk and X-ray corona, and/or ripples or rims in the disk.

Wavelength dependences of the optical/UV and X-ray luminosity correlations of quasars

ABSTRACT The interband correlations between optical/ultraviolet (UV) and X-ray luminosities of active galactic nuclei (AGNs) are important for understanding the disc–coronal connection, as well as using AGN as standard candles for cosmology. It is conventional to measure the X-ray luminosity at rest-frame 2 keV and compare to the UV luminosity at the rest-frame 2500 Å, but the wavelength dependence was never well explored. In this work, we adopt a well-defined sample of 1169 unobscured quasars in the redshift range 0.13–4.51, and apply the direct-correlation method to explore how the correlation with the 2 keV luminosity changes at different optical/UV wavelengths, from 1280 to 5550 Å where the spectral quality is high. We find that the luminosity at all UV continuum wavelengths correlates with the X-ray luminosity similarly to that at 2500 Å, and that these correlations are better than at the optical wavelengths. Strong self-correlation is also found in the broad-band optical/UV continuum, supporting the scenario that it is dominated by the disc emission. Correlations of various emission lines are also investigated (e.g. C iv, C iii], Mg ii, Hβ, and [O iii]λλ4959/5007), including the Baldwin effect and correlations involving linewidths. We find the forms of these line correlations are different, and they are also different from their underlying continua, suggesting various complexities in the line-generation process. We discuss these results in the disc-wind scenario. Our study confirms that the rest-frame 2500 Å is a good wavelength to represent the optical/UV continual properties of quasars, and shows the advantages of the direct-correlation method.

Quasar Factor Analysis—An Unsupervised and Probabilistic Quasar Continuum Prediction Algorithm with Latent Factor Analysis

Since their first discovery, quasars have been essential probes of the distant Universe. However, due to our limited knowledge of its nature, predicting the intrinsic quasar continua has bottlenecked their usage. Existing methods of quasar continuum recovery often rely on a limited number of high-quality quasar spectra, which might not capture the full diversity of the quasar population. In this study, we propose an unsupervised probabilistic model, quasar factor analysis (QFA), which combines factor analysis with physical priors of the intergalactic medium to overcome these limitations. QFA captures the posterior distribution of quasar continua through generatively modeling quasar spectra. We demonstrate that QFA can achieve the state-of-the-art performance, ∼2% relative error, for continuum prediction in the Lyα forest region compared to previous methods. We further fit 90,678 2 < z < 3.5, signal-to-noise ratio >2 quasar spectra from Sloan Digital Sky Survey Data Release 16 and found that for ∼30% quasar spectra where the continua were ill-determined with previous methods, QFA yields visually more plausible continua. QFA also attains ≲1% error in the 1D Lyα power spectrum measurements at z ∼ 3 and ∼4% in z ∼ 2.4. In addition, QFA determines latent factors representing more physical motivation than principal component analysis. We investigate the evolution of the latent factors and report no significant redshift or luminosity dependency except for the Baldwin effect. The generative nature of QFA also enables outlier detection robustly; we showed that QFA is effective in selecting outlying quasar spectra, including damped Lyα systems and potential Type II quasar spectra.

6-Endo-dig cyclization: Flexible enforce to develop synthetic route in organic syntheses

The organic ring closure reaction of diverse acyclic compounds is governed mostly by the Baldwin rule. The ring closure compounds shows emergent application. In recent years, ring closure reactions that are favoured by the Baldwin rules have received a lot of attention. In particular, the Baldwin rule favours the usage of sp- geometrical (diagonal) molecules in the cyclization reaction. The endo-dig cyclization help for synthesis of bulky compound in simple manner via radical coupling. The radical coupling method help for synthesis of various cyclized compounds, also heterocyclic compounds like, three – eight memebered ring compounds. Also, the endo dig cyclization used for synthesis of C-C, C-N, C-O, C-S bond forming compounds. From the all ring closing reaction, 6-endo dig cyclization has great important for synthesis of highly active 6, 7, 8 membered ring compounds. The formed 6-endo dig cyclized product has selective activity against various field cosmetics, medicinal, dye, agrochemical. There are come list of organic compounds are synthesis via 6-endo-dig cyclization like, carbazole, fused benzimidazole, fused pyrimidine, oxazole, chromenos, pyridine, quinoline etc., analogues. The 6-endo-dig cyclization reaction proceed presence of transition metal catalyst and with out catalyst. The 6-endo-dig cyclization processes can be used to synthesise a wide range of 6 membered heterocycles and carbocycles. This review compiles the significant uses of 6-endo-dig cyclization in organic synthesis from a variety of perspectives.

Regioselective electrochemical oxidative radical ortho-(4 + 2)/ipso-(3 + 2) cyclization

Achieving regioselectivity in radical cyclization reactions is of central importance, yet extremely challenging. Although Baldwin's rules provided guidance on the addition of radical species with alkenes/alkynes, the ortho-/ipso-selectivity of the cyclic reaction between radical species (especially alkyl and alkenyl radical) and aryl groups is still ambiguous. Herein, we develop an electrochemically enabled regioselective ortho-(4 + 2)/ipso-(3 + 2) cyclization of alkyl/alkenyl radicals with aryl groups, which provides a series of tetrahydronaphthalene and spirocarbocycle derivatives, exhibiting a broad substrate scope and functional group tolerance. Alkyl/alkenyl radicals are generated by Cp2Fe-mediated electrochemical oxidative radical addition of benzylic malonates with alkenes and alkynes. The method avoids the use of chemical oxidant/base/noble metal, the pre-functionalization of substrates, and the over-oxidation of compounds. Theoretical studies reveal that the dominant factor promoting the alkene-preferred ortho-addition is the favorable interaction energy; the alkyne-preferred ipso-addition regioselectivity is controlled by the distortion energy. Notably, this strategy is regarded as an important supplement to Baldwin's rules for radical cyclization.

Environmental hormesis in living systems: The role of hormetic trade-offs

Hormesis (low-dose stimulation and high-dose inhibition) can be accompanied by hormetic trade-offs, that is, stimulation of some traits and inhibition (trade-off 1) or invariability (trade-off 2) of others. Currently, trade-off options and their biological significance are insufficiently studied. Therefore, the review analyses trade-off types, their relationship with asynchronous stress responses of indicators, the importance of trade-offs for preconditioning, hormesis transgenerational effects, fitness, and evolution. The analysis has shown that hormetic trade-offs 1 and 2 can be observed in evolutionarily distant groups of organisms and at different biological levels (cells, individuals, populations, and communities) with abiotic and biotic stressors, as well as various pollutants. Trade-offs 1 and 2 are found both between different functional traits (e.g., self-maintenance and reproduction in animals, growth and defense in plants), and between the endpoints of the same functional trait (e.g., seed weight and seed number in plants). Asynchronous responses of indicators to a low-dose stressor can lead to hormetic trade-offs in two cases: 1) these indicators have different responses (hormesis, inhibition or zero reaction) in the same dose range; 2) these indicators have hormetic responses with different hormetic zones. Trade-offs can have a positive, negative or zero effect on preconditioning, offspring, and fitness of the population. Trade-offs can potentially affect evolution in two ways: 1) the creation of trends in genotype selection; 2) participation in the assimilation of phenotypic adaptations in the genotype through the Baldwin effect (selection of mutations copying adaptive phenotypes).

6-Endo-dig vs 5-exo-dig: Exploring Radical Cyclization Preference with First-, Second-, and Third-row Linkers using High-level Quantum Chemical Methods.

As an expansion upon Baldwin rules, the cyclization reactions of hex-5-yn-1-yl radical systems with different first-, second-, and third-row linkers are explored at the CCSD(T) level via means of the SMD(benzene)-G4(MP2) thermochemical protocol. Unlike C, O, and N linkers, systems with B, Si, P, S, Ge, As, and Se linkers are shown to favor 6-endo-dig cyclization. This offers fundamental insights into the rational synthetic design of cyclic compounds. A thorough analysis of stereoelectronic effects, cyclization barriers, and intrinsic barriers illustrates that structural changes alter the cyclization preference by mainly impacting 5-exo-dig reaction barriers. Based on the high-level computational modeling, we proceed to develop a new tool for cyclization preference prediction from the correlation between cyclization barriers and radical structural parameters (e.g., linker bond length and bond angle). A strong correlation is found between the radical attack trajectory angle and the reaction barrier heights, i.e., cyclization preference. Finally, the influence of stereoelectronic effects on the two radical cyclization pathways is further investigated in stereoisomers of hypervalent silicon system, which provides novel insight into cyclization control.

A measure of cosmological distance using the C IV Baldwin effect in quasars

We use the anticorrelation between the equivalent width (EW) of the C IV 1549 Å emission line and the continuum luminosity in the quasars rest frame (Baldwin effect) to measure their luminosity distance as well as estimate cosmological parameters. We obtain a sample of 471 Type I quasars with the UV-optical spectra and EW (C IV) measurements in the redshift range of 2.3 &lt; z &lt; 7.1 including 25 objects at 5 &lt; z &lt; 7.1, which can be used to investigate the C IV Baldwin effect and determine cosmological luminosity distance. The relation EW(C IV) ∝ (λLλ)γ can be applied to check the inverse correlation between the C IV EW and Lλ of quasars and give their distance, and the data suggest that the EW of C IV is inversely correlated with continuum monochromatic luminosities. On the other hand, we also consider dividing the Type I quasar sample into various redshift bins, which can be used to check if the C IV EW–luminosity relation depends on the redshift. Finally, we apply a combination of Type I quasars and Type Ia supernovae (SNIa) of the Pantheon sample to test the property of dark energy concerning whether or not its density deviates from the constant, and give the statistical results.

Integrating neuroplasticity and evolution

Neuroplasticity and evolutionary biology have been prominent fields of study for well over a century. However, they have advanced largely independently, without consideration of the benefits of integration. We propose a new framework by which researchers can begin to examine the evolutionary causes and consequences of neuroplasticity. Neuroplasticity can be defined as changes to the structure, function or connections of the nervous system in response to individual experience. Evolution can alter levels of neuroplasticity if there is variation in neuroplasticity traits within and between populations. Neuroplasticity may be favored or disfavored by natural selection depending on the variability of the environment and the costs of neuroplasticity. Additionally, neuroplasticity may affect rates of genetic evolution in many ways: for example, decreasing rates of evolution by buffering against selection or increasing them via the Baldwin effect, by increasing genetic variation or by incorporating evolved peripheral changes to the nervous system. These mechanisms can be tested using comparative and experimental approaches and by examining patterns and consequences of variation in neuroplasticity among species, populations and individuals.

Pnictogen‐Bonding Catalysts, Compared to Tetrel‐Bonding Catalysts: More Than Just Weak Lewis Acids

AbstractA hyperresponsive tool to assess supramolecular catalysis, the cyclization of di‐epoxides into cyclic ethers is used to elucidate the difference between pnictogen‐bonding and Lewis acid catalysis systematically. For all stereoisomers, most tested catalysts follow the Baldwin rules. Brønsted acid and anion–π catalysis afford almost only Baldwin products. Lewis acids such as SbCl3, BF3 and BiCl3 give the poorest selectivity, with at least 50 % Baldwin (B) products for all stereoisomers. In clear contrast, optimized pnictogen‐bonding catalysts operating on the Sb(III) and the Sb(V) level give the fused anti‐Baldwin (A) bicycles as the main product of trans epoxides, independent of syn or anti relation of the two epoxides. In the cis series, Sb(III) pnictogen‐bonding catalysts afford BA products almost exclusively for syn diastereomers, while anti diastereomers give equal amounts of BA and AB products. Sb(V) pnictogen‐bonding catalysts show similarly special trends. These unique characteristics support that pnictogen‐bonding catalysis differs from Lewis acid catalysis and can arguably be defined as its non‐covalent counterpart, just like hydrogen‐bonding catalysis is understood and appreciated as the non‐covalent counterpart of Brønsted acid catalysis. Computational studies on the origin of anti‐Baldwin selectivity reveal Sb(V) catalysts with an introvert deep σ hole surrounded by an almost planar ring of ligands. Central pnictogen‐bond attraction against peripheral steric repulsion then forces the epoxide to break open. In contrast, transient antimony oxidation in cyclic intermediates accounts for the chemoselectivity of Sb(III) catalysts. Presumably due to insufficient accessibility of their σ holes, the activity of tetrel‐bonding catalysts is negligible. The division between powerful pnictogen‐bonding and irrelevant tetrel‐bonding catalysts does not exist with the respective orthodox Lewis acids and thus supports that σ‐hole and Lewis acid catalysis are not the same.

Free rider recognition—A missing link in the Baldwinian model of music evolution

The interactions between species-specific predispositions and cultural plasticity in the development of human musical behavior have recently become the rationale for a possible Baldwinian origin of human musicality. In the previously suggested Baldwinian scenarios of music origin, social bonding has been indicated as the crucial adaptive value that became the main cause of the co-evolutionary process that led to our musicality. However, the adaptive value of social bonding does not explain the cultural variability of musical expressions that enabled the Baldwinian evolution of musicality. The main aim of this article is to show that free rider recognition, along with social bonding and signaling commitment, could have been a possible adaptive function of hominin musical rituals. In the proposed scenario, free rider recognition became a “flywheel” of the arms race between deception and cooperation. As a result, the interplay between the canalization and plasticity of musical learning became a part of music evolution. This process created a cultural niche in which hominin vocal learning was specialized in the imitation of discrete pitch and rhythm.

An Extensive Study of Blazar Broad Emission Line: Changing-look Blazars and the Baldwin Effect

It is known that the blazar jet emissions are dominated by nonthermal radiation, while the accretion disk jets are normally dominated by thermal emission. In this work, our aim is to study the connection between the two types of emission by investigating the correlation between the blazar emission-line intensity property, which embodies the nature of an accretion disk, and the γ-ray flux property, which is the representative of jet emission. We compiled a sample of 656 blazars with available emission-line equivalent widths (EWs), the GeV γ-ray flux, and the spectral energy distribution (SED) information from the literature. In this work, we found 55 previous blazar candidates of uncertain types (BCUs) that are now identified as flat-spectrum radio quasars (FSRQs), and found 52 “changing-look” blazars based on their EWs, 45 of which are newly confirmed. These changing-look blazars have a larger accretion ratio () than BL Lacertae (BL Lac) objects. In addition, we suggest that the lower synchrotron peak blazars (LSPs) could be the source of changing-look blazars because 90.7% of the changing-look blazars in this work are confirmed as LSPs. An anticorrelation between EW and continuum intensity, the so-called global “Baldwin effect” (BEff), has been confirmed. We suggest that the steeper global BEff observed for the blazar than for radio-quiet active galactic nuclei (RQ-AGNs) is caused by the inverse Compton scattering of broad-emission-line photons. This interpretation is further supported by the positive correlation between the emission-line EW and intrinsic inverse Compton luminosity.

Extreme X-Ray Reflection in the Nucleus of the Seyfert Galaxy NGC 5033

NGC 5033 is an intriguing Seyfert galaxy because its subclassification may change with time, and because optical and submillimeter observations find that the massive black hole does not sit at the dynamical center of the galaxy, pointing to a past merger. We obtained a new optical spectrum of NGC 5033 using the 200″ Hale telescope at Palomar that clearly reveals a broad Hβ line (FWHM = 5400 ± 300 km s−1). This signals a clear view of the optical broad line region and requires Seyfert-1.5 designation. Some spectra obtained in the past suggest a Seyfert-1.9 classification, potentially signaling a variable or “changing-look” geometry. Our analysis of a 2019 Chandra spectrum of the massive black hole reveals very little obscuration, also suggesting a clean view of the central engine. However, the narrow Fe Kα emission line is measured to have an equivalent width of EW eV. This value is extremely high compared to typical values in unobscured active galactic nuclei . Indeed, the line is persistently strong in NGC 5033: the line equivalent width in a 2002 XMM-Newton snapshot is EW eV, similar to the EW eV equivalent width measured using ASCA in 1999. These results can likely be explained through a combination of an unusually high covering factor for reflection, and fluxes that are seen out of phase owing to light travel times. We examine the possibility that NGC 5033 may strengthen evidence for the X-ray Baldwin effect.