Unusual Formation Research Articles

MANNICH REACTION’S MESMERIZING MANIFESTATIONS

After introduction of a new natural or synthetic chemical entity as a drug, the focus of research has always shifted to the modification of this chemical entity with the objective of improving ADMET properties, formulations for its efficient delivery, solubility, stability, organoleptic properties, reduction of toxicity, expansion of pharmacological range, formation of precursors, condensation products, complexation, prevention of formation of trace impurities and more. For example, the analgesic and antipyretic drug antipyrine, one of the earliest synthetic drugs, forms an intermolecular hydrogen bond with salicylic acid to give the stable compound antipyrine salicylate, also known as salipyrin. During the development of an aqueous drug formulation containing salipyrin and hexamine, 112 years ago, the unusual formation of a precipitate after some time did not go unnoticed by the young pharmacist and chemist Carl Mannich at Berlin University. Mannich then went on to explain the possible mechanism of formation of the condensation product, later to be known as the first Mannich compound or Mannich base, in a seminal, 21-page publication along with his student Krösche. The explanation was as much brilliant as it was accurate. He recognised that it was a generally applicable reaction, which would open the doors to the then difficult-to- synthesize 1,3-ketamines and which would allow the formation of open and cyclic compounds containing nitrogen – and to the world of natural product chemistry. An artistic view of the first Mannich base, which also happened to be tris-symmetrical, is reproduced below.

Weak Gravitational Lensing around Low Surface Brightness Galaxies in the DES Year 3 Data

We present galaxy-galaxy lensing measurements using a sample of low surface brightness galaxies (LSBGs) drawn from the Dark Energy Survey Year 3 (Y3) data as lenses. LSBGs are diffuse galaxies with a surface brightness dimmer than the ambient night sky. These dark-matter-dominated objects are intriguing due to potentially unusual formation channels that lead to their diffuse stellar component. Given the faintness of LSBGs, using standard observational techniques to characterize their total masses proves challenging. Weak gravitational lensing, which is less sensitive to the stellar component of galaxies, could be a promising avenue to estimate the masses of LSBGs. Our LSBG sample consists of 23,790 galaxies separated into red and blue color types at g−i≥0.60 and g−i<0.60, respectively. Combined with the DES Y3 shear catalog, we measure the tangential shear around these LSBGs and find signal-to-noise ratios of 6.67 for the red sample, 2.17 for the blue sample, and 5.30 for the full sample. We use the clustering redshifts method to obtain redshift distributions for the red and blue LSBG samples. Assuming all red LSBGs are satellites, we fit a simple model to the measurements and estimate the host halo mass of these LSBGs to be . We place a 95% upper bound on the subhalo mass at . By contrast, we assume the blue LSBGs are centrals, and place a 95% upper bound on the halo mass at log(Mhost/M⊙)<11.84. We find that the stellar-to-halo mass ratio of the LSBG samples is consistent with that of the general galaxy population. This work illustrates the viability of using weak gravitational lensing to constrain the halo masses of LSBGs.

Formation of Close-in Neptunes around Low-mass Stars through Breaking Resonant Chains

Conventional planet formation theories predict a paucity of massive planets around small stars, especially very low-mass (0.1−0.3 M ⊙) mid-to-late M dwarfs. Such tiny stars are expected to form planets of terrestrial sizes but not much bigger. However, this expectation is challenged by the recent discovery of LHS 3154 b, a planet with period of 3.7 days and minimum mass of 13.2 M ⊕ orbiting a 0.11 M ⊙ star. Here, we propose that close-in Neptune-mass planets like LHS 3154 b formed through an anomalous series of mergers from a primordial compact system of super-Earths. We perform simulations within the context of the “breaking the chains” scenario, in which super-Earths initially form in tightly spaced chains of mean-motion resonances before experiencing dynamical instabilities and collisions. Planets as massive and close-in as LHS 3154 b (M p ∼ 12−20 M ⊕, P < 7 days) are produced in ∼1% of simulated systems, in broad agreement with their low observed occurrence. These results suggest that such planets do not require particularly unusual formation conditions but rather are an occasional by-product of a process that is already theorized to explain compact multiplanet systems. Interestingly, our simulated systems with LHS 3154 b-like planets also contain smaller planets at around ∼30 days, offering a possible test of this hypothesis.

The Mediastinal Distortions

The case we present involves an atypically developed thoracic aorta, resulting in the consecutive displacement of the trachea and esophagus, combined with the unusual formation of vascular bridges between the ascending and descending thoracic aorta and the arising supraaortic branches. This represents a pathological entity further associated with a cardiac condition of Sick Sinus Syndrome and heterotopy of the excitation center in the pulmonary veins. Multiple descriptions of the combination of dextrocardia and Sick Sinus Syndrome have been reported by Aurora Bakalli et al. 2021 (1), as well as the combination of dextrocardia, persistent left superior vena cava, and Sick Sinus Syndrome by Gangliang Guo et al. 2017 (2), and another case of dextrocardia and Sick Sinus Syndrome by Junqian Luo et al. 2022 (3). Such combinations of anomalies have not been reported in larger statistical collections to date.

Post–peak petrochronology and C–O–H fluid influx in the lower crust: A case study of garnet–orthopyroxene granulites from the Rauer Islands, East Antarctica

Garnet–orthopyroxene granulites from the Rauer Islands (East Antarctica) provide a spectacular example to investigate the late fluid evolution, metamorphic duration, and behavior of monazite and zircon in response to metamorphic reactions and fluid–rock interaction. Here, we characterize the secondary fluid inclusions in peritectic garnet and orthopyroxene, which occur as multiphase inclusions along micro–fractures. Inclusions are composed of siderite, pyrophyllite, calcite, quartz and residual CO2, representing stepdaughter phases resulting from the interactions between C–O–H fluid and its hosts at variable temperatures during retrogression. Zircon grains show clear core–rim structure, which yield 206Pb/238U ages of 540–507 Ma and 527–490 Ma, respectively. Index inclusions and internal structures suggest that the cores document the timing of peak and post–peak decompression while the growth of rims corresponds to melt crystallization during the final cooling. The UPb systems in zircons are considered to have not been obviously affected by fluid or melt–mediated modification. The unusual formation of monazites in garnet–orthopyroxene granulites may be linked with the elevated phosphorus budget as a result of apatite dissolution during the prograde melting of the rocks. Detailed investigations suggest that the crystallization of monazites occurred both at peak and post–decompression stages, whose isotopic systematics has been completely reset due to melt–mediated dissolution–precipitation. The spurious dates for monazites (522–495 Ma) are highly coinstantaneous with the dating results for zircon rims, further supporting this view. Therefore, we conclude that the late carbonic fluid influx cannot result in marked U(Th)–Pb resetting in zircon and monazite. Instead, anatectic melt may have played an important role in the disturbance of isotopic systematics in monazites, especially for long–lived high–grade metamorphic terranes. Combined with previously published data, we propose that the Pan–African metamorphic event in the Rauer Islands may have reached the peak at around ∼540 Ma, followed by a protracted post–peak evolution that lasted for at least ∼50 Myr. This study highlights the importance of an integrated investigation of fluid and index mineral inclusions, as well as the chemical signatures of zircon and monazite, to interpret chronological data correctly.

Unusual formations in the B. R. Chinchorro Bank: Miniature atolls

AbstractThere are unique reef patches in the Biosphere Reserve Banco Chinchorro reef lagoon that have an unusual formation. They appear to be miniature atolls. These formations are at a depth of 2–6 m, and present flourishing coral growth, whereas a few meters away others are strongly decayed. To define the cause of this phenomenon, an analysis of three of these formations was carried out to try to relate the structure of the corals that make up these formations to environmental factors. We recorded in tidal cycles, 12 environmental parameters, and micronutrients. Despite their closeness, two patches show high biodiversity, whereas the third shows low diversity. These results show notable differences between the three patches resulting from position on the reef (leeward and windward), in addition, these patterns relate to the undercurrent of possible relict water that drains from the lagoon microsystem of the main island of the reef, Cayo Centro, toward the miniature atolls.

Transmission electron microscopy reveals clusters of Au–Ag nanoparticles formed in TiO2 thin film, with enhanced plasmonic response

This work reports on the influence of nanoparticle (NP) size distribution and the chemical nature of gold (Au) and/or silver (Ag) NPs in the localized surface plasmon resonance (LSPR) responses. The NPs were produced embedded in a titanium dioxide (TiO2) thin film, deposited by reactive magnetron sputtering technique followed by in-vacuum thermal treatment at 400 °C. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) gave quantitative key information in terms of both the size and distribution of the noble metal NPs. The average Feret diameter was 17 nm (σ = 8) and 55 nm (σ = 28) for Au/TiO2 and Ag/TiO2 films, respectively, while the Au–Ag/TiO2 film showed intermediate values, with an average size of 22 nm (σ = 9). HAAD-STEM, complemented by EDX chemical mapping, revealed an unusual formation of cluster structures containing local distributions of bimetallic (alloyed) Au–Ag NPs. The synergetic characteristics and properties of such bimetallic Au–Ag NPs resulted in an outstanding LSPR sensitivity compared to the monometallic counterparts. Furthermore, the analysis of the average nearest neighbor distances (about one order of magnitude lower than counterparts) suggests the existence of plasmonic hotspots relevant to be explored in sensing and surface-enhanced spectroscopies.

Laser Engineering Nanocarbon Phases within Diamond for Science and Electronics.

Diamond, as the densest allotrope of carbon, displays a range of exemplary material properties that are attractive from a device perspective. Despite diamond displaying high carbon-carbon bond strength, ultrashort (femtosecond) pulse laser radiation can provide sufficient energy for highly localized internal breakdown of the diamond lattice. The less-dense carbon structures generated on lattice breakdown are subject to significant pressure from the surrounding diamond matrix, leading to highly unusual formation conditions. By tailoring the laser dose delivered to the diamond, it is shown that it is possible to create continuously modified internal tracks with varying electrical conduction properties. In addition to the widely reported conducting tracks, conditions leading to semiconducting and insulating written tracks have been identified. High-resolution transmission electron microscopy (HRTEM) is used to visualize the structural transformations taking place and provide insight into the different conduction regimes. The HRTEM reveals a highly diverse range of nanocarbon structures are generated by the laser irradiation, including many signatures for different so-called diaphite complexes, which have been seen in meteorite samples and seem to mediate the laser-induced breakdown of the diamond. This work offers insight into possible formation methods for the diamond and related nanocarbon phases found in meteorites.

Synthesis of N-heterocyclic amides from imidazoheterocycles through convergent paired electrolysis.

An efficient ring opening of imidazoheterocycles induced by a direct C-H azidation resulting in an unusual formation of N-heterocyclic amides has been successfully developed through convergent paired electrolysis. A broad scope of pyridylbenzamides could be obtained in moderate to excellent yields under exogenous-oxidant, electrolyte- and metal-free electrochemical conditions. The methodology was transferred to continuous flow conditions resulting in notable improvements particularly in terms of cost-efficiency over traditional batch versions.

Unusual formation of air bubbles in the arms of the California two-spot octopus, Octopus bimaculatus Verrill, 1883 during handling in captivity

Unusual formation of air bubbles in the arms of the California two-spot octopus, Octopus bimaculatus Verrill, 1883 during handling in captivity

Unusual formation of Ir(III) complexes with non‐symmetrical NacNac ligands: Synthesis, characterization, and evaluation of catalytic activity in transfer hydrogenation reduction reactions

A new type of trans‐dichloro‐Ir(III) complexes derived from non‐symmetrical NacNac‐type ligands was unexpectedly obtained as the main reaction product from the former ligands and the dimeric species [Ir(COD)Cl2]. One equivalent of LH was reacted with an excess of [Ir(COD)Cl]2 in dichloromethane or toluene as solvent and at room temperature. The general formula of the product is [IrCl2(COD)L] and was isolated as a sole product instead of the expected Ir(I) compound [Ir(COD)L]; all the new Ir(III) were prepared in high yields as microcrystalline solids. They were all stable under laboratory atmosphere, lasting for weeks in solution and for months in solid state. The structure of each compound was examined by 1D and 2D nuclear magnetic resonance (NMR) and high‐resolution mass spectrometry (HRMS). Complex 1k was selected for an X‐ray diffraction study. Finally, an evaluation was made of the catalytic activity of all complexes in the transfer hydrogenation reaction of ketones and imines.

TOI-332 b: a super dense Neptune found deep within the Neptunian desert

ABSTRACT To date, thousands of planets have been discovered, but there are regions of the orbital parameter space that are still bare. An example is the short period and intermediate mass/radius space known as the ‘Neptunian desert’, where planets should be easy to find but discoveries remain few. This suggests unusual formation and evolution processes are responsible for the planets residing here. We present the discovery of TOI-332 b, a planet with an ultra-short period of 0.78 d that sits firmly within the desert. It orbits a K0 dwarf with an effective temperature of 5251 ± 71 K. TOI-332 b has a radius of $3.20^{+0.16}_{-0.12}$ R⊕, smaller than that of Neptune, but an unusually large mass of 57.2 ± 1.6 M⊕. It has one of the highest densities of any Neptune-sized planet discovered thus far at $9.6^{+1.1}_{-1.3}$ g cm−3. A 4-layer internal structure model indicates it likely has a negligible hydrogen-helium envelope, something only found for a small handful of planets this massive, and so TOI-332 b presents an interesting challenge to planetary formation theories. We find that photoevaporation cannot account for the mass-loss required to strip this planet of the Jupiter-like envelope it would have been expected to accrete. We need to look towards other scenarios, such as high-eccentricity migration, giant impacts, or gap opening in the protoplanetary disc, to try and explain this unusual discovery.

Central-to-Axial Chirality: Asymmetric Organocatalytic Synthesis of Axially Chiral Chalcones via Exocyclic Dihydronaphthalenes.

Asymmetric synthesis of an unprecedented exocyclic dihydronaphthalene and an axially chiral naphthalene chalcone has been disclosed. Good to excellent asymmetric induction is achieved. The success is attributed to the unusual formation of exocyclic dihydronaphthalene, which plays a crucial role in ensuring axial chirality. This is the first report of exocyclic molecules capable of enabling the synthesis of axially chiral chalcones via stepwise asymmetric vinylogous domino double-isomerization using secondary amine catalysis.

A Re-appraisal of the Challenges Associated with Detecting Alien Signals and Technosigniatures

The Rare Earth Hypothesis contends that Earth’s unusual formation and distinct evolutionary pathways led to the unlikely emergence of Homo sapiens. This contention is developed further by combining the universal principles of the Newtonian n-body problem and Darwinism to argue that there is also an inherent randomness in the sequence, timing, duration and nature of evolutionary outcomes on alien worlds. This has two important implications. Firstly, where alien life might emerge, evolutionary pathways must differ considerably to those on Earth. Within this, intelligence is not the goal of evolution nor is it necessarily the best adaptation for a given niche; there is no systematic, inexorable progression towards higher intelligence and technology. Secondly, the chances of an advanced alien civilisation emerging from a separate, random evolutionary pathway with matching technology, and proximate signalling in deep time are vanishingly small. This re appraisal of the challenges associated with detecting alien signals has the advantage of using two key universal principles without relying explicitly on anthropocentric assumptions. Keywords: Fermi Paradox, Rare Earth Hypothesis, Alien Signals, SETI, Exoplanets

An accessory muscle belly or an accessory muscle head? An unusual arrangement of muscles in the anterior compartment of the forearm

PurposeKnowledge of the unusual arrangement of the flexor pollicis longus (FPL) muscle is important as the variable tendon may be a rare cause of carpal tunnel syndrome.MethodsDuring a routine dissection at the Department of Anatomy, an unusual formation of the FPL muscle was observed in a formalin embalmed Central European cadaver.ResultsThis report presents a variation of the FPL muscle, where the muscle split and formed a separate accessory head inserting into the first lumbrical muscle. Moreover, a tendinous interconnection was present between the FPL muscle tendon and the tendon of the aberrant muscle head.ConclusionThe cases described by previous literature, concerning the Linburg–Comstock variation or the accessory head of the first lumbrical muscle originating from the FPL muscle, are closest to the present case. Such variation has a clinical significance ranging from the functional limitation of the thumb and index finger movement to the potential median nerve compression.

Unusual Formation of 1,2,4-Oxadiazine Core in Reaction of Amidoximes with Maleic or Fumaric Esters.

We have developed a simple and convenient method for the synthesis of 3-aryl- and 3-hetaryl-1,2,4-oxadiazin-5-ones bearing an easily functionalizable (methoxycarbonyl)methyl group at position 6 via the reaction of aryl or hetaryl amidoximes with maleates or fumarates. The conditions for this reaction were optimized. Different products can be synthesized selectively in good yields depending on the base used and the ratio of reactants: substituted (1,2,4-oxadiazin-6-yl)acetic acids, corresponding methyl esters, or hybrid 3-(aryl)-6-((3-(aryl)-1,2,4-oxadiazol-5-yl)methyl)-4H-1,2,4-oxadiazin-5(6H)-ones. The reaction is tolerant to substituents' electronic and steric effects in amidoximes. As a result, a series of 2-(5-oxo-3-(p-tolyl)-5,6-dihydro-4H-1,2,4-oxadiazin-6-yl)acetic acids, their methyl esters, and 1,2,4-oxadiazoles based on them were prepared and characterized by HRMS, 1H, and 13C NMR spectroscopy. The structures of three of them were elucidated with X-ray diffraction.

Genome mining of fungal globin-like enzymes for catalyzing the synthesis of linear terpenes.

Genome mining for the search and discovery of two new globin-like enzymes, TriB fromFusarium poae and TutaA from Schizophyllum commne, are involved in the synthesis of two linear terpenes tricinonoic acid (1) and 2-butenedioic acid (3). Both in vivo heterologous biosynthesis and in vitro biochemical assays showed that these two enzymes catalyzed the C-C double bond cleavage of a cyclic sesquiterpene precursor (-)-germacrene D (7) and a linear diterpene backbone schizostain (2), respectively. Our work presents an unusual formation mechanism of linear terpenes from fungi and expands the functional skills of globin-like enzymes in the synthesis of terpene compounds.

Ultrastrong nanotwinned titanium alloys through additive manufacturing.

Titanium alloys, widely used in the aerospace, automotive and energy sectors, require complex casting and thermomechanical processing to achieve the high strengths required for load-bearing applications. Here we reveal that additive manufacturing can exploit thermal cycling and rapid solidification to create ultrastrong and thermally stable titanium alloys, which may be directly implemented in service. As demonstrated in a commercial titanium alloy, after simple post-heat treatment, adequate elongation and tensile strengths over 1,600 MPa are achieved. The excellent properties are attributed to the unusual formation of dense, stable and internally twinned nanoprecipitates, which are rarely observed in traditionally processed titanium alloys. These nanotwinned precipitates are shown to originate from a high density of dislocations with a dominant screw character and formed from the additive manufacturing process. The work here paves the way to fabricate structural materials with unique microstructures and excellent properties for broad applications.

Reading the CARDs: The Imprint of Accretion History in the Chemical Abundances of the Milky Way's Stellar Halo

In the era of large-scale spectroscopic surveys in the Local Group, we can explore using chemical abundances of halo stars to study the star formation and chemical enrichment histories of the dwarf galaxy progenitors of the Milky Way (MW) and M31 stellar halos. In this paper, we investigate using the chemical abundance ratio distributions (CARDs) of seven stellar halos from the Latte suite of FIRE-2 simulations. We attempt to infer galaxies’ assembly histories by modeling the CARDs of the stellar halos of the Latte galaxies as a linear combination of template CARDs from disrupted dwarfs, with different stellar masses M ⋆ and quenching times t 100. We present a method for constructing these templates using present-day dwarf galaxies. For four of the seven Latte halos studied in this work, we recover the mass spectrum of accreted dwarfs to a precision of <10%. For the fraction of mass accreted as a function of t 100, we find the residuals of 20%–30% for five of the seven simulations. We discuss the failure modes of this method, which arise from the diversity of star formation and chemical enrichment histories that dwarf galaxies can take. These failure cases can be robustly identified by the high model residuals. Although the CARDs modeling method does not successfully infer the assembly histories in these cases, the CARDs of these disrupted dwarfs contain signatures of their unusual formation histories. Our results are promising for using CARDs to learn more about the histories of the progenitors of the MW and M31 stellar halos.

Leveraging structural and 2D-QSAR to investigate the role of functional group substitutions, conserved surface residues and desolvation in triggering the small molecule-induced dimerization of hPD-L1

Small molecules are rising as a new generation of immune checkpoints’ inhibitors, with compounds targeting the human Programmed death-ligand 1 (hPD-L1) protein are pioneering this area of research. Promising examples include the recently disclosed compounds from Bristol-Myers-Squibb (BMS). These molecules bind specifically to hPD-L1 through a unique mode of action. They induce dimerization between two hPD-L1 monomers through the hPD-1 binding interface in each monomer, thereby inhibiting the PD-1/PD-L1 axis. While the recently reported crystal structures of such small molecules bound to hPD-L1 reveal valuable insights regarding their molecular interactions, there is still limited information about the dynamics driving this unusual complex formation. The current study provides an in-depth computational structural analysis to study the interactions of five small molecule compounds in complex with hPD-L1. By employing a combination of molecular dynamic simulations, binding energy calculations and computational solvent mapping techniques, our analyses quantified the dynamic roles of different hydrophilic and lipophilic residues at the surface of hPD-L1 in mediating these interactions. Furthermore, ligand-based analyses, including Free-Wilson 2D-QSAR was conducted to quantify the impact of R-group substitutions at different sites of the phenoxy-methyl biphenyl core. Our results emphasize the importance of a terminal phenyl ring that must be present in any hPD-L1 small molecule inhibitor. This phenyl moiety overlaps with a very unfavorable hydration site, which can explain the ability of such small molecules to trigger hPD-L1 dimerization.