Unusual Inversion Research Articles

Comparative Phylogenomic Study of Malaxidinae (Orchidaceae) Sheds Light on Plastome Evolution and Gene Divergence.

Malaxidinae is one of the most confusing groups in the Orchidaceae classification. Previous phylogenetic analyses have revealed that the relationships between the taxa in Malaxidinae have not yet been reliably established, using only a few plastome regions and nuclear ribosomal internal transcribed spacer (nrITS). In the present study, the complete plastomes of Oberonia integerrima and Crepidium purpureum were assembled using high-throughput sequencing. Combined with publicly available complete plastome data, this resulted in a dataset of 19 plastomes, including 17 species of Malaxidinae. The plastome features and phylogenetic relationships were compared and analyzed. The results showed the following: (1) Malaxidinae species plastomes possess the quadripartite structure of typical angiosperms, with sizes ranging from 142,996 to 158,787 bp and encoding from 125 to 133 genes. The ndh genes were lost or pseudogenized to varying degrees in six species. An unusual inversion was detected in the large single-copy region (LSC) of Oberonioides microtatantha. (2) Eight regions, including ycf1, matK, rps16, rpl32, ccsA-ndhD, clpP-psbB, trnFGAA-ndhJ, and trnSGCU-trnGUCC, were identified as mutational hotspots. (3) Based on complete plastomes, 68 protein-coding genes, and 51 intergenic regions, respectively, our phylogenetic analyses revealed the genus-level relationships in this subtribe with strong support. The Liparis was supported as non-monophyletic.

Facile One-Pot Synthesis of Polysubstituted Pyridinium Salts by Annulation of Enamines with Alkynes.

An efficient and facile synthesis of highly substituted pyridinium salts through the annulation of enamines with alkynes is reported herein. A Ag2 CO3 /HNTf2 synergistically acting catalyst system was developed and used in a condensation reaction between carbonyl substrates and propargylamine to afford structurally diverse pyridinium salts. A mechanistic investigation shows that this one-pot transformation proceeded via selective 6-endo-dig cyclization of the in situ generated propargylenamine and protonolysis of the resulting vinyl-silver intermediate. The reaction conditions are mild, and the substrate scope is broad. During the cyclization, an unusual inversion of the normal reactivity of α,β-unsaturated carbonyl systems was observed.

МОВОЗНАВЧІ ПОГЛЯДИ ІВАНА ОГІЄНКА НА ПОНЯТТЯ «ПОРЯДОК СЛІВ» КРІЗЬ ПРИЗМУ ФОРМАЛЬНО-ГРАМАТИЧНОЇ ТА КОМУНІКАТИВНОЇ ПАРАДИГМИ

The article grounds the relevance of the regularities of the construction of sentence structure in accordance with the peculiarities of word order with the help of intonation, the speaker’s communicative intent, and the grammatical laws of the Ukrainian language. The main attention is focused on the fact that the interpretation of the sen-tence order of the Ukrainian language as fl uent seems to be incorrect. It is ap-propriate to use the concept of «direct word order» and «indirect word order» (inverse word order»). The origins of the formation and development of the outlined concepts date back to the birth of the formal-grammatical paradigm of language research (Ivan Ohiienko’s reasoning), which later received a broader interpretation in the communicative paradigm (the modern stage of the develop-ment of the Ukrainian language).The following conceptual provisions regarding the given issue are high-lighted in Ivan Ohiienko’s linguistic legacy: all syntactic components of a sen-tence are assigned a certain place in a sentence, the position of sentence compo-nents is caused by the intonation of the speaker and the grammatical laws of the Ukrainian language, inversion is a stylistic aspect of using an unusual word or-der. In addition, the linguist points out such grammatical categories and concepts as valence («words are paired»), semantic approach («the meaning of a word in a sentence»), the identifi cation of grammatical features of the Ukrainian language (the change in the semantic and syntactic meaning of a word according to its place in a sentence). All these testify to the linguistic talent of Ivan Ohiienko and the fact that the linguist was ahead of his time.The linguist pointed out the melodiousness of the Ukrainian language. In the linguist’s opinion, inversion is ordinary and unusual. Ivan Ohiienko believes that ordinary inversion is used only in artistic speech, while unusual inversion should be eradicated from speech. The linguist proved the limited possibilities of a logical approach to the analysis of syntactic units, and thus substantiated the formal-grammatical paradigm

META-REFERENTIAL REALITY IN THE ABYSS OF MEDIA IMAGES AND THEORIES

McLuhan’s statement “the medium is the message”, made at the time of the expansion of television in the 1960s, was confirmed by the advent of the Internet, social media platforms and the digital transformation of modern society. The media form encircles the recipients, becoming an environment more real than reality, much like Baudrillard’s simulacrum. “Immersed” in a media kaleidoscope in which “pictures within a picture” are endlessly multiplied, users find it increasingly difficult to distinguish facts from interpretations, facts from factoids, lost like “Alice in Wonderland” in the virtual space of never-ending stories. Technological progress has preserved all the old media, while producing new ones, in a way similar to the Russian “matryoshka dolls”, but has pushed the truth and moral dilemmas into the background. Entertainment has become the main media content, information is delivered in the “infotainment” form, with the rapid succession of images as a popularized “montage of attractions”. Marx’s fascination with machines and productive forces as grounds of a “social existence that determines men’s consciousness” has undergone an unusual inversion: the media production represents and creates a worldview in a much more sophisticated way than heavy industry, which as a relic of the past becomes an ecological threat to humanity and the planet. “Reality”, the one word that, at the insistence of writer Nabokov, should always appear in quotation marks, is an astonishing artifact of the media and their powerful masters, and the Earth itself has been utilized as Duchamp’s “readymade”, thus becoming an artwork subjected to relentless exploitation for profit. Mastering Manovich’s “language of new media” is necessary for understanding modern information and visual culture, in order to make communication between people possible at all, because the contemporary culture is meta-referential and self-centered. A critical understanding of the world, which requires media literacy and continuous media education, is the only way to avoid complicity in the collapse of reality under the weight of media images that erase the boundaries between reality and fiction, facts and theoretical interpretations.

Coordinatively Unsaturated Amidotitanocene Cations with Inverted σ and π Bond Strengths: Controlled Release of Aminyl Radicals and Hydrogenation/Dehydrogenation Catalysis.

Cationic amidotitanocene complexes [Cp2 Ti(NPhAr)][B(C6 F5 )4 ] (Cp=η5 -C5 H5 ; Ar=phenyl (1 a), p-tolyl (1 b), p-anisyl (1 c)) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti-N bond in 1 a-c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a-c undergo photolytic Ti-N cleavage to release Ti(III) species and aminyl radicals ⋅NPhAr. Reaction of 1 b with H3 BNHMe2 results in fast homolytic Ti-N cleavage to give [Cp2 Ti(H3 BNHMe2 )][B(C6 F5 )4 ] (3). 1 a-c are highly active precatalysts in olefin hydrogenation and silanes/amines cross-dehydrogenative coupling, whilst 3 efficiently catalyzes amine-borane dehydrogenation. The mechanism of olefin hydrogenation was studied by DFT and the cooperative H2 activation key step was disclosed using the Activation Strain Model (ASM).

Unusual Racemization of Tertiary P-Chiral Ferrocenyl Phosphines.

Tertiary phosphines are generally known to withstand inversion under moderate conditions. In this work, a remarkable racemization process of three P‐chiral ferrocenyl phosphines is reported. Subjected to conventional column chromatography as highly enantioenriched compounds, they greatly experienced racemization when collected at the column outlet within minutes. Initially, attention was drawn to this unusual inversion behavior after observing that the superb enantiomeric excess of these ligands (>95 % ee in all cases) was almost lost in their corresponding ruthenium(II) complexes. Successively excluding possible racemization causes, these P‐chiral ferrocenyl phosphines were found to undergo a significant, acid‐catalyzed racemization process at room temperature within a few minutes. This process is mainly observed during standard column chromatography by using conventional silica or alumina, but can also be triggered deliberately by addition of certain acids. Therefore, the stereochemical preservation of P‐chiral phosphines during their purification may per se not always be guaranteed, since column chromatography is the most frequently used technique for purifying such types of compounds.

Understanding the photophysical properties of rhenium(I) compounds coordinated to 4,7-diamine-1,10-phenanthroline: synthetic, luminescence and biological studies.

In the present study, the photophysical properties and preliminary time-dependent density functional theory (TD-DFT) data of new rhenium(i) polypyridyl compounds, fac-[Re(L)(Am2phen)(CO)3]0/+, where Am2phen = 4,7-diamine-1,10-phenanthroline and L = Cl and ethyl isonicotinate (et-isonic), provided new insights into excited-state deactivation through an unusual inversion between two metal-to-ligand charge-transfer excited states. In addition, their cellular uptake using breast cancer (MCF-7) and melanoma (SkMel-147 and SkMel-29) cell lines and bioactivity were investigated and their cell-killing mechanism and protein expression were also studied. Preliminary TD-DFT results showed that both compounds exhibited a strong and broad absorption band around 300-400 nm which corresponds to a combination of ILAm2phen and MLCTRe→Am2phen transitions, and a strong contribution of charge transfer transition MLCTRe→et-isonic for fac-[Re(et-isonic)(Am2phen)(CO)3]+ is also observed. In contrast to typical Re(i) polypyridyl complexes, the substitution of Cl with the et-isonic ligand showed a bathochromic shift of the emission maxima, relatively low emission quantum yield and fast lifetime. Photophysical investigation of the fac-[ReCl(et-isonic)2(CO)3] compound provided meaningful information on the excited state manifold of the fac-[Re(L)(Am2phen)(CO)3]0/+ complexes. As shown in the absorption profile, a remarkable inversion of the lowest-lying excited state takes place from the usually observed MLCTRe→Am2phen to the unusual MLCTRe→et-isonic. The lipophilicity of the positive-complex was higher than that of the non-charge compound and the same trend for the activity against cells was observed, in the absence of light. In addition, flow cytometry and Western Blot analyses showed an overexpression of pro-caspase-9, suggesting a caspase proteolytic cascade through an intrinsic-pathway apoptosis mechanism. The photophysical properties of these compounds reported herein provide new fundamental insights into the understanding of substituent groups on polypyridyl ligands which are relevant to practical development.

Anisotropic upper critical field of pristine and proton-irradiated single crystals of the magnetically ordered superconductor RbEuFe4As4

We present a study of the upper critical field, H$_{c2}$, of pristine and proton-irradiated RbEuFe$_4$As$_4$ crystals in pulsed magnetic fields of up to 65 T. The data for H$_{c2}$ reveal pronounced downwards curvature, particularly for the in-plane field orientation, and a superconducting anisotropy that decreases with decreasing temperature. These features are indicative of Pauli paramagnetic limiting. For the interpretation of these data, we use a model of a clean single-band superconductor with an open Fermi surface in the shape of a warped cylinder, which includes strong paramagnetic limiting. Fits to the data reveal that the in-plane upper critical field is Pauli paramagnetic limited, while the out-of-plane upper critical field is orbitally limited and that the orbital and paramagnetic fields have opposite anisotropies. A consequence of this particular combination is the unusual inversion of the anisotropy, $H_{c2}^{ab} < H_{c2}^c$, of the irradiated sample at temperatures below 10 K. The fits also yield an in-plane Maki parameter, $\alpha_M^{110} \approx$ 2.6, exceeding the critical value for the formation of the Fulde-Ferrell-Larkin-Ovchinnikov state. Nevertheless, the current measurements did not reveal direct evidence for the occurrence of this state.

Pericentric inversion of chromosome 7 in human being associated with recurrent ICSI failure: A case report

Assisted reproductive techniques is specially a boon for severe male factor infertility with non-obstructive azoospermia (NOAZ) and severe oligospermia ( less than 5 million/ml). To study the unusual pericentric inversion in a recurrent ICSI failure case, cytogenetic analysis was done from peripheral blood lymphocytes. Semen analysis revealed that the man had Oligoasthenoteratozoospermia with sperm count of 0.9 million/ml. A karyogram revealed pericentromeric inversion of Chromosome 7. It could be accommodated on models that location of the breakpoint harbours critical genes for spermatogenesis (swm, swm2 and STAG3). Pericentromeric Inversion for chromosome 7 is a rare finding. It may be the etiopathogenic for partial spermatogenetic arrest and recurrent ICSI failure. The children born to such couples must also be analyzed and kept under observation for any clinical indications.

Solvent-dependent inversion of circular dichroism signal in naproxen: An unusual effect!

The electronic circular dichroism (ECD) spectra of naproxen enantiomers were studied as a function of solvents using experimental (circular dichroism) and theoretical (time-dependent density functional theory) approaches. The (R)- and (S)-naproxen enantiomers presented an unusual inversion in their ECD signals in the presence of ethanol and water when compared with polar aprotic solvents such as acetonitrile. From a practical point of view, these findings deserve great attention because these solvents are widely used for high-performance liquid chromatography analysis in quality control of chiral pharmaceutical drugs. This is particularly relevant to naproxen because the (S)-naproxen has anti-inflammatory properties, whereas (R)-naproxen is hepatotoxic. A time-dependent density functional theory computer simulation was conducted to investigate the signal inversion using the solvation model based on density, a reparameterization of polarized continuum model. Electronic circular dichroism signals of conformers were calculated by computer simulation and their contribution to the combined spectra obtained according to Boltzmann weighting. It was found that the experimentally observed ECD signal inversion can be associated with the minor or major contribution of different conformers of naproxen.

The Batture Effect

On a narrow strip of land between the Mississippi River and the U.S. Army Corps of Engineers’ flood control levees in New Orleans, a squatters’ community called the Batture exhibits an unusual inversion of conventional assumptions regarding hazard awareness and development security. For a New Orleanian to willingly take up residence on the “wrong side” of the levee is to break the most fundamental rule of the city’s spatial economy and collective psychology. This article proposes the existence of a Batture Effect , a mode of insurgent citizenship whereby hidden environmental threats are made visible and small-scale architectural, urban, and psychological adaptation measures are tested. As an adaptive design strategy, organic in its development over time and responsive to the immediate needs of residents, the occupation of the Batture demonstrates a homesteader’s approach to land appropriation. In calling into question land-use and ownership, the urban planning process and its associated spatial agency, and the role of the individual in disaster preparedness, this guerilla urbanism suggests relevant lessons to the practice of landscape architecture and urban planning.

Influence of intramolecular hydrogen bonds on regioselectivity of glycosylation. Synthesis of lupane-type saponins bearing the OSW-1 saponin disaccharide unit and its isomers

A series of lupane-type saponins bearing OSW-1 disaccharide unit as well as its regio- and stereoisomers were prepared and used for the structure–activity relationships (SAR) study. Unexpected preference for 1→4-linked regioisomers and an unusual inversion of the conformation of the sugar rings were noted. Cytotoxic activity of new lupane compounds was evaluated in vitro and revealed that some saponins exhibited an interesting bioactivity profile against human cancer cell lines. Influence of the protecting groups on the cytotoxicity was investigated. These results open the way to the synthesis of various lupane-type triterpene and saponin derivatives as potential anticancer compounds.

Prominent intraspecific genetic divergence within Anopheles gambiae sibling species triggered by habitat discontinuities across a riverine landscape.

The Anopheles gambiae complex of mosquitoes includes malaria vectors at different stages of speciation, whose study enables a better understanding of how adaptation to divergent environmental conditions leads to evolution of reproductive isolation. We investigated the population genetic structure of closely related sympatric taxa that have recently been proposed as separate species (An. coluzzii and An. gambiae), sampled from diverse habitats along the Gambia river in West Africa. We characterized putatively neutral microsatellite loci as well as chromosomal inversion polymorphisms known to be associated with ecological adaptation. The results revealed strong ecologically associated population subdivisions within both species. Microsatellite loci on chromosome-3L revealed clear differentiation between coastal and inland populations, which in An. coluzzii is reinforced by a unusual inversion polymorphism pattern, supporting the hypothesis of genetic divergence driven by adaptation to the coastal habitat. A strong reduction of gene flow was observed between An. gambiae populations west and east of an extensively rice-cultivated region apparently colonized exclusively by An. coluzzii. Notably, this 'intraspecific' differentiation is higher than that observed between the two species and involves also the centromeric region of chromosome-X which has previously been considered a marker of speciation within this complex, possibly suggesting that the two populations may be at an advanced stage of differentiation triggered by human-made habitat fragmentation. These results confirm ongoing ecological speciation within these most important Afro-tropical malaria vectors and raise new questions on the possible effect of this process in malaria transmission.

Modulating ion current rectification generating high energy output in a single glass conical nanopore channel by concentration gradient

Abstract Inspired by biological systems that have the inherent skill to generate considerable bioelectricity from the salt content in fluids with highly selective ion channels and pumps on cell membranes, herein, a fully abiotic, single glass conical nanopores energy-harvesting is demonstrated. Ion current rectification (ICR) in negatively charged glass conical nanopores is shown to be controlled by the electrolyte concentration gradient depending on the direction of ion diffusion. The degree of ICR is enhanced with the increasing forward concentration difference. An unusual rectification inversion is observed when the concentration gradient is reversely applied. The maximum power output with the individual nanopore approaches 104 pW. This facile and cost-efficient energy-harvesting system has the potential to power tiny biomedical devices or construct future clean-energy recovery plants.

Independent Ordering of Two Interpenetrating Magnetic Sublattices in the Double Perovskite Sr2CoOsO6

The insulating, fully ordered, double perovskite Sr2CoOsO6 undergoes two magnetic phase transitions. The Os(VI) ions order antiferromagnetically with a propagation vector k = (1/2, 1/2, 0) below TN1 = 108 K, while the high-spin Co(II) ions order antiferromagnetically with a propagation vector k = (1/2, 0, 1/2) below TN2 = 70 K. Ordering of the Os(VI) spins is accompanied by a structural distortion from tetragonal I4/m symmetry to monoclinic I2/m symmetry, which reduces the frustration of the face centered cubic lattice of Os(VI) ions. Density functional theory calculations show that the long-range Os-O-Co-O-Os and Co-O-Os-O-Co superexchange interactions are considerably stronger than the shorter Os-O-Co interactions. The poor energetic overlap between the 3d orbitals of Co and the 5d orbitals of Os appears to be responsible for this unusual inversion in the strength of short and long-range superexchange interactions.

Interdependence of Conformational and Chemical Reaction Dynamics during Ion Assembly in Polar Solvents

We have utilized time-resolved vibrational spectroscopy to study the interdependence of the conformational and chemical reaction dynamics of ion assembly in solution. We investigated the chemical interconversion dynamics of the LiNCS ion pair and the (LiNCS)(2) ion-pair dimer, as well as the spectral diffusion dynamics of these ionic assemblies. For the strongly coordinating Lewis base solvents benzonitrile, dimethyl carbonate, and ethyl acetate, we observe Li(+) coordination by both solvent molecules and NCS(-) anions, while the weak Lewis base solvent nitromethane shows no evidence for solvent coordination of Li(+) ions. The strong interaction between the ion-pair dimer structure and the Lewis base solvents leads to ion-pair dimer solvation dynamics that proceed more slowly than the ion-pair dimer dissociation. We have attributed the slow spectral diffusion dynamics to electrostatic reorganization of the solvent molecules coordinated to the Li(+) cations present in the ion-pair dimer structure and concluded that the dissociation of ion-pair dimers depends more critically on longer length scale electrostatic reorganization. This unusual inversion of the conformational and chemical reaction rates does not occur for ion-pair dimer dissociation in nitromethane or for ion pair association in any of the solvents.

Stereoselective Allylation of Ketones: Explanation for the Unusual Inversion of the Induced Stereochemistry in the Auxiliary‐Mediated Crotylation and Pentenylation of Butanone by DFT Calculations

Auxiliary-mediated domino crotylations and pentenylations of butanone yield homoallylic ethers with two newly formed stereogenic centers. With our norpseudoephedrine-derived auxiliary, we observed the formation of anti isomers exclusively, and the nature of the major isomer was independent of the substrate double bond geometry. Interestingly, there is a switch in induced selectivity when going from crotylation to pentenylation. Here, we present the computational rationalization for this behavior by identification of the relevant transition states (TSs), the energies of which were determined by using the B3LYP/6-31+G(d) level of theory in combination with the PCM/UAKS method to include the effects exerted by the solvent dichloromethane. To quickly narrow down the number of potentially relevant TSs from the whole set of 288 and 864 TSs for the crotylation and pentenylation, respectively, we employed a screening process based on B3LYP//AM1 energies. The predicted selectivities are in good agreement with experimentally determined ones. Furthermore, the obtained results also facilitate an explanation of the selectivities obtained in hexenylations and heptenylations. Finally, activation energies were determined that account for the significantly longer reaction times than those for the domino allylation with unsubstituted trimethylallylsilane.

Shape induced anomalies in vortex pinning and dynamics of superconducting antidot arrays with spherical cavities

Using electrochemical deposition of Pb in the pores of templates prepared by self-assembly from colloidal suspensions of polystyrene latex spheres, well ordered superconducting antidot arrays with spherically shaped holes are fabricated. In contrast to conventional lithographic arrays the samples with spherical cavities demonstrate significantly reduced pinning strength favoring the formation of commensurate states. The ac-flux penetration acquires a hybrid intra- and intervalley regime. For high ac drives an unusual inversion to paramagnetic ac shielding is found at commensurate states.

Further studies on enantioselective synthesis of (+)-anatoxin- a using enyne metathesis: unexpected inversion of chirality via a skeletal rearrangement of 9-azabicyclo[4.2.1]nonene derivative

The formal total synthesis of (+)-anatoxin- a was accomplished using enyne metathesis as a key step. It is very interesting that (+)-anatoxin- a was synthesized from ( S)-pyroglutamic acid via an unusual inversion of chirality, which is rationalized in terms of a skeletal rearrangement of 9-azabicyclo[4.2.1]nonene derivative at the stage of oxymercuration of the diene.

A Tracer Study of Porous Anodic Alumina

The present study employs a tungsten tracer incorporated into the aluminum substrate to investigate the development of porosity in anodic alumina formed in phosphoric acid electrolyte. An unusual inversion of the tracer distribution is revealed as the tracer layer traverses the barrier region. Although initially incorporated into the barrier layer at locations beneath pore bases, associated with the scalloped metal/oxide interface, the tracer at these locations subsequently lags behind that found at the cell walls. The behavior is contrary to expectations of a field-assisted dissolution model of pore development, with usual migration behaviors of film species in the barrier layer. However, the findings are consistent with pore formation due mainly to flow of alumina from the barrier layer toward the cell walls, driven by film growth stresses. Flow of film material can also account for the presence of phosphorus species in the film and the increased thickness of the film relative to that of the oxidized metal. Anodic alumina films are used extensively in protection and functionalization of aluminum alloys, in electronics through aerospace to architecture. The films are usually formed in aqueous electrolytes, with two morphological types recognized that depend upon composition of the electrolyte, pH, current density, voltage, temperature, etc. Fig. 1. 1-4 Barrier films consist of compact, amorphous alumina of uniform thickness, up to a few hundred nanometers. Porous films comprise a thin barrier layer next to the metal and an outer layer of porous alumina, up to tens of m thick. 2,3 The pores are of approximately cylindrical section and extend from the film surface to the barrier layer. The thickness of the barrier layer and the diameter of the pores are related to the forming voltage, with ratios of 1n m V 1 , while the thickness of the porous layer depends primarily upon the anodizing charge for a particular current density. The porosity has often been explained by massively increased dissolution of the alumina at the pore base under the high electric field of the barrier layer. 5 An early suggestion was made of a role of oxide flow in the dissolution process, with flow occurring due to electrostriction stresses, estimated to be of the order 100 MPa and sufficient to deform oxides. 6