Inversion Coordinate Research Articles

Tomographic reconstructions of the fast-ion phase space using imaging neutral particle analyser measurements

In this paper we demonstrate how the inversion, in energy and major radius (E, R) coordinates, of imaging neutral particle analyser (INPA) measurements can be used to obtain the fast-ion distribution. The INPA is most sensitive to passing ions with energies in the range (20–150) keV and pitches near 0.5 in the core and 0.7 near the plasma edge. Inversion of synthetic signals, via 0th-order Tikhonov and Elastic Net regularization, were performed to demonstrate the capability of recovering the ground truth fast-ion 2D phase-space distribution resolved in major radius and energy, even in the presence of moderate noise levels (10%). Finally, we apply our method to measure the 2D phase-space distribution in an MHD quiescent plasma at ASDEX Upgrade and find good agreement with the slowing down fast-ion distribution predicted by TRANSP.

Triple Inverse Sandwich versus End-On Diazenido: Bonding Motifs across a Series of Rhenium-Lanthanide and -Actinide Complexes.

While synthesizing a series of rhenium-lanthanide triple inverse sandwich complexes, we unexpectedly uncovered evidence for rare examples of end-on lanthanide dinitrogen coordination for certain heavy lanthanide elements as well as for uranium. We begin our report with the synthesis and characterization of a series of trirhenium triple inverse sandwich complexes with the early lanthanides, Ln[(μ-η5:η5-Cp)Re(BDI)]3(THF) (1-Ln, Ln = La, Ce, Pr, Nd, Sm; Cp = cyclopentadienide, BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate). However, as we moved across the lanthanide series, we ran into an unexpected result for gadolinium in which we structurally characterized two products for gadolinium, namely, 1-Gd (analogous to 1-Ln) and a diazenido dirhenium double inverse sandwich complex Gd[(μ-η1:η1-N2)Re(η5-Cp)(BDI)][(μ-η5:η5-Cp)Re(BDI)]2(THF)2 (2-Gd). Evidence for analogues of 2-Gd was spectroscopically observed for other heavy lanthanides (2-Ln, Ln = Tb, Dy, Er), and, in the case of 2-Er, structurally authenticated. These complexes represent the first observed examples of heterobimetallic end-on lanthanide dinitrogen coordination. Density functional theory (DFT) calculations were utilized to probe relevant bonding interactions and reveal energetic differences between both the experimental and putative 1-Ln and 2-Ln complexes. We also present additional examples of novel end-on heterobimetallic lanthanide and actinide diazenido moieties in the erbium-rhenium complex (η8-COT)Er[(μ-η1:η1-N2)Re(η5-Cp)(BDI)](THF)(Et2O) (3-Er) and uranium-rhenium complex [Na(2.2.2-cryptand)][(η5-C5H4SiMe3)3U(μ-η1:η1-N2)Re(η5-Cp)(BDI)] (4-U). Finally, we expand the scope of rhenium inverse sandwich coordination by synthesizing divalent double inverse sandwich complex Yb[(μ-η5:η5-Cp)Re(BDI)]2(THF)2 (5-Yb), as well as base-free, homoleptic rhenium-rare earth triple inverse sandwich complex Y[(μ-η5:η5-Cp)Re(BDI)]3 (6-Y).

Open-Circuit Fault Diagnosis of Three-Phase Permanent Magnet Machine Utilizing Normalized Flux-Producing Current

In this paper, an open-circuit fault diagnostic method is proposed for three-phase permanent magnet machines. By individually applying inverse coordination transformation to <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">d</i> - and <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">q</i> -axis currents, per-phase current can be decomposed into flux- and torque-producing currents. Their post-fault behaviors are found to be highly related with the fault types and locations. Hence, the normalized flux-producing current can be used as a single fault index to detect and identify both open-switch and open-phase faults. Since the established fault index is close to zero, the proposed fault diagnostic method is naturally robust to load/speed variations. In addition, a low decision threshold can be set to reduce fault diagnostic time. The robustness and effectiveness of the proposed method are verified by the experiments on one prototype.

Acid Violet 3: A Base-Activated Water-Soluble Photoswitch.

Acidic azo dyes are widely used for their vibrant colors. However, if their photophysics were better understood and controllable, they could be integrated into many more applications such as photosensing, photomedicine, and nonlinear optics. Here, the proton-controlled photophysics of a widely used acid, hydrazo dye, acid violet 3 (AV3) is explored. Density functional theory is used to predict the ground- and excited-state potential energy surfaces, and the proposed photoisomerization mechanism is confirmed with spectroscopic experiments. The ground-state and first two excited-state surfaces of the three readily accessible protonation states, AV3-H, AV3, and AV3+H, are investigated along both the dihedral rotation and inversion coordinates. The deprotonated AV3-H undergoes photoisomerization with blue light (λex = 453 nm) through a dihedral rotation mechanism. Upon the formation of the cis-isomer, the reversion of AV3-H is predicted to occur through a mixed rotational and inversion mechanism. In contrast, AV3 and its protonated form, AV3+H, do not undergo photoisomerization because there is no driving force for either the rotation or inversion of the azo bond in the excited state. In addition, when the azo bond is acidic, the ground-state dihedral rotation reversion mechanism barrier is lower. The mechanistic insights gained here through the combination of theory and experiment provide a roadmap to control the reactivity of AV3 across 11 orders of magnitude of proton concentration, making them interesting candidates for a range of pharmaceuticals.

Series of new cobalt (II) and nickel (II) trinuclear fluorotrifluoroacetates with tetrahydrofuran – contribution to the inverse coordination chemistry and unique cations

Abstract The six new trinuclear fluorocarboxylates with tetrahydrofuran (THF) molecules as terminal ligands are presented. The structures of compounds have been determined by single-crystal X-ray diffraction. According to the structure data, complexes of nickel (II) and cobalt (II) form isomorphous series, namely [K(CF3COOH)6][M3(μ3-F)(CF3COO)6(THF)3] (M = Co (I) and Ni (II)), Na[M3(μ3-F)(CF3COO)6(THF)(CF3COOH)2] (M = Co (III) and Ni (IV)) and [Li(CF3COOH)4][M3(μ3-F)(CF3COO)6(THF)3] (M = Co (V) and Ni (VI)). In crystal structures of I, II, V and VI, previously unknown cations [K(CF3COOH)6]+ and [Li(CF3COOH)4]+ have been detected. All substances were studied by IR spectroscopy, and bands sensitive to the nature of metal atoms included in the compounds have been found. The inverse coordination of tridentate fluoride-ion in cobalt (II) and nickel (II) fluorocarboxylates is discussed in the article.

On the Redox Equilibrium of TPP/TPPO Containing Cu(I) and Cu(II) Complexes

Copper(II) clusters of the type [CuII4OCl6L4] (L = ligand or solvent) are a well-studied example of inverse coordination compounds. In the past, they have been studied because of their structural, magnetic, and spectroscopic features. They have long been believed to be redox-inactive compounds, but recent findings indicate a complex chemical equilibrium with diverse mononuclear as well as multinuclear copper(I) and copper(II) compounds. Furthermore, depending on the ligand system, such cluster compounds have proven to be versatile catalysts, e.g., in the oxidation of cyclohexane to adipic acid. This report covers a systematic study of the formation of [CuII4OCl6(TPP)4] and [CuII4OCl6(TPPO)4] (TPP = triphenylphosphine, PPh3; TPPO = triphenylphosphine oxide, O=PPh3) as well as the redox equilibrium of these compounds with mononuclear copper(I) and copper(II) complexes such as [CuIICl2(TPPO)2], [{CuIICl2}2(TPPO)2], [{CuIICl2}3(TPPO)2], [{CuII4Cl4}(TPP)4], and [CuICl(TPP)n] (n = 1–3).

CO Inversion on a NaCl(100) Surface: A Multireference Quantum Embedding Study.

We develop a multireference quantum embedding model to investigate a recent experimental observation of the isomerization of vibrationally excited CO molecules on a NaCl(100) surface [Science 2020, 367, 175-178]. To explore this mechanism, we built a reduced potential energy surface of CO interacting with NaCl(100) using a second-order multireference perturbation theory, modeling the adsorbate-surface interaction with our previously developed active space embedding theory (ASET). We considered an isolated CO molecule on NaCl(100) and a high-coverage CO monolayer (1/1), and for both we generated potential energy surfaces parametrized by the CO stretching, adsorption, and inversion coordinates. These surfaces are used to determine stationary points and adsorption energies and to perform a vibrational analysis of the states relevant to the inversion mechanism. We found that for near-equilibrium bond lengths, CO adsorbed in the C-down configuration is lower in energy than in the O-down configuration. Stretching of the C-O bond reverses the energetic order of these configurations, supporting the accepted isomerization mechanism. The vibrational constants obtained from these potential energy surfaces show a small (< 10 cm-1) blue- and red-shift for the C-down and O-down configurations, respectively, in agreement with experimental assignments and previous theoretical studies. Our vibrational analysis of the monolayer case suggests that the O-down configuration is energetically more stable than the C-down one beyond the 16th vibrational excited state of CO, a value slightly smaller than the one from quasi-classical trajectory simulations (22nd) and consistent with the experiment. Our analysis suggests that CO-CO interactions in the monolayer play an important role in stabilizing highly vibrationally excited states in the O-down configuration and reducing the barrier between the C-down and O-down geometries, therefore playing a crucial role in the inversion mechanism.

Molecular engineering of an inverse hexacopper(II) coordination complex with a photoactive metallacyclophane centroligand as prototype of a magnetic photoswitch

A primary goal of molecular spintronics is detecting the response of the spins from a single magnetic molecule to an external stimulus and, eventually, being able to implement logic quantum memory capabilities for information data storage and processing applications in quantum computation. Having this in mind, a novel hexanuclear oxamatocopper(II) complex of formula {[Cu2(naba)2][Cu(pmdien)]4}(ClO4)4·8H2O (2) [naba = N,N'-1,5-naphthalenebis(oxamate) and pmdien = N,N,N’,N”,N”-pentamethyldiethylenetriamine] has been prepared by the reaction of stoichiometric amounts of (nBu4N)4[Cu2(naba)2] · 4H2O (1) (nBu4N+ = tetra-n-butylammonium cation) and [Cu(pmdien)](ClO4)2 (1:4 molar ratio) in water. 2 exhibits a ladder-like “dimer-of-trinuclears” structure featuring a photoactive dicopper(II) naphthalenophane core acting as inverse coordination centre (centroligand) towards four peripheral [Cu(pmdien)]2+ groups through the outer amidate/carboxylate oxygen atoms of the oxamato fragments. 2 undergoes a unique magnetic photoswitching ON/OFF behaviour upon UV light irradiation because of an intramolecular (“pseudo-bimolecular”) photocycloaddition of the two facing naphthalene spacers through the more reactive carbon atoms at the 1,4 and 1’,4’ positions of the benzene rings to afford the putative [4 + 4] cycloaddition product c-2. Hence, the two oxamato-bridged S = 1/2 CuII3 linear units antiferromagnetically coupled within the CuII6 precursor (2, ON state) become magnetically uncoupled in the corresponding [4 + 4] photocycloaddition product (c-2, OFF state) [jeff = –2.13 (2) and 0 cm−1 (c-2); H = – jeffSA.SB with SA = SB = 1/2]. This new example of inverse coordination complex constitutes thus a potential candidate to molecular magnetic photoswitch in the “bottom-up” approach to nanometer-scale spintronic and quantum computing devices.

Low back pain influences trunk-lower limb joint coordination and balance control during standing in persons with lower limb loss

BackgroundBalance is sustained through multi-joint coordination in response to postural perturbations. Low back pain alters postural responses; however, it is unknown how coordination between the trunk and lower extremities affects center of mass control during standing balance among persons with limb loss, particularly those with back pain. MethodsForty participants with unilateral lower limb loss (23 with back pain) stood with eyes open and closed on a firm surface, while wearing IMUs on the sternum, pelvis, and bilaterally on the thigh, shank, and foot. A state-space model with Kalman filter calculated sagittal trunk, hip, knee, and ankle joint angles. Fuzzy entropy quantified center of mass variability of sagittal angular velocity at the sacrum. Normalized cross-correlation functions identified coordination patterns (trunk-hip, trunk-knee, trunk-ankle). Multiple linear regression predicted fuzzy entropy from cross-correlation values for each pattern, with body mass and amputation level as covariates. FindingsWith eyes open, trunk-lower limb joint coordination on either limb did not predict fuzzy entropy. With eyes closed, positive trunk-hip coordination on the intact limb predicted fuzzy entropy in the pain group (p = 0.02), but not the no pain group. On the prosthetic side, inverse trunk-hip coordination patterns predicted fuzzy entropy in pain group (p = 0.03) only. InterpretationPersons with limb loss and back pain demonstrated opposing coordination strategies between the lower limbs and trunk when vision was removed, perhaps identifying a mechanism for pain recurrence. Vision is the dominant source of balance stabilization in this population, which may increase fall risk when visual feedback is compromised.

Synthesis, structural studies, and photophysical properties of heteroleptic inverse-coordination clusters.

Two series of hyper-coordinated halide-centered M12 cuboctahedral clusters, [M12(μ12-X){S2P(OnPr)2}6{CCPh}4](PF6), 1a-c and 2a-c (where M = Cu, 1; Ag, 2; X = Cl, a; Br, b; I, c), were synthesized and fully characterized by ESI-MS, multi-NMR spectroscopy, IR and UV-Vis spectroscopy, photoluminescence analysis, and single-crystal X-ray crystallography. Structures 1c, 2b, and 2c show a twelve-coordinated halide encapsulated in the M12 cage, which is stabilized by six dithiophosphate and four alkynyl ligands. Compound 2b is the first Ag(I) cluster containing a twelve-coordinated bromide. The structural features of all six clusters are highly similar, providing a comparison basis of the inverse coordination for halides. Besides, the detailed structural analysis illustrates how the inverse coordination of a halide has influenced the size of the cuboctahedral M12 framework.

Quantitative Investigation of Hand Grasp Functionality: Thumb Grasping Behavior Adapting to Different Object Shapes, Sizes, and Relative Positions.

This paper is the first in the two-part series quantitatively modelling human grasp functionality and understanding the way human grasp objects. The aim is to investigate the thumb movement behavior influenced by object shapes, sizes, and relative positions. Ten subjects were requested to grasp six objects (3 shapes × 2 sizes) in 27 different relative positions (3 X deviation × 3 Y deviation × 3 Z deviation). Thumb postures were investigated to each specific joint. The relative position (X, Y, and Z deviation) significantly affects thumb opposition rotation (Rot) and flexion (interphalangeal (IP) and metacarpo-phalangeal (MCP)), while the object property (object shape and size) significantly affects thumb abduction/adduction (ABD) motion. Based on the F value, the Y deviation has the primary effects on thumb motion. When the Y deviation changing from proximal to distal, thumb opposition rotation (Rot) and flexion (IP and MCP joint) angles were increased and decreased, respectively. For principal component analysis (PCA) results, thumb grasp behavior can be accurately reconstructed by first two principal components (PCs) which variance explanation ratio reached 93.8% and described by the inverse and homodromous coordination movement between thumb opposition and IP flexion. This paper provides a more comprehensive understanding of thumb grasp behavior. The postural synergies can reproduce the anthropomorphic motion, reduce the robot hardware, and control dimensionality. All of these provide a more accurate and general basis for the design and control of the bionic thumb and novel wearable assistant robot, thumb function assessment, and rehabilitation.

Inverse Coordination-The Janus Face of Coordination Chemistry

I would like to draw attention to the novel chemical concept of inverse coordination, which discloses another face of coordination chemistry (practically ignored so far as a distinct field) and deals with the formation of metal complexes in which the donor and acceptor positions are reversed.

InvertypeR: Bayesian inversion genotyping with Strand-seq data

BackgroundSingle cell Strand-seq is a unique tool for the discovery and phasing of genomic inversions. Conventional methods to discover inversions with Strand-seq data are blind to known inversion locations, limiting their statistical power for the detection of inversions smaller than 10 Kb. Moreover, the methods rely on manual inspection to separate false and true positives.ResultsHere we describe “InvertypeR”, a method based on a Bayesian binomial model that genotypes inversions using fixed genomic coordinates. We validated InvertypeR by re-genotyping inversions reported for three trios by the Human Genome Structural Variation Consortium. Although 6.3% of the family inversion genotypes in the original study showed Mendelian discordance, this was reduced to 0.5% using InvertypeR. By applying InvertypeR to published inversion coordinates and predicted inversion hotspots (n = 3701), as well as coordinates from conventional inversion discovery, we furthermore genotyped 66 inversions not previously reported for the three trios.ConclusionsInvertypeR discovers, genotypes, and phases inversions without relying on manual inspection. For greater accessibility, results are presented as phased chromosome ideograms with inversions linked to Strand-seq data in the genome browser. InvertypeR increases the power of Strand-seq for studies on the role of inversions in phenotypic variation, genome instability, and human disease.

Coordination Behavior of [Cp″2Zr(µ1:1-As4)] towards Lewis Acids.

The functionalization of the arsenic transfer reagent [Cp″2Zr(η1:1-As4)] (1) focuses on modifying its properties and enabling a broader scope of reactivity. The coordination behavior of 1 towards different Lewis-acidic transition metal complexes and main group compounds is investigated by experimental and computational studies. Depending on the steric requirements of the Lewis acids and the reaction temperature, a variety of new complexes with different coordination modes and coordination numbers could be synthesized. Depending on the Lewis acid (LA) used, a mono-substitution in [Cp″2Zr(µ,η1:1:1:1-As4)(LA)] (LA = Fe(CO)4 (4); B(C6F5)3 (7)) and [Cp″2Zr(µ,η3:1:1-As4)(Fe(CO)3)] (5) or a di-substitution [Cp″2Zr(µ3,η1:1:1:1-As4)(LA)2] (LA = W(CO)5 (2); CpMn(CO)2 (3); AlR3 (6, R = Me, Et, iBu)) are monitored. In contrast to other coordination products, 5 shows an η3 coordination in which the butterfly As4 ligand is rearranged to a cyclo-As4 ligand. The reported complexes are rationalized in terms of inverse coordination.

Resilience, plasticity and robustness in gene expression during aging in the brain of outbred deer mice

BackgroundGenes that belong to the same network are frequently co-expressed, but collectively, how the coordination of the whole transcriptome is perturbed during aging remains unclear. To explore this, we calculated the correlation of each gene in the transcriptome with every other, in the brain of young and older outbred deer mice (P. leucopus and P. maniculatus).ResultsIn about 25 % of the genes, coordination was inversed during aging. Gene Ontology analysis in both species, for the genes that exhibited inverse transcriptomic coordination during aging pointed to alterations in the perception of smell, a known impairment occurring during aging.In P. leucopus, alterations in genes related to cholesterol metabolism were also identified. Among the genes that exhibited the most pronounced inversion in their coordination profiles during aging was THBS4, that encodes for thrombospondin-4, a protein that was recently identified as rejuvenation factor in mice. Relatively to its breadth, abolishment of coordination was more prominent in the long-living P. leucopus than in P. maniculatus but in the latter, the intensity of de-coordination was higher.ConclusionsThere sults suggest that aging is associated with more stringent retention of expression profiles for some genes and more abrupt changes in others, while more subtle but widespread changes in gene expression appear protective. Our findings shed light in the mode of the transcriptional changes occurring in the brain during aging and suggest that strategies aiming to broader but more modest changes in gene expression may be preferrable to correct aging-associated deregulation in gene expression.

Prediction of two-dimensional Cu2C with polyacetylene-like motifs and Dirac nodal line

The design of novel two-dimensional (2D) materials with unique atomistic configurations and exotic properties are highly desirable for material science. Here, we report the prediction of 2D ${\mathrm{Cu}}_{2}\mathrm{C}$ layers featuring unique carbon motifs with Dirac nodal lines through evolutionary algorithm searches in conjunction with first-principles calculations. The global minimum $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Cu}}_{2}\mathrm{C}$ is an exciting new structure featuring one-dimensional (1D) zigzag carbon chains sandwiched by two hexagonal-close-packed copper monolayers, conferring to our predicted ground-state 2D $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{Cu}}_{2}\mathrm{C}$ an inverse coordination structure. This polyacetylene-like motif $(\mathrm{poly}\text{\ensuremath{-}}{\mathrm{C}}_{2})$ is also encountered in $\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{Cu}}_{2}\mathrm{C}$. Remarkably, the electronic band structure of $\ensuremath{\alpha}$ and $\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{Cu}}_{2}\mathrm{C}$ phases containing polyacetylene-like chains display a 1D Dirac nodal line, which is protected by the glide plane symmetry. Fermi velocities $({v}_{f})$ as high as $2.45\ifmmode\times\else\texttimes\fi{}{10}^{5}$ and $3.85\ifmmode\times\else\texttimes\fi{}{10}^{5}$ m/s are calculated for $\ensuremath{\alpha}$ and $\ensuremath{\gamma}\text{\ensuremath{-}}{\mathrm{Cu}}_{2}\mathrm{C}$ phases, respectively. This work is an effective effort to design and stabilize the 2D copper carbide layers with exotic structures and nodal lines.

Practical Challenges of Inverse and Definite-Time Overcurrent Protection Coordination in Modern Industrial and Commercial Power Distribution System

The characteristics of an overcurrent relay (OCR) in protection coordination are determined by adjusting the current and time delay function. This characteristic is adjusted once, fixed, and expected to overcome any disturbances in the system, which raises the risk of incorrect operation of the protection system, such as an overlapping trip or the incapability to limit the current exposure in the protected equipment. This article summarizes different efforts to overcome the modern challenges of overcurrent protection coordination (OCPC) in low or medium voltage industrial and commercial distribution systems. A brief background is introduced from a general perspective and then specifically describes in detail the problem of equipment coordination with a thorough link among mathematical concepts and fundamentals in practice. The operation challenges and ideas to avoid incorrect performance, under normal operation, are discussed. Finally, the article proposes a new optimization method based on the combination of the firefly algorithm and target remedy to overcome such challenges. The optimization considers the combination of inverse-time (ANSI 51) and definite-time (ANSI 50) function in OCR. The method is described and validated in the IEEE 242.2001 to meet the existing regulation of protection coordination. By assessing the critical cases, this article is expected to enhance the OCPC under different fault scenarios with complex coordination of time-current curves.

Mapping of Adaptive Traits Enabled by a High-Density Linkage Map for Lake Trout.

Understanding the genomic basis of adaptative intraspecific phenotypic variation is a central goal in conservation genetics and evolutionary biology. Lake trout (Salvelinus namaycush) are an excellent species for addressing the genetic basis for adaptive variation because they express a striking degree of ecophenotypic variation across their range; however, necessary genomic resources are lacking. Here we utilize recently-developed analytical methods and sequencing technologies to (1) construct a high-density linkage and centromere map for lake trout, (2) identify loci underlying variation in traits that differentiate lake trout ecophenotypes and populations, (3) determine the location of the lake trout sex determination locus, and (4) identify chromosomal homologies between lake trout and other salmonids of varying divergence. The resulting linkage map contains 15,740 single nucleotide polymorphisms (SNPs) mapped to 42 linkage groups, likely representing the 42 lake trout chromosomes. Female and male linkage group lengths ranged from 43.07 to 134.64 centimorgans, and 1.97 to 92.87 centimorgans, respectively. We improved the map by determining coordinates for 41 of 42 centromeres, resulting in a map with 8 metacentric chromosomes and 34 acrocentric or telocentric chromosomes. We use the map to localize the sex determination locus and multiple quantitative trait loci (QTL) associated with intraspecific phenotypic divergence including traits related to growth and body condition, patterns of skin pigmentation, and two composite geomorphometric variables quantifying body shape. Two QTL for the presence of vermiculations and spots mapped with high certainty to an arm of linkage group Sna3, growth related traits mapped to two QTL on linkage groups Sna1 and Sna12, and putative body shape QTL were detected on six separate linkage groups. The sex determination locus was mapped to Sna4 with high confidence. Synteny analysis revealed that lake trout and congener Arctic char (Salvelinus alpinus) are likely differentiated by three or four chromosomal fissions, possibly one chromosomal fusion, and 6 or more large inversions. Combining centromere mapping information with putative inversion coordinates revealed that the majority of detected inversions differentiating lake trout from other salmonids are pericentric and located on acrocentric and telocentric linkage groups. Our results suggest that speciation and adaptive divergence within the genus Salvelinus may have been associated with multiple pericentric inversions occurring primarily on acrocentric and telocentric chromosomes. The linkage map presented here will be a critical resource for advancing conservation oriented genomic research on lake trout and exploring chromosomal evolution within and between salmonid species.

Вивчення спорідненості до мембран допоміжних речовин й фармакологічно активних інгредієнтів методами флуоресцентних і спінових зондів

Мета дослідження – порівняльне вивчення спорідненості до ліпосом з фосфатидилхоліну низки гідрофільних неводних розчинників пропіленгліколю (ПГ), поліетиленгліколей (ПЕГ) з молекулярною масою 400 і 1500 (ПЕГ­400 і ПЕГ­1500), що успішно застосовуються за створення м’яких лікарських форм як допоміжні речовини. Проведено аналіз результатів, отриманих за допомогою методу флуоресцентних зондів, і розрахунок константи дисоціації (Кд) неводних розчинників ПГ, ПЕГ­400 і ПЕГ­1500 з мембранами ліпосом з фосфатидилхоліну графічним методом у зворотних координатах. Показано, що Кд = 2,5 моль/л для ПГ і Кд = 4 • 10 ­1 моль/л для ПЕГ­400. Аналіз спектрів електронно­парамагнітного резонансу (ЕПР) у зворотних координатах дозволив оцінити Кд для ПЕГ­1500, що дорівнює 10­1 моль/л. Досліджено вплив ПГ і ПЕГ­400 на мембрани ліпосом. ПГ і ПЕГ­400 ефективно зв’язуються з мембраною ліпосом, витісняючи флуоресцентний зонд з мембрани в воду. Це може бути одним із механізмів впливу ПГ і ПЕГ­400 на біодоступність, коли фармакологічно активні інгредієнти (ФАІ) можуть витиснятися в воду молекулами допоміжних речовин, сповільнюючи процес всмоктування ФАІ. Введення ПЕГ­400 у суспензію ліпосом призводить до розпушення мембран, тобто, до зменшення щільності упаковки фосфоліпідів у мембранах, що може призводити до зміни їхньої проникності та підвищенню біодоступності. Дія ПГ на мембрани є більш м’якою, ніж ПЕГ­400. Вочевидь у зоні всмоктування ФАІ на мембрані паралельно відбувається процес всмоктування низькомолекулярних допоміжних речовин, наприклад, неводних розчинників. Причому всмоктування ліпофільних ФАІ може відбуватися в оточенні розчинників (допоміжних речовин), що призводить до збільшення біодоступності ФАІ. У разі конкуренції за місця зв’язування на мембранах клітин біоповерхонь між ФАІ і неводними розчинниками більш низька (на кілька порядків) спорідненість розчинників до мембран компенсується значною кількістю розчинників у м’якій лікарській формі порівняно з ФАІ. Механізмом підвищення біосумісності за допомогою ПЕГ є здатність їхніх молекул за рахунок компактизації (спіралізації) або розпушення приймати оптимальну конформацію структури, надаючи свої гідрофобні або полярні групи для оптимального зв’язування з наночастинками, лікарськими речовинами та біооб’єктами.

Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium.

The reaction of the magnesium(i) complexes [{(Arnacnac)Mg}2], (Arnacnac = HC(MeCNAr)2, Ar = Dip (2,6-iPr2C6H3), Dep (2,6-Et2C6H3), Mes (2,4,6-Me3C6H2), Xyl (2,6-Me2C6H3)) with fullerene C60 afforded a series of hydrocarbon-soluble fulleride complexes [{(Arnacnac)Mg} n C60], predominantly with n = 6, 4 and 2. 13C{1H} NMR spectroscopic studies show both similarities (n = 6) and differences (n = 4, 2) to previously characterised examples of fulleride complexes and materials with electropositive metal ions. The molecular structures of [{(Arnacnac)Mg} n C60] with n = 6, 4 and 2 can be described as inverse coordination complexes of n [(Arnacnac)Mg]+ ions with C60 n- anions showing predominantly ionic metal-ligand interactions, and include the first well-defined and soluble complexes of the C60 6- ion. Experimental studies show the flexible ionic nature of the {(Arnacnac)Mg}+···C60 6- coordination bonds. DFT calculations on the model complex [{(Menacnac)Mg}6C60] (Menacnac = HC(MeCNMe)2) support the formulation as an ionic complex with a central C60 6- anion and comparable frontier orbitals to C60 6- with a small HOMO-LUMO gap. The reduction of C60 to its hexaanion gives an indication about the reducing strength of dimagnesium(i) complexes.