Triple-Decker Hexaazamacrocyclic Lanthanide(III) Complexes: Structure, Magnetic Properties, and Temperature-Dependent Luminescence.

The reaction of fluoride anions with mononuclear rare-earth(III) complexes of the hexaazamacrocycle derived from 2,6-diformylpyridine and ethylenediamine affords trinuclear coordination compounds . The X-ray crystal structures of these complexes show triplex cationic complexes where the three roughly parallel macrocyclic lanthanide(III) units are linked by bis-μ-F bridges. The detailed analysis of the photophysical properties of the and complexes reveals different temperature dependence of luminescence intensity and luminescence decay time of the Eu(III) and Tb(III) derivatives.

Scoring donor lungs for graft failure risk: The Lung Donor Risk Index (LDRI).

Lung transplantation lags behind other solid organ transplants in donor lung utilization due, in part, to uncertainty regarding donor quality. We sought to develop an easy-to-use donor risk metric that, unlike existing metrics, accounts for a rich set of donor factors. Our study population consisted of n = 26 549 adult lung transplant recipients abstracted from the United Network for Organ Sharing Standard Transplant Analysis and Research file.

Solid state structures and solution behaviour of tetranuclear lanthanide(III) carbonate-bridged coordination compounds of chiral 3 + 3 amine macrocycle.

The linking of two dinuclear macrocyclic units of large triphenolic hexaazamine by two carbonate anions results in the formation of dimeric tetranuclear Sm(III), Eu(III) and Gd(III) complexes. These complexes were initially obtained serendipitously by fixation of atmospheric carbon dioxide and subsequently obtained in a rational way by the application of carbonate salts. The X-ray crystal structures of these isomorphic complexes show highly folded conformation of the macrocycle.

Transplanting candidates with stacked risks negatively affects outcomes.

Background: Lung transplant (LT) centers are increasingly evaluating patients with multiple risk factors for adverse outcomes. The effects of these stacked risks remains unclear. Our aim was to determine the relationship between the number of comorbidities and post-transplant outcomes.

Imine- and Amine-Type Macrocycles Derived from Chiral Diamines and Aromatic Dialdehydes.

The condensation of aromatic dialdehydes with chiral diamines, such as 1,2--diaminocyclohexane, leads to various enantiopure or -type macrocyclic Schiff bases, including [2 + 2], [3 + 3], [4 + 4], [6 + 6] and [8 + 8] condensation products. Unlike most cases of macrocycle synthesis, the [3 + 3] macrocycles of this type are sometimes obtained in high yields by direct condensation without a metal template. Macrocycles of other sizes from this family can often be selectively obtained in high yields by a suitable choice of metal template, solvent, or chirality of the building blocks.

Sorting Phenomena and Chirality Transfer in Fluoride-Bridged Macrocyclic Rare Earth Complexes.

The reaction of fluoride anions with mononuclear lanthanide(III) and yttrium(III) hexaaza-macrocyclic complexes results in the formation of dinuclear fluoride-bridged complexes. As indicated by X-ray crystal structures, in these complexes two metal ions bound by the macrocycles are linked by two or three bridging fluoride anions, depending on the type of the macrocycle. In the case of the chiral hexaaza-macrocycle L1 derived from -1,2-diaminocyclohexane, the formation of these μ-fluorido dinuclear complexes is accompanied by enantiomeric self-recognition of macrocyclic units.

Chirality transfer between hexaazamacrocycles in heterodinuclear rare earth complexes.

Both the chiral hexaazamacrocyle L1 based on trans-1,2-diaminocyclohexane and the achiral hexaazamacrocyle L2 based on ethylenediamine form lanthanide(iii) dinuclear μ-hydroxo bridged complexes which have been characterized by NMR and CD spectroscopy. The homodinuclear complexes of the type [Ln(L1)(μ-OH)](NO) (Ln = Nd, Eu, Tb and Yb) have been synthesized in the enantiopure form and the X-ray crystal structures of Nd, Eu and Yb derivatives have been determined. The heterodinuclear cationic complexes [Ln(L1)Ln'(L2)(μ-OH)X] have been generated and characterized in solution by using the mononuclear complexes of L1 and L2 as substrates.

Sensitivity of Safe Trajectory in a Game Environment to Determine Inaccuracy of Radar Data in Autonomous Navigation.

This article provides an analysis of the autonomous navigation of marine objects, such as ships, offshore vessels and unmanned vehicles, and an analysis of the accuracy of safe control in game conditions for the cooperation of objects during maneuvering decisions. A method for determining safe object strategies based on a cooperative multi-person positional modeling game is presented. The method was used to formulate a measure of the sensitivity of safe control in the form of a relative change in the payment of the final game; to determine the final deviation of the safe trajectory from the set trajectory of the autonomous vehicle movement; and to calculate the accuracy of information in terms of evaluating the state of the control process.

Trinuclear and Hexanuclear Lanthanide(III) Complexes of the Chiral 3+3 Macrocycle: X-ray Crystal Structures and Magnetic Properties.

A new triphenolic hexaaza chiral macrocyclic amine L forms trinuclear complexes 1-3 with rare earth metal lanthanide(III) ions (Ln = Dy, Eu, and Y) with the general formula [LnL(μ-OH)(NO)(HO)]· xCHOH. The crystal structures of the nitrate derivatives of this type reveal the presence of a {Ln(μ-OH)} core within the macrocycle. For the chloride derivative of dysprosium(III) 4, a duplex of the trinuclear compound is formed to give the hexanuclear [DyL(μ-OH)(μ-O)(μ-Cl)Cl(HO)] compound, in which two trinuclear macrocyclic units are linked by bridging chloride anions, supplemented by a hydrogen bond connecting the central oxo and hydroxo bridges as well as by weak interactions at the periphery of the macrocycle.

Characteristics of women who do not consult a doctor: a population-based study.

OBJECTIVE To analyze the prevalence of not consulting a doctor within a year. METHODS Cross-sectional population-based study, including women aged 20-60 years, living in the urban area of São Leopoldo, state of Rio Grande do Sul, in 2015. The association between variables and outcome was assessed using prevalence ratios and 95% confidence intervals (95%CI).

Chiral Cryptates Derived from a Hexaazamacrocycle.

The reactions of hexaazamacrocycle 1 with 2,6-bis(bromomethyl)pyridine or 2,6-bis[(tosyloxy)methyl)]pyridine in the presence of appropriate carbonates result in the formation of derivatives of cryptand 6: enantiopure azacryptates of sodium and potassium. Crystal structures of these compounds indicate interaction of a metal ion with four pyridine nitrogen atoms and four tertiary amine atoms. The competition reactions monitored by NMR spectroscopy indicate preferential binding of Na over K as well as higher affinity of 6 for Na in comparison with the [2.

Hexanuclear and Trinuclear Metal Complexes of a Giant Octadecaaza Macrocycle.

A large macrocyclic ligand containing six pyridine fragments and six diaminocyclopentane fragments is able to form hexanuclear Zn(II) and Ni(II) complexes as well as a trinuclear Zn(II) complex. X-ray crystal structures of these complexes indicate quite different ligand conformations. In the hexanuclear Zn(II) derivative with chloride counteranions metal ions have a distorted-trigonal-bipyramidal geometry and occupy loop sections formed by the highly folded macrocycle, which adopts a globular shape.

Multinuclear Ni(ii), Cu(ii) and Zn(ii) complexes of chiral macrocyclic nonaazamine.

The chiral macrocyclic amines R-L and S-L derived from the 3 + 3 condensation of 2,6-diformylpyridine and (1R,2R)-1,2-diaminocyclohexane or (1S,2S)-1,2-diaminocyclohexane form enantiopure trinuclear Ni(ii) and Cu(ii) complexes [Ni(L)(HO)Cl]Cl and [Cu(L)Cl]Cl and form the dinuclear complex [Zn(L)Cl](ZnCl) with Zn(ii). The X-ray crystal structures of these complexes indicate remarkably different conformations of the ligand and different binding modes of the chloride anions. The structure of the copper(ii) derivative [Cu(R-L)Cl]Cl·CHCN·7.

From 2 + 2 to 8 + 8 Condensation Products of Diamine and Dialdehyde: Giant Container-Shaped Macrocycles for Multiple Anion Binding.

The combination of 2,6-diformylpyridine and trans-1,2-diaminocyclopentane fragments results in 2 + 2, 3 + 3, 4 + 4, 6 + 6, and 8 + 8 macrocyclic imine condensation products. These imines can be reduced to the corresponding 2 + 2, 3 + 3, 4 + 4, 6 + 6, and 8 + 8 macrocyclic amines. The X-ray crystal structures of their protonated derivatives show a rich variety of macrocycle conformations ranging from a stepped 2 + 2 macrocycle to a multiply folded 8 + 8 macrocycle of globular shape.

Chiral 2 + 3 Keto-Enamine Pseudocyclophanes Derived from 1,3,5-Triformylphloroglucinol.

The reactions of 1,3,5-triformylphloroglucinol with (1R,2R)-1,2-diaminocyclohexane, (1R,2R)-1,2-diphenylethylenediamine, or (R)-2,2'-diamino-1,1'-binaphthyl result in the formation of enantiopure [2 + 3] keto-enamine condensation products, in contrast to analogous reactions of 1,3,5-triformylbenzene, where [4 + 6] Schiff base cages are formed. The X-ray crystal structure of the diaminocyclohexane 2 + 3 derivative as well as modeled structures of other compounds of this type show cyclophane-like molecules with close contact between the phloroglucinol rings. Density Functional Theory (DFT) calculations confirm that there is a sizable π-π interaction between these rings influencing the conformation of these molecules.

Trinuclear Cage-Like Zn(II) Macrocyclic Complexes: Enantiomeric Recognition and Gas Adsorption Properties.

Three zinc(II) ions in combination with two units of enantiopure [3+3] triphenolic Schiff-base macrocycles 1, 2, 3, or 4 form cage-like chiral complexes. The formation of these complexes is accompanied by the enantioselective self-recognition of chiral macrocyclic units. The X-ray crystal structures of these trinuclear complexes show hollow metal-organic molecules.

Lanthanide(III) and lead(II) complexes of a chiral nonaaza macrocyclic amine based on 1,2-diaminocyclopentane.

The macrocyclic nonaaza 3 + 3 amine based on diaminocyclopentane forms enantiopure helical complexes with lanthanide(III) ions. In contrast to analogous complexes based on 1,2-trans-diaminocyclohexane, no clear helicity process is observed. Crystal structures of these compounds show tight helical wrapping of the macrocycle around the lanthanide(III) ion leading to the formation of a double helix.

Expansion of a 2 + 2 macrocycle into a 6 + 6 macrocycle: template effect of cadmium(II).

The reaction of trans-1,2-diaminocyclopentane with 2,6-diformylpyridine results in formation of 2 + 2, 3 + 3, and 4 + 4 Schiff base macrocycles as well as trace amounts of 6 + 6 and 8 + 8 macrocycles. In contrast, the 6 + 6 Schiff base macrocycle is a dominant product of the reaction of the isolated 2 + 2 macrocycle with excess of cadmium(II) chloride. The X-ray crystal structure of the protonated amine derivative of the 6 + 6 macrocycle reveals an unusual container-like conformation with the S6 axis.

[The influence of the outpatient cardiologic rehabilitation on the physical fitness at patients after a STEMI].

Unlabelled: Myocardial infraction, sudden cardiac death next is one of the most serious clinical demonstrations of ischaemic heart diseases. It is characterized by an irreversible destruction (necrosis) of a part of cardiac muscle, caused by severe narrowing or blood clot (thrombosis) in the lumen of coronary arteries. The long-term, systematic and individually selected program of the physical rehabilitation has a beneficial effect to the improvement in the physical fitness at patients, after an myocardial infarction.

Incorporation of trinuclear lanthanide(III) hydroxo bridged clusters in macrocyclic frameworks.

A cluster of lanthanide(III) or yttrium(III) ions, Ln3(μ3-OH)2, (Ln(III) = Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Yb(III), or Y(III)) can be bound in the center of a chiral macrocyclic amines H3L1(R), H3L1(S), and H3L2(S) obtained in a reduction of a 3 + 3 condensation product of (1R,2R)- or (1S,2S)-1,2-diaminocyclohexane and 2,6-diformyl-4-methylphenol or 2,6-diformyl-4-tertbutylphenol. X-ray crystal structures of the Nd(III), Sm(III), Gd(III), Dy(III), and Y(III) complexes reveal trinuclear complexes with Ln(III) ions bridged by the phenolate oxygen atoms of the macrocycle as well as by μ3-hydroxo bridges. In the case of the Nd(III) ion, another complex form can be obtained, whose X-ray crystal structure reveals two trinuclear macrocyclic units additionally bridged by hydroxide anions, corresponding to a [Ln3(μ3-OH)]2(μ2-OH)2 cluster encapsulated by two macrocycles.

Anion and solvent induced chirality inversion in macrocyclic lanthanide complexes.

A series of the lanthanide(III) or yttrium(III) complexes of the type [LnL(NO3)(H2O)2](NO3)2, [LnL(NO3)(H2O)](NO3)2, [LnL(H2O)2](NO3)3, and [LnLCl(H2O)2]Cl2 where L is an all-R or all-S enantiomer (L(R) or L(S)) of the chiral hexaaza macrocycle, 2(R),7(R),18(R),23(R)- or 2(S),7(S),18(S),23(S)-1,8,15,17,24,31-hexaazatricyclo[25.3.1.

[Faulty posture and selected respiratory indicators].

The Aim Of The Study: Was to diagnose the body posture of physiotherapy students of the Medical University of Lodz and to determine the relationship between selected respiratory indicator and the incidence of faulty posture in the studied group.

Material And Methods: 196 students of Medical University of Lodz were included in the study. Posture assessment was conducted using Kasperczyk's points method.

Contrasting enantioselective DNA preference: chiral helical macrocyclic lanthanide complex binding to DNA.

There is great interest in design and synthesis of small molecules which selectively target specific genes to inhibit biological functions in which particular DNA structures participate. Among these studies, chiral recognition has been received much attention because more evidences have shown that conversions of the chirality and diverse conformations of DNA are involved in a series of important life events. Here, we report that a pair of chiral helical macrocyclic lanthanide (III) complexes, (M)-Yb[L(SSSSSS)](3+) and (P)-Yb[L(RRRRRR)](3+), can enantioselectively bind to B-form DNA and show remarkably contrasting effects on GC-rich and AT-rich DNA.

Controlling the macrocycle size by the stoichiometry of the applied template ion.

Reaction of 4-tert-butyl-2,6-diformylphenol with (1R,2R)- or (1S,2S)-1,2-diaminocyclohexane in the presence of 1 equivalent of Zn(2+) ions leads to selective formation of a chiral 2+2 macrocycle. Application of 0.5 equivalent of Zn(2+) ions under the same conditions leads to selective formation of a chiral 3+3 macrocycle, which forms a cavitand-shaped trinuclear double-decker complex with Zn(II).