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The peripheral blood NK cell diversity is highly complex. Recent studies have described more than a thousand phenotypes sharing NK cell receptors (NKRs), across the leukocyte lineages. Previously, we have found that accentuated NK p46 phenotype has prognostic value for NK cytotoxicity status, and is characteristic for patients with recurre implantation failure (RIF). In a blinded investigation we studied blood samples from IVF women at the day of embryo transfer (pre-implantation genetic diagnosis [PGD] tested embryos n=116; not tested embryos n=219). 102 early pregnant women were also tested and 152 women in their 11th to 13th week of pregnancy served as controls. We studied NK p46 expression by flow cytometry and anti-cardiolipin antibody (aCL) levels. aCL results were transmitted to the clinic but NK p46 expression was blinded (for us and for the clinic) and not analyzed before termination of the study (end of last pregnancy). Association of p46 phenotype with clinical pregnancy rate (CPR), pregnancy failure (PF) rate and life birth rate (LBR) were analyzed. aCL positive and IvIg treated cases were excluded. IVF success was extremely dependent on p46 NK phenotype in patients with PGD tested embryos. Elevated p46 expression on NK (>93%) as well as decreased (<66%) significantly reduced CPR (OR 12.7 and 3.8) without affecting pregnancy failure frequency but with decreased LBR. Both accentuations (taken together) resulted in a significant reduction of LBR (OR 3.9 p=0.019) compared with non-accentuated phenotypes (p46 levels 66-93%). Elevated NK cell levels (>14.5% weekly) were associated with PF (OR 3.1 p=0.069), but not significantly with reduced LBR. In contrast, numbers of NKCD335+ lymphocytes (>11.5%) were a significant predictor of PF (OR-4.0 p<0.05) and decreased LBR (OR 2.1 p=0.06) but did not affect CPR. At the same time, elevated numbers of NKCD335neg lymphocytes (>4%) were also associated with decreased LBR (OR-3.6 p=0.03), decreased CPR and increased PF rate. In patients with decreased NKCD335++ numbers (<14%), we found a significant association with IVF failure. We found a similar association in IVF patients without PGD testing but at lower significance levels regardless the higher number of. Naturally conceived early pregnant women with elevated NKCD335 expression have significant elevated PF rates (OR 17; p=0,008) similar to women with decreased NKCD335neg subsets. A favorable value for pregnant women was similar to 95% confidence interval obtained from the control group (11-13 weeks of pregnancy). Accentuated increased or decreased CD335 expression on NK was associated with embryo implantation failure. Balanced CD335 levels form a condition favorable for implantation. Elevated numbers of p46+NK (CD3-CD56+CD335+) predicts pregnancy failures at higher significance levels than elevated NK cell numbers. Elevated numbers of p46negNK (CD3-CD56+CD335-) indicate reduced LBR. Accentuation of p46 expression on NK cells is associated with reproductive failures. In combination with PGD it provides a powerful prediction algorithm and treatment option. [ABSTRACT FROM AUTHOR]

Chemical composition is leading among the numerous factors that determine the spin transition properties of coordination compounds. Classic dicyanometallic bridges {M(CN) 2 } - are commonly used to build Hofmann-like spin-crossover frameworks, but some extended bridges are also synthetically available. In this paper, we describe a successful synthesis of two very similar spin-crossover frameworks that differ in the cyanometallic bridges involved, namely [Fe(etpz) 2 {Ag(CN) 2 } 2 ] (1) and {Fe(etpz) 2 [Ag 2 (CN) 3 ][Ag(CN) 2 ]} (2) (where etpz = 2-ethylpyrazine). Magnetic and Mössbauer studies demonstrated the occurrence of abrupt one-step high-spin (HS) ↔ low-spin (LS) transitions for both complexes. The spin transition temperatures are T 1/2 ↓ = 233 K and T 1/2 ↑ = 243 K for 1 and T 1/2 ↓ = 188 K and T 1/2 ↑ = 191 K for 2 with thermal hysteresis loops of 10 K for 1 and 3 K for 2. The bridging mononuclear [Ag(CN) 2 ] - units and Fe II cations assemble to form infinite 2D layers in the structure of 1. Interestingly, compound 2 forms 2D layers of Fe II cations bridged by both binuclear [Ag 2 (CN) 3 ] - and mononuclear [Ag(CN) 2 ] - units. The structures of 1 and 2 comprise different types of intermolecular interactions including Ag⋯Ag and Ag⋯N etpz , which induce the creation of supramolecular 3D frameworks. The synergy between metallophilic interactions and the spin transition is also confirmed by the variation of Ag⋯Ag distances during spin crossover. The characterization of such analogues allowed us to analyze in detail the effect of the cyanometallic bridge on the structure of new frameworks and on the bistability in Hofmann-like complexes.

A mononuclear square-planar Cu II complex of (5-methyl-1 H -pyrazol-3-yl)carbamate, [Cu(C 5 H 6 N 3 O 2 ) 2 ]·4H 2 O, was synthesized using a one-pot reaction from 5-methyl-3-pyrazolamine and copper(II) acetate in water under ambient conditions. The adsorption of carbon dioxide from air was facilitated by the addition of di-ethano-lamine to the reaction mixture. While di-ethano-lamine is not a component of the final product, it plays a pivotal role in the reaction by creating an alkaline environment, thereby enabling the adsorption of atmos-pheric carbon dioxide. The central copper(II) atom is in an (N 2 O 2 ) square-planar coordination environment formed by two N atoms and two O atoms of two equivalent (5-methyl-1 H -pyrazol-3-yl)carbamate ligands. Additionally, there are co-crystallized water mol-ecules within the crystal structure of this compound. These co-crystallized water mol-ecules are linked to the Cu II mononuclear complex by O-H⋯O hydrogen bonds. According to Hirshfeld surface analysis, the most frequently observed weak inter-molecular inter-actions are H⋯O/O⋯H (33.6%), H⋯C/C⋯H (11.3%) and H⋯N/N⋯H (9.0%) contacts., (© Sirenko et al. 2023.)

The crystal structure of the title salt, bis-(3-carb-oxy-1-methyl-pyridinium) octa-bromide, 2C 7 H 8 NO 2 + ·Br 8 2- , consists of 3-carb-oxy-1-methyl-pyridinium ( N -methyl-nicotinic acid) cations, which are stacked between relatively rare [Br 8 ] 2- anions. The polybromide [Br 8 ] 2- anion has point group symmetry and can be described as being composed of two [Br 3 ] - anions connected with a Br 2 mol-ecule in a Z -shaped manner. Contacts between neighboring octa-bromide anions ensure the creation of pseudo-polymeric chains propagating along [111]. The organic cations are located between anionic chains and are connected to each other through O-H⋯O hydrogen bonds and to the [Br 8 ] 2- anions through π⋯Br inter-actions that induce the creation of a supra-molecular tri-periodic network. In addition, the presence of weak C-H⋯Br contacts leads to the creation of layers, which align parallel to (11)., (© Sirenko et al. 2023.)

Lead halide hybrid perovskites incorporating chiral organic cations attract considerable attention due to their promising application in multifarious optoelectronic devices. However, the examples of chiral hybrid perovskites are still limited, which greatly impedes their further studies in various optoelectronic fields. Herein, we report on new low-dimensional lead-halide hybrid perovskites incorporating the enantiopure chiral α-amino acid L-proline. Two hybrid perovskites (L-proH)PbBr 3 ·H 2 O ( Pro-PbBr 3 ) and (L-proH) 4 Pb 3 Br 10 ·4H 2 O ( Pro-Pb 3 Br 10 ) have been synthesized by employing different ratios of organic and inorganic precursors. According to structural analysis, the inorganic sublattice of compound Pro-PbBr 3 is built of one-dimensional (1D) [PbX 3 ] ∞ n - lead halide chains, whereas the inorganic sublattice of compound Pro-Pb 3 Br 10 is built upon a rare two-dimensional (2D) [Pb 3 Br 10 ] ∞ 4 n - honeycomb-type inorganic framework. Hirshfeld surface analysis revealed an important role of various hydrogen bonding interactions in providing the binding between organic and inorganic parts of these hybrid perovskites. The optical band gap values of new hybrid perovskites as estimated using the Tauc plot approach are 4.19 eV ( Pro-PbBr 3 ) and 4.13 eV ( Pro-Pb 3 Br 10 ). Also, new compounds display low-temperature broadband photoluminescence which can be attributed to the self-trapped excitons. These results show the potential of α-proline for constructing novel and highly demanded chiral hybrid perovskites, which will hold great promise for further optoelectronic applications.

The peripheral blood NK cell diversity is highly complex. Recent studies have described more than a thousand phenotypes sharing NK cell receptors (NKRs), across the leukocyte lineages. Previously, we have found that accentuated NK p46 phenotype has prognostic value for NK cytotoxicity status, and is characteristic for patients with recurrent implantation failure (RIF). In a blinded investigation we studied blood samples from IVF women before embryo transfer (pre-implantation genetic tested [PGT] embryos n = 116; not tested embryos n = 219). We studied NKp46 expression by flow cytometry and anti-cardiolipin antibody (aCL) levels. aCL results were transmitted to the clinic but NKp46 expression was blinded (for us and for the clinic) and not analyzed before termination of the study (end of last pregnancy). Association of NKp46 phenotype with clinical pregnancy rate (CPR), pregnancy failure (PF) rate and life birth rate (LBR) were analyzed. aCL positive and IvIg treated cases were excluded. IVF success was dependent on p46 NK phenotype in patients with PGT embryos. Elevated p46 expression on NK (>93%) as well as decreased (<66%) significantly reduce CPR (OR 12.7 and 3.8) without affecting pregnancy failure frequency. Both accentuations (taken together) resulted in a significant reduction of LBR (OR 3.9 p = 0.019) compared with non-accentuated phenotypes (p46 levels 66-93%). Elevated NK cell levels (>14.5% weakly) were associated with PF (OR 3.1 p = 0.069), but not significantly with reduced LBR. In contrast, numbers of NKCD335+ lymphocytes (>11.5%) were a significant predictor of PF (OR-4.0 p<0.05) and decreased LBR (OR 2.1 p = 0.06). At the same time, accentuated numbers of NKCD335neg lymphocytes (<0.7 and >4%) were also associated with decreased LBR (OR 2,65 p = 0.05). In patients with NKCD335++ numbers (<5 and >21%), we found a weakly association with IVF failure. We found similar associations in IVF patients without PGT -A but at lower significance levels regardless the higher number of patients. Impact of NKp46 phenotype for IVF success was significant in patients with donor's ET and almost imperceptible in patients > 35y.o. with own embryo transfer. Accentuated increased or decreased CD335 expression on NK was associated with embryo implantation failure. Balanced CD335 levels form a condition favorable for implantation. Elevated numbers of p46+NK (CD3-CD56+CD335+) predicts pregnancy failures at higher significance levels than elevated NK cell numbers. Elevated numbers of p46negNK (CD3-CD56+CD335-) indicate reduced LBR. Accentuation of p46 expression on NK cells is associated with reproductive failures. In combination with PGD it provides a powerful prediction algorithm and treatment option., Competing Interests: Declaration of Competing Interest Authors not have conflict of interest., (Copyright © 2022. Published by Elsevier B.V.)

Novel chiral hybrid perovskites are highly demanded for various advanced applications such as spintronics, optoelectronics, photovoltaics etc . However, the scope of these new materials is still limited. Herein, we present new 2D hybrid perovskites based upon chiral α-amino acid L-histidine. The generalized formula of these new compounds can be denoted as (L-HisH) 2 PbBr x I 4- x (where L-His = L-histidine; x = 4, 3, 2, 1, 0.4 and 0). All perovskites are characterized by a very similar structural motif that consists of corner-sharing lead halide octahedra arranged in one-layer thin inorganic slabs interleaved by organic layers established by L-histidinium(1+) cations. L-Histidine provides a breaking of spatial parity of these perovskites that results in their non-centrosymmetric crystal structures. These compounds show a multiband absorption up to 590 nm for iodide perovskite. In addition, new compounds display pronounced single-peak photoluminescence, which finely blue shifts upon the gradual substitution of iodine by bromine. New perovskites exhibit excellent thermal stability up to 490 K and 445 K for bromide and iodide compounds, respectively. These results show the ability of L-histidine to produce novel and highly demanded chiral hybrid perovskites.

Spin-crossover complexes with multistep transitions attract much attention due to their potential applications as multi-switches and for data storage. A four-step spin crossover is observed in the new iron(II)-based cyanometallic guest-free framework compound Fe(2-ethoxypyrazine) 2 {Ag(CN) 2 } 2 during the transition from the low-spin to the high-spin state. A reverse process occurs in three steps. Crystallographic studies reveal an associated stepwise evolution of the crystal structures. Multiple transitions in the reported complex originate from distinct Fe II sites which exist due to the packing of the ligand with a bulky substituent., (© 2022 Wiley-VCH GmbH.)

9-Amino-acridinium chloride N , N -di-methyl-formamide monosolvate, C 13 H 11 N 2 + Cl - ·C 3 H 7 NO, crystallizes in the monoclinic space group P 2 1 / c. The salt was crystallized from N , N -di-methyl-formamide. The asymmetric unit consists of two C 13 H 11 N 2 + Cl - formula units. The 9-amino-acridinium (9-AA) mol-ecules are protonated with the proton on the N atom of the central ring. This N atom is connected to an N , N -di-methyl-formamide mol-ecule by a hydrogen bond. The H atoms of the amino groups create short contacts with two chloride ions. The 9-AA cations in adjacent layers are oriented in an anti-parallel manner. The mol-ecules are linked via a network of multidirectional π-π inter-actions between the 9-AA rings, and the whole lattice is additionally stabilized by electrostatic inter-actions between ions., (© Fritsky et al. 2021.)

In the asymmetric unit of the title coordination compound, {[Cu(CN)(C 4 H 3 OC 2 H 5 N 2 )][Cu(CN)]} n , there are two Cu atoms with different coordination environments. One Cu I ion is coordinated in a triangular coordination geometry by the N atom of the 2-eth-oxy-pyrazine mol-ecule and by two bridging cyanide ligands, equally disordered over two sites exchanging C and N atoms, thus forming polymeric chains parallel to the c axis. The other Cu atom is connected to two bridging cyanide groups disordered over two sites with an occupancy of 0.5 for each C and N atom, and forming an almost linear polymeric chain parallel to the b axis. In the crystal, the two types of chain, which are orthogonal to each other, are connected by cuprophilic Cu⋯Cu inter-actions [2.7958 (13) Å], forming two-dimensional metal-organic coordination layers parallel to the bc plane. The coordination framework is further stabilized by weak long-range (electrostatic type) C-H⋯π inter-actions between cyano groups and 2-eth-oxy-pyrazine rings., (© Partsevska et al. 2019.)

Problem: NK lymphocytes play critical yet poorly defined role in implantation and during development in early pregnancy., Methods of Study: Recently, we showed that the proportion of NK that expressed CD69⁺ after incubation with K562 (CD69(stim)) cells reflected the NK population excitation potential. In the present study, we investigate the significance of NK activation levels in predicting embryo implantation., Results: A qualitative analysis of values distribution in two groups showed that 25/33 (75.8%) women who became pregnant had CD69(stim) levels that were >30 but <60% (conditionally normal zone). In contrast, CD69(stim) levels in patients who failed to become pregnant were either elevated, as in 10/51 (19.6%), or reduced, as in 20/51 (39.2%) of the patients. Accentuated CD69(stim) levels were predictive for implantation failure, extremely significant for decreased (OR 6.9, p=0.0004) and not quite significant for increased CD69(stim) levels (OR 3.9, p=0.062). Accordingly, conditionally normal CD69(stim) levels were favourable for implantation (OR 4.46, p=0.0032)., Conclusion: We confirm that actual peripheral blood natural killer cells activation status have an influence on embryo implantation. We showed that exactly normal NK cell activity predicting successful implantation., (Copyright © 2013 Elsevier GmbH. All rights reserved.)