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In this paper, we have provided some fixed point results for self-mappings fulfilling generalized contractive conditions on altered metric spaces. In addition, some applications of the main results to continuous data dependence of the fixed points of operators defined on these spaces were shown.

Protocols for the synthesis of the bulky polyfluorinated triarylboranes 2,6‐(C6F5)2C6F3B(C6F5)2 (1), 2,6‐(C6F5)2C6F3B[3,5‐(CF3)2C6H3] (2), 2,4,6‐(C6F5)3C6H2B(C6F5)2 (3), 2,4,6‐(C6F5)3C6H2B[3,5‐(CF3)2C6H3] (4) were developed. All boranes are water tolerant and according to the Gutmann‐Beckett method, 1–3 display Lewis acidities larger than that of the prominent B(C6F5)3., Water tolerant boranes: The synthesis and characterization of bulky polyfluorinated triarylboranes 2,6‐(C6F5)2C6F3B(C6F5)2 (1), 2,6‐(C6F5)2C6F3B[3,5‐(CF3)2C6H3] (2), 2,4,6‐(C6F5)3C6H2B(C6F5)2 (3), 2,4,6‐(C6F5)3C6H2B[3,5‐(CF3)2C6H3] (4) is presented. Unlike the prominent B(C6F5) („BCF“), 1–4 are water tolerant and 1–3 even show larger Lewis acidities, as determined by the Gutmann‐Beckett method.

Transiente, aus Bis(m-terphenyl)fluorpniktogenendurch Fluorid-Abstraktion gebildete Phosphenium- und Ar-senium-Ionen vollzogen einen intramolekularen elektrophilenAngriff, gefolgt von einer Methylgruppenwanderung und bil-deten isolierbare 9-Phospha- und 9-Arsena-Fluorenium-Ionen.

The bis(ferrocenyl)phosphenium ion, [Fc2P]+, reported by Cowley et al. (J. Am. Chem. Soc. 1981, 103, 714–715), was the only claimed donor‐free divalent phosphenium ion. Our examination of the molecular and electronic structure reveals that [Fc2P]+ possesses significant intramolecular Fe⋅⋅⋅P contacts, which are predominantly electrostatic and moderate the Lewis acidity. Nonetheless, [Fc2P]+ undergoes complex formation with the Lewis bases PPh3 and IPr to give the donor–acceptor complexes [Fc2P(PPh3)]+ and [Fc2P(IPr)]+ (IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazole‐2‐ylidene)., Lineup of suspects: Interest in kinetically stabilized pnictogenium ions prompted the re‐investigation of the bis(ferrocenyl)phosphenium ion, the only claimed donor‐free divalent phosphenium ion. Iron was found guilty of charge compensation.

Organic light-emitting diodes (OLEDs) are revolutionizing display applications. In this aspect, luminescent complexes of precious metals such as iridium, platinum, or ruthenium still playing a significant role. Emissive compounds of earth-abundant copper with equivalent performance are desired for practical, large-scale applications such as solid-state lighting and displays. Copper(I)-based emitters are well-known to suffer from weak spin-orbit coupling and a high reorganization energy upon photoexcitation. Here we report a cationic organo-copper cluster [Cu4(PCP)3]+ (PCP = 2,6-(PPh2)2C6H3) that features suppressed nonradiative decays, giving rise to a robust narrow-band green luminophore with a photoluminescent (PL) efficiency up to 93%. PL decay kinetics corroborated by DFT calculations reveal a complex emission mechanism involving contributions of both thermally activated delayed fluorescence and phosphorescence. This robust compound was solution-processed into a thin film in prototype OLEDs with external quantum efficiency up to 11% and a narrow emission bandwidth (65 nm fwhm).

In this paper, we introduce a new contraction-type mapping and provide a fixed-point theorem which generalizes and improves some existing results in the literature. Thus, we prove that the Boyd and Wong theorem (1969) and, more recently, the fixed-point results due to Wardowski (2012), Turinici (2012), Piri and Kumam (2016), Secelean (2016), Proinov (2020), and others are consequences of our main result. An application in integral equations and some illustrative examples are indicated.

The reaction of 2,6-F2 C6 H3 SiMe3 with Ph2 PLi provided 2,6-(Ph2 P)2 C6 H3 SiMe3 (1), which can be regarded as precursor for the novel anionic tridentate ligand [2,6-(Ph2 P)2 C6 H3 ]- (PCP)- . The reaction of 1 with [AuCl(tht)] (tht=tetrahydrothiophene) afforded 2,6-(Ph2 PAuCl)2 C6 H3 SiMe3 (2). The subsequent reaction of 2 with CsF proceeded with elimination of Me3 SiF and yielded the neutral tetranuclear complex linear-[Au4 Cl2 (PCP)2 ] (3) comprising a string-like arrangement of four Au atoms. Upon chloride abstraction from 3 with NaBArF4 (ArF =3,5-(CF3 )2 C6 H3 ) in the presence of tht, the formation of the dicationic tetranuclear complex linear-[Au4 (PCP)2 (tht)2 ](BArF4 )2 (4) was observed, in which the string-like structural motif is retained. Irradiation of 4 with UV light triggered a facile rearrangement in solution giving rise to the dicationic tetranuclear complex cyclo-[Au4 (PCP)2 (tht)2 ](BArF4 ) (5), which comprises a rhomboidal motif of four Au atoms. In 3-5, the Au atoms are associated by a number of significant aurophilic interactions. The atom-economic and selective reaction of 3 with HgCl2 yielded the neutral trinuclear bimetallic complex [HgAu2 Cl3 (PCP)] (6) comprising significant metallophilic interactions between the Au and Hg atoms. Therefore, 6 may be also regarded as a metallopincer complex [ClHg(AuCAu)] between HgII and the anionic tridentate ligand [2,6-(Ph2 PAuCl)2 C6 H3 ]- (AuCAu)- containing a central carbanionic binding site and two "gold-arms" contributing pincer-type chelation trough metallophilic interactions. Compounds 1-6 were characterized experimentally by multinuclear NMR spectroscopy and X-ray crystallography and computationally using a set of real-space bond indicators (RSBIs) derived from electron density (ED) methods including Atoms In Molecules (AIM), the Electron Localizability Indicator (ELI-D) as well as the Non-Covalent Interaction (NCI) Index.

Fluoride abstraction from bis‐m‐terphenylelement fluorides (2,6‐Mes2C6H3)2EF (E=P, As) generated the highly reactive phosphenium ion [(2,6‐Mes2C6H3)2P]+ and the arsenium ion [(2,6‐Mes2C6H3)2As]+, which immediately underwent intramolecular electrophilic substitution and formation of an 1,2,4‐trimethyl‐6‐mesityl‐5‐m‐terphenyl‐benzo[b]phospholium ion and an 1,2,4‐trimethyl‐6‐mesityl‐5‐m‐terphenyl‐benzo[b]arsolium ion, respectively. The formation of the latter involved a methyl group migration from the ortho‐position of a flanking mesityl group to the meta‐position. This reactivity of [(2,6‐Mes2C6H3)2E]+ (E=P, As) is in sharp contrast to the related stibenium ion [(2,6‐Mes2C6H3)2Sb]+ and bismuthenium ion [(2,6‐Mes2C6H3)2Bi]+, which have been recently isolated and fully characterized (Angew. Chem. Int. Ed. 2018, 57, 10080–10084). On the basis of DFT calculations, a mechanism for the rearrangement of the phosphenium and arsenium ions into the phospholium and arsolium ions is proposed, which is not feasible for the stibenium and bismuthenium ions., The fluoride abstraction from the bis(m‐terphenyl)element fluorides (P, As) using the Lewis acids EtAlCl2 and [Et3Si(toluene)]+, respectively, provided the transient phosphenium and arsenium ion [(2,6‐Mes2C6H3)2As]+ which rearrange readily into the protonated 9‐phospha‐ and 9‐arsena‐fluorenes.

We recently communicated (Angew. Chem. Int. Ed., 2018, 57, 5917–5920) the transmetallation of [6-Ph2P(O)-Ace-5-]2Hg (1) with Pb(OAc)4, which, after work-up with HCl in Et2O, provided the first aryl lead trichloride, 6-Ph2P(O)-Ace-5-PbCl3 (2), and 6-Ph2P(O)-Ace-5-HgCl (3). With LiCl, 1 forms a complex, [{[6-Ph2P(O)-Ace-5]2Hg}2Li]Cl (1a), that shows no reactivity towards Pb(OAc)4 anymore, which highlights the role of the intramolecularly coordinated P(O) functionality in transmetallation. In this work, we have broadened the scope of the transmetallation reagent by the reaction of 1 with SnCl4, SbCl3 and BiCl3 giving rise to the formation of 6-Ph2P(O)-Ace-5-SnCl3 (4), 6-Ph2P(O)-Ace-5-SbCl2 (5) and 6-Ph2P(O)-Ace-5-BiCl2 (6), respectively. The high Lewis acidity permits 4 and 5 to undergo complexation with THF, whereas no such complexes were formed with 2 and 6. The molecular structures of 1a, 3, 4, 4·THF, 5, 5·THF and 6 were established by X-ray crystallography. The different P–O distances of 2, 4, 4·THF, 5, 5·THF and 6, reflecting the relative strength of the P(O)⋯E coordination (E = Pb, Sn, Sb, Bi), were discussed. The nature of the P(O)⋯E interactions of 2, 4, 4·THF, 5, 5·THF and 6 was studied using a set of real-space bond indicators (RSBIs).

One recent and prolific direction in the development of fixed point theory is to consider an operator T:X→X defined on a metric space (X,d) which is an F—contraction, i.e., T verifies a condition of type τ+F(d(T(x),T(y))≤F(d(x,y)), for all x,y∈X, T(x)≠T(y), where τ>0 and F:(0,∞)→R satisfies some suitable conditions which ensure the existence and uniqueness for the fixed point of operator T. Moreover, the notion of F-contraction over a metric space (X,d) was generalized by considering the notion of (G,H)—contraction, i.e., a condition of type G(d(Tx,Ty))≤H(d(x,y)), for all x,y∈X, Tx≠Ty for some appropriate G,H:(0,∞)→R functions. Recently, the abovementioned F-contraction theory was extended to the setup of cone metric space over the topological left modules. The principal objective of this paper is to introduce the concept of vectorial dislocated metric space over a topological left module and the notion of A-Cauchy sequence, as a generalization of the classical Cauchy sequence concept. Furthermore, based on the introduced concept, a fixed point result is provided for an operator T:X→X, which satisfies the condition (G,H)—contraction, where G,H are defined on the interior of a solid cone.

In this paper, we introduce the concept of cone metric space over a topological left module and we establish some coincidence and common fixed point theorems for self-mappings satisfying a condition of Lipschitz type. The main results of this paper provide extensions as well as substantial generalizations and improvements of several well known results in the recent literature. In addition, the paper contains an example which shows that our main results are applicable on a non-metrizable cone metric space over a topological left module. The article proves that fixed point theorems in the framework of cone metric spaces over a topological left module are more effective and more fertile than standard results presented in cone metric spaces over a Banach algebra.

Transient phosphenium and arsenium ions, generated by fluoride abstraction from bis(m‐terphenyl)fluoropnictogens, underwent intramolecular electrophilic attack prior to methyl group migration and gave rise to isolable 9‐phospha‐ and 9‐arsena‐fluorenium ions., Chemical rollercoaster ride: Attempts to prepare phosphenium and arsenium ions of the type [(2,6‐{Me5C6}2C6H3)2E]+ (E=P; E=As) lead to the isolation of two‐isomer mixtures of phospha‐ and arsena‐fluorenium ions. These arenium ions were isolated and structurally characterized. They are high‐energy species that undergo subsequent, solvent‐dependent reactions leading to thermodynamically favored products.

Novel E,C,E'-pincer supported silyl cations (E, E' = O, S, Se, Au) were prepared in three steps starting from 2,6-F2C6H3SiMe2H (1a) and 2,6-Br2C6H3SiMe2H (1b), which were first converted in two complementary ways into 2,6-(Ph2P)(2)C6H3SiMe2H (2). The oxidation of 2 with H2O2 center dot urea, S-8, and Se-8 afforded 2,6-(Ph2PE)(2)C6H3SiMe2H (3a, E = O; 3b, E = S; 3c, E = Se) and 2-(Ph2PE)-6-(Ph2P)-C6H3SiMe2H (4b, E = S; 4c, E = Se), which were reacted to the E,C,E-supported silyl cations [2,6-(Ph2PE)(2)C6H3SiMe2](+) (5a, E = O, counterion Br-3(-); 5b, E = S, counterion B(C6F5)(4)(-); 5c, E = Se, counterion B(C6F5)(4)(-)), the E,C-supported silyl cations [2-(Ph2PE)-6-(Ph2P)C6H3SiMe2](+) (6b, E = S, not isolated; 6c, E = Se, not isolated), the O,C,S-supported silyl cation [2-(Ph2PS)-6-(Ph2PO)C6H3SiMe2](+) (7, counterion B(C6F5)(4)(-)) as well as the E,C,Au-supported silyl cations [2-(Ph2PAuC6F5)-6-(Ph2PE)C6H3SiMe2](+) (8b, E = S, counterion [B{3,5-(CF3)(2)C6H3}(4)](-); 8c, E = Se, [B{3,5-(CF3)(2)C6H3}(4)](-)) using Br-2, O-2, S-8, (tht)AuC6F5, Ph3C[B(C6F5)(4)] and Ph3C[B{3,5-(CF3)(2)C6H3}(4)]. All compounds were characterized by multinuclear (H-1, C-13, F-19, Si-29, P-31, Se-77) NMR spectroscopy, ESI MS spectrometry and X-ray crystallography (2, 3a center dot H2O, 3b, 3c, 4b, 5a, 5c, 7, 8b, 8c). The gas phase structures of 2, 3a-c, 5a-c (fully optimized) and 8b, 8c (single-point calculations) were studied at the B3PW91/6-311+G(2df,p) level of theory. A set of real-space bonding indicators (RSBIs) derived from the theoretically calculated electron and pair densities were analyzed utilizing the atoms-in molecules (AIM) and electron-localizability indicator (ELI-D) space partitioning schemes.

OLED technology beyond small or expensive devices requires light-emitters, luminophores, based on earth-abundant elements. Understanding and experimental verification of charge transfer in luminophores are needed for this development. An organometallic multicore Cu complex comprising Cu–C and Cu–P bonds represents an underexplored type of luminophore. To investigate the charge transfer and structural rearrangements in this material, we apply complementary pump-probe X-ray techniques: absorption, emission, and scattering including pump-probe measurements at the X-ray free-electron laser SwissFEL. We find that the excitation leads to charge movement from C- and P- coordinated Cu sites and from the phosphorus atoms to phenyl rings; the Cu core slightly rearranges with 0.05 Å increase of the shortest Cu–Cu distance. The use of a Cu cluster bonded to the ligands through C and P atoms is an efficient way to keep structural rigidity of luminophores. Obtained data can be used to verify computational methods for the development of luminophores., Nature Communications, 11 (1), ISSN:2041-1723

Transmetallation of Pb(OAc)4 with R2 Hg (1), followed by treatment with HCl in Et2 O, provided RPbCl3 (2), the first kinetically stabilized monoorganolead trihalide that resists reductive elimination under ambient conditions. The kinetic stabilisation relies on an intramolecularly coordinating O-donor substituent (R=6-Ph2 P(O)-Ace-5-). The gram-scale preparation of 2 was key for the synthesis of unsymmetrically substituted diaryllead dichlorides RR'PbCl2 (3 a, R'=Ph; 3 b, R'=4-MeOC6 H4 ; 3 c, R'=4-Me2 NC6 H4 ).

The reaction of 2,6‐F2C6H3SiMe3 with Ph2PLi provided 2,6‐(Ph2P)2C6H3SiMe3 (1), which can be regarded as precursor for the novel anionic tridentate ligand [2,6‐(Ph2P)2C6H3]− (PCP)−. The reaction of 1 with [AuCl(tht)] (tht=tetrahydrothiophene) afforded 2,6‐(Ph2PAuCl)2C6H3SiMe3 (2). The subsequent reaction of 2 with CsF proceeded with elimination of Me3SiF and yielded the neutral tetranuclear complex linear‐[Au4Cl2(PCP)2] (3) comprising a string‐like arrangement of four Au atoms. Upon chloride abstraction from 3 with NaBArF 4 (ArF=3,5‐(CF3)2C6H3) in the presence of tht, the formation of the dicationic tetranuclear complex linear‐[Au4(PCP)2(tht)2](BArF 4)2 (4) was observed, in which the string‐like structural motif is retained. Irradiation of 4 with UV light triggered a facile rearrangement in solution giving rise to the dicationic tetranuclear complex cyclo‐[Au4(PCP)2(tht)2](BArF 4) (5), which comprises a rhomboidal motif of four Au atoms. In 3–5, the Au atoms are associated by a number of significant aurophilic interactions. The atom‐economic and selective reaction of 3 with HgCl2 yielded the neutral trinuclear bimetallic complex [HgAu2Cl3(PCP)] (6) comprising significant metallophilic interactions between the Au and Hg atoms. Therefore, 6 may be also regarded as a metallopincer complex [ClHg(AuCAu)] between HgII and the anionic tridentate ligand [2,6‐(Ph2PAuCl)2C6H3]− (AuCAu)− containing a central carbanionic binding site and two “gold‐arms” contributing pincer‐type chelation trough metallophilic interactions. Compounds 1–6 were characterized experimentally by multinuclear NMR spectroscopy and X‐ray crystallography and computationally using a set of real‐space bond indicators (RSBIs) derived from electron density (ED) methods including Atoms In Molecules (AIM), the Electron Localizability Indicator (ELI‐D) as well as the Non‐Covalent Interaction (NCI) Index., Heavy metal interactions: The synthesis and characterization of several tetranuclear gold complexes and of a trinuclear bimetallic (metallopincer) complex featuring metallophilic interactions is described in this work.

Efforts to prepare an elusive donor-free phosphenium ion, [R2 P]+ , led us to synthesize functionalized fluorophosphonium cations of the type [R2 P(F)X]+ (X=SiEt3 , H, F), which were obtained from the related neutral fluorophosphines R2 PF and R2 PF3 upon protonation and reaction with solvated [Et3 Si]+ ions (R=2,6-Mes2 C6 H3 ). The hypothetical reductive elimination of [R2 P(F)SiEt3 ]+ and [R2 P(F)H]+ affording [R2 P]+ , Et3 SiF and HF, respectively, was calculated to be endothermic by 40.1 and 190.6 kJ mol-1 .

The cultural landscape of the southern part of historic province Bukovina (situated in North-East of Romania) is a resource for a sustainable development of tourism in the area, being considered that the tourist product and service supply combine Bucovina's main assets: nature and culture [1]. Named the "Land of Beech", well known for its vast forests, Bukovina was the region where the woodworking craftsmanship has taken shape since ancient times. Here we can talk about a real development of the wood culture (wood was used to build the house, the barn, the stables, the gate and the fence, to make the furniture inside the dwelling, for example the dowry chest, the table, the bed, the dish shelf, the kneading-trough, the barrels, the spoons, the loom, the spinning wheel, the spindle, the towing torch). This wood culture was influenced by historical and geographic factors, it had particularities from one area to another regarding the working techniques, especially due to the influence of the German, Polish and Slovak colonists, who came to Bukovina after its annexation by the Austrians (1774). Recently, the preservation of cultural landscape, as a solution that contributes to a sustainable development of the region, was brought again to the attention of specialists. To have access to all written resources, could be a challenge, if we take into consideration that most of them were produced between 1960-1990, in a limited number, with a limited circulation. The present paper will result of the documentation work of the authors, that have centralized all bibliographic resources that are relevant for the material patrimony of Bukovina.

Triorganobismuthines R(C6F5)2Bi (1) and R[2,4,6-(C6F5)3C6H2]2Bi (2) [R = 2-(Me2NCH2)C6H4] were synthesized by reaction of RBiBr2 with C6F5MgBr and 2,4,6-(C6F5)3C6H2Li, respectively, in a 1 : 2 molar ratio. The Bi-chiral bromides R(C6F5)BiBr (3), R(Mes)BiBr (4), and R(Ph)BiBr (5) were obtained from RBiBr2 and C6F5MgBr, MesMgBr or PhMgBr, or from PhBiBr2 and RLi, in a 1 : 1 molar ratio. The molecular structures of 1–5 were determined by single-crystal X-ray diffraction and are discussed taking into account the chirality of the species. Supramolecular aspects in the solid state are presented. The solution behaviour of the title compounds, including dynamic aspects, are discussed on the basis of multinuclear (1H, 13C, 19F) NMR spectroscopy.

In this paper, we establish some conditions for the existence and uniqueness of the monotonic solutions for nonhomogeneous systems of first-order linear differential equations, by using a result of the fixed points theory for sequentially complete gauge spaces.

Kinetically stabilized congeners of carbenes, R2 C, possessing six valence electrons (four bonding electrons and two non-bonding electrons) have been restricted to Group 14 elements, R2 E (E=Si, Ge, Sn, Pb; R=alkyl or aryl) whereas isoelectronic Group 15 cations, divalent species of type [R2 E]+ (E=P, As, Sb, Bi; R=alkyl or aryl), were unknown. Herein, we report the first two examples, namely the bismuthenium ion [(2,6-Mes2 C6 H3 )2 Bi][BArF4 ] (1; Mes=2,4,6-Me3 C6 H2 , ArF =3,5-(CF3 )2 C6 H3 ) and the stibenium ion [(2,6-Mes2 C6 H3 )2 Sb][B(C6 F5 )4 ] (2), which were obtained by using a combination of bulky meta-terphenyl substituents and weakly coordinating anions.

Substituted phenols with a m-terphenyl backbone 2,4,6-R3C6H2OH [R=2,4,6-Me3C6H2 (1), Me5C6 (2)] were synthesized using Kumada cross-coupling reactions between 2,4,6-I3C6H2OH and the corresponding Grignard reagent. Both compounds were structurally characterized in solution by 1H and 13C NMR spectroscopy and HRMS. The molecular structures of 1 and 2 were determined by single-crystal X-ray diffraction.

Closely following the procedure for the preparation of the base-stabilized dichlorosilylene complex NHCDipp ⋅SiCl2 reported by Roesky, Stalke, and co-workers (Angew. Chem. Int. Ed. 2009, 48, 5683-5686), a few crystals of the salt [NHCDipp -H⋅⋅⋅Cl⋅⋅⋅H-NHCDipp ]Si(SiCl3 )3 were isolated, aside from the reported byproduct [NHCDipp -H+ ⋅⋅⋅Cl- ], and characterized by X-ray crystallography (NHCDipp =N,N-di(2,6-diisopropylphenyl)imidazo-2-ylidene). They contain the weakly coordinating anion Si(SiCl3 )3- , which was also obtained in high yields upon deprotonation of the conjugate Bronsted acid HSi(SiCl3 )3 with NHCDipp or PMP (PMP=1,2,2,6,6-pentamethylpiperidine). The acidity of HSi(SiCl3 )3 was estimated by DFT calculations to be substantially higher than those of other H-silanes. Further DFT studies on the electronic structure of Si(SiCl3 )3- , including the electrostatic potential and the electron localizability, confirmed its low basicity and nucleophilicity compared with other silyl anions.

The second-order nucleophilic substitution (SN 2) reaction at a silicon atom is scrutinized by means of snapshots along a pseudoreaction coordinate. Phosphine and fluoride represent both attacking and leaving groups in the modeled SN 2 reaction. In the experimentally obtained 5-diphenylphosphinoacenaphth-6-yl-dimethylfluorosilane, 1, the phosphine and fluorosilane moieties are forced into immediate proximity through an acenaphthyl scaffold, that is, they exhibit peri interactions that serve as the model of the reactant ion-molecule complex and starting point for a theoretical potential-energy surface (PES) scan. Upon dissociation of fluoride, the experimentally obtained silylphosphonium cation 2 serves as a model of the product and end point of the PES scan. The pseudoreaction pathway is studied using geometric, energetic, spectroscopic, molecular-orbital, and topological real-space bonding indicators. It becomes evident that it is crucial to combine such methods to understand the pseudoreaction because they reveal different aspects based on different sensitivity to dispersive, electrostatic, and polar-covalent contributions to bonding, as shown by the reduced density gradient analysis. For example, atoms-in-molecules theory describes a late topological catastrophe, whereas the electron localizability indicator describes an early concerted reaction and natural resonance theory describes a more gradual change of properties. This case study encourages the use of a well-balanced toolbox equipped with complementary methods to emphasize different aspects of bonding.

Autophagy, a homeostatic process involved in nutrient regeneration and immune responses, may be involved in intracellular killing of M. tuberculosis. Several studies linked variation in autophagy genes with susceptibility to pulmonary tuberculosis, but others did not confirm these findings. We genotyped single nucleotide polymorphisms (SNPs) in the ATG5 (rs2245214, c.574-12777G>C) and NOD2 (rs2066844, c.2104C>T) genes for 256 pulmonary tuberculosis patients and 330 unrelated healthy controls in Romania. Both SNPs have been reported as relevant for the autophagy process and potentially for susceptibility to active pulmonary tuberculosis. In our study, the polymorphisms in ATG5 and NOD2 were not associated with tuberculosis. This suggests that the two genetic variants we focused on are not related to the risk for developing active TB in a Romanian population.

Triorganobismuthines R(C6F5)2Bi (1) and R[2,4,6-(C6F5)3C6H2]2Bi (2) [R = 2-(Me2NCH2)C6H4] were synthesized by reaction of RBiBr2 with C6F5MgBr and 2,4,6-(C6F5)3C6H2Li, respectively, in a 1 : 2 molar ratio. The Bi-chiral bromides R(C6F5)BiBr (3), R(Mes)BiBr (4), and R(Ph)BiBr (5) were obtained from RBiBr2 and C6F5MgBr, MesMgBr or PhMgBr, or from PhBiBr2 and RLi, in a 1 : 1 molar ratio. The molecular structures of 1-5 were determined by single-crystal X-ray diffraction and are discussed taking into account the chirality of the species. Supramolecular aspects in the solid state are presented. The solution behaviour of the title compounds, including dynamic aspects, are discussed on the basis of multinuclear ((1)H, (13)C, (19)F) NMR spectroscopy.

Genetic variants in the CARD9 gene predispose to inflammatory disorders and chronic infectious diseases. Tuberculosis (TB), a chronic infectious disease affecting the lung, is lethal in Card9-deficient mice. We hypothesized that polymorphisms in the CARD9 gene influence TB progression and disease-associated lung damage in humans. We tested genotype distributions of the CARD9 polymorphisms rs4077515, rs10781499 and rs10870077 in TB patients and healthy subjects in a Caucasian cohort. SNPs were in linkage disequilibrium and none of the haplotypes was significantly enriched in the TB group. We determined total and differential leukocyte count, erythrocyte sedimentation rate and plasma abundance of cytokines and chemokines as markers for systemic inflammation and scored chest X-rays to assess lung involvement in TB subjects. Most disease parameters segregated independently of the CARD9 haplotypes. In contrast to multifactorial chronic inflammation, selected genetic variants in the CARD9 gene leave host responses apparently unaffected in TB, at least in the population analyzed here.

The authors continue a started series of articles about extrapulmonary tuberculosis (EPTB) with the assessment of the mycobacterial lesions discovered on tissue samples of the oral cavity structures in the Department of Pathology of the Emergency County Hospital of Craiova, Romania, and the review of the cases reported in the literature available, between 1990 and 2013.The studied material consisted, for our series, of samples obtained by biopsy or surgical excision, including the salivary glands and excluding the lymph nodes from 17 patients histopathologically diagnosed with tuberculosis and, for review series, 190 papers selected from PubMed database.The number of cases reported increased throughout the studied period. Most cases came from departments connected with oral pathology but also from various medical and surgical departments. In general, patients were adults with a mean age of around 40 years, with twice as many men than women, without no information or no clinical suspicion of tuberculosis (TB) at the admission. When reported, the provisional diagnostic was oriented most often towards neoplastic proliferation. There was no information about human immunodeficiency virus (HIV) testing in more than half of the case reports but when existed the result was two-fold more frequently negative than positive. TB lesions of the oral cavity were more often primary infections than secondary. From morphological point of view, the granuloma cellular population included both epithelioid and Langhans cells in most of the cases, the necrosis, present in most of the cases, displayed the whole range of morphological features, but mainly the acidophilic, microgranular one and the perilesional fibrosis was absent in almost all of the cases. As a whole, well-differentiated granulomas were the most frequent, usually of grade II - reactive type ("homeostatic") but with a significant contingent of grade I - hyperplastic ("protective") granulomas. Local extension was usually not present and, when present, regional lymph nodes were mainly involved. Coexistence of TB lesions with a neoplastic proliferation was very rare and when present it was mainly located in the parotid gland. Apart from this general profile, particular, individual profiles were observed for each of the oral cavity segments.TB lesions in the oral cavity are indeed a rare event but no swelling or ulcer in the oral cavity should be disregarded by the medical practitioners because it could be tuberculosis.

Smoking is a major public health problem with medical, social, and financial implications. We conducted a retrospective analysis of data resulting from enrollment and completion of a smoking cessation program of a number of 399 subjects of both gender, who presented consecutively in 2009 to the Smoking Cessation Counseling Medical Office of the Iasi Clinical Rehabilitation Hospital. The treatment for smoking cessation was represented either by bupropion or varenicline, administered by the usual scheme. Smoking severity was quantified by pack - years, determining the carbon monoxide in the exhaled air, both at baseline and at the end of the treatment period, and by Fagerstrom test for nicotine dependence. In female patients, the severity of smoking was significantly lower (P = 0.000) but their male counterparts responded better to treatment. Also, varenicline seemed to have a stronger therapeutic effect then bupropion while their adverse effects were similar.