Treatment challenges and health conditions among people living with HIV with or without substance use disorder in the Russian Federation.

We quantified treatment challenges faced by people living with HIV (PLHIV) in Russia. Cross-sectional data of 150 PLHIV in Russia were from the 2019 Positive Perspectives Survey. Mean age was 38.3 y. Two-thirds (68.0%[102/150]) had ever disguised their HIV pills, and 43.3%[65/150] said they would be stressed if someone saw their HIV pills. Overall, 14.7%[22/150] reported being ever diagnosed with substance use disorder (SUD). Self-rated optimal health was significantly lower among those with vs without a report of SUD on multiple health domains: sexual (40.9%[9/22] vs. 70.3%[90/128], p = 0.007), physical (22.7%[5/22] vs. 68.0%[87/128], p < 0.001), and overall health (27.3%[6/22] vs. 68.8%[88/128], p < 0.001). Those reporting SUD were more likely to miss HIV medication ≥ 1 time in the past month because they used recreational drugs (age and gender-adjusted prevalence ratio [APR] = 8.23, 95%CI = 6.99-9.68), could not afford their medication (APR = 3.28, 95%CI = 2.90-3.72), had to work (APR = 3.27, 95%CI = 2.97-3.60), or to avoid side effects (APR = 2.62, 95%CI = 2.37-2.89). Furthermore, self-reported SUD was strongly associated with numerous poor health conditions, including self-reported diagnosis of cancer (APR = 6.67, 95%CI = 5.24-8.48), mental illness (APR = 5.01, 95%CI = 4.53-5.55), and liver disease (APR = 4.29, 95%CI = 3.98-4.61). The distinct patterns of poorer health-related outcomes among PLHIV with SUD underscore the need to address behavioral and psychosocial challenges as part of holistic HIV care.

Spirocyclic Nitroxides as Versatile Tools in Modern Natural Sciences: From Synthesis to Applications. Part I. Old and New Synthetic Approaches to Spirocyclic Nitroxyl Radicals.

Spirocyclic nitroxyl radicals (SNRs) are stable paramagnetics bearing spiro-junction at a-, b-, or g-carbon atom of the nitroxide fragment, which is part of the heterocyclic system. Despite the fact that the first representatives of SNRs were obtained about 50 years ago, the methodology of their synthesis and their usage in chemistry and biochemical applications have begun to develop rapidly only in the last two decades. Due to the presence of spiro-function in the SNRs molecules, the latter have increased stability to various reducing agents (including biogenic ones), while the structures of the biradicals (SNBRs) comprises a rigid spiro-fused core that fixes mutual position and orientation of nitroxide moieties that favors their use in dynamic nuclear polarization (DNP) experiments. This first review on SNRs will give a glance at various strategies for the synthesis of spiro-substituted, mono-, and bis-nitroxides on the base of six-membered (piperidine, 1,2,3,4-tetrahydroquinoline, 9,9'(10H,10H')-spirobiacridine, piperazine, and morpholine) or five-membered (2,5-dihydro-1H-pyrrole, pyrrolidine, 2,5-dihydro-1H-imidazole, 4,5-dihydro-1H-imidazole, imidazolidine, and oxazolidine) heterocyclic cores.

Magnetic Properties of π-Conjugated Hybrid Phenoxyl-Nitroxide Radicals with Extended π-Spin Delocalization.

A series of stable and genuinely organic open-shell systems, π-conjugated phenoxyl-nitroxide free radicals (hybrid phenoxyl-nitroxide radicals), have been synthesized and their magnetic properties in the crystalline state investigated, revealing their usefulness as new building blocks for molecular magnetic materials. The salient electronic structure of the hybrid phenoxyl-nitroxide radicals is extended π-spin delocalization from the nitroxide moiety, mediating the localization effect intrinsic to nitroxide radicals. Five representative hybrid radicals containing an aliphatic, aromatic, and heteroaromatic substituent in the side part of the compact hybrid radical centers were synthesized, and their molecular/crystal structures in the crystalline state were determined by X-ray diffraction analyses. CW X-band ESR, 1H-ENDOR spectroscopy, and DFT calculations for the hybrid radicals confirmed that an unpaired spin delocalizes over the whole molecular frame including the nonconjugated fragments, suggesting the possibility of tuning their electronic properties through substituent effects in the crystalline state. Significant influence of the phenoxyl moiety on the electronic structure was analyzed in terms of the g-tensor calculations. The SQUID magnetization measurements revealed that the nitroxides bearing alkyl or aromatic substituents behave as 3D Curie-Weiss paramagnets with weak antiferromagnetic (AFM) (Θ = -1 to -2.6 K) or ferromagnetic (FM) (Θ = +0.33 K) spin-spin exchange interactions. On the other hand, heteroaromatically substituted hybrid phenoxyl-nitroxide showed significant AFM interactions with J/kB = -25.6 K. The analysis of the bulk magnetic properties based on the crystallographic data and DFT calculations revealed competition between the intermolecular AFM and FM interactions which originate from the C-O(phenoxyl)···Me(nitroxide) or (N)O-C(arom) infinite 1D head-to-tail chains and the C(arom)-C(arom) head-over-tail dimers forming 3D networks in their crystal lattices.

5-Aryl-2-(3,5-dialkyl-4-hydroxyphenyl)-4,4-dimethyl-4H-imidazole 3-Oxides and Their Redox Species: How Antioxidant Activity of 1-Hydroxy-2,5-dihydro-1H-imidazoles Correlates with the Stability of Hybrid Phenoxyl-Nitroxides.

Cyclic nitrones of the imidazole series, containing a sterically hindered phenol group, are promising objects for studying antioxidant activity; on the other hand, they can form persistent hybrid phenoxyl-nitroxyl radicals (HPNs) upon oxidation. Here, a series of 5-aryl-4,4-dimethyl-4H-imidazole 3-oxides was obtained by condensation of aromatic 2-hydroxylaminoketones with 4-formyl-2,6-dialkylphenols followed by oxidation of the initially formed N-hydroxy derivatives. It was shown that the antioxidant activity of both 1-hydroxy-2,5-dihydroimidazoles and 4H-imidazole 3-oxides increases with a decrease in steric volume of the alkyl substituent in the phenol group, while the stability of the corresponding HPNs generated from 4H-imidazole 3-oxides reveals the opposite tendency.

Ferromagnetically Coupled S=1 Chains in Crystals of Verdazyl-Nitronyl Nitroxide Diradicals.

Thermally stable organic diradicals with a triplet ground state along with large singlet-triplet energy gap have significant potential for advanced technological applications. A series of phenylene-bridged diradicals with oxoverdazyl and nitronyl nitroxide units were synthesized via a palladium-catalyzed cross-coupling reaction of iodoverdazyls with a nitronyl nitroxide-2-ide gold(I) complex with high yields. The diradicals exhibit high stability and do not decompose in an inert atmosphere up to 180 °C. For the diradicals, both substantial AF (ΔEST ≈-64 cm-1 ) and FM (ΔEST ≥25 and 100 cm-1 ) intramolecular exchange interactions were observed. The sign of the exchange interaction is determined both by the bridging moiety (para- or meta-phenylene) and by the type of oxoverdazyl block (C-linked or N-linked). Upon crystallization, diradicals with the triplet ground state form unique one-dimensional exchange-coupled chains with strong intra- and weak inter-diradical ferromagnetic coupling.

Trityl-Aryl-Nitroxide-Based Genuinely g-Engineered Biradicals, As Studied by Dynamic Nuclear Polarization, Multifrequency ESR/ENDOR, Arbitrary Wave Generator Pulse Microwave Waveform Spectroscopy, and Quantum Chemical Calculations.

Trityl and nitroxide radicals are connected by π-topologically controlled aryl linkers, generating genuinely g-engineered biradicals. They serve as a typical model for biradicals in which the exchange (J) and hyperfine interactions compete with the g-difference electronic Zeeman interactions. The magnetic properties underlying the biradical spin Hamiltonian for solution, including J's, have been determined by multifrequency CW-ESR and 1H ENDOR spectroscopy and compared with those obtained by quantum chemical calculations. The experimental J values were in good agreement with the quantum chemical calculations. The g-engineered biradicals have been tested as a prototype for AWG (Arbitrary Wave Generator)-based spin manipulation techniques, which enable GRAPE (GRAdient Pulse Engineering) microwave control of spins in molecular magnetic resonance spectroscopy for use in molecular spin quantum computers, demonstrating efficient signal enhancement of specific weakened hyperfine signals. Dynamic nuclear polarization (DNP) effects of the biradicals for 400 MHz nuclear magnetic resonance signal enhancement have been examined, giving efficiency factors of 30 for 1H and 27.8 for 13C nuclei. The marked DNP results show the feasibility of these biradicals for hyperpolarization.

Aromatic SNF-Approach to Fluorinated Phenyl tert-Butyl Nitroxides.

The interaction of octafluorotoluene (1a), as well as pentafluorobenzonitrile (1b) with tert-butylamine, followed by the oxidation of thus formed tert-butylanilines (2a,b) with meta-chloroperoxybenzoic acid led to functionalized perfluorinated phenyl tert-butyl nitroxides [namely, 4-(N-tert-butyl(oxyl)amino)heptafluorotoluene (3a) and 4-(N-tert-butyl(oxyl)amino)tetrafluorobenzonitrile (3b)] with nearly quantitative total yields. The molecular and crystal structures of nitroxide 3a were proved by single crystal X-ray diffraction analysis. The radical nature of both nitroxides was confirmed by ESR data. The interaction of Cu(hfac)2 with the obtained nitroxides 3a,b gave corresponding trans-bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ2O,O')bis{4-(N-tert-butyl(oxyl)amino)perfluoroarene-κO}copper (II) complexes ([Cu(hfac)2(3a)2] and [Cu(hfac)2(3b)2]). X-ray crystal structure analysis showed square bipyramid coordination of a centrally symmetric Cu polyhedron with the axial positions occupied by oxygen atoms of the nitroxide groups. Magnetic measurements revealed intramolecular ferromagnetic exchange interactions between unpaired electrons of Cu(II) ions and paramagnetic ligands, with exchange interaction parameters JCu-R reaching 53 cm-1.

Unique Superparamagnetic-like Behavior Observed in Non-π-delocalized Nitroxide Diradical Compounds Showing Discotic Liquid Crystalline Phase.

A unique superparamagnetic-like behavior and a large "positive magneto-LC effect" were observed in the solid phases and the hexagonal columnar (Colh ) liquid crystalline (LC) phase, respectively, of novel achiral non-π-delocalized nitroxide diradical compounds (R,S)-1, which showed polymorphism in the solid phases (solids I and II). The SQUID magnetization measurement revealed that (1) (R,S)-1 containing a small amount of racemic diastereomers (R*,R*)-1 possessed an unusual and large temperature-independent magnetic susceptibility (χTIM >0) component in the original nanocrystalline solid I that was responsible for the observed superparamagnetic-like behavior under low magnetic fields and did not arise from the contamination by extrinsic magnetic metal or metal ion impurities, besides ordinary temperature-dependent paramagnetic susceptibility (χpara >0) and temperature-independent diamagnetic susceptibility (χdia <0) components, (2) a large increase in molar magnetic susceptibility (χM ) (positive magneto-LC effect) that occurred at the solid I-to-liquid crystal transition upon heating was preserved as an additional χTIM increase in the resulting polymorphic nanocrystalline solid II by cooling, and (3) such unique magnetic phenomena were induced by thermal processing for (R,S)-1 or by adding a small amount of (R*,R*)-1 to (R,S)-1 as the impurity.

Magnetically Manipulable Ionic Liquid Crystals Incorporating Neutral Radicals.

Invited for this month's cover are the collaborating groups of Dr. Yoshiaki Uchida from Osaka University, Japan, Prof. Rui Tamura and Prof. Masahito Sugiyama from Kyoto University, Japan and Dr. Dmitrii G. Mazhukin from Novosibirsk State University, Russia. The cover picture depicts a contrast between localized spins and conductive ions in the newly-synthesized ionic liquid crystalline (ILC) nitroxide radicals. The ILC droplet of the new compounds is magnetically manipulable. More information can be found in the Full Paper by Yoshiaki Uchida, Rui Tamura, and co-workers.

Magnetically Manipulable Ionic Liquid Crystals Incorporating Neutral Radical Moiety.

With a view to fabricating a new remote input-output system by applying functional ionic liquid crystalline (ILC) materials, we have developed novel ILC compounds containing a nitroxide radical unit in the organic cations, which show an enantiotropic smectic A (SmA) phase. We have implemented the magnetic manipulation of a droplet of one of the ILC compounds on the basis of the intermolecular magnetic interactions between radical moieties. This ILC monoradical compound shows a 55 % larger increase in paramagnetic susceptibility at the solid-to-LC melting point in the first heating process than the non-ionic LC monoradical compounds. It is most likely owing to the nanosegregation of strongly bonded ionic and non-ionic moieties. The increased molar magnetic susceptibility is preserved not only in the SmA phase but also in the isotropic liquid and solid phases during the first cooling process.

Circle of life: the common hamster (Cricetus cricetus) adaptations to the urban environment.

Traditionally, urbanization has been seen as a negative phenomenon for biota. However, changes in the environmental parameters induced by urbanization might be favorable for some species. Over the past half-century, the common hamster has actively populated cities, establishing populations in some European, Russian and Kazakhstan cities. Based on integrative methods, we investigated free-range common hamsters inhabiting Simferopol from 2015 to 2018 to reveal possible adaptations to the urbanized environment across several parameters, including lifespan, hibernation period, reproductive activity and body mass. Results show that in urban areas, the common hamster demonstrates an extremely short hibernation period compared to other localities, possibly due to enhanced food resources from urban forestry (walnuts, locus and hazelnut), allowing the species to start breeding very early (February) and finish as late as October. We present the first evidence of polyandry for this species: mating of receptive females with several males and subsequent confirmation of multiple paternity. Despite high reproductive potential, the lifespan of the common hamster in urban conditions is generally very short (less than 1 year). We speculate that in the process of synurbization, the common hamster's innate plasticity across many life history traits permits it to successfully colonize throughout a wide range of habitats, with the ability to form novel adaptations to urban environments.

Low genetic diversity and epidemiological significance of Listeria monocytogenes isolated from wild animals in the far east of Russia.

The causative agent of listeriosis, a serious disease of humans and animals, Listeria monocytogenes is a ubiquitous bacterium that inhabits both anthropogenic and pristine environments. We report L. monocytogenes isolation from wild animals, humans, food and the environment of a far eastern region of Russia. In total, 654 samples of internal organs of small rodents belonging to the Muridae and Cricetidae families, and 986 samples of the liver and muscles of mollusks and fish were examined to obtain 7 and 14 independent L. monocytogenes isolates, respectively. The wild animal isolates were compared with human (n=9), food (n=8) and environmental (n=3) isolates obtained in the same region. Twenty of the 21 wild animal isolates belonged to the serovar 4b. The serovars 4b, 1/2a, 1/2b, and 4b, 1/2a, 1/2b, 1/2c were found between human and food isolates, respectively. All isolates were characterized into molecular subtypes by DNA sequencing of the 618 bp internal fragment of the house keeping gene prs and 621 bp internal fragment of the virulence gene inlB. Sequence analysis revealed 4 and 13 alleles for prs and inlB fragments, respectively. Distinct prs and inlB alleles clustered into two groups consistently with established phylogenetic lineages. Among isolates of every lineage, the nucleotide diversity of the prs fragment was low; the nucleotide diversity of the inlB fragment was low among wild animal isolates and higher among human isolates. All rodent isolates and 10 of 14 marine organism isolates carried the same allele of the inlB fragment, which was also found among environmental (two of three), food (two of eight) and human (two of nine) isolates.