Electronic Structure and d-d Spectrum of Metal-Organic Frameworks with Transition-Metal Ions.

The electronic structure of metal-organic frameworks (MOFs) containing transition metal (TM) ions represents a significant and largely unresolved computational challenge due to limited solutions to the quantitative description of low-energy excitations in open d-shells. These excitations underpin the magnetic and sensing properties of TM MOFs, including the observed remarkable spin-crossover phenomenon. We introduce the effective Hamiltonian of crystal field approach to study the d-d spectrum of MOFs containing TM ions; this is a hybrid QM/QM method based on the separation of crystal structure into d- and s,p-subsystems treated at different levels of theory. We test the method on model frameworks, carbodiimides, and hydrocyanamides and a series of M-MOF-74 (M = Fe, Co, Ni) and compare the computational predictions to experimental data on magnetic properties and Mössbauer spectra.

Chemical Kinetics of Metal Single Atom and Nanocluster Formation on Surfaces: An Example of Pt on Hexagonal Boron Nitride.

The production of atomically dispersed metal catalysts remains a significant challenge in the field of heterogeneous catalysis due to coexistence with continuously packed sites such as nanoclusters and nanoparticles. This work presents a comprehensive guidance on how to increase the degree of atomization through a selection of appropriate experimental conditions and supports. It is based on a rigorous macro-kinetic theory that captures relevant competing processes of nucleation and formation of single atoms stabilized by point defects. The effects of metal-support interactions and deposition parameters on the resulting single atom to nanocluster ratio as well as the role of metal centers formed on point defects in the kinetics of nucleation have been established, thus paving the way to guided synthesis of single atom catalysts. The predictions are supported by experimental results on sputter deposition of Pt on exfoliated hexagonal boron nitride, as imaged by aberration-corrected scanning transmission electron microscopy.

Detection of coronaviruses in insectivorous bats of Fore-Caucasus, 2021.

Coronaviruses (CoVs) pose a huge threat to public health as emerging viruses. Bat-borne CoVs are especially unpredictable in their evolution due to some unique features of bat physiology boosting the rate of mutations in CoVs, which is already high by itself compared to other viruses. Among bats, a meta-analysis of overall CoVs epizootiology identified a nucleic acid observed prevalence of 9.8% (95% CI 8.7-10.9%). The main objectives of our study were to conduct a qPCR screening of CoVs' prevalence in the insectivorous bat population of Fore-Caucasus and perform their characterization based on the metagenomic NGS of samples with detected CoV RNA. According to the qPCR screening, CoV RNA was detected in 5 samples, resulting in a 3.33% (95% CI 1.1-7.6%) prevalence of CoVs in bats from these studied locations. BetaCoVs reads were identified in raw metagenomic NGS data, however, detailed characterization was not possible due to relatively low RNA concentration in samples. Our results correspond to other studies, although a lower prevalence in qPCR studies was observed compared to other regions and countries. Further studies should require deeper metagenomic NGS investigation, as a supplementary method, which will allow detailed CoV characterization.

Clinical cases of infectious endocarditis in cats.

Infectious endocarditis (IE) is a contagious polyposis ulcerative inflammation of the endocardium, accompanied by lesions of the heart valve apparatus and endothelium by various pathogenic and opportunistic pathogens. Mainly mitral and aortic valves are affected, less often - tricuspid valve. The purpose of this study was to report two cases of IE in cats. Due to the low prevalence of the disease in cats, there is no clear diagnostic algorithm, so the diagnostic search is complicated. In both cases, autonomic lesions of the heart valve apparatus were observed. In the first clinical case, we could hardly diagnose the disease because of its rapid progression: initial echocardiogram result was normal, but after 48 hours, the cat's condition became much worse, and 18 hours later, it died. In the second case, histopathological examination confirmed an infectious inflammatory process of the endocardium and myocardium of unclear genesis. However, the presence of lower respiratory tract infection and the absence of additional laboratory tests, such as bacterial blood culture and PCR diagnosis, limited us in proposing a hypothesis about the origin and etiology of IE.

A endocardite infecciosa (EI) é uma polipose contagiosa inflamação ulcerativa do endocárdio, acompanhada de lesões do aparelho valvar cardíaco e do endotélio por diversos agentes patogênicos e oportunistas. Principalmente as válvulas mitral e aórtica são afetadas, com menos frequência a válvula tricúspide. O objetivo deste estudo foi relatar dois casos de EI em gatos. Devido à baixa prevalência da doença em gatos, não existe um algoritmo diagnóstico claro, por isso a busca diagnóstica é complicada. Em ambos os casos foram observadas lesões autonômicas do aparelho valvar cardíaco. No primeiro caso clínico, dificilmente conseguimos diagnosticar a doença devido à sua rápida progressão: o resultado inicial do ecocardiograma foi normal, mas após 48 horas o estado do gato piorou muito e, 18 horas depois, veio a óbito. No segundo caso, o exame histopatológico confirmou processo inflamatório infeccioso do endocárdio e miocárdio de gênese incerta. No entanto, a presença de infecção do trato respiratório inferior e a ausência de exames complementares de laboratório, como hemocultura bacteriana e diagnóstico por PCR, nos limitaram a propor uma hipótese sobre a origem e etiologia da EI.

Analytical Model of CVD Growth of Graphene on Cu(111) Surface.

Although the CVD synthesis of graphene on Cu(111) is an industrial process of outstanding importance, its theoretical description and modeling are hampered by its multiscale nature and the large number of elementary reactions involved. In this work, we propose an analytical model of graphene nucleation and growth on Cu(111) surfaces based on the combination of kinetic nucleation theory and the DFT simulations of elementary steps. In the framework of the proposed model, the mechanism of graphene nucleation is analyzed with particular emphasis on the roles played by the two main feeding species, C and C2. Our analysis reveals unexpected patterns of graphene growth, not typical for classical nucleation theories. In addition, we show that the proposed theory allows for the reproduction of the experimentally observed characteristics of polycrystalline graphene samples in the most computationally efficient way.

Local perturbations of periodic systems. Chemisorption and point defects by GoGreenGo.

We present a software package GoGreenGo-an overlay aimed to model local perturbations of periodic systems due to either chemisorption or point defects. The electronic structure of an ideal crystal is obtained by worldwide-distributed standard quantum physics/chemistry codes, and then processed by various tools performing projection to atomic orbital basis sets. Starting from this, the perturbation is addressed by GoGreenGo with use of the Green's functions formalism, which allows evaluating its effect on the electronic structure, density matrix, and energy of the system. In the present contribution, the main accent is made on processes of chemical nature, such as chemisorption or doping. We address a general theory and its computational implementation supported by a series of test calculations of the electronic structure perturbations for benchmark model solids: simple, face-centered, and body-centered cubium systems. In addition, more realistic problems of local perturbations in graphene lattice, such as lattice substitution, vacancy, and "on-top" chemisorption, are considered.

X-ray micro-computed tomography in the assessment of penile cavernous fibrosis in a rabbit castration model.

BACKGROUND: Current assessment methods of penile cavernous fibrosis in animal models have limitations due to the inability to provide complex and volume analysis of fibrotic alterations. OBJECTIVE: The aim was to evaluate micro-computed tomography for assessment of cavernous fibrosis and compare it with histological, histochemical, immunohistochemical, and RT-PCR analysis. MATERIALS AND METHODS: A controlled trial was performed involving 25 New Zealand male rabbits with induced testosterone deficiency by orchidectomy. Penile samples were obtained before and after 7, 14, 21, and 84 days from orchidectomy. We consistently performed (a) gray value analysis of corpora cavernosa 3D models reconstructed after micro-computed tomography, (b) morphometry of smooth muscles/connective tissue ratio, collagen type I/III ratio, and area of TGF-beta-1 expression in corpora cavernosa, and (c) RT-PCR of TGF-beta-1 expression. RESULTS: Micro-computed tomography allowed visualization of penile structures at a resolution comparable to light microscopy. Gray values of corpora cavernosa decreased from 1673 (1512-1773) on the initial day to 1184 (1089-1232) on the 21st day (p < 0.005). However, on the 84th day, it increased to 1610 (1551-1768). On 21st and 84th days, there was observed a significant decrease in smooth muscle/connective tissue ratio and a significant increase in collagen type I/III ratio (p < 0.05). TGF-beta1 expression increased on the 84th day according to immunohistochemistry (p < 0.005). RT-PCR was impossible to conduct due to the absence of RNA in obtained samples after micro-CT. DISCUSSION AND CONCLUSIONS: Micro-computed tomography provided 3D visualization of entire corpora cavernosa and assessment of radiodensity alterations by gray value analysis in fibrosis progression. We speculate that gray value changes at early and late fibrosis stages could be related to tissue reorganization. RT-PCR is impossible to conduct on tissue samples studied by micro-CT due to RNA destruction. We also suggest that micro-computed tomography could negatively affect the immunohistochemical outcome, as a significant increase of TGF-beta-1 expression occurs later than histological fibrotic signs.

Learning Curve and Early Results of Interlaminar and Transforaminal Full-Endoscopic Resection of Lumbar Disc Herniations.

Background Full-endoscopic spinal surgery is an evolving technique. A laborious learning phase is inevitable due to the complexity of the orientation and instrumentation. The goal of the present study is to evaluate a single surgeon's learning curve and early outcomes in full-endoscopic resection of lumbar disc herniations. Methods This was a prospective non-controlled single-surgeon cohort study. In 54 patients with 57 herniations, 41 interlaminar and 16 transforaminal resections were performed. Surgery time, severity of adhesive process in the spinal canal, complication rates and clinical outcomes (VAS, ODI, custom questionnaire, recurrence and re-operation rate) were assessed. Results In the interlaminar group, operative time has decreased from 60 ± 20 min in the first 20 operations to 45 ± 14 min in the following 17 (p=0.023). In the transforaminal group, operative time has decreased from 60 ± 16 min in the first 7 operations to 41 ± 12 min in following 9 (p=0.023). Severe adhesive process in spinal canal was associated with duration of symptoms greater than 2 years, longer surgery and higher risk of surgical complications. Four recurrent disc herniations were re-operated using full-endoscopic technique. VAS, ODI and pain medications significantly decreased in both groups and in re-operated patients. Conclusion The plateau of the learning curve and good short-term clinical results of full-endoscopic interlaminar and transforaminal surgery may be achieved after twenty operations, given extensive previous experience in microsurgery. Risk of complications at the learning phase may be decreased by excluding the patients with symptoms lasting over two years.

Deductive molecular mechanics of four-coordinated carbon allotropes.

Deductive molecular mechanics is applied to study the relative stability and mechanical properties of carbon allotropes containing isolated σ-bonds. Our approach demonstrates numerical accuracy comparable to that of density-functional theory, but achieved with dramatically lower computational costs. We also show how the relative stability of carbon allotropes may be explained from a chemical perspective using the concept of strain of bonds (or rings) in close analogy to theoretical organic chemistry. Besides that, the role of nonbonding electrostatic interactions as the key factor causing the differences in mechanical properties (in particular, hardness) of the allotropes is emphasized and discussed. The ADAMAS program developed on the basis of this study fairly reproduces spatial and electronic structure as well as mechanical properties of carbon allotropes.

Relative stability of diamond and graphite as seen through bonds and hybridizations.

The relative stability of the two most important forms of elemental carbon, diamond and graphite, is readdressed from a newly developed perspective as derived from historically well-known roots. Unlike other theoretical studies mostly relying on numerical methods, we consider an analytical model to gain fundamental insight into the reasons for the quasi-degeneracy of diamond and graphite despite their extremely different covalent bonding patterns. We derive the allotropes' relative energies and provide a qualitative picture predicting a quasi-degenerate electronic ground state for graphite (graphene) and diamond at zero temperature. Our approach also gives numerical estimates of the energy difference and interatomic separations in good agreement with experimental data and recent results of hybrid DFT modeling, although obtained with a much smaller numerical but highly transparent effort. An attempt to extend this treatment to the lowest energy allotropes of silicon proves to be successful as well.

Femtosecond Laser-Assisted Intraocular Lens Fragmentation: Low Energy Transection.

PURPOSE: To describe a case of femtosecond laser-assisted hydrophobic intraocular lens transection. METHODS: Case report. RESULTS: Femtosecond laser-assisted transection of a one-piece acrylic hydrophobic intraocular lens for explantation via a small surgical incision was successfully performed with low energy parameters. CONCLUSIONS: This case illustrates a novel and effective clinical application of the femtosecond laser. [J Refract Surg. 2017;33(9):646-648.].

A Zirconium Macrocyclic Metal-Organic Framework with Predesigned Shape-Persistent Apertures.

A microporous metal-organic framework (MOF) was synthesized from [Zr6 O4 (OH)4 (C6 H5 COO)12 ] clusters and a triacid ligand based on a shape-persistent arylene ethynylene macrocycle. This framework, dubbed Zr-MCMOF, is held together by metal-ligand coordination and multiple weak interactions: hydrogen bonding, [π⋅⋅⋅π] stacking, and [C-H⋅⋅⋅π] interactions. The rigid ligand has a 9 Å-wide central void, which serves as a predesigned aperture for the 1D channels; all of the porosity of Zr-MCMOF comes from the ligand. The resulting framework possesses high hydrolytic and thermal stability and a flexible structure unique among Zr-based MOFs.

Mesoporous Fluorinated Metal-Organic Frameworks with Exceptional Adsorption of Fluorocarbons and CFCs.

Two mesoporous fluorinated metal-organic frameworks (MOFs) were synthesized from extensively fluorinated tritopic carboxylate- and tetrazolate-based ligands. The tetrazolate-based framework MOFF-5 has an accessible surface area of 2445 m(2) g(-1), the highest among fluorinated MOFs. Crystals of MOFF-5 adsorb hydrocarbons, fluorocarbons, and chlorofluorocarbons (CFCs)-the latter two being ozone-depleting substances and potent greenhouse species-with weight capacities of up to 225%. The material exhibits an apparent preference for the adsorption of non-spherical molecules, binding unusually low amounts of both tetrafluoromethane and sulfur hexafluoride.

Expanded Porphyrin-Anion Supramolecular Assemblies: Environmentally Responsive Sensors for Organic Solvents and Anions.

Porphyrins have been used frequently to construct supramolecular assemblies. In contrast, noncovalent ensembles derived from expanded porphyrins, larger congeners of naturally occurring tetrapyrrole macrocycles, are all but unknown. Here we report a series of expanded porphyrin-anion supramolecular assemblies. These systems display unique environmentally responsive behavior. Addition of polar organic solvents or common anions to the ensembles leads to either a visible color change, a change in the fluorescence emission features, or differences in solubility. The actual response, which could be followed easily by the naked eye, was found to depend on the specifics of the assembly, as well as the choice of analyte. Using the ensembles of this study, it proved possible to differentiate between common solvents, such as diethyl ether, THF, ethyl acetate, acetone, alcohol, acetonitrile, DMF, and DMSO, identify complex solvent systems, as well as distinguish between the fluoride, chloride, bromide, nitrate, and sulfate anions.

A mesoporous metal-organic framework based on a shape-persistent macrocycle.

A mesoporous Zn-based metal-organic framework (MOF) was prepared from a shape-persistent phenylene ethynylene macrocycle functionalized with three -COOH groups. The rigid ligand has a ∼9 Å wide central cavity which serves as a predesigned pore. The macrocycles [π···π] stack into pairs, with their carboxylate groups connected via three Zn3O14C6H2 clusters. The resulting MOF has a void volume of 86%.

Absorbate-induced piezochromism in a porous molecular crystal.

Atmospherically stable porous frameworks and materials are interesting for heterogeneous solid-gas applications. One motivation is the direct and selective uptake of pollutant/hazardous gases, where the material produces a measurable response in the presence of the analyte. In this report, we present a combined experimental and theoretical rationalization for the piezochromic response of a robust and porous molecular crystal built from an extensively fluorinated trispyrazole. The electronic response of the material is directly determined by analyte uptake, which provokes a subtle lattice contraction and an observable bathochromic shift in the optical absorption onset. Selectivity for fluorinated absorbates is demonstrated, and toluene is also found to crystallize within the pore. Furthermore, we demonstrate the application of electronic structure calculations to predict a physicochemical response, providing the foundations for the design of electronically tunable porous solids with the chemical properties required for development of novel gas-uptake media.

macrocycle embrace: encapsulation of fluoroarenes by m-phenylene ethynylene host.

We report structural characterization of a new member of m-phenylene ethynylene ring family. This shape-persistent macrocycle also co-crystallizes with hexafluoro-, 1,2,4,5-tetrafluoro-, 1,3,5-trifluoro, and 1,4-difluorobenzene. The four complexes are almost isostructural, and all show the fluoroarene included into the central cavity of the macrocycle. Characterized by multiple short C - H⋅⋅⋅F - C contacts, these inclusion complexes further dimerize in the solid state into a 2+2 assembly, in which the two macrocycles embrace each other by their large hydrophobic groups that are rotated by 60° relative to one another.

Thermally robust and porous noncovalent organic framework with high affinity for fluorocarbons and CFCs.

Metal-organic and covalent organic frameworks are porous materials characterized by outstanding thermal stability, high porosities and modular synthesis. Their repeating structures offer a great degree of control over pore sizes, dimensions and surface properties. Similarly precise engineering at the nanoscale is difficult to achieve with discrete molecules, since they rarely crystallize as porous structures. Here we report a small organic molecule that organizes into a noncovalent organic framework with large empty pores. This structure is held together by a combination of [N-H···N] hydrogen bonds between the terminal pyrazole rings and [π···π] stacking between the electron-rich pyrazoles and electron-poor tetrafluorobenzenes. Such a synergistic arrangement makes this structure stable to at least 250 °C and porous, with an accessible surface area of 1,159 m(2) g(-1). Crystals of this framework adsorb hydrocarbons, CFCs and fluorocarbons-the latter two being ozone-depleting substances and potent greenhouse species-with weight capacities of up to 75%.

Superhydrophobic perfluorinated metal-organic frameworks.

Three perfluorinated Cu-based metal-organic frameworks (MOFs) were prepared starting from extensively fluorinated biphenyl-based ligands accessed via C-H functionalization. These new materials are highly hydrophobic: with water contact angles of up to 151 ± 1°, they are among the most water-repellent MOFs ever reported.

Copper-promoted sulfenylation of sp2 C-H bonds.

An auxiliary-assisted, copper catalyzed or promoted sulfenylation of benzoic acid derivative ß-C-H bonds and benzylamine derivative γ-C-H bonds has been developed. The method employs disulfide reagents, copper(II) acetate, and DMSO solvent at 90-130 °C. Application of this methodology to the direct trifluoromethylsulfenylation of C-H bonds was demonstrated.