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Background and objectivePsoriasis is a systemic inflammatory condition with poor cholesterol transport measured by cholesterol efflux capacity (CEC) that is associated with a heightened risk of cardiovascular disease (CVD). In psoriasis patients, we sought to characterize the lipoprotein profile by size using a novel nuclear magnetic resonance algorithm in patients with low CEC compared to normal CEC.MethodsLipoprotein profile was assessed using the novel nuclear magnetic resonance LipoProfile-4 deconvolution algorithm. Aortic vascular inflammation (VI) and non-calcified burden (NCB) were characterized via positron emission tomography-computed tomography and coronary computed tomography angiography. To understand the relationship between lipoprotein size and markers of subclinical atherosclerosis, linear regression models controlling for confounders were constructed.ResultsPsoriasis patients with low CEC had higher more severe psoriasis (p = 0.04), VI (p = 0.04) and NCB (p = 0.001), concomitant with smaller high-density lipoprotein (HDL) (p < 0.001) and low-density lipoprotein (LDL) particles (p < 0.001). In adjusted models HDL size (β = −0.19; p = 0.02) and LDL size (β = −0.31; p < 0.001) associated with VI and NCB. Lastly, HDL size strongly associated with LDL size in fully adjusted models (β = −0.27; p < 0.001).ConclusionThese findings demonstrate that in psoriasis, low CEC associates with a lipoprotein profile comprised of smaller HDL and LDL particles which correlates with vascular health and may be driving early onset atherogenesis. Further, these results demonstrate a relationship between HDL and LDL size and provide novel insights into the complexities of HDL and LDL as biomarkers of vascular health.

Supplemental material, sj-pdf-1-vmj-10.1177_1358863X231171948 for Machine learning demonstrates top predictors of lipid-rich necrotic core modulation over 1 year in psoriasis by Christin G Hong, Haiou Li, Philip M Parel, Alexander R Berg, Nidhi Patel, Harry Choi, Heather L Teague, Eric Munger, Andrew J Buckler, Alexander V Sorokin and Nehal N Mehta in Vascular Medicine

Supplemental material, sj-pdf-2-vmj-10.1177_1358863X231171948 for Machine learning demonstrates top predictors of lipid-rich necrotic core modulation over 1 year in psoriasis by Christin G Hong, Haiou Li, Philip M Parel, Alexander R Berg, Nidhi Patel, Harry Choi, Heather L Teague, Eric Munger, Andrew J Buckler, Alexander V Sorokin and Nehal N Mehta in Vascular Medicine

Supplemental material, sj-pdf-1-vmj-10.1177_1358863X231171948 for Machine learning demonstrates top predictors of lipid-rich necrotic core modulation over 1 year in psoriasis by Christin G Hong, Haiou Li, Philip M Parel, Alexander R Berg, Nidhi Patel, Harry Choi, Heather L Teague, Eric Munger, Andrew J Buckler, Alexander V Sorokin and Nehal N Mehta in Vascular Medicine

Supplementary Material 1

Supplemental material, sj-pdf-2-vmj-10.1177_1358863X231171948 for Machine learning demonstrates top predictors of lipid-rich necrotic core modulation over 1 year in psoriasis by Christin G Hong, Haiou Li, Philip M Parel, Alexander R Berg, Nidhi Patel, Harry Choi, Heather L Teague, Eric Munger, Andrew J Buckler, Alexander V Sorokin and Nehal N Mehta in Vascular Medicine

The paper discusses the issues of ventilating in deep quarries caused by the intensification of blasting operations at great depths, the increased distance of ore truck transportation to the daylight area, constant change in the geometrical parameters of the quarry, its microrelief and direction of mining, and increased isolation of the mined space from the environment. We provide a brief analysis of the current tools for forced airflow in deep quarries, which showed that the use of forced ventilation is often challenging since it leads to high energy consumption, high level of noise exceeding the permissible parameters, and high speeds of forced air flows may blow the dust off the quarry surfaces. The article presents methods and tools developed at the Siberian Federal University for intensifying the natural airflow in deep quarries by changing the air density at the entrance and exit points of the pit, as well as heating the shady areas using mirrors and solar energy, which do not interfere with mining and blasting operations.

Supplemental Material, sj-docx-1-jps-10.1177_24755303211000757 for Identifying Top Predictors of Change in Noncalcified Coronary Burden in Psoriasis by Machine Learning Over 1-Year by Eric Munger, Amit K. Dey, Justin Rodante, Martin P. Playford, Alexander V. Sorokin, Xin Tian, Colin O. Wu, Ahmed Hasan, Marcus Y. Chen, Joel M. Gelfand, Mohsin Saleet Jafri and Nehal N. Mehta in Journal of Psoriasis and Psoriatic Arthritis

This study hypothesized that there is an association between chronic stress (as indexed by resting amygdalar activity [AmygA]), hematopoietic system activity (HMPA), and subclinical cardiovascular indexes (aortic vascular inflammation [VI] and noncalcified coronary plaque burden [NCB]) in psoriasis (PSO). The study also hypothesized that treatment of PSO would improve these parameters.PSO is a stress-related chronic inflammatory condition that is associated with increased prevalence of subclinical cardiovascular disease (CVD). In individuals without PSO, stress has been linked to CVD through a serial biological pathway that involves the amygdala, hematopoietic tissues, and atherosclerotic plaques.A total of 164 consecutive patients with PSO and 47 healthy volunteers underwent 18-fluorodeoxyglucose positron emission tomography/computed tomography scans for assessment of AmygA, HMPA, and VI, as well as coronary computed tomography angiography scans for quantifying NCB. Furthermore, a consecutive subset of 30 patients with severe PSO (Psoriasis Area Severity Index Score10) were followed at 1 year to assess the relationship between skin disease improvement and AmygA, HMPA, VI, and NCB.The PSO cohort was middle-aged (mean age: 50 years), had low cardiovascular risk (Framingham risk score: median: 3) and had mild to moderate PSO activity (median Psoriasis Area Severity Index Score: 5.6). AmygA was higher in patients with PSO compared to volunteer participants. AmygA was associated with HMPA (bone marrow activity: β = 0.20, p = 0.01) and subclinical CVD (VI: β = 0.31, p 0.001; NCB: β = 0.27, p 0.001) The AmygA-CVD association was in part mediated by HMPA (VI: 20.9%, NCB: 36.7%). Following 1 year of PSO treatment in those with severe disease, improvement in skin disease was accompanied by a reduction in AmygA, bone marrow activity, and VI, with no progression of NCB.In PSO, a chronic inflammatory disease state, AmygA, which is a manifestation of chronic stress, substantially contributes to the risk of subclinical CVD. Additional studies that use psychometric measures of stress are required to explore therapeutic impact.

A combination of MS and computation on μ-nitrido bridged diiron complexes reveals H2O2 binding to the complex and generates an oxidant capable of oxidizing methane., Iron(iv)–oxo species have been identified as the active intermediates in key enzymatic processes, and their catalytic properties are strongly affected by the equatorial and axial ligands bound to the metal, but details of these effects are still unresolved. In our aim to create better and more efficient oxidants of H-atom abstraction reactions, we have investigated a unique heteroleptic diiron phthalocyanine complex. We propose a novel intramolecular approach to determine the structural features that govern the catalytic activity of iron(iv)–oxo sites. Heteroleptic μ-nitrido diiron phthalocyanine complexes having an unsubstituted phthalocyanine (Pc1) and a phthalocyanine ligand substituted with electron-withdrawing alkylsulfonyl groups (PcSO2R) were prepared and characterized. A reaction with terminal oxidants gives two isomeric iron(iv)–oxo and iron(iii)–hydroperoxo species with abundances dependent on the equatorial ligand. Cryospray ionization mass spectrometry (CSI-MS) characterized both hydroperoxo and diiron oxo species in the presence of H2O2. When m-CPBA was used as the oxidant, the formation of diiron oxo species (PcSO2R)FeNFe(Pc1) 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O was also evidenced. Sufficient amounts of these transient species were trapped in the quadrupole region of the mass-spectrometer and underwent a CID-MS/MS fragmentation. Analyses of fragmentation patterns indicated a preferential formation of hydroperoxo and oxo moieties at more electron-rich iron sites of both heteroleptic μ-nitrido complexes. DFT calculations show that both isomers are close in energy. However, the analysis of the iron(iii)–hydroperoxo bond strength reveals major differences for the (Pc1)FeN(PcSO2R)FeIIIOOH system as compared to (PcSO2R)FeN(Pc1)FeIIIOOH system, and, hence binding of a terminal oxidant will be preferentially on more electron-rich sides. Subsequent kinetics studies showed that these oxidants are able to even oxidize methane to formic acid efficiently.

Oxidized starch is important for paper coating because of its good mechanical and sizing properties. Traditionally, starch oxidation is performed by different heavy metals as catalysts and chlorites or chlorines as oxidizing agents. In this study, an environmentally friendly method was developed, utilizing iron tetrasulfophthalocyanine as a catalyst only in small amounts and hydrogen peroxide as a clean oxidant. It has been previously shown that the method works well, but analysis of the kinetic data as well as catalyst deactivation was difficult because of the semibatch operation mode. In this study, hydrogen peroxide was employed in a batch mode, allowing more simple analysis methods for determining the degree of substitution, starch degradation, and hydrogen peroxide decomposition kinetics. Additionally, the effect of adding the catalyst continuously into the solution, as well as the influence of ultrasound treatment on starch prior to oxidation, was studied. The batch-mode results showed DSCOOH = 0.73...

The article is dedicated to the heir to the throne Nicholas Alexandrovich (the future Tsar Nicholas II) visiting Tomsk and the Imperial Tomsk University on July 5 and 6, 1891, while he was returning from his trip to the east. On the basis of the available scientific literature, documents, including those being introduced into scientific circulation for the first time, and the periodical press, the article reconstructs the history of the Tsar’s visit to Russia’s first higher education institution in Asia. The article is meant for those interested in the history of the Romanov kin as well as the history of higher learning and science in Russia.

The synthesis of the iron phthalocyanine bearing four fused tetraaza macrocycles starting from N,N',N '',N'''-tetrakis(p-tolylsulfonyl)triethylenetetraamine and 1,2-dibromo-4,5-bis-(bromomethyl) benzene is reported. The exchange of protecting tosyl groups by acetyl groups was necessary to obtain iron phthalocyanine. The efficiency of iron phthalocyanine as oxidation catalyst was tested for the practically important oxidation of 2,3,6-trimethylphenol (TMP) at different reaction conditions.

mu-Nitrido-bis [tetra-(hexyl-sulfonyl)phthalocyaninatoiron] (3a) and mu-nitrido-bis [tetra-(tert-butylsulfonyl)phthalocyaninatoiron] (3b) complexes have been prepared and fully characterized by electrospray ionization mass spectrometry, UV-Vis, FTIR, EPR, Mossbauer techniques as well as by X-ray photoelectron and Fe K-edge X-ray absorption spectroscopies. Small changes at the periphery of the phthalocyanine ligand introduce a difference in the iron oxidation state. While 3b with tert-butyl substituents is a neutral complex with a mixed-valence Fe-3.5-N-Fe-3.5 structural unit, 3a having n-hexyl substituents is an oxidized cationic Fe-IV-N-Fe-IV complex. The structural parameters of N-bridged diiron phthalocyanine with a Fe-3.5-N-Fe-3.5 unit were determined for the first time. Iron atoms in 3b are displaced out of plane by 0.24 angstrom and the Fe-N bond distance of the linear Fe-N-Fe fragment is equal to 1.67 angstrom. Both complexes selectively catalyze benzylic oxidation of alkyl aromatic compounds by (BuOOH)-Bu-t. Toluene was oxidized to benzoic acid with 80% selectivity, and the total turnover number was as high as 197. p-Toluic acid was the principal product of p-xylene oxidation. In this case the turnover number achieved 587 substrate molecules per molecule of catalyst. The described catalytic system is complementary to the recently reported system based on mu-nitrido diiron tetrabutylphthalocyanine-H2O2 which effectively oxidizes the benzene ring.

RESUMEN: Se presentan los resultados de la oxidación alílica de los monoterpenos limoneno y a-pineno usando metaloftalocianinas inmovilizadas en sílica como catalizadores biomiméticos. Se evaluó el efecto del metal en la producción de carvona y verbenona, observándose el siguiente orden de reactividad: Fe > Co> Cr > Mn > Cu. Los mayores rendimientos hacia verbenona, 15%, se obtuvieron con los catalizadores FePcS-S y CoPcS-S ABSTRACT: Results of allylic oxidation of limonene and a-pinene monoterpenes using silica inmovilized metallophthalocyanines as biomimetic catalyts are presented. The effect of the metal was evaluated on the production of verbenone and carvone. The following order of reactivity was observed: Fe > Co> Cr > Mn > Cu. Higher yields to verbenone, 15%, were obtained over FePcS-S and CoPcS-S. COL0001941

The oxidation of 2,4,6-trichlorophenol (TCP) with H2O2 or KHSO 5 catalyzed by iron(III) tetrasulfophthalocyanine (FePcS) supported on a cationic ion-exchange resin (Amberlite IRA 900) is reported. In order to obtain the catalytic oxidative degradation of the aromatic ring of TCP, the supported catalyst FePcS-Amberlite should be pre-saturated with the substrate since the phenolate form of TCP is strongly adsorbed by the cationic resin. In these conditions, the oxidation of TCP is observed even when the aqueous phase is deprived of acetonitrile, an organic solvent able to enhance the activity with the soluble catalyst by displacement of the dimer-monomer equilibrium towards momeric active species. The dispersion of FePcS monomers onto the support is a way to avoid the formation of inactive dimers., L'oxydation du 2,4,6-trichlorophenol (TCP) avec H2O2 ou KHSO5 catalysee par le complexe du fer(III) de la tetrasulfophtalocyanine (FePcS) supporte sur une resine cationique echangeuse d'ions est decrite. Afin d'obtenir la degradation catalytique du cycle aromatique du TCP, le catalyseur supporte FePcS-Amberlite doit etre pre-sature avec le substrat etant donne que la forme phenolate du TCP est fortement adsorbee par la resine cationique. Dans ces conditions, l'oxydation du TCP est observee meme lorsque le milieu reactionnel est prive d'acetonitrile, un solvant organique permettant d'ameliorer l'activite du catalyseur en solution par deplacement de l'equilibre dimere-monomere en faveur d'especes monomeres actives. La dispersion des monomeres FePcS sur le support est un moyen d'eviter la formation des dimeres inactifs en catalyse.

We examined functional and evolutionary patterns in the recently constructed set of 5,873 clusters of predicted orthologs from seven eukaryotic genomes. The analysis reveals a conserved core of largely essential eukaryotic genes as well as major diversification and innovation associated with evolution of eukaryotic genomes., Background Sequencing the genomes of multiple, taxonomically diverse eukaryotes enables in-depth comparative-genomic analysis which is expected to help in reconstructing ancestral eukaryotic genomes and major events in eukaryotic evolution and in making functional predictions for currently uncharacterized conserved genes. Results We examined functional and evolutionary patterns in the recently constructed set of 5,873 clusters of predicted orthologs (eukaryotic orthologous groups or KOGs) from seven eukaryotic genomes: Caenorhabditis elegans, Drosophila melanogaster, Homo sapiens, Arabidopsis thaliana, Saccharomyces cerevisiae, Schizosaccharomyces pombe and Encephalitozoon cuniculi. Conservation of KOGs through the phyletic range of eukaryotes strongly correlates with their functions and with the effect of gene knockout on the organism's viability. The approximately 40% of KOGs that are represented in six or seven species are enriched in proteins responsible for housekeeping functions, particularly translation and RNA processing. These conserved KOGs are often essential for survival and might approximate the minimal set of essential eukaryotic genes. The 131 single-member, pan-eukaryotic KOGs we identified were examined in detail. For around 20 that remained uncharacterized, functions were predicted by in-depth sequence analysis and examination of genomic context. Nearly all these proteins are subunits of known or predicted multiprotein complexes, in agreement with the balance hypothesis of evolution of gene copy number. Other KOGs show a variety of phyletic patterns, which points to major contributions of lineage-specific gene loss and the 'invention' of genes new to eukaryotic evolution. Examination of the sets of KOGs lost in individual lineages reveals co-elimination of functionally connected genes. Parsimonious scenarios of eukaryotic genome evolution and gene sets for ancestral eukaryotic forms were reconstructed. The gene set of the last common ancestor of the crown group consists of 3,413 KOGs and largely includes proteins involved in genome replication and expression, and central metabolism. Only 44% of the KOGs, mostly from the reconstructed gene set of the last common ancestor of the crown group, have detectable homologs in prokaryotes; the remainder apparently evolved via duplication with divergence and invention of new genes. Conclusions The KOG analysis reveals a conserved core of largely essential eukaryotic genes as well as major diversification and innovation associated with evolution of eukaryotic genomes. The results provide quantitative support for major trends of eukaryotic evolution noticed previously at the qualitative level and a basis for detailed reconstruction of evolution of eukaryotic genomes and biology of ancestral forms.

İlk ?? -nitrido demir ftalosiyanin nonsübstitue ftalosiyanindi ve organik çözücülerde çözünmemesi saflaştırma işlemini zorlaştırıyordu. İlk defa ?? -nitrido ftalosiyaninler oksidasyon katalizörü olarak grubumuz tarafından kullanıldı. Elektron verici (tert-butyl) sübstitüe ? -nitrido ftalosiyanin grubumuzda sentezlendi ve metan ve benzenenin etkili bir oksidasyonunu gösterdi. Daha sonra elektron çekici gruplar bağlı ?? -nitrido ftalosiyaninler hazırlamaya karar verdik ve katalitik özelliklerinin bu gruplar ile nasıl değiştiğini kontrol ettik. Elektron çekici gruplar olarak alkilsülfonilleri seçtik. Yeni 6 tane alkilsülfonil sübstitüe ?? -nitrido ftalosiyaninler hazırladık ve (ESI-MS), UV-Vis, FTIR, EPR ile karakterize ettik. Hekzil ve t-bütilsülfonil ?? -nitrido ftalosiyaninlerin karakterizasyonu için ayrıca Mössbauer, XPS ve Fe K-edge X-ray spektroskopisi (XANES, EXAFS) kullanıldı. Metil, etil ve hekzil ?? -nitrido ftalosiyaninler katyonik (PcFeIVNFeIVPc)+N3- iken t-bütil, adamantil ve siklohekzil ?? -nitrido ftalosiyaninler nötraldir PcFeIIINFeIVPc.Bu altı ?? -nitrido ftalosiyaninlerin katalitik aktiviteleri TBHP ile toluene, p-ksilen ve alkollerin oksidasyonunda çalışıldı. Oksidasyon reaksiyonunda solvent kullanılmadı, bu çevre ve endüstri bakımından çok önemli bir avantajdır. Reaksiyon şartları alifatik C-H oksidasyonu için duyarlıdır. Reaksiyon ortamında çok çok az miktarda aromatik oksidasyon ürünleri elde edildi.Ayrıca sıcaklık ve oksidant miktarının artırılmasının oksidasyona etkisi de incelendi.Hekzil ve t-bütil ?? -nitrido ftalosiyaninler solventsiz ortamda alkollerin aldehit veya ketonlara oksidasyonunda katalizör olarak kullanıldı. Benzil alkolün oksidasyonu standart reaksiyon olarak ele alındı. Farklı alkollerin oksidasyonu hekzil ve t-bütil ?? -nitrido ftalosiyanin katalizörler ile yapıldı. Ana ürün aldehitti. Elektron çekici ?? -nitrido ftalosiyanin aromatik ve alifatik alkollerin oksidasyonunda alışılmışın dışında selektivite gösterdi. The first ?? -nitrido diiron phthalocyanine was unsubstituted complex and it was insoluble in organic solvents which makes difficult its purification. Firstly, µ-nitrido bridged binuclear complexe was used as oxidation catalysts in our group. Electron donating substituted (tert-butyl) ? -nitrido diiron phthalocyanine was sythesized in our group and this complex was showed efficient oxidation of methane and benzene. After using electron donating substituted ? -nitrido diiron phthalocyanine as oxidation xatalyst, we decided to prepare µ-nitrido diiron phthalocyanine with electron-withdrawing substituents and to check how the change of the structure of this complex influences on its catalytic properties. We choise alkylsulfonyl as electron-withdrawing substituents. Six novel N-bridged diiron complexes bearing small (methyl, ethyl and hexylsulfonyl) and bulky (tert butyl, adamantyl and cyclohexyl) electron-withdrawing substituents have been prepared and characterized by electrospray ionization mass spectrometry (ESI-MS), UV-Vis, FTIR, EPR and for two complexes which were hexylsulfonyl and tert-butylsulfonyl, Mössbauer techniques, X-ray photoelectron spectroscopy (XPS) and Fe K-edge X-ray absorption spectroscopy (XANES, EXAFS, high resolution K ? emission spectroscopy) in this thesis. The state of these complexes depends on the size of the substituents. While methylsulfonyl, ethylsulfonyl and hexylsulfonyl substituents are cationic (PcFeIVNFeIVPc)+N3- complexes, bulkier tert-butylsulfonyl, adamantylsulfonyl and cyclohexylsulfonyl substituents are formally neutral PcFeIIINFeIVPc complexes.These six ? -nitrido diiron phthalocyanines? catalytic activity with tBuOOH has been studied in the aromatic oxidation of toluene, p-xylene and alcohols. In the oxidation reaction, solvents didn?t used because it is important advantage from environmental and industrial points of view. There were three main oxidation products which were benzyl alcohol, benzaldehyde and benzoic acid in oxidation of toluene. The reaction condition were selective to oxidation of aliphatic C-H bond. Only traces of products of aromatic oxidation, p-cresol and 2-methyl-1,4-benzoquinone, were detected by GC-MS. We had similar result for oxidation of p-xylene. The oxidation products were benzylic oxidation products which were 4-methylbenzyl alcohol , p-tolualdehyde and p-toluic acid.We also investigated the effect of temperature, catalyst concentration and amount of oxidant. Indeed, oxidation of toluene and p-xylene were tested by supported ? -nitrido diiron phthalocyanines.The solvent-free selective oxidation of alcohols to aldehydes and ketones by tBuOOH (TBHP) with hexyl sulfonyl and tert-butylsulfonyl substituted µ-nitrido bridged diiron phthalocyanine as catalysts. Benzyl alcohol was first examined as a standart substrate with TBHP as oxidant. Considering the solubility of the catalysts in alcohols, the oxidation reaction was carried out without additional solvent in the presence of a catalytic amount of hexyl sulfonyl and tert-butylsulfonyl substituted µ-nitrido bridged diiron phthalocyanine. Different alcohols oxidized by µ-nitrido diiron phthalocyanines. The main product was aldehyde for oxidation of alcohols. Temperature effect and oxidant amount on benzyl alcohol oxidation were investigated. Electron-withdrawing substituted µ-nitrido bridged diiron phthalocyanine catalysts exhibited an unusual selectivity in the oxidation of aromatic and aliphatic alcohols. 197