Hydrodeoxygenation of anisole over SBA-15-supported Ni, Pd, and Pt mono- and bimetallic catalysts: effect of the metal's nature on catalytic activity and selectivity.

Monometallic Ni, Pd and Pt and bimetallic catalysts formed by combinations of the above metals supported on SBA-15 silica were synthesized, characterized and tested in the hydrodeoxygenation reaction of anisole. The objective of the work was to detect the effect of the nature of metals on the activity of the catalysts at different steps of anisole hydrodeoxygenation: hydrogenation of the aromatic ring of anisole and C-O bond cleavage in the intermediate cyclohexyl methyl ether. The support and the catalysts were characterized by N2 physisorption, X-ray diffraction, UV-vis diffuse reflectance spectroscopy, temperature-programmed reduction, scanning electron microscopy-energy dispersive X-ray spectroscopy, transmission electron microscopy and HAADF-STEM. The catalytic activity tests were carried out in a batch reactor at 280 °C and 7.3 MPa pressure. The activity results show that the NiPd/SBA-15 catalyst had the greatest ability for hydrogenation of the aromatic ring of anisole, while its NiPt/SBA-15 analog resulted in better activity for C-O bond hydrogenolysis. The bimetallic NiPt/SBA-15 catalyst showed the best catalytic performance in the HDO of anisole ascribed to the formation of a Ni-Pt alloy. On the other hand, the combination of Pd and Pt metals in the PdPt/SBA-15 catalyst resulted in the formation of bimetallic particles with Pd-rich and Pt-rich domains, showing high selectivity for the formation of the cyclohexyl methyl ether, which can be useful for the hydrogenation of aromatic rings in O-containing reactants with the formation of saturated O-containing products. According to the characterization results (HAADF-STEM), the different catalytic behavior of NiPd/SBA-15, NiPt/SBA-15, and PdPt/SBA-15 catalysts could be attributed to different characteristics of the bimetallic active phases in them.

Boosting the Hydrodeoxygenation Activity and Selectivity of Ni/(M)-SBA-15 Catalysts by Chemical Alteration of the Support.

The influence of the acid sites in the hydrodeoxygenation of anisole performed over Ni catalysts supported on SBA-15 modified with metal oxides (Ni/M-SBA-15, M = Ti, Zr, Al, or Nb) was demonstrated. Catalysts were characterized by SEM-EDX, nitrogen physisorption, XRD, UV-visible DRS, TPR, TPD of ammonia, IR-Py, O2 chemisorption, and high-resolution transmission electron microscopy. The mesoporous structure and the hexagonal arrangement of the supports were maintained in the catalysts. Ni catalysts supported on modified M-SBA-15 exhibited a higher metal-support interaction, an increase in the acidity and, as a consequence, improved selectivity to cyclohexane. The deoxygenation reaction rate constants increased as Ni/SBA-15 < Ni/Ti-SBA-15 < Ni/Nb-SBA-15 < Ni/Zr-SBA-15 < Ni/Al-SBA-15, which is attributed to the increase in the amount and strength of acid sites, especially of the Brønsted ones, which promotes the cleavage of the C-O bond. It is also important to keep the metal/acid sites together to obtain high activity and selectivity to hydrodeoxygenated products.

Brown adipose tissue thermogenesis among young adults in northeastern Siberia and Midwest United States and its relationship with other biological adaptations to cold climates.

OBJECTIVES: Recent research suggests that brown adipose tissue (BAT) plays a functional role in non-shivering thermogenesis; however, few studies have examined population variation in BAT or its relationship with other mechanisms of adaptation to cold stress. This study characterized BAT thermogenesis and other adaptive responses to low temperatures among Indigenous Siberian young adults and young adults living near Chicago, IL. MATERIALS AND METHODS: We recruited 72 Yakut participants (42 females; 30 males) and 54 participants in Evanston, IL (40 females; 14 males). Anthropometric dimensions and resting metabolic rate (RMR) were measured, and we calculated percent divergence in RMR from expected values (divRMR). We also quantified change in supraclavicular temperature, sternum temperature, and energy expenditure after a mild cooling condition. RESULTS: Participants in Yakutia were less likely to shiver during the cooling condition (p < .05) and exhibited significantly greater evidence of BAT thermogenesis, warmer sternum temperatures, and higher divRMR than participants in Evanston (p < .05). Additionally, the relationship between change in supraclavicular temperature and energy expenditure differed between the two samples. CONCLUSIONS: Yakut young adults displayed greater evidence of BAT thermogenesis in response to mild cooling compared with young adults living near Chicago, IL. Furthermore, the relationship between BAT thermogenesis and change in energy expenditure appears to be stronger among Yakut adults. Adults that exhibited greater metabolic response to cold stress, such as higher BAT thermogenesis and divRMR, maintained warmer sternum temperatures. These results highlight the degree to which adaptation to cold climates involves multiple integrated biological pathways.

Evidence for a sensitive period of plasticity in brown adipose tissue during early childhood among indigenous Siberians.

OBJECTIVES: Evolutionary theorists have debated the adaptive significance of developmental plasticity in organisms with long lifespans such as humans. This debate in part stems from uncertainty regarding the timing of sensitive periods. Does sensitivity to environmental signals fluctuate across development or does it steadily decline? We investigated developmental plasticity in brown adipose tissue (BAT) among indigenous Siberians in order to explore the timing of phenotypic sensitivity to cold stress. METHODS: BAT thermogenesis was quantified using infrared thermal imaging in 78 adults (25 men; 33 women). Cold exposure during gestation, infancy, early childhood, middle childhood, and adolescence was quantified using: (1) the average ambient temperature across each period; (2) the number of times daily temperature dropped below -40°F during each period. We also assessed past cold exposure with a retrospective survey of participation in outdoor activities. RESULTS: Adult BAT thermogenesis was significantly associated with the average temperature (p = 0.021), the number of times it was below -40°F (p = 0.026), and participation in winter outdoor activities (p = 0.037) during early childhood. CONCLUSIONS: Our results suggest that early childhood represents an important stage for developmental plasticity, and that culture may play a critical role in shaping the timing of environmental signals. The findings highlight a new pathway through which the local consequences of global climate change may influence human biology, and they suggest that ambient temperature may represent an understudied component of the developmental origins of health and disease.

Brown adipose tissue, energy expenditure, and biomarkers of cardio-metabolic health among the Yakut (Sakha) of northeastern Siberia.

OBJECTIVES: This study provides the first investigation of non-shivering thermogenesis (NST) and brown adipose tissue (BAT) activity among an indigenous circumpolar population, the Yakut of northeastern Siberia. The study also examines the health significance of BAT activity in this population by testing the relationships between BAT thermogenesis and biomarkers of cardio-metabolic disease risk, such as percent body fat and blood glucose and cholesterol levels. METHODS: Data were collected in the Sakha Republic (Yakutia) for 31 men and 43 women. Change in energy expenditure and BAT thermogenesis were quantified after a 30-minute mild cooling condition. Anthropometric dimensions, blood glucose, and lipid levels were also collected. RESULTS: On average, the skin temperature of the supraclavicular area was constant after cooling while the skin temperature of a point on the sternum dropped significantly (P < .001), thus suggesting the presence of active supraclavicular BAT among Yakut adults. Participants with evidence of greater BAT thermogenesis exhibited a larger percent change in energy expenditure (% ΔEE) and an increase in respiratory quotient (RQ) after cooling (P ≤ .05). While there was no relationship between BAT activity and blood lipid levels, BAT thermogenesis was positively associated with blood glucose levels (P < .01). CONCLUSIONS: Yakut adults exhibit evidence of active BAT deposits. Given that there is a significant relationship between BAT activity and % ΔEE, it is possible that BAT plays a role in NST among Yakut adults. While the relationship between BAT and body composition is inconclusive, participants with greater BAT seemed to preferentially utilize glucose during cold stress exposure.

Lifestyle mediates seasonal changes in metabolic health among the yakut (sakha) of northeastern siberia.

OBJECTIVES: Among indigenous circumpolar populations, extreme seasonality influences food availability and energy metabolism. Furthermore, subsistence patterns and wage labor opportunities shift with season. Thus, health measures among circumpolar populations likely exhibit seasonal changes that are influenced by lifestyle factors. This study examines how markers of cardio-metabolic health vary between summer and winter as a function of an individual's lifestyle and sex among the Yakut of northeastern Siberia. METHODS: Anthropometric dimensions, serum lipids and glucose levels, blood pressure, and lifestyle data were collected for a sample of 115 Yakut participants (71 women, 44 men) in Berdygestiakh, Sakha Republic, Russia in the summer of 2009 and winter of 2011. RESULTS: Men and women experienced significant increases in total and HDL cholesterol and triglyceride levels from summer to winter. Women exhibited winter-time increases in adiposity and glucose levels. Men who reported greater market integration were more likely to have lower winter blood pressure levels. Additionally, time spent fishing was associated with lower winter-time LDL cholesterol, while foraging time was associated with higher HDL cholesterol. CONCLUSIONS: While seasonal changes in anthropometric dimensions were modest, Yakut men and women experienced significant increases in total cholesterol and HDL cholesterol from summer to winter. These results also suggest that while Yakut individuals with greater subsistence participation are more buffered from adverse seasonal changes in cholesterol levels, they may be at a greater risk for winter increases in blood pressure. Furthermore, the interactions between lifestyle and seasonal change in metabolic health appear to differ between Yakut women and men. Am. J. Hum. Biol. 28:868-878, 2016. © 2016Wiley Periodicals, Inc.

Adiponectin, hemoglobin, and cardiovascular risk in an indigenous siberian population.

OBJECTIVES: Adipose tissue hypoxia appears to play a role in promoting chronic inflammation and the development of obesity-related cardiovascular and metabolic diseases, yet the underlying mechanisms are not well understood. The aim of the present research is to examine whether adiponectin levels (an adipocyte-derived hormone with anti-inflammatory properties) are inversely correlated with hemoglobin levels in an indigenous Siberian population. METHODS: The study was conducted among 252 Yakut adults (≥18 years; 135 females) from Berdygestiakh, Sakha Republic, Russia. Measurements included anthropometric dimensions (body mass index [BMI], waist circumference [WC], and percent body fat) and blood levels of hemoglobin and adiponectin. RESULTS: Yakut females had higher adiponectin concentrations than males (15.1 ± 9.8 vs. 11.7 ± 10.6 µg/ml; P < 0.001), whereas males had higher hemoglobin levels (14.4 ± 1.4 vs. 12.6 ± 1.5 g/dL; P < 0.001). Body composition measures in both sexes were negatively associated with adiponectin and positively associated with hemoglobin. After adjusting for central adiposity and smoking, adiponectin levels were negatively correlated with hemoglobin levels in men (P < 0.05), but not in women (P = 0.511). CONCLUSIONS: This investigation provides some support for the involvement of hypoxia-related dysregulation of adiponectin associated with obesity and potentially cardiovascular disease. Am. J. Hum. Biol. 28:580-583, 2016. © 2015 Wiley Periodicals, Inc.

Socio-demographic predictors of sleep complaints in indigenous Siberians with a mixed economy.

OBJECTIVES: Socio-demographic indicators closely relate to sleep in industrialized populations. However we know very little about how such factors impact sleep in populations undergoing industrialization. Within populations transitioning to the global economy, the preliminary evidence has found an inconsistent relationship between socio-demographics and sleep complaints across countries and social strata. MATERIALS AND METHODS: Surveys were conducted on a sample of rural Sakha (Yakut) adults (n = 168) during the autumn of 2103 to assess variation in socio-demographics and sleep complaints, including trouble sleeping and daytime sleepiness. Socio-demographic variables included age, gender, socioeconomic measures, and markers of traditional/market-based lifestyle. We tested whether the socio-demographic variables predicted sleep complaints using bivariate analyses and multiple logistic regressions. RESULTS: Trouble sleeping was reported by 18.5% of the participants and excessive daytime sleepiness (EDS) by 17.3%. Trouble sleeping was significantly predicted by older age, female gender, and mixing traditional and market-based lifestyles. EDS was not significantly predicted by any socio-demographic variable. DISCUSSION: These findings support the few large-scale studies that found inconsistent relationships between measures of socioeconomic status and sleep complaints in transitioning populations. Employing a mix of traditional and market-based lifestyles may leave Sakha in a space of vulnerability, leading to trouble sleeping.

Do physical activity and sedentary behavior relate to cardio-metabolic risk factor clustering in indigenous Siberian adults?

OBJECTIVES: To investigate whether having multiple risk factors for cardio-metabolic disease is associated with objectively measured physical activity or sedentary behavior within a sample of Yakut (Sakha) of Siberia. METHODS: This cross sectional study involved 63 Yakut adults (32 men) who were measured for cardio-metabolic risk factors. Free living physical activity and sedentary behavior were calculated from waist accelerometry. Correlations and t-tests were used to assess the relationship between moderate-vigorous physical activity (MVPA), sedentary behavior (SB), and individual risk factors and clustering of risk factors. RESULTS: These Yakut were physically active, with 54.4% spending at least 30 min in MVPA, with men being more active than women and women having less favorable cardio-metabolic profiles. These Yakut spent about 7.5 h in SB a day. SB was not related to cardio-metabolic risk factors. MVPA was significantly and negatively related to waist circumference and risk factor clustering in men and the total sample. MVPA was not related to women's risk factors. CONCLUSIONS: Objectively measured physical activity was related to lower risk of cardio-metabolic risk factor clustering within this sample of Yakut men, but not women. SB was not related to cardio-metabolic indicators. Physical activity may contribute to a reduction in clustering of metabolic risk factors within indigenous circumpolar populations.

Objectively measured physical activity and sedentary behaviour of Yakut (Sakha) adults.

BACKGROUND: Circumpolar regions are undergoing social and economic transition, which often corresponds to a behavioural transition. Yet, physical activity and sedentary behaviour are rarely objectively measured within these groups. AIM: This study aimed to characterize objectively measured physical activity and sedentary behaviour in a sample of indigenous Siberians. SUBJECTS AND METHODS: Yakut (Sakha) adults (n = 68, 32 men) underwent anthropometry, interviews and wore a triaxial accelerometer for two days. Time spent in moderate-to-vigorous physical activity (MVPA) or sedentary behaviour was calculated using a single axis and also all three axes. RESULTS: Men spent significantly more time in MVPA than women, although no sex difference was found in sedentary behaviour. Participants were far more active and less sedentary when classified using all three axes (vector magnitude) than a single axis. Television viewing time significantly related to sedentary behaviour in men only. CONCLUSION: The Yakut have gender differences in amount and predictors of physical activity and sedentary behaviour. Triaxial accelerometry is more sensitive to daily physical activity in free living populations than single axis.

Three-component reaction of tautomeric amidines with 3-ferrocenylmethylidene-2,4-pentanedione. Formation of polymeric coordination complexes of potassium ferrocenyl-(hexahydro)pyrimidoxides.

Acetamidine hydrochloride and p-aminobenzamidine dihydrochloride interact with 3-ferrocenylmethylidene-2,4-pentanedione at 80-82 °C in the presence of K2CO3 in the water-alcohol medium in two tautomeric forms (the amidoimine and enediamine ones) with formation of mixtures of pyrimidine and piperidone derivatives and polymeric coordination complexes of potassium ferrocenyl(hexahydro)pyrimidoxides. The structure of the resultant compounds is elucidated on the basis of IR, 1H- and 13C-NMR spectroscopy, mass spectrometry and elemental analysis data. The crystal structures of 6-ferrocenyl-4-hydroxy-4-methyl-2-piperidone, potassium 6-ferrocenyl-4-methyl-2-methylidene(hexahydro)pyrimidin-4-oxide and 2-(4-aminophenyl)-4-ferrocenyl-6-methyl-pyrimidine were determined by X-ray analysis of suitable single crystals.

Seasonal and socioeconomic influences on thyroid function among the Yakut (Sakha) of Eastern Siberia.

OBJECTIVES: Previous research has shown that the extreme cold and short day lengths of polar winters promote increased production and uptake of thyroid hormones, resulting in marked declines in free triiodothyronine (fT3). However, this "polar T3 syndrome" has been documented almost exclusively on small samples of male sojourners and little is known about seasonal changes in thyroid function among indigenous circumpolar groups. The present study addresses this gap by examining seasonal changes in thyroid hormone levels among the indigenous Yakut (Sakha) of northeastern Siberia. METHODS: Anthropometric dimensions and thyroid measures (fT3, free thyroxine [fT4], thyroid-stimulating hormone [TSH]) were obtained on two occasions (July/August, 2009 and January 2011) on a sample of 134 Yakut adults (51 men, 83 women) from the village of Berdygestiakh, Sakha Republic/Yakutia, Russia. RESULTS: Yakut men and women both displayed significant declines in fT3 and fT4, and significant increases in TSH from summer to winter despite showing only modest seasonal changes in body mass and composition. Among men, gains in fat-free mass (FFM) were associated with larger reductions in fT3 and greater increases in TSH. Men living more traditional lifeways showed larger winter declines in fT4 and greater increases in TSH. CONCLUSIONS: The Yakut exhibited significant winter declines in fT3 levels similar to other circumpolar groups studied. However, the magnitude of seasonal change was greater in the Yakut, perhaps reflecting their distinctive metabolic physiology. Lifestyle factors play a mediating role in thyroid responses, such that men with more traditional lifeways had more exaggerated seasonal changes.

4-Ferrocenylpyridine- and 4-ferrocenyl-3-ferrocenylmethyl-3,4-dihydropyridine-3,5-dicarbonitriles: multi-component synthesis, structures and electrochemistry.

The reactions of 2-cyano-3-ferrocenylacrylonitrile (1) with malononitrile (2) in a MeOH/H2O or 2-PrOH/H2O medium in the presence of Na2CO3 afforded 6-alkoxy-2-amino-4-ferrocenylpyridine-3,5-dicarbonitriles 3a,b (multi-component condensation) and 6-alkoxy-2-amino-4-ferrocenyl-3-ferrocenylmethyl-3,4-dihydropyridine-3,5-dicarbonitriles 4a,b (multi-component cyclodimerization). Analogous reactions of 1 with 2 in an MeOH/H2O medium in the presence of NaOH, piperidine, or morpholine gave compounds 3a, 4a and 2-amino-4-ferrocenyl-6-hydroxy-, 6-piperidino- and 6-morpholinopyridine-3,5-dicarbonitriles 3c-e, respectively. The structures of the compounds 3b, 4a and 4b were established by the spectroscopic data and X-ray diffraction analysis. The electrochemical behaviour of compounds 3b, 3d and 4b was investigated by means of cyclic voltammetry.

Circumpolar adaptation, social change, and the development of autoimmune thyroid disorders among the Yakut (Sakha) of Siberia.

OBJECTIVES: Alterations in thyroid function appear to play a central role in adaptation to Arctic environments. Increased thyroid activity in indigenous circumpolar populations is associated with upregulated metabolism, including elevated basal metabolic rate (BMR); however, little is known about the possible health consequences of these climate-induced changes on thyroid function. The focus of the present study is to determine the prevalence of autoimmune thyroid disorders and their lifestyle and metabolic correlates among a sample of indigenous Yakut adults from northeastern Siberia. METHODS: Anthropometric dimensions, health data, and plasma samples were collected among 281 adults (143 women, 138 men; ≥18 years old) from the rural community of Berdygestiakh (62°N, 127°E; pop. 4,900), Sakha Republic (Yakutia), Russia. BMR measurements were available for 96 women and 98 men. Free triiodothyronine (T(3) ), free thyroxine (T(4) ), thyroid stimulating hormone (TSH), and anti-thyroid peroxidase antibody (TPOAb) levels were determined using enzyme immunoassay. RESULTS: Twenty-two percent of women and 6% of men had clinically elevated (>30 IU/ml) TPOAb. TPOAb was positively correlated with TSH (P < 0.01), T(3) (P < 0.05), and T(4) (P < 0.05) in women and showed a positive trend with T(4) (P = 0.06) in men. Monthly household income was significantly positively correlated with TPOAb in men (P < 0.01) and showed a trend among women (P = 0.06). CONCLUSIONS: Although preliminary, these findings document higher than expected TPOAb levels among Yakut women and suggest possible consequences of increased thyroid activity associated with circumpolar adaptation and social change.

Dendrimers containing ferrocene and porphyrin moieties: synthesis and cubic non-linear optical behavior.

Dendrons with ferrocenyl ended groups joined by styryl moieties were attached to a porphyrin core. All the dendrons used for dendrimer synthesis showed trans configuration. The chemical structure of the first generation dendron was confirmed by X-ray crystallographic studies. The structure of the synthesized dendrimers was confirmed by 1H- and 13C-NMR, electrospray mass spectrometry and elemental analysis. Cubic non-linear optical behavior of the ferrocene and porphyrin-containing dendrimers was studied in solid thin films by THG Maker-Fringe technique at 1,260 nm.

Intramolecular transformations of 3-cyanoamino- and 3-cyanoimino-1,2-diferrocenylcyclopropenes.

3-Cyanoamino-1,2- and -2,3-diferrocenylcyclopropenes 6a,b and 11a,b prepared by the reaction of diferrocenylcyclopropenylium salts with sodium cyanamide undergo smooth intramolecular transformations with both conservation of the three-membered ring [affording 3-cyanoimino-1,2-diferrocenylcyclopropene (8)] and its opening [affording Z-3-morpholino- and Z-3-piperidino-3-(cyanoimino)-1,2-diferrocenylprop-1-enes 7a,b and Z-3-cyanoimino-2,3-diferrocenyl-1-methylthioprop-1-ene (10)]. 3-Cyano-imino-1,2-diferrocenylcyclopropene (8) reacts with hydrazine to form 3-amino-6-ferrocenyl-5-ferrocenylmethyl-1,2,4-triazine (12) and Z-2,3-diferrocenylacrylohydrazide N-cyanoimide (13) as a result of intramolecular transformations. The structures of the compounds obtained were determined by IR, (1)H- and (13)C-NMR spectroscopy and mass spectrometry. The structures of compounds 7a and 10 were additionally confirmed by their X-ray diffraction analysis data.

Synthesis of allyl-bearing dendrimers with a resorcinarene core and their supramolecular complexes with fullerene C60.

Dendritic branches of poly(arylether) with peripherial allyl chains have been attached to a resorcinarene core. Dendrimers of first, second, and third generation were synthesized. Viability to form supramolecular complexes with fullerene C60 was studied with three dendrimers of first, second, and third generation. All the compounds were characterized by 1H, 13C NMR, FTIR, UV-vis spectroscopy, MALDI-TOF, FAB+ mass spectra, and elemental analysis. Strong pi-pi, CH-pi, and n-pi interactions between the dendrimers and the fullerene C60 were detected in the supramolecular complexes by UV-vis, FTIR, and 13C CP-MAS NMR.

1,3-bis(diarylmethylidene)-2-methylidenecyclohexanes in cycloaddition and cyclodimerization reactions. The role of stereoelectronic factors.

Cycloaddition and cyclodimerization reactions of 1,3-dibenzylidene- and 1,3-bis(p-methoxybenzylidene)-2-methylidenecyclohexanes, i.e., the diaryltrienes with fixed S-cis-configurations of exocyclic double bonds are studied. These compounds undergo in situ cyclodimerization of the [4 + 2]-type upon dehydration of the precursor tertiary alcohols and form endo-adducts in the Diels-Alder reaction with N-phenylmaleimide. In the presence of CF3COOH, acid-catalyzed cyclodimerization takes place leading to methylidene-substituted spirocyclodimers, which undergo intramolecular cyclization upon prolonged contact with CF3COOH to form a fused carbocyclic system containing a central, 'three-petal' fragment of six-membered rings.