Obesity Duration and Cardiometabolic Disease.

Cardiovascular disease risk is known to be influenced by both the severity of a risk factor and the duration of exposure (eg, LDL [low-density lipoprotein] cholesterol, tobacco smoke). However, this concept has been largely neglected within the obesity literature. While obesity severity has been closely linked with cardiometabolic diseases, the risk of developing these conditions among those with obesity may be augmented by greater obesity duration over the life span. Few longitudinal or contemporary studies have investigated the influence of both factors in combination-cumulative obesity exposure-instead generally focusing on obesity severity, often at a single time point, given ease of use and lack of established methods to encapsulate duration. Our review focuses on what is known about the influence of the duration of exposure to excess adiposity within the obesity-associated cardiometabolic disease risk equation by means of summarizing the hypothesized mechanisms for and evidence surrounding the relationships of obesity duration with diverse cardiovascular and metabolic disease. Through the synthesis of the currently available data, we aim to highlight the importance of a better understanding of the influence of obesity duration in cardiovascular and metabolic disease pathogenesis. We underscore the clinical importance of aggressive early attention to obesity identification and intervention to prevent the development of chronic diseases that arise from exposure to excess body weight.

Food consumption patterns related to excess weight and obesity in Spanish preschoolers.

PURPOSE: The aims of this study were (1) to identify the different food consumption patterns among Spanish preschoolers and (2) to examine the association between having a different food consumption pattern and the odds of having excess weight (i.e., overweight or obesity) or obesity among this population. METHODS: This was a nationwide cross-sectional study with data from the Spanish National Health Survey-2017. All preschoolers (aged 3-5 years) with complete information on all the variables analyzed were selected. The frequency of consumption of the fourteen food groups was evaluated by a food frequency questionnaire. Excess weight/obesity were computed following the World Health Organization criteria. A hierarchical cluster analysis using Ward's method (i.e., based on squared Euclidean distances) and k-means were performed including all food group consumption. A total sample of 663 was included in the cluster analysis. RESULTS: Three different clusters were established. Compared to the healthiest food consumption pattern (Cluster 1), higher odds of excess weight (OR = 1.51; CI: 95%, 1.02-2.25) and obesity (OR = 1.59; CI: 95%, 1.01-2.51) were found for participants with the unhealthiest food consumption pattern (Cluster 3). CONCLUSION: Having a food consumption pattern considered unhealthy (i.e., low intake of vegetables/fruits, high consumption of confectionery products, sugar-sweetened beverages, fast-food, and snacks) was associated with presenting excess weight/obesity among Spanish preschoolers. IMPACT: No studies have examined the specific food consumption patterns associated with excess weight or obesity among Spanish preschoolers. The unhealthiest food consumption pattern was characterized by a food consumption pattern that included a lower intake of vegetables and fruits and a higher consumption of confectionery products, sugar-sweetened beverages, fast-food, and snacks. Having a food consumption pattern considered unhealthy was associated with a higher prevalence of excess weight and obesity in comparison with other healthier food consumption patterns.

Correction: Metal-organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C-H bond activation and functionalization reactions.

Correction for 'Metal-organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C-H bond activation and functionalization reactions' by Saba Daliran et al., Chem. Soc. Rev., 2022, https://doi.org/10.1039/d1cs00976a.

Metal-organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C-H bond activation and functionalization reactions.

Although C-H functionalization is one of the simplest reactions, it requires the use of highly active and selective catalysts. Recently, C-H-active transformations using porous materials such as crystalline metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs) as well as amorphous porous-organic polymers (POPs) as new emerging heterogeneous catalysts have attracted significant attention due to their promising activity and potential material tunability. These porous solids offer exceptional structural uniformity, facile tunability and permanent porosity. In addition, tuning the catalytic selectivity of these porous materials can be achieved through engineering their site microenvironments, such as metal node substitution, linker changes, node/linker functionalization, and pore modification. The present review provides an overview of the current state of the art on MOFs, COFs and POPs as advanced catalysts for various C-H bond activation reactions, providing details about their chemo-, regio-, and stereo-selectivity control, comparing their performance with that of other catalysts, triggering additional research by showing the present limitations and challenges in this area, and providing a perspective for future developments.

Blocking Lipid Uptake Pathways Does not Prevent Toxicity in Adipose Triglyceride Lipase (ATGL) Deficiency.

Lipid accumulation in nonadipose tissues can cause lipotoxicity, leading to cell death and severe organ dysfunction. Adipose triglyceride lipase (ATGL) deficiency causes human neutral lipid storage disease and leads to cardiomyopathy; ATGL deficiency has no current treatment. One possible approach to alleviate this disorder has been to alter the diet and reduce the supply of dietary lipids and, hence, myocardial lipid uptake. However, in this study, when we supplied cardiac Atgl KO mice a low- or high-fat diet, we found that heart lipid accumulation, heart dysfunction, and death were not altered. We next deleted lipid uptake pathways in the ATGL-deficient mice through the generation of double KO mice also deficient in either cardiac lipoprotein lipase or cluster of differentiation 36, which is involved in an lipoprotein lipase-independent pathway for FA uptake in the heart. We show that neither deletion ameliorated ATGL-deficient heart dysfunction. Similarly, we determined that non-lipid-containing media did not prevent lipid accumulation by cultured myocytes; rather, the cells switched to increased de novo FA synthesis. Thus, we conclude that pathological storage of lipids in ATGL deficiency cannot be corrected by reducing heart lipid uptake.

Nickel-Catalysed Cross-Electrophile Coupling of Benzyl Bromides and Sulfonium Salts towards the Synthesis of Dihydrostilbenes.

A nickel-catalysed reductive cross-coupling reaction between benzyl sulfonium salts and benzyl bromides is reported. Simple, stable and readily available sulfonium salts have shown their ability as leaving groups in cross-electrophile coupling, allowing the formation of challenging sp3 -sp3 carbon-carbon bonds, towards the synthesis of interesting dihydrostilbene derivatives. In addition, benzyl tosyl derivatives have been demonstrated to be suitable substrates for reductive cross-coupling by in-situ formation of the corresponding sulfonium salt.

Treatment of Obesity in Mitigating Metabolic Risk.

Through diverse mechanisms, obesity contributes to worsened cardiometabolic health and increases rates of cardiovascular events. Effective treatment of obesity is necessary to reduce the associated burdens of diabetes mellitus, cardiovascular disease, and death. Despite increasing cardiovascular outcome data on obesity interventions, only a small fraction of the population with obesity are optimally treated. This is a primary impetus for this article in which we describe the typical weight loss, as well as the associated impact on both traditional and novel cardiovascular disease risk factors, provided by the 4 primary modalities for obtaining weight loss in obesity-dietary modification, increasing physical activity, pharmacotherapy, and surgery. We also attempt to highlight instances where changes in metabolic risk are relatively specific to particular interventions and appear at least somewhat independent of weight loss. Finally, we suggest important areas for further research to reduce and prevent adverse cardiovascular consequences due to obesity.

Simple Rules for Complex Near-Glass-Transition Phenomena in Medium-Sized Schiff Bases.

Glass-forming ability is one of the most desired properties of organic compounds dedicated to optoelectronic applications. Therefore, finding general structure-property relationships and other rules governing vitrification and related near-glass-transition phenomena is a burning issue for numerous compound families, such as Schiff bases. Hence, we employ differential scanning calorimetry, broadband dielectric spectroscopy, X-ray diffraction and quantum density functional theory calculations to investigate near-glass-transition phenomena, as well as ambient- and high-pressure molecular dynamics for two structurally related Schiff bases belonging to the family of glycine imino esters. Firstly, the surprising great stability of the supercooled liquid phase is shown for these compounds, also under high-pressure conditions. Secondly, atypical self-organization via bifurcated hydrogen bonds into lasting centrosymmetric dimers is proven. Finally, by comparing the obtained results with the previous report, some general rules that govern ambient- and high-pressure molecular dynamics and near-glass transition phenomena are derived for the family of glycine imino esters. Particularly, we derive a mathematical formula to predict and tune their glass transition temperature (Tg) and its pressure coefficient (dTg/dp). We also show that, surprisingly, despite the presence of intra- and intermolecular hydrogen bonds, van der Waals and dipole-dipole interactions are the main forces governing molecular dynamics and dielectric properties of glycine imino esters.

Fluorinated Sulfinates as Source of Alkyl Radicals in the Photo-Enantiocontrolled ß-Functionalization of Enals.

The generation of sulfonyl radicals has long been known as a flexible strategy in a wide range of different sulfonylative transformations. Meanwhile their use in alkylation processes has been somehow limited due to their inherent difficulty in evolving to less-stable radicals after sulfur dioxide extrusion. Herein we report a convenient strategy that involves gem-difluorinated sulfinates as an "upgrading-mask", allowing these precursors to decompose into their corresponding alkyl radicals. The electron-donor character of sulfinates in the formation of an electron donor-acceptor (EDA) complex with transient iminium ions is displayed, achieving the first example of a stereocontrolled light-driven insertion of gem-difluoro derivatives into unsaturated aldehydes. This methodology is compatible with flow conditions, maintaining identical levels of enantiocontrol.

Organocatalytic Strategies for the Development of the Enantioselective Inverse-electron-demand Hetero-Diels-Alder Reaction.

Cycloaddition reactions, in particular Diels-Alder reactions, have attracted a lot of attention from organic chemists since they represent one of the most powerful methodologies for the construction of carbon-carbon bonds. In particular, inverse-electron-demand hetero-Diels-Alder reactions have been an important breakthrough for the synthesis of heterocyclic compounds. Among all their variants, the organocatalytic enantioselective version has been widely explored since the asymmetric construction of diversely functionalized scaffolds under reaction conditions encompassed within the green chemistry field is of great interest. In this review, a profound revision on the latest advances on the organocatalytic asymmetric inverse-electron demand hetero-Diels-Alder reaction is shown.

Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers.

New 1,2-azolylamidino complexes cis-[Ru(bipy)2(NH═C(R)az*-κ2N,N)](OTf)2 (R = Me, Ph; az* = pz, indz, dmpz) are synthesized via chloride abstraction after a subsequent base-catalyzed coupling of a nitrile with the previously coordinated 1,2-azole. The synthetic procedure allows the easy obtainment of complexes having different electronic and steric 1,2-azoylamidino ligands. All of the compounds have been characterized by 1H, 13C, and 15N NMR and IR spectroscopy and by monocrystal X-ray diffraction. Photophysical studies support their phosphorescence, whereas their electrochemistry reveals reversible RuII/RuIII oxidations between +1.13 and +1.25 V (vs SCE). The complexes have been successfully used as catalysts in the photooxidation of different thioethers, the complex cis-[Ru(bipy)2(NH═C(Me)dmpz-κ2N,N)]2+ showing better catalytic performance in comparison to that of [Ru(bipy)3]2+. Moreover, the significant catalytic performance of the dimethylpyrazolylamidino complex is applied to the preparation of the drug modafinil, which is obtained using ambient oxygen as an oxidant. Finally, mechanistic assays suggest that the oxidation reaction follows a photoredox route via oxygen radical anion formation.

Comparison of Aortic Gradient and Ventricular Mass after Valve Replacement for Aortic Stenosis with Rapid Deployment, Sutureless, and Conventional Bioprostheses.

BACKGROUND: The use of rapid deployment and sutureless aortic prostheses is increasing. Previous reports have shown promising results on haemodynamic performance and mortality rates. However, the impact of these bioprostheses on left ventricular mass (LVM) regression remains unknown. We decided to study the changes in remodelling and LVM regression in isolated severe aortic stenosis treated with conventional or Perceval® or Intuity® valves. METHOD AND RESULTS: From January 2011 to January 2016, 324 bioprostheses were implanted in our centre. The collected characteristics were divided into 3 groups: conventional valves, Perceval®, and Intuity®, and they were analysed after 12 months. There were 183 conventional valves (56%), 72 Perceval® (22%), and 69 Intuity® (21.2%). The statistical analysis showed significant differences in transprosthetic postoperative peak gradient (23 [18-29] mm Hg vs. 21 [16-29] mm Hg and 18 [14-24] mm Hg, p < 0.001), ventricular mass electrical criteria regression (Sokolow and Cornell products), and 1-year survival (90 vs. 93% and 97%, log rank p value = 0.04) in conventional, Perceval®, and Intuity® groups. CONCLUSIONS: We observed differences in haemodynamic, electrocardiographic, and echocardiographic parameters related to the different types of prosthesis. Patients with the Intuity® prosthesis had the highest reduction in peak aortic gradient and the higher ventricular mass regression. Besides, patients with the Intuity® prosthesis had less risk of mortality during follow-up than the other two groups. Further studies are needed to confirm these findings.

Recent Visible Light and Metal Free Strategies in [2+2] and [4+2] Photocycloadditions.

When aiming to synthesize molecules with elevated molecular complexity starting from relatively simple starting materials, photochemical transformations represent an open avenue to circumvent analogous multistep procedures. Specifically, light-mediated cycloadditions remain as powerful tools to generate new bonds begotten from non-very intuitive disconnections, that alternative thermal protocols would not offer. In response to the current trend in both industrial and academic research pointing towards green and sustainable processes, several strategies that meet these requirements are currently available in the literature. This Minireview summarizes [2+2] and [4+2] photocycloadditions that do not require the use of metal photocatalysts by means of alternative strategies. It is segmented according to the cycloaddition type in order to give the reader a friendly approach and we primarily focus on the most recent developments in the field carried out using visible light, a general overview of the mechanism in each case is offered as well.

Investigating the Impact of Usability on Energy Efficiency of Web-based Personal Health Records.

Usability plays an important role in eHealth applications for their widespread adoption. These software systems have been studied in depth in the literature from this perspective. However, the energy consumption of information systems in the eHealth domain lacks comprehensive research. In this paper, the relationship between the energy consumption of the main components of a PC and the usability evaluations of graphical user interfaces (GUI) were studied in client applications. For this purpose, personal health records (PHR) were used as a case study. A set of 4 web-based PHRs were evaluated with the performance of 20 common tasks in the aforementioned systems. The usability evaluations were carried out by 4 experts. A total of 8 heuristics particularly designed for electronic health record systems and based on the Nielsen usability heuristics were employed. The instantaneous energy values of the power supply and the monitor were collected with an energy consumption measuring equipment. As a result, the following significant correlations were found. In NoMoreClipboard between the Memory heuristic and the power supply (rs = 0.495, p = 0.044), and the Minimalist heuristic and the monitor (rs = - 0.513, p = 0.035). In PatientsLikeMe between the Minimalist heuristic and the power supply (rs = - 0.479, p = 0.083), as well as in the Error heuristic and the power supply (rs = - 0.638, p = 0.014). Finally, in Health Companion between the Match heuristic and the power supply (rs = - 0.481, p = 0.043), and the Error heuristic and the power supply again (rs = - 0.602, p = 0.008). Apart from that, the tasks were divided into those with excellent and fair usability. Those tasks with high usability scores were evaluated to detect whether they also had low energy consumption during task performance. Significant differences were found in PatientsLikeMe with respect to the Error heuristic and the power supply (212.39 ± 18.85W). Significant differences were also found in Health Companion with respect to the Match heuristic and the power supply (199.91 ± 7.19W). The results were discussed to reveal the fundamentals of how implementing usability can impact on energy costs when running client applications.

Corrigendum to "Energy efficiency in software: A case study on sustainability in personal health records" [J. Clean. Prod. 282 (2021) 124262].

[This corrects the article DOI: 10.1016/j.jclepro.2020.124262.].

Energy efficiency in software: A case study on sustainability in personal health records.

A personal health record is an eHealth technology in which users can observe their progress over time for a given condition. A research gap was identified in the literature concerning the study of the amount of energy that these systems need for their operation, and the energy efficiency that may be attained depending on their design. After the selection of five representative personal health records, a total of 20 tasks commonly done, and based on previous work, were performed with regard to two proposed scenarios, namely patient use and health personnel usage. The power consumption of the main components of a host machine was measured during the performance of the proposed duties. To that end, a hardware tool called the Energy Efficiency Tester was employed. The data collected were analyzed statistically, and significant differences were found in the respective consumption of the display (χ2 (4) = 23.782, p = 0.000), the processor (χ2 (4) = 29.018, p = 0.000) and the whole PC (χ2 (4) = 28.582, p = 0.000). For all of these components, NoMoreClipBoard was the personal health record that required the least energy (57.699 W for the display, 3.162 W for the processor and 181.113 W for the whole PC). A total of two strong correlations were found in the energy consumption between the hard disk and the graphics card (r = 0.791, p < 0.001), and the processor and the PC (r = 0.950, p < 0.001). Some features generated special amounts of power consumption, such as the news wall found on PatientsLikeMe, or the use of load icons that had an impact on most PC components. In addition, an in-depth analysis of the user interfaces was performed. A discussion was carried out on the design of the user interfaces, also taking into account recommendations drawn from the literature, checking for their implementation in the personal health records selected. With the aim of promoting sustainability among software developers, a best practice guideline on sustainable software design was proposed. Basic sustainability recommendations were collected for professionals to consider when developing a software system in general, and a personal health record in particular.

Light-Driven Enantioselective Synthesis of Pyrroline Derivatives by a Radical/Polar Cascade Reaction.

Herein, a light-driven, atom-economical process that provides access to enantiomerically enriched substituted chiral 1-pyrroline derivatives is introduced. The strategy involves the distal functionalization of acyl heterocycles through a hydrogen-atom transfer (HAT) process and the use of tailor-made ketimines as reliable electrophilic partners. This transformation is translated into an enantiomerically controlled radical/polar cascade reaction in which water is produced as the sole by-product and stereoselectivity is dictated by coordination to a chiral-at-rhodium catalyst.

Photocatalytic Water-Soluble Cationic Platinum(II) Complexes Bearing Quinolinate and Phosphine Ligands.

Cationic Pt(II) complexes ([Pt(QO/S)(P∧P)]X), having 8-oxy or 8-thioquinolinate (QO/S) and seven different mono- or bidentate phosphines as ligands, have been synthesized and characterized. The photophysical, stability, and photocatalytic properties of those complexes were studied and compared to that of the parent [Pt(QO/S)(dmso)(Cl)]. The coordination of phosphines induced a red-shift in the absorption energy of the MLCT band, whereas the emission wavelength of the complexes only depended on the nature of the quinolinate ligand. Moreover, the photocatalytic activity of the Pt(II) complexes was evaluated in the oxidation of sulfides using atmospheric oxygen as an oxidant. All the complexes were active photocatalysts for that transformation, with [Pt(QO)(BINAP)]Cl and [Pt(QO)(SEGPHOS)]Cl (BINAP: 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, SEGPHOS: (4,4'-bibenzodioxole)-5,5'-diyldiphosphine) exhibiting high catalytic performance and stability. In addition, the enhanced water solubility of the complexes allowed performance of the photooxidation reaction under environmentally friendly conditions. In particular, the catalyst [Pt(QS)(dppe)]Cl, bearing 8-thioquinolinate and diphenylphosphinoethate (dppe) as ligands, successfully catalyzed the oxidation of a variety of sulfides using water as a solvent.

Asymmetric trifluoromethylthiolation of azlactones under chiral phase transfer catalysis.

The first enantioselective method for the installation of the SCF3 group at the C-4 position of azlactones is described in the present communication under quinidinium phase transfer catalysis. The higher performance of substrates containing electron-rich 2-aryl groups at the azlactone was rationalized using DFT calculations.

On-Surface Driven Formal Michael Addition Produces m-Polyaniline Oligomers on Pt(111).

On-surface synthesis is emerging as a highly rational bottom-up methodology for the synthesis of molecular structures that are unattainable or complex to obtain by wet chemistry. Here, oligomers of meta-polyaniline, a known ferromagnetic polymer, were synthesized from para-aminophenol building-blocks via an unexpected and highly specific on-surface formal 1,4 Michael-type addition at the meta position, driven by the reduction of the aminophenol molecule. We rationalize this dehydrogenation and coupling reaction mechanism with a combination of in situ scanning tunneling and non-contact atomic force microscopies, high-resolution synchrotron-based X-ray photoemission spectroscopy and first-principles calculations. This study demonstrates the capability of surfaces to selectively modify local molecular conditions to redirect well-established synthetic routes, such as Michael coupling, towards the rational synthesis of new covalent nanostructures.