Applying reticular synthesis to the design of Cu-based MOFs with mechanically interlocked linkers

The concept of“robust dynamics”describes the incorporation of mechanically interlocked molecules(MIMs)into metal-organic framework(MOF)materials such that large amplitude motions(e.g.,rotation or translation of a macrocycle)can occur inside the free volume pore of the MOF.To aid in the preparation of such materials,reticular synthesis was used herein to design rigid molecular building blocks with predetermined ordered structures starting from the well-known MOF NOTT-101.New linkers were synthesized that have a T-shape,based on a triphenylene tetra-carboxylate strut,and their incorporation into Cu(II)-based MOFs was investigated.The single-crystal structures of three new MOFs,UWCM-12(fof),β-UWCM-13(loz),UWCM-14(lil),with naked T-shaped linkers were determined;β-UWCM-13 is the first reported example of the loz topology.A fourth MOF,UWDM-14(lil)is analogous to UWCM-14(lil)but contains a[2]rotaxane linker.Variable-temperature,²H solid-state NMR was used to probe the dynamics of a 24-membered macrocycle threaded onto the MOF skeleton.     

Tetrahydroindoles as Multipurpose Screening Compounds and Novel Sirtuin Inhibitors

Indoles are privileged structures in medicinal and bioorganic chemistry that are particularly well suited to serve as platforms for diversity. Among many other therapeutic areas, the indole scaffold has been used to design aromatic compounds useful to interfere with enzymes engaged in the regulation of substrate acylation status, such as sirtuins. However, the planarity of the indole ring is not necessarily optimal for all target enzymes, especially when functionalization with aromatic side chains is required. Replacement of flat scaffolds by nonplanar molecular cores dominated by sp³ hybridization is a common strategy to avoid the disadvantages associated with poor solubility and high promiscuity, while covering less-well-explored areas of chemical space. Thus, we synthesized fragment-like tetrahydroindoles suitable for fragment-based drug discovery as well as a well-characterized small library intended as multipurpose screening compounds. For proof of principle, these compounds were screened against sirtuins 1–3, enzymes known to be addressable by indoles. We found that 2,6,6-trimethyl-4-oxo-4,5,6,7-tetrahydro-1H-indole-3-carboxamides are potent and selective SIRT2 inhibitors. Compound 16 t displayed an IC₅₀ value of 0.98 μm and could serve as exquisite starting point for hit-to-lead profiling.     

Preparation and physicochemical study of jute and glass composites of epoxy resin of (2E, 6E)-bis(4-hydroxybenzylidene)cyclohexanone

Polymer Bulletin - Jute and glass composites of epoxy resin of (2E, 6E)-bis(4-hydroxybenzylidene)cyclohexanone (EBHBC) were prepared by compressing molding technique using three different hardeners...     

Sex and Depot Differences in Palmitoleic Acid Content of Human Blood and Fat

Palmitoleic acid has been classified as an insulin-sensitizing lipokine, but evidence for this from human studies has been inconsistent. We hypothesized that this is related to either the types of samples or conditions under which samples are collected. We measured plasma palmitoleic acid and total free fatty acids (FFA) using ultra-performance liquid chromatography in blood samples collected from 34 adults under a variety of conditions. We collected duplicate samples of adipose (n = 10), FFA (n = 9), and very low density lipoprotein triacylglycerol (VLDL-TAG) (n = 7) to measure the palmitoleic acid as a percentage of total fatty acids. We tested whether the percentage of palmitoleic acid was correlated with insulin resistance, as measured by homeostatic model of insulin resistance (HOMA-IR). Adipose stearoyl-coenzyme A desaturase 1 (SCD-1) protein was measured by capillary Western blotting. FFA-palmitoleic acid percentage increased as a function of total FFA and was greater (p < 0.005) in females than males. Adipose palmitoleic acid percentage was greater in females than males (p < 0.001), as was adipose SCD-1. Palmitoleic acid was greater in femoral fat than in abdominal fat in both females and males (p < 0.001), and correlated positively with HOMA-IR only in females. The test–retest reliability values for percentage palmitoleic acid were 7 ± 10% for adipose, 24 ± 26% for VLDL, and 53 ± 31% for FFA. Because FFA-palmitoleic acid percentage varies as a function of total FFA, investigators should re-evaluate how palmitoleic acid data is presented. The positive relationship between adipose palmitoleic acid and HOMA-IR in females suggests that it is not a potent insulin-sensitizing lipokine in humans.     

Characterizing physical habitat preferences and thermal refuge occupancy of brook trout (Salvelinus fontinalis) and Atlantic salmon (Salmo salar) at high river temperatures

Anthropogenic influences, including climate change, are increasing river temperatures in northern and temperate regions and threatening the thermal habitats of native salmonids. When river temperatures exceed the tolerance levels of brook trout and Atlantic salmon, individuals exhibit behavioural thermoregulation by seeking out cold‐water refugia – often created by tributaries and groundwater discharge. Thermal infrared (TIR) imagery was used to map cold‐water anomalies along a 53 km reach of the Cains River, New Brunswick. Trout and salmon parr did not use all identified thermal anomalies as refugia during higher river temperature periods (>21°C). Most small‐bodied trout (8–30 cm) were observed in 80% of the thermal anomalies sampled. Large‐bodied trout (>35 cm) required a more specific set of physical habitat conditions for suitable refugia, that is, 100% of observed large trout used 30% of the anomalies sampled and required water depths >65 cm within or adjacent to the anomaly. Densities of trout were significantly higher within anomalies compared with areas of ambient river temperature. Salmon parr were less aligned with thermal anomalies at the observed temperatures, that is, 59% were found in 65% of the sampled anomalies; and densities were not significantly different within/ outside anomalies. Salmon parr appeared to aggregate at 27°C, and after several events over 27°C variability in aggregation behaviour was observed – some fish aggregated at 25°C, others did not. We stipulate this is due to variances of thermal fatigue. Habitat suitability curves were developed for velocity, temperature, depth, substrate, and deep water availability to characterize conditions preferred by fish during high‐temperature events. These findings are useful for managers as our climate warms, and can potentially be used as a tool to help conserve and enhance thermal refugia for brook trout and Atlantic salmon in similar systems.     

Analyzing the Operational Materials on Crack Formation in Blades of Francis Turbines at the Krasnoyarsk HPP

Equipment of the Krasnoyarsk HPP is considered as an example to analyze the dependence of crack formation in runner blades on the operating conditions of t     

Investigation on the effect of EDM process variables and environments on acoustic emission signals

Abstract

The performance of electrical discharge machining (EDM) primarily depends on the spark quality generated in the inter-electrode gap (IEG) between the tool and workpiece. A method for obtaining accurate information about the spark gap is required to effectively monitor the EDM process. The rise and fall of thermal energy in the discharge zone at a rapid rate during the dielectric breakdown produces high-pressure shock waves. This work explores the suitability of using acoustic emission (AE) generated from these shock waves and the elastic AE waves released on the workpiece due to the induced stress to monitor the performance and spark gap in EDM. The information content of the AE signals acquired at various machining conditions was extracted using AE RMS, spectral energy and peak amplitude. These features were able to well discriminate the machining condition, tool material, workpiece material, flushing pressure, current density, the initial surface roughness of the tool. Additionally, the AE signal features had a good and consistent correlation with the performance parameters, including material removal rate, surface roughness (Ra and Rq) and tool wear. The findings lay the groundwork to develop an effective, non-intrusive in-situ AE-monitoring system for performance and IEG condition in EDM.     

High‐intensity sweeteners in espresso coffee: ideal and equivalent sweetness and time–intensity analysis

The efficient substitution of sucrose by a sweetener in beverages requires the application of some sensory techniques. First, one must determine the concentrations of the sweeteners under study, equivalent in sweetness to the ideal sucrose concentration. In addition, it is fundamental to determine which is most similar to sucrose. The objectives of this study were to determine the ideal sweetness for espresso coffee and the equivalent concentrations in sweetness of different sweeteners, as well as characterise the time–intensity profile of each sweetener in relation to sweetness. The sweeteners evaluated were sucralose, aspartame, neotame, a cyclamate/saccharin mixture (2:1) and stevia. The sucrose concentration considered ideal by consumers was 12.5% (w/v), and the equivalent concentrations of the sweeteners were 0.0159% for sucralose, 0.0549% for aspartame, 0.0016% for neotame, 0.0359% for the cyclamate/saccharin mixture and 0.0998% for stevia. The time–intensity analysis indicated that possibly the sweeteners neotame, aspartame and sucralose would be the best substitutes for sucrose.