Z-Selectivity in Olefin Metathesis with Chelated Ru Catalysts: Computational Studies of Mechanism and Selectivity

The mechanism and origins of Z-selectivity in olefin metathesis with chelated Ru catalysts were explored using density functional theory. The olefin approaches from the “side” position of the chelated Ru catalysts, in contrast to reactions with previous unchelated Ru catalysts that favor the bottom-bound pathway. Steric repulsions between the substituents on the olefin and the N-substituent on the N-heterocyclic carbene ligand lead to highly selective formation of the Z product

Antioxidant and anti-dyslipidemic effects of polysaccharidic extract from sea cucumber processing liquor

Sea cucumber is a seafood of high nutritional value. During its processing, sea cucumber processing liquor is routinely produced, which is usually discarded as waste. The chemical composition of this processing liquor is similar to sea cucumbers themselves. Hence, valuable ingredients, such as functional polysaccharides, could be obtained from them. Results Biologically active polysaccharides from sea cucumber processing liquor were extracted through protease hydrolysis and electroosmosis. The analysis revealed that the polysaccharide extract from sea cucumber processing liquor (PESCPL) is predominantly composed of mannose, in addition to some glucose and fucose. The antioxidant activity of PESCPL was analyzed using in vitro. It was demonstrated that PESCPL could effectively scavenge 1,1-diphenyl-2-picrylhydrazyl radicals, hydroxyl radicals, and superoxide anion radicals. The effect of PESCPL was investigated in vivo by using mice model fed with high-fat diets with/without PESCPL supplement. It was shown that PESCPL could increase the catalase and superoxide dismutase activity in the serum and decrease serum malonaldehyde content. Furthermore, mice fed with PESCPL diet showed a considerable decrease in the serum cholesterol and triglyceride levels and an increase in high-density lipoprotein cholesterol levels. Conclusions Our research highlights that PESCPL is a natural antioxidant and could be utilized as a therapeutic supplement for dyslipidemia

Transpositional reactivation of the Dart transposon family in rice lines derived from introgressive hybridization with Zizania latifolia

<p>Abstract</p> <p>Background</p> <p>It is widely recognized that interspecific hybridization may induce "genome shock", and lead to genetic and epigenetic instabilities in the resultant hybrids and/or backcrossed introgressants. A prominent component involved in the genome shock is reactivation of cryptic transposable elements (TEs) in the hybrid genome, which is often associated with alteration in the elements' epigenetic modifications like cytosine DNA methylation. We have previously reported that introgressants derived from hybridization between <it>Oryza sativa </it>(rice) and <it>Zizania latifolia </it>manifested substantial methylation re-patterning and rampant mobilization of two TEs, a <it>copia </it>retrotransposon <it>Tos17 </it>and a MITE <it>mPing</it>. It was not known however whether other types of TEs had also been transpositionally reactivated in these introgressants, their relevance to alteration in cytosine methylation, and their impact on expression of adjacent cellular genes.</p> <p>Results</p> <p>We document in this study that the <it>Dart </it>TE family was transpositionally reactivated followed by stabilization in all three studied introgressants (RZ1, RZ2 and RZ35) derived from introgressive hybridization between rice (cv. Matsumae) and <it>Z. latifolia</it>, while the TEs remained quiescent in the recipient rice genome. Transposon-display (TD) and sequencing verified the element's mobility and mapped the excisions and re-insertions to the rice chromosomes. Methylation-sensitive Southern blotting showed that the <it>Dart </it>TEs were heavily methylated along their entire length, and moderate alteration in cytosine methylation patterns occurred in the introgressants relative to their rice parental line. Real-time qRT-PCR quantification on the relative transcript abundance of six single-copy genes flanking the newly excised or inserted <it>Dart</it>-related TE copies indicated that whereas marked difference in the expression of all four genes in both tissues (leaf and root) were detected between the introgressants and their rice parental line under both normal and various stress conditions, the difference showed little association with the presence or absence of the newly mobilized <it>Dart-</it>related TEs.</p> <p>Conclusion</p> <p>Introgressive hybridization has induced transpositional reactivation of the otherwise immobile <it>Dart</it>-related TEs in the parental rice line (cv. Matsumae), which was accompanied with a moderate alteration in the element's cytosine methylation. Significant difference in expression of the <it>Dart</it>-adjacent genes occurred between the introgressants and their rice parental line under both normal and various abiotic stress conditions, but the alteration in gene expression was not coupled with the TEs.</p

Textural and biochemical changes of scallop Patinopecten yessoensis adductor muscle during low-temperature long-time (LTLT) processing

In this study, the effects of low-temperature long-time (LTLT) processing on the quality of Patinopecten yessoensis adductor muscle (PYAM) were investigated at 55°C. The texture of processed PYAM was characterized by textural profile analysis (TPA), and significant increases of cook loss, hardness, and shear force with time during LTLT processing were observed. The degradation of structural proteins was analyzed by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE), and fragments with molecular weights of 208 kDa (myosin heavy chain, MHC), 97 kDa (paramyosin) and 35–40 kDa, respectively, were among the main products. Chemical characterization revealed elevated levels of activity in cathepsin L and caspase-3 and oxidation of proteins and lipids. Electron spin resonance spin trapping indicated reactive oxygen species (ROS) production in the PYAM during LTLT processing. Based on these results, it is proposed that the sequence of events in PYAM during LTLT processing includes ROS→ endogenous enzyme (involving caspase-3 and cathepsin L) activation →protein degradation→quality changes (texture and color). This revelation helps to further our understanding of the LTLT processing of PYAM, which would lead to better quality control for PYAM products

Enhanced Photocatalytic Activity of W-Doped and W-La-Codoped TiO 2

W-doped TiO2 and W-La-codoped TiO2 nanomaterials were successfully synthesized via the sol-gel method. The products were characterized by X-ray diffraction, UV-vis diffuse reflectance spectrophotometer, transmission electron microscopy, and X-ray photoelectron spectroscopy. The presence of W and La results in significant red shift of absorption edge for TiO2-based nanomaterials. The weight ratios of La and W in the composites play important roles in the absorption edge for TiO2-based nanomaterials. The photocatalytic activities of both W-doped TiO2 and W-La-codoped TiO2 photocatalysts for decolorization of methyl orange solution were evaluated under simulated sunlight irradiation. The results showed that both W-doped and W-La-codoped can effectively improve the photocatalytic behaviors of TiO2 nanomaterials ascribed to the improved photoinduced charge carriers separation, enhanced light absorption, and large surface area. Furthermore, W-La-codoped TiO2 exhibited higher photocatalytic activity than W-doped TiO2. Considering their high photocatalytic activity, the doped TiO2 nanomaterials could be applied in wastewater treatment and environmental purification

Improved Visible Light Photocatalytic Activity for TiO 2

S/Zn codoped TiO2 nanomaterials were synthesized by a sol-gel method. X-ray diffraction, UV-vis diffuse reflectance spectroscopy, transmission electron microscopy, photoluminescence spectroscopy, and X-ray photoelectron spectroscopy were used to characterize the morphology, structure, and optical properties of the prepared samples. The introduction of Zn and S resulted in significant red shift of absorption edge for TiO2-based nanomaterials. The photocatalytic activity was evaluated by degrading reactive brilliant red X-3B solution under simulated sunlight irradiation. The results showed S/Zn codoped TiO2 exhibited higher photocatalytic activity than pure TiO2 and commercial P25, due to the photosynergistic effect of obvious visible light absorption, efficient separation of photoinduced charge carriers, and large surface area. Moreover, the content of Zn and S in the composites played important roles in photocatalytic activity of TiO2-based nanomaterials

Z-Selective Ethenolysis with a Ruthenium Metathesis Catalyst: Experiment and Theory

The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups

Association between daytime nap duration and risks of frailty: Findings from the China Health and Retirement Longitudinal Study

IntroductionNight sleep duration and total sleep duration are associated with frailty. However, the association between daytime nap duration and the risks of frailty has not been explored thoroughly.MethodsThis study used data from the China Health and Retirement Longitudinal Study (CHARLS). Participants aged 60 years and older at baseline were included in this study. Individuals with daytime nap duration were categorized into four groups: no napping, short napping (&lt; 30 min), moderate napping (30–89 min), and extended napping (≥90 min). Frailty was assessed using a modified Physical Frailty Phenotype (PFP) scale. Non-frail participants at baseline were followed up for 4 years. The association between nap duration and risks of frailty at baseline and incident frailty was evaluated by logistic regression and discrete-time Cox regression analyses, respectively.ResultsIn total, 5,126 participants were included in this study. For individuals with night sleep duration of ≥9 h, short nappers showed higher odds [odds ratio (OR) = 4.08, 95% confidence interval (CI): 1.30–12.78] for frailty compared with non-habitual nappers at baseline, while moderate nappers were less likely to be frail (OR = 0.18, 95% CI: 0.04–0.73). In the follow-up study, short nappers showed higher risks for frailty compared with participants of the no napping group with night sleep duration of &lt; 6 h [hazard ratio (HR) = 1.91, 95% CI: 1.07–3.43] or 6–9 h (HR = 1.97, 95% CI: 1.18–3.30). Compared with short nappers, older adults with extended napping (HR = 0.41, 95% CI: 0.22–0.77) showed lower risks for frailty in those with night sleep duration of 6–9 h. For individuals with night sleep duration of ≥9 h, moderate napping (HR = 0.20, 95% CI: 0.05–0.77) decreased the risks for frailty compared with short napping.ConclusionAmong older adults with night sleep duration of &lt; 9 h, short nappers posed higher risks for frailty compared with non-habitual nappers. Extended naps for those with a night sleep duration of 6–9 h or moderate naps for those with night sleep duration of ≥9 h could lower the risk of frailty compared with short naps. Future studies on the timing, purpose, frequency, and quality of daytime napping and objectively measured nap duration are needed to explore the association between daytime napping and risks of frailty