Sodium hydroxide as pretreatment and fluorosurfactant-capped gold nanoparticles as sensor for the highly selective detection of cysteine

A sensor for detecting cysteine (Cys) in a solution of fluorosurfactant (FSN)-capped gold nanoparticles (AuNPs) has been developed. Under acidic conditions, FSN-capped AuNPs are aggregated in the presence of homocysteine (HCys) and Cys but not in the presence of cysteinylglycine, glutathione, and gamma-glutamycysteine. When adding NaOH to a solution of HCys, the five-membered ring transition state is formed through intramolecular hydrogen abstraction. By contrast, it is difficult for Cys to form a four-membered ring transition state after Cys has been pretreated with NaOH. As a result, the HCys-induced aggregation of the FSN-capped AuNPs is suppressed because the five-membered ring transition state exhibits relatively larger steric hindrance and has stronger interaction with the FSN molecules. Thus, we can discriminate between Cys and HCys on the basis of different aggregation kinetics. Under the optimum condition, the selectivity of the probe for Cys in aqueous solutions is remarkably high over the other aminthiols. Note that HCys and Cys have very similar structure and pK(a) value. We have validated the applicability of our method through the analyses of Cys in urine samples. It is believed that this approach has great potential for the detection of Cys in biological samples.     

Micellar electrokinetic biofluid analysis of biogenic amines using on-line sample concentration and UV laser-induced native fluorescence detection

A simple and sensitive sweeping micellar electrokinetic chromatography method coupled with UV laser-induced native fluorescence detection has been developed for quantitative analysis of biogenic amines in biofluids. The background electrolyte comprised 30 mmol L⁻¹ phosphoric acid and 20 mmol L⁻¹ sodium dodecyl sulfate. The concentration limits of detection of analytes using sweeping-micellar electrokinetic chromatography (sweeping-MEKC) were in the range 7–100 nmol L⁻¹, which were 250–3600-fold improvement for dopamine, DOPA and epinephrine compared with conventional capillary zone electrophoresis. An improvement of approximately 20-fold was observed for all analytes compared with typical micellar electrokinetic chromatography conditions. Baseline separation was achieved for the all analytes within 12 min and migration-time and peak-area repeatability were better than RSD 0.35% and 5.68%, respectively. The developed method was applied to measure the biogenic amines in biofluids extracted from wheat phloem sap, human plasma and human urine.     

Enantioselective organocatalytic formal [3 + 3]-cycloaddition of alpha,beta-unsaturated aldehydes and application to the asymmetric synthesis of (-)-isopulegol hydrate and (-)-cubebaol

[reaction: see text] The first highly enantioselective organocatalyzed carbo [3 + 3] cascade cycloaddition of alpha,beta-unsaturated aldehydes is reported. Using this methodology, crotonaldehyde is converted to 6-hydroxy-4-methylcyclohex-1-enecarbaldehyde, which is used in the synthesis of (-)-isopulegol hydrate, (-)-cubebaol, and p-tolualdehyde as well as (-)-6-hydroxy-4-methyl-1-cyclohexene-1-methanol acetate, an intermediate in the total synthesis of lycopodium alkaloid magellanine. Other alpha,beta-unsaturated aldehydes give rise to chiral cyclohexadienes via formal [4 + 2] reactions.     

Comparisons of <Emphasis Type=Italic>n</Emphasis>th-order kinetic algorithms and kinetic model simulation on HMX by DSC tests

Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) is a typical highly energetic material that has been widely used in national defense industries since the 1940s. The aim of this study was to establish a reaction kinetic model on thermal decomposition properties via differential scanning calorimetry (DSC) by well-known kinetic equations and kinetic model simulation. Furthermore, the aim also was to compare kinetic algorithms for thermal decomposition energy parameters under various conditions. Experimental results highly depended on the reliability of the kinetic concept applied, which is essentially defined by the proper choice of a mathematical model of a reaction. In addition, the correctness of the methods is used for kinetics evaluation.     

Diffusiophoresis in suspensions of highly charged soft particles

Diffusiophoresis phenomenon of aoft particles suspended in binary electrolyte solutions is explored theoretically in this study based on the spherical cell model, focusing on the chemiphoresis component in absence of diffusion potential. Both the electrostatic and hydrodynamic aspects of the boundary confinement, or steric effect, due to the presence of neighboring particles are examined extensively under various electrokinetic conditions. Significant local extrema are found in mobility profiles expressed as functions of the Debye length in general, synchronized with the strength of the motion-inducing double layer polarization. Moreover, a seemingly peculiar phenomenon is observed that the soft particles may move faster in more concentrated suspensions. The competition between the simultaneous enhancement of the motion-inducing electric driving force and the motion-retarding hydrodynamic drag force from the boundary confinement effect of the neighboring particles is found to be responsible for it. The above findings are also demonstrated experimentally in a very recent study on the diffusiophoretic motion of soft particles through porous collagen hydrogels. The results presented here are useful in various practical applications of soft particles like drug delivery.     

Module-Designed Carbon-Coated Separators for High-Loading,High-Sulfur-Utilization Cathodes in Lithium–Sulfur Batteries

Lithium–sulfur batteries have great potential as next-generation energy-storage devices because of their high theoretical charge-storage capacity and the low cost of the sulfur cathode. To accelerate the development of lithium–sulfur technology, it is necessary to address the intrinsic material and extrinsic technological challenges brought about by the insulating active solid-state materials and the soluble active liquid-state materials. Herein, we report a systematic investigation of module-designed carbon-coated separators, where the carbon coating layer on the polypropylene membrane decreases the irreversible loss of dissolved polysulfides and increases the reaction kinetics of the high-loading sulfur cathode. Eight different conductive carbon coatings were considered to investigate how the materials’ characteristics contribute to the lithium–sulfur cell’s cathode performance. The cell with a nonporous-carbon-coated separator delivered an optimized peak capacity of 1112 mA∙h g⁻¹ at a cycling rate of C/10 and retained a high reversible capacity of 710 mA∙h g⁻¹ after 200 cycles under lean-electrolyte conditions. Moreover, we demonstrate the practical high specific capacity of the cathode and its commercial potential, achieving high sulfur loading and content of 4.0 mg cm⁻² and 70 wt%, respectively, and attaining high areal and gravimetric capacities of 4.45 mA∙h cm⁻² and 778 mA∙h g⁻¹, respectively.     

The Synthesis of Alanine Oligopeptides

The oligopeptides of alanine (penta-, deca-, and pentadeca-) were synthesized by solid phase method and new peptide-resin cleaving reagent TFA-BBr₃ was used to cleave the peptides from resin-support. Penta-alanine was also synthesized by liquid phase for the comparision and FAB-Mass method was used to determine the molecular weight of penta-alanine. HPLC separation of these new oligopeptides were described.     

Photoswitchable Composite Polymer Electrolytes Using Spiropyran-Immobilized Nanoporous Templates

Composite polymer electrolytes (CPEs) with smart, stimuli-responsive characteristics have gained considerable attention owing to their noninvasive manipulation and applications in future technologies. To address this potential, in this work, we demonstrate photoresponsive composite polymer electrolytes, consisting of gel polymer electrolyte (GPE) and spiropyran-immobilized nanoporous anodic aluminum oxide (SP-AAO) templates. Under UV irradiation, the close SP form isomerizes to the open merocyanine (MC) form, creating extremely polarized AAO surfaces; whereas, under visible light irradiation, the MC form reverts to the SP form, creating neutral surface conditions. The electrostatic interactions between ions and AAO surfaces are investigated by attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy. Moreover, the behavior of ionic conductivity of the GPE@SP-AAO is found to be consistent with the kinetics of isomerization tracked by UV-Vis spectroscopy. This work provides a promising platform for developing next-generation photoelectronic smart devices.     

Deficiency of optineurin enhances osteoclast differentiation by attenuating the NRF2-mediated antioxidant response

Abnormally increased resorption contributes to bone degenerative diseases such as Paget’s disease of bone (PDB) through unclear mechanisms. Recently, the optineurin (OPTN) gene has been implicated in PDB, and global OPTN knockout mice (Optn^−/−) were shown to exhibit increased formation of osteoclasts (osteoclastogenesis). Growing evidence, including our own, has demonstrated that intracellular reactive oxygen species (ROS) stimulated by receptor activator of nuclear factor kappa-B ligand (RANKL) can act as signaling molecules to promote osteoclastogenesis. Here, we report that OPTN interacts with nuclear factor erythroid-derived factor 2-related factor 2 (NRF2), the master regulator of the antioxidant response, defining a pathway through which RANKL-induced ROS could be regulated for osteoclastogenesis. In this study, monocytes from Optn^−/− and wild-type (Optn^+/+) mice were utilized to differentiate into osteoclasts, and both qRT-PCR and tartrate-resistant acid phosphatase (TRAP) staining showed that the Optn^−/− monocytes exhibited enhanced osteoclastogenesis compared to the Optn^+/+ cells. CellROX^® staining, qRT-PCR, and Western blotting indicated that OPTN deficiency reduced the basal expression of Nrf2, inhibited the expression of NRF2-responsive antioxidants, and increased basal and RANKL-induced intracellular ROS levels, leading to enhanced osteoclastogenesis. Coimmunoprecipitation (co-IP) showed direct interaction, and immunofluorescence staining showed perinuclear colocalization of the OPTN-NRF2 granular structures during differentiation. Finally, curcumin and the other NRF2 activators attenuated the hyperactive osteoclastogenesis induced by OPTN deficiency. Collectively, our findings reveal a novel OPTN-mediated mechanism for regulating the NRF2-mediated antioxidant response in osteoclasts and extend the therapeutic potential of OPTN in the aging process resulting from ROS-triggered oxidative stress, which is associated with PDB and many other degenerative diseases.Subject terms: Mechanisms of disease, Stress signalling