Comprehensive 1H and 13C NMR assignment of 13 protobassic acid saponins

This study aimed to carry out complete ¹H and ¹³C NMR assignment of 13 protobassic acid saponins, including arganins A–C ( 1 – 3 ) and F ( 4 ), butyrosides B–D ( 5 – 7 ), tieghemelin ( 8 ), 3′-O-glucosyl-arganin C ( 9 ), Mi-saponins A–C ( 10 – 12 ), and mimusopsin ( 13 ), recorded in methanol-d₄. This was accomplished by the analysis of high-resolution one-dimensional (1D) NMR (¹H and ¹³C), two-dimensional (2D) NMR (¹H–¹H COSY, HSQC, and HMBC), and selectively excited 1D TOCSY spectra. Before this study, ¹H and ¹³C NMR data of arganins A–C ( 1 – 3 ) and F ( 4 ) were partially assigned. Our effort leads to their complete assignment, especially the glycon residue, and revises some reported data. Some revisions of the ¹H and ¹³C NMR data in the glycon part of butyroside C ( 6 ), tieghemelin ( 8 ), Mi-saponin A ( 10 ), and mimusopsin ( 13 ) were made. Those data of butyrosides B and D ( 5 & 7 ) and Mi-saponin B ( 11 ), which had not been recorded in methanol-d₄, are provided. In addition, the ¹H and ¹³C NMR data of Mi-saponin C ( 12 ) are reported for the first time. These data, being recorded in methanol-d₄, should be more friendly for use as a reference for identifying the related triterpenoid saponins.     

LC-MS Quantification of Site-Specific Phosphorylation Degree by Stable-Isotope Dimethyl Labeling Coupled with Phosphatase Dephosphorylation

Protein phosphorylation is a crucial post-translational modification that plays an important role in the regulation of cellular signaling processes. Site-specific quantitation of phosphorylation levels can help decipher the physiological functions of phosphorylation modifications under diverse physiological statuses. However, quantitative analysis of protein phosphorylation degrees is still a challenging task due to its dynamic nature and the lack of an internal standard simultaneously available for the samples differently prepared for various phosphorylation extents. In this study, stable-isotope dimethyl labeling coupled with phosphatase dephosphorylation (DM + deP) was tried to determine the site-specific degrees of phosphorylation in proteins. Firstly, quantitation accuracy of the (DM + deP) approach was confirmed using synthetic peptides of various simulated phosphorylation degrees. Afterwards, it was applied to evaluate the phosphorylation stoichiometry of milk caseins. The phosphorylation degree of Ser130 on α-S1-casein was also validated by absolute quantification with the corresponding synthetic phosphorylated and nonphosphorylated peptides under a selected reaction monitoring (SRM) mode. Moreover, this (DM + deP) method was used to detect the phosphorylation degree change of Ser82 on the Hsp27 protein of HepG2 cells caused by tert-butyl hydroperoxide (t-BHP) treatment. The results showed that the absolute phosphorylation degree obtained from the (DM + deP) approach was comparable with the relative quantitation resulting from stable-isotope dimethyl labeling coupled with TiO₂ enrichment. This study suggested that the (DM + deP) approach is promising for absolute quantification of site-specific degrees of phosphorylation in proteins, and it may provide more convincing information than the relative quantification method.     

Cascade One‐Pot Synthesis of Orange‐Red‐Fluorescent Polycyclic Cinnolino[2,3‐f]phenanthridin‐9‐ium Salts by Palladium(II)‐Catalyzed C−H Bond Activation of 2‐Azobiaryl Compounds and Alkenes

Quaternary ammonium salts were synthesized in moderate to good yields through double oxidative C?H bond activation on azobenzenes. The mechanism of the highly regioselective reaction of 2‐azobiaryls with alkenes to give orange‐red‐fluorescent cinnolino[2,3‐f]phenanthridin‐9‐ium salts and 15H‐cinnolino[2,3‐f]phenanthridin‐9‐ium‐10‐ide is proposed to involve ortho C?H olefination of the 2‐azobiaryl compound with the alkene, intramolecular aza‐Michael addition, concerted metalation–deprotonation (CMD), reductive elimination, and oxidation.     

DNA‐Templated Copper Nanoprobes: Overview,Feature, Application,and Current Development in Detection Technologies

Metal nanoprobes have recently attracted board research interestinr their application in establishing sensing systems due to their unique optical, electrical, physical, and chemical properties. In comparison to gold and silver nanoprobes, analytical platform based on copper nanoprobes (Cu‐NPs) is still in the early stages of development. In this review, we focus on single‐stranded, and double‐stranded DNA capped Cu‐NPs sensing systems which have been designed for various analytes, including metal ions, anions, small molecules, biomolecules (DNA, RNA, and protein, etc.). In addition, the application of Cu‐NPs in biological labeling or bio‐imaging platforms has also been introduced and summarized.     

Vorticity-streamfunction formulation of unsteady incompressible flow past a cylinder: Sensitivity of the computed flow field to the location of the outflow boundary

The influence of the location of the outflow computational boundary on the unsteady incompressible flow past a circular cylinder at Reynolds number 100 is examined. The vorticity-streamfunction formulation of the Navier-Stokes equations is used in all computations. Two types of outflow boundary conditions are subjected to a series of tests in which the domain length is gradually reduced. The traction-free condition performs well in most cases and allows the outflow boundary to be located as close as 6.5 cylinder diameters from the body. The other boundary condition type is not as forgiving, but has the advantage of being simpler to implement and can still provide reasonably accurate solutions. It is also observed that both condition types can influence the flow field strongly and globally when the boundary is brought closer than 2.5 diameters from the body. In such cases the temporal periodicity of the solution is lost.     

Ferromagnetism study of Co<Subscript>0.2</Subscript>Mg<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript>0.8−<Emphasis Type="Italic">x</Emphasis></Subscript>O films prepared by the sol–gel method

Co_0.2Mg _x Zn_0.8−x O films prepared with different molar ratio of magnesium acetate to zinc acetate were deposited on substrates by the sol–gel technique. X-ray diffraction, photoluminescence (PL) and ferromagnetism measurements were used to characterize the Co_0.2Mg _x Zn_0.8−x O diluted magnetic semiconductors. The acceptor-like defects were determined in the PL band and the intensity of the acceptor-related PL increased with increasing Mg concentration. Therefore, an increase in the number of the acceptor-like defects (zinc vacancies especially) in the Co_0.2Mg _x Zn_0.8−x O film may lead to the enhancement of the magnetic properties. It is worth noting that changes in Mg concentration and the number of the acceptor-like defects are important issues for producing strong ferromagnetism Co_0.2Mg _x Zn_0.8−x O films prepared by the sol–gel method.     

Improved Synthesis of Asymmetric Curcuminoids and Their Assessment as Antioxidants

In this paper, the syntheses of twelve asymmetric curcumin analogs using Pabon’s method are reported. Generally, the previously reported yields of asymmetric curcuminoids, such as 9a (53%), 9c (38%), and 9k (38%), have been moderate or low. Herein, we propose that the low yields were due to the presence of water and n-BuNH₂ in the reaction media. To prove this formulated hypothesis, we have demonstrated that the yields can be improved by adding molecular sieves (MS) (4 Å) to the reaction mixture, thus reducing the interference of water. Therefore, improved yields (41–76%) were obtained, except for 9b (36.7%), 9g (34%), and 9l (39.5%). Furthermore, compounds 9b, 9d, 9e, 9f, 9g, 9h, 9i, 9j, and 9l are reported herein for the first time. The structures of these synthetic compounds were determined by spectroscopic and mass spectrometry analyses. The free radical scavenging ability of these synthetic asymmetric curcuminoids was evaluated and compared to that of the positive control butylated hydroxytoluene (BHT). Among the synthesized asymmetric curcuminoids, compounds 9a (IC₅₀ = 37.57 ± 0.89 μM) and 9e (IC₅₀ = 37.17 ± 1.76 μM) possessed effective 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging abilities, and compounds 9h (IC₅₀ = 11.36 ± 0.65 μM) and 9i (IC₅₀ = 10.91 ± 0.77 μM) displayed potent 2,2’-azinobis-(3-ethylbenzthiazoline-6-sulphonate) (ABTS) radical scavenging abilities comparable to that of curcumin (IC₅₀ = 10.14 ± 1.04 μM). Furthermore, all the synthetic asymmetric curcuminoids were more active than BHT.     

Semi-fragile spatial watermarking based on local binary pattern operators

Local binary pattern (LBP) operators, which measure the local contrast within a pixel's neighborhood, have been successfully applied to texture analysis, visual inspection, and image retrieval. In the paper, we present a novel semi-fragile spatial watermarking method based on LBP operators by using the local pixel contrast for the embedding and extraction of watermarks. We also propose a general framework for multi-level image watermarking. Experimental results show that the proposed watermarking methods are robust against commonly-used image processing operations, such as additive noise, luminance change, contrast adjustment, color balance, and JPEG compression. At the same time, they achieve good invisibility, fragility, and image tamper detection and localization with less computational cost.     

The influence of lanthanum doping on the physical and electrical properties of BTV ferroelectric thin films

In this study, the ferroelectricity of as-deposited Bi_3.9La_0.1Ti_2.9V_0.1O₁₂ (BLTV), Bi_3.9Ti_2.9V_0.1O₁₂ (BTV), and Bi₄Ti₃O₁₂ (BIT) thin films was prepared and compared by rf magnetron sputtering technology. For the BLTV, BTV, and BIT thin films deposited on Pt/Ti/SiO₂/Si and SiO₂/Si substrate, the physical and electrical characteristics of lanthanum doped BTV (BLTV) were better than those of BIT and BTV thin films. Regarding the physical properties, the micro-structure of as-deposited BTV and BLTV thin films were obtained and compared by XRD patterns and SEM images. The BLTV and BTV thin films were also exhibited clear the ferroelectricity. The remanent polarization (P _r ) of as-deposited BLTV thin films was 11 μC/cm² as the measured frequency of 100 kHz. It was higher than those of BTV thin films. Finally, the polarization of BLTV thin film capacitor decreased by 9%, while that of the BTV decreased by 15% after the fatigue test with 10⁹ switching cycles.     

Voltage-controlled optical switch in planar nematic liquid crystal film

This study presents an integrated device that consists of a directional coupler and an electro-optic switch. The device is designed to include a nematic liquid crystal cell, comprising a grating-like electrode. Applying the appropriate voltage to the cell yields a periodically distributed refractive index. An incident polarized beam will couple to an adjacent channel if it is parallel to the channel. The coupling efficiency is controlled by applied voltage. An obliquely injected polarized beam will be reflected and refracted in the channel, and propagated along a curved path. The route of the beam can be controlled by applying the voltage. A multiport routing was achieved for voltage modulation. In addition, the distribution of refractive index is also investigated by employing conoscopic technique experimentally and numerically.