Dearomatization of 3-Aminophenols for Synthesis of Spiro[chromane-3,1'-cyclohexane]-2',4'-dien-6'-ones via Hydride Transfer Strategy-Enabled [5+1] Annulations.

The Sc(OTf)3-catalyzed dearomative [5+1] annulations between readily available 3-aminophenols and O-alkyl ortho-oxybenzaldehydes were developed for synthesis of spiro[chromane-3,1'-cyclohexane]-2',4'-dien-6'-ones. The "two-birds-with-one-stone" strategy was disclosed by the dearomatization of phenols and direct α-C(sp3)-H bond functionalization of oxygen through cascade condensation/[1,5]-hydride transfer/dearomative-cyclization process. In addition, the antifungal activity assay and derivatizations of products were conducted to further enrich the utility of the structure.

Organic Geochemical Evidence for the Formation of Condensate from Coaly Source Rocks in the Wumaying Buried Hill of the Huanghua Depression, Bohai Bay Basin.

Although oil and gas from coaly source rocks have been widely discovered worldwide, the role of oil generated from coal measures in marine-continental coaly deposits during the Carboniferous-Permian period in the Bohai Bay Basin has long been a subject of debate. The recent discovery of a condensate reservoir in the Wumaying buried hill within the Huanghua Depression of the Bohai Bay Basin offers new potential insights into this issue. In this study, we employed organic geochemical methods to explore the possibility of the Carboniferous-Permian coal deposit being a primary source of the condensate. The distribution of light hydrocarbons and the biomarker assemblage indicate that the condensate did not undergo significant secondary alterations such as thermal cracking, gas invasion fractionation, or biodegradation. The hydrocarbon generation potential of the Carboniferous-Permian coaly source rocks suggests that they could be an important contributor to the formation of condensate. High pristine/phytane ratios (1.0-7.5), an abundant presence of benzene series, and the dominance of C29 steranes (>50%) within the condensate could be indicative of coaly organic matter. These features are comparable to those found in coaly source rocks. Moreover, the stable carbon isotopic compositions of n-alkanes in the condensate, ranging from -26.0 to -30.0‰, correlate well with those from coaly mudstone (-25.4 to -30.0‰). This suggests that the condensate of the Wumaying buried hill may predominantly originate from the Carboniferous-Permian coaly mudstone. When integrated with the geological background, the results distinctly demonstrate that the Carboniferous-Permian coaly source rocks have significantly contributed to the formation of the condensate reservoir in the Wumaying buried hill. This provides an essential reference for future exploration of oil and gas resources derived from the carboniferous-Permian coaly source rocks in the Bohai Bay Basin.

Coprecipitation-based synchronous chlorantraniliprole encapsulation with chitosan: carrier-pesticide interactions and release behavior.

BACKGROUND: Controlled-release pesticide formulations have emerged as a promising approach towards sustainable pest control. Herein, an environment-friendly formulation of insecticide chlorantraniliprole (CAP) was fabricated through a simple approach of coprecipitation-based synchronous encapsulation by chitosan (CTS), with carrier-pesticide interaction mechanism and release behavior investigated. RESULTS: The resulting CAP/CTS controlled-release formulation (CCF) showed a good loading content of 28.1% and a high encapsulation efficiency of 75.6%. Instrument determination in combination with molecular dynamics (MD) simulations displayed that the primary interactions between CAP and CTS were physical adsorption and complicated hydrogen (H)-bonds, which formed dominantly between NH in amides [or nitrogen (N) in ring structures] of CAP and hydroxyl (or amino) groups of CTS, as well as oxygen (O) in CAP with hydrogen in CTS or H2 O molecules. The in vitro release tests exhibited obvious pH/temperature sensitivity, with release dynamics following the first-order or Ritger-Peppas model. As the temperature increased, the CAP release process of the Ritger-Peppas model changed from Case-II to anomalous transport, and ultimately to a Fickian diffusion mechanism. The control effect against Plutella xylostella larvae also was evaluated by toxicity tests, where comparable efficacy of CCF to the commercial suspension concentrate was obtained. CONCLUSION: The innovative, easy-to-prepare CCF can be used as a formulation with obvious pH/temperature sensitivity and good efficacy on target pests. This work contributes to the development of efficient and safe pesticide delivery systems, especially using the natural polymer materials as carriers. © 2023 Society of Chemical Industry.

One-pot construction of epoxy resin nanocarrier delivering abamectin and its efficacy on plant root-knot nematodes.

BACKGROUND: The complex preparation process and storage instability of nanoformulations hinders their development and commercialization. In this study, nanocapsules loaded with abamectin were prepared by interfacial polymerization at room temperature and ordinary pressure using the monomers of epoxy resin (ER) and diamine. The potential mechanisms of primary amine and tertiary amine in influencing the shell strength of the nanocapsules and the dynamic stability of abamectin nanocapsules (Aba@ER) in the suspension system were systematically researched. RESULTS: The tertiary amine catalyzed the self-polymerization of epoxy resin into linear macromolecules with unstable structures. The structural stability of the diamine curing agent with a primary amine group played a key role in enhancing the structural stability of the polymers. The intramolecular structure of the nanocapsule shell formed by isophorondiamine (IPDA) crosslinked epoxy resin has multiple spatial conformations and a rigid saturated six-membered ring. Its structure was stable, and the shell strength was strong. The formulation had stable dynamic changes during storage and maintained excellent biological activity. Compared with emulsifiable concentrate (EC), Aba@ER/IPDA had superior biological activity, and the field efficacy on tomato root-knot nematode was enhanced by approximately 31.28% at 150 days after transplanting. CONCLUSION: Aba@ER/IPDA, which has excellent storage stability and simple preparation technology, can provide a nanoplatform with industrial prospects for efficient pesticide delivery. © 2023 Society of Chemical Industry.

Engineering Atomic-to-Nano Scale Structural Homogeneity towards High Corrosion Resistance of Amorphous Magnesium-Based Alloys.

Magnesium-based amorphous alloys have aroused broad interest in being applied in marine use due to their merits of lightweight and high strength. Yet, the poor corrosion resistance to chloride-containing seawater has hindered their practical applications. Herein, we propose a new strategy to improve the chloride corrosion resistance of amorphous Mg65Cu15Ag10Gd10 alloys by engineering atomic-to-nano scale structural homogeneity, which is implemented by heating the material to the critical temperature of the liquid-liquid transition. By using various electrochemical, microscopic, and spectroscopic characterization methods, we reveal that the liquid-liquid transition can rearrange the local structural units in the amorphous structure, slightly decreasing the alloy structure's homogeneity, accelerate the formation of protective passivation film, and, therefore, increase the corrosion resistance. Our study has demonstrated the strong coupling between an amorphous structure and corrosion behavior, which is available for optimizing corrosion-resistant alloys.

Left ventricular systolic and diastolic dyssynchrony to improve cardiac resynchronization therapy response in heart failure patients with dilated cardiomyopathy.

BACKGROUND: The systolic and diastolic dyssynchrony is physiologically related, but measure different left ventricular mechanisms. Left ventricular systolic mechanical dyssynchrony (systolic LVMD) has shown significant clinical values in improving cardiac resynchronization therapy (CRT) response in the heart failure patients with dilated cardiomyopathy (DCM). Our recent study demonstrated that LV diastolic dyssynchrony (diastolic LVMD) parameters have important prognostic values for DCM patients. However, there are a limited number of studies about the clinical value of diastolic LVMD for CRT. This study aims to explore the predictive values of both systolic LVMD and diastolic LVMD for CRT in DCM patients. METHODS: Eighty-four consecutive CRT patients with both DCM and complete left bundle branch block (CLBBB) who received gated resting SPECT MPI at baseline were included in the present study. The phase analysis technique was applied on resting gated short-axis SPECT MPI images to measure systolic LVMD and diastolic LVMD, characterized by phase standard deviation (PSD) and phase histogram bandwidth (PBW). CRT response was defined as ≥ 5% improvement of LVEF at 6-month follow-up. Variables with P < 0.10 in the univariate analysis were included in the multivariate cox analysis. RESULTS: During the follow-up period, 59.5% (50 of 84) patients were CRT responders. The univariate cox regression analysis showed that at baseline QRS duration, non-sustained ventricular tachycardia (NS-VT), systolic PSD, systolic PBW, diastolic PSD, diastolic PBW, scar burden and LV lead in the scarred myocardium were statistically significantly associated with CRT response. The multivariate cox regression analysis showed that QRS duration, NS-VT, systolic PSD, systolic PBW, diastolic PSD, and diastolic PBW were independent predictive factors for CRT response. Furthermore, the rate of CRT response was 94.4% (17 of 18) in patients whose LV lead was in the segments with both the first three late contraction and the first three late relaxation; by contrast, the rate of CRT response was only 6.7% (1 of 15, P < 0.000) in patients whose LV lead was in the segments with neither the first three late contraction nor the first three late relaxation. CONCLUSION: Both systolic LVMD and diastolic LVMD from gated SPECT MPI have important predictive values for CRT response in DCM patients. Pacing at LV segments with both late contraction and late relaxation has potential to increase the CRT response.

Compact terahertz spectrometer based on sequential modulation of disordered rough surfaces.

We present herein a compact terahertz (THz) spectrometer in which transmission intensity distribution associated with dispersive interference effects in disordered random surfaces are used for reconstructing the frequency contents of an incoming THz beam. The device sweeps the frequency-dependent parameter of a roughened transmission plate through lateral displacement or electro-optic modulation. 2D transmission intensities are sequentially captured by a single detector for a range of modulation depths. With a calibration data set as the reference, one can reconstruct the spectra of the probe THz beam by solving a system of simultaneous linear equations. A smoothing Tikhonov regularization approach has been implemented to improve the accuracy of the spectral reconstruction. The reported compact, broadband, high-resolution THz spectrometer is well suited for portable THz spectroscopy applications.