Late-Stage Glycosylation of Peptides by Methionine-Directed ß-C(sp3)-H Functionalization with 1-Iodoglycals.

Using l-methionine (Met) as the endogenous directing group, we developed Pd-catalyzed ß-C(sp3)-H glycosylation of peptides with 1-iodoglycals. A wide range of tri- to hexapeptides containing the Ala-Met motifs underwent Ala C-H glycosylation under the standard conditions to give the glycopeptides smoothly. 15 proteinogenic amino acids (with easily removable protecting groups) were well tolerated. Control experiments indicated that Met acted as a N,S-bidentate directing group and exhibited an effect superior to other amino acid residues such as l-aspartic acid (Asp), l-asparagine (Asn), and S-protected l-cysteine (Cys). In addition, further transformation by HFIP-promoted 1,4-elimination furnished another type of glycopeptide with the 1,3-diene motif, which provides a handle for further derivatization.

RIS-Assisted D2D Communication over Nakagami-m Fading with RSMA.

In this study, we investigated reconfigurable intelligent surface (RIS)-assisted device-to-device (D2D) communication systems over Nakagami-m fading channels. To enhance the reliability of RIS-assisted D2D communications, we utilized the rate-splitting multiple access (RSMA) technique to maximize the achievable ergodic rate for our considered systems. Specifically, both devices decoded the common symbol by treating private symbols as interference, and then each private symbol was decoded by treating the other as interference. In order to maximize the achievable ergodic rate at the destination, we analyzed the achievable ergodic rate of the RIS link and the D2D link, and the destination jointly decoded both symbols transmitted from the source and device by involving the maximum ratio combination (MRC). We obtained a closed-form expression for the achievable ergodic rate of the proposed RIS-assisted D2D communication system. Finally, we investigated the influence of power allocation factors and the number of reflective elements on the achievable ergodic rate. As seen by the numerical results, there was a good match between the analysis and simulation results, as well as significant superiority compared with existing works.

Distribution, sources, and eco-risk of Current-Use Pesticides (CUPs) in the coastal waters of the northern Shandong Peninsula, China.

This study investigated the spatial distributions and seasonal variations of 19 CUPs in the coastal areas of the Shandong Peninsula and its surrounding rivers and assessed their ecological risk. In freshwater and seawater, insecticides (chlorpyrifos, methoxychlor, and pyridaben), as well as fungicides (fenarimol) and herbicides (dichlobenil) were the main pollutants (Detection Frequency: 100 %). Spatially, during winter, the regional pollution levels of Σ19CUPs in seawater showed a trend of Laizhou Bay (LZB, mean:4.13 ng L-1) > Yellow River Estuary (YRE, mean:2.57 ngL-1) > Bohai Bay (BHB, mean:2.21 ng L-1) > Yanwei Area (YWA, mean:1.94 ng L-1). The similarities of major substances between rivers and the marine environment suggest that river discharge is the main source of CUPs pollution in coastal areas. In summer, CUPs in rivers posed a high risk. In winter, the risk significantly decreased, indicating a moderate overall risk. Seawater exhibited a low risk in winter.

Structural Transformation between a Nematic Loose Packing and a Randomly Stacked Close Packing of Granular Disks.

Packing structures of granular disks are reconstructed using magnetic resonance imaging techniques. As packing fraction increases, the packing structure transforms from a nematic loose packing to a dense packing with randomly oriented stacks. According to our model based on Edwards' volume ensemble, stack structures are statistically favored when the effective temperature decreases, which has a lower structural anisotropy than single disks, and brings down the global orientational order consequently. This mechanism identified in athermal granular materials can help us understand the nonergodic characteristics of disklike particle assemblies such as discotic mesogens and clays.

Ocean current redistributed the currently using Organoamine Pesticides in Arctic summer water.

In a comprehensive study on the presence and distribution of Currently Using Organoamine Pesticides (CUOAPs) in the Arctic Ocean, this study collected and analyzed 36 surface seawater samples during the summer of 2021. The study detected 36 CUOAPs, 17 of these compounds at levels exceeding the Method Detection Limits (MDLs). Concentrations of CUOAPs ranged from 0.11 to 2.94 ng/L, exhibiting an average of 1.83 ± 0.83 ng/L. Spatial distribution analysis revealed lower CUOAP concentrations in the central Arctic Ocean, with Cycloate constituting the most abundant component (23.66 %). The investigation identified terrestrial inputs and long-range atmospheric transport as potential sources of CUOAPs in the Arctic Ocean region. The origins of individual CUOAPs appeared to be associated with application procedures and their propensity for co-occurrence at low latitudes. The study also examined the role of ocean currents in the transport and redistribution of CUOAPs in surface seawater across different regions. While ocean currents played a significant role, the influence of sea ice cover on CUOAP distribution was minimal. An ecological risk assessment analysis underscored the need for regional attention to the presence of CUOAPs in the Arctic Ocean.

Occurrence, seasonal variations, and eco-risk of currently using organochlorine pesticides in surface seawater of the East China Sea and Western Pacific Ocean.

We studied 19 targets currently using organochlorine pesticides (CUOCPs) from 98 samples in the Western Pacific Ocean and the East China Sea collected in 2019, 2020, and 2021. The samples were analyzed using a novel High-throat/High-volume Solid-Phase Extraction method. Eighteen individual CUOCPs were above the method detection limits. The levels of ∑19CUOCPs ranged from 0.13 to 17.80 ng/L, with an average of 3.13 ± 14.67 ng/L. Dicofol was the main pollutant in the Western Pacific Ocean, while Pyridaben dominated the East China Sea. In the summer, land-source input was the primary source in the Western Pacific Ocean and the East China Sea. Historical residues were the main source in the East China Sea in spring. In the summer, the ecological risk assessment results indicated a relatively low risk to the Western Pacific Ocean and the East China Sea.

Structural evolution of granular cubes packing during shear-induced ordering.

Packings of granular particles may transform into ordered structures under external agitation, which is a special type of out-of-equilibrium self-assembly. Here, evolution of the internal packing structures of granular cubes under cyclic rotating shearing has been analyzed using magnetic resonance imaging techniques. Various order parameters, different types of contacts and clusters composed of face-contacting cubes, as well as the free volume regions in which each cube can move freely have been analyzed systematically to quantify the ordering process and the underlying mechanism of this granular self-assembly. The compaction process is featured by a first rapid formation of orientationally ordered local structures with faceted contacts, followed by further densification driven by free-volume maximization with an almost saturated degree of order. The ordered structures are strongly anisotropic with contacting ordered layers in the vertical direction while remaining liquid-like in the horizontal directions. Therefore, the constraint of mechanical stability for granular packings and the thermodynamic principle of entropy maximization are both effective in this system, which we propose can be reconciled by considering different depths of supercooling associated with various degrees of freedom.

Cubatic structural transformation of the packing of granular cylinders.

Packing structures of granular cylinders with the aspect ratio close to one have been reconstructed with the help of magnetic resonance imaging techniques. By controlling the container boundary conditions and preparation protocols, a structural transformation from a disordered liquid-like state to an orientationally ordered state with cubatic symmetry at a high packing fraction is observed. This ordering process is accompanied by the formation of more faceted contacts, which lower the elastic energy between jammed granular particles to drive the transformation. With the help of Edwards' volume ensemble theory, this granular structural transformation is explained using a phenomenological thermodynamic model and a self-consistent mean-field statistical mechanical model. Both models predict a sharp but continuous change of order parameter when the effective granular temperature is lowered. The intrinsic difference and connection between this granular structural transformation and the entropy-driven phase transition of conventional thermal hard-particle systems are discussed.

Self-assembly of FeIII-TAML-based microstructures for rapid degradation of bisphenols.

Iron(III)-tetraamidomacrocyclic ligand (FeIII-TAML) activators have drawn great attentions due to the high reactivity to degrade organic pollutants. However, previous studies showed that the reactivity and stability of FeIII-TAML were both strongly pH-dependent, which dramatically decrease at lower pH levels. Herein, FeIII-TAML/DODMA (dimethyldioctadecylammonium chloride) microspheres with diameters ranging from 100 to 2000 nm were synthesized via a surfactant-assisted self-assembly technique. The newly synthesized FeIII-TAML/DODMA composite exhibits superior reactivity compared to free FeIII-TAML as indicated by the degradation of bisphenols (i.e., bisphenol A and its analogues) over a wide pH range (i.e., pH 4.5-10.0). Based on the adsorption results and quantitative structure-activity relationship (QSAR) models, the enhanced reactivity of FeIII-TAML/DODMA is mainly ascribed to the hydrophobic sorption of bisphenols. Moreover, the enhanced ionization of the axial water molecule associated with FeIII-TAML could further enhance the reactivity of synthesized microcomposites, which was confirmed by the results of infrared and Raman spectra. Furthermore, FeIII-TAML/DODMA shows distinct acid-resistance as explained by the protection of the hydrophobic alkyl chains of DODMA. This novel method would provide a simple and effective strategy to expand the application of FeIII-TAML in a wide pH range and render FeIII-TAML/DODMA microstructure as a potential catalyst for treatment of bisphenol compounds.