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A TEMPO-promoted method was developed for the synthesis of symmetric bis- N -Mannich bases via sequential activation of two α,α'-amino C(sp 3 )-H bonds of N , N -dimethylanilines under mild conditions. This methodology was further extended for monoimidation of α-amino-functionalized methylanilines to give unsymmetric N -Mannich bases in good to high yields. Several control experiments were performed, and the coupling reaction outcomes indicated that the oxoammonium (TEMPO + ) species is involved in the reaction.

Superhydrophobic surfaces are imperative in flexible polymer foams for diverse applications; however, traditional surface coatings on soft skeletons are often fragile and can hardly endure severe deformation, making them unstable and highly susceptible to cyclic loadings. Therefore, it remains a great challenge to balance their mutual exclusiveness of mechanical robustness and surface water repellency on flexible substrates. Herein, we describe how robust superhydrophobic surfaces on soft poly(dimethylsiloxane) (PDMS) foams can be achieved using an extremely simple, ultrafast, and environmentally friendly flame scanning strategy. The ultrafast flame treatment (1-3 s) of PDMS foams produces microwavy and nanosilica rough structures bonded on the soft skeletons, forming robust superhydrophobic surfaces (i.e., water contact angles (WCAs) > 155° and water sliding angles (WSAs) < 5°). The rough surface can be effectively tailored by simply altering the flame scanning speed (2.5-15.0 cm/s) to adjust the thermal pyrolysis of the PDMS molecules. The optimized surfaces display reliable mechanical robustness and excellent water repellency even after 100 cycles of compression of 60% strain, stretching of 100% strain, and bending of 90° and hostile environmental conditions (including acid/salt/alkali conditions, high/low temperatures, UV aging, and harsh cyclic abrasion). Moreover, such flame-induced superhydrophobic surfaces are easily peeled off from ice and can be healable even after severe abrasion cycles. Clearly, the flame scanning strategy provides a facile and versatile approach for fabricating mechanically robust and surface superhydrophobic PDMS foam materials for applications in complex conditions.

Various mycotoxins widely co-exist in agro-products, and their combined effects cause toxicity and potential carcinogenicity to humans and animals. In this work, we developed an economical and sensitive quantum dots (QDs)/QD microbead (QDs/QB)-based multiplex immunochromatographic assay (mICA) for the rapid detection of fumonisin B 1 (FB 1 ), zearalenone (ZEN), and ochratoxin A (OTA) without the building-up process of mycotoxin conjugates. QDs and QBs were selected as fluorescent reporters and conjugated with antimycotoxin monoclonal antibodies for improving sensitivity. Furthermore, phage-displayed FB 1 , ZEN, and OTA mimotope peptide-based soluble and monovalent fusions to maltose-binding protein (MBP) were applied onto the test line of the mICA as the mimetic coating antigen. Under the optimized conditions, the visual detection limits (vLODs) of peptide-MBP-based mICA could be obtained as 0.25 ng/mL for FB 1 , 3.0 ng/mL for ZEN, and 0.5 ng/mL for OTA within 10 min. The results for spiked real sample detection indicate good accuracy, reproducibility, and practicability. In addition, the proposed mICA was comparable with ultraperformance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) in terms of reliability in detecting FB 1 , ZEN, and OTA using natural samples. From the point of promoting commercial production, these time-saving and low-cost peptide-MBP antigens applied in ICA might provide promising potential for promoting productivity and decreasing the cost of production.

Enriching the functionality of ferroelectric materials with visible-light sensitivity and multiaxial switching capability would open up new opportunities for their applications in advanced information storage with diverse signal manipulation functions. We report experimental observations of robust intralayer ferroelectricity in two-dimensional (2D) van der Waals layered α-In 2 Se 3 ultrathin flakes at room temperature. Distinct from other 2D and conventional ferroelectrics, In 2 Se 3 exhibits intrinsically intercorrelated out-of-plane and in-plane polarization, where the reversal of the out-of-plane polarization by a vertical electric field also induces the rotation of the in-plane polarization. On the basis of the in-plane switchable diode effect and the narrow bandgap (∼1.3 eV) of ferroelectric In 2 Se 3 , a prototypical nonvolatile memory device, which can be manipulated both by electric field and visible light illumination, is demonstrated for advancing data storage technologies.

Different from so far reported oxacalix[4]crown-based host-guest motifs in which oxacalix[4]crowns act only as hydrogen bond acceptors, a [2]pseudorotaxane-type tetranitro-oxacalix[4]crown/urea host-guest recognition motif was developed in which tetranitro-oxacalix[4]crown played a role as both a hydrogen bond donor and an acceptor to stabilize the resulting supramolecular complex. Furthermore, on the basis of a [2]pseudorotaxane complex formed from a tetranitro-oxacalix[4]crown and an axle containing a secondary ammonium ion and a urea group, a [2]rotaxane-based molecular switch was created, in which the oxacalix[4]crown wheel was able to reversibly translocate between the secondary ammonium binding site and the urea binding site of the axle under acid-base stimulation.

A shape-persistent cryptand 1, containing two face-to-face oriented electron-deficient 2,4,6-triphenyl-1,3,5-triazine units separated by approximately 7 Å, and bridged by two rigid 1,8-naphthyridine linkers and a pentaethylene oxide loop, is created for capturing polycyclic aromatic hydrocarbons. Cryptand 1 formed 1:1 complexes with PAH guest molecules, such as phenanthrene (6), anthracene (7), pyrene (8), triphenylene (9), and tetraphene (10). The single-crystal structure of complex 6⊂1 revealed that 6 was included in the cavity of 1 via face-to-face π···π stacking interactions. Soaking crystalline 1 in a toluene solution of anthracene resulted in anthracene from the toluene solution being picked up by the crystalline solid of 1.

An acid-base-responsive supramolecular host-guest system based on a planarly chiral A1/A2-diamino-substituted pillar[5]arene (1)/imidazolium ion recognition motif was created. The pillar[4]arene[1]diaminobenzene 1 can bring an electron-deficient imidazolium cation into its cylindrically shaped cavity under neutral or basic conditions and release it under acidic conditions.

Acid rain (AR) impacts forest health by leaching calcium (Ca) away from soils and plants. Ca is an essential element and participates in various plant physiological responses. In the present study, the protective role of exogenous Ca in alleviating AR stress in Liquidambar formosana Hance at the physiological and proteomic levels was examined. Our results showed that low Ca condition resulted in the chlorophyll content and photosynthesis decreasing significantly in L. formosana leaves; however, these effects could be reversed by high Ca supplementation. Further proteomic analyses successfully identified 81 differentially expressed proteins in AR-treated L. formosana under different Ca levels. In particular, some of the proteins are involved in primary metabolism, photosynthesis, energy production, antioxidant defense, transcription, and translation. Moreover, quantitative real time polymerase chain reaction (qRT-PCR) results indicated that low Ca significantly increased the expression level of the investigated Ca-related genes, which can be reversed by high Ca supplementation under AR stress. Further, Western blotting analysis revealed that exogenous Ca supply reduced AR damage by elevating the expression of proteins involved in the Calvin cycle, reactive oxygen species (ROS) scavenging system. These findings allowed us to better understand how woody plants respond to AR stress at various Ca levels and the protective role of exogenous Ca against AR stress in forest tree species.

A novel tricylic host molecule 1 that consists of two pillar[5]arene units and a crown ether ring was found to selectively bind two kinds of guest molecules with different shapes, sizes, and electronic constitutions, namely 1,4-dicyanobutane G1 and paraquat G2, with its two macrocyclic subunits, to form a four-component complex 2G1⊂1⊃G2. An (1)H NMR study of stepwise bindings of G1 and G2 to host 1 in CDCl3/DMSO-d6 revealed that the strength of the association between complex 2G1⊂1 and guest G2 was only one-fourth of that between free 1 and G2, demonstrating a negative heterotropic cooperativity of G1 in the binding of G2 to host 1.

A pillar[5]arene-crown ether fused bicyclic host 1 was found to be able to recognize an imidazolium ion G1 by its pillar[5]arene subunit and a viologen ion G2 by its crown ether receptor discriminatively. The simultaneous binding of G1 and G2 by 1 resulted in the formation of a three-component host-guest complex G1⊂1⊃G2. Negative heterotropic cooperative effects were displayed by G1 and G2 in their binding to 1 and were investigated by stepwise bindings of G1 and G2 to 1.

A novel trispyrazine-pillared prismatic bicycooxacalixaromatic ligand L is synthesized, and its application in metal-mediated self-assembly is described. Under self-assembly conditions, single chain, double-stranded cross-linked coordination polymer and two-dimensional (2D) coordination polymeric networks were formed via M-L (Ag(+), Cu(2+), and Zn(2+)) coordinative interactions. Structural analyses revealed that the antiparallelly arranged one-dimensional coordination polymers (Cu(2+) and Zn(2+)) are arranged to generate well-defined voids to host aromatic guests (benzene) via C-H···π and π···π interactions, while the double-stranded cross-linked coordination polymer (Ag(+)) contains a rhomboidal [Ag2(L(3))2] (L(3): tridentate ligand) cage motif to include a benzene guest; the "thicker" (thickness: ac 5 Å) 2D coordination polymeric networks (Ag(+), Cu(2+), and Zn(2+)), however, are all formed by connection of one or two kinds of topologically different metallomacrocyclic cage units. These unique metallomacrocyclic cage units in the 2D coordination polymeric networks are capable of hosting different guest species. For instance, the rhomboidal [M2(L(3))2] (M = Ag(+), Cu(2+)) cage units were found to host a benzene or a nitrate anion; a hexahedral [M3(L(3))3] (M = Ag(+)) cage was found to host a ligand L or a DMF molecule; the hexahedral [M4(L(3))4] (M = Cu(2+)) cage was found to host four solvent molecules of benzene; and the rectangular [M3(L(3))3] (M = Cu(2+), Zn(2+)) cage units, however, were found to host two THF molecules. The results highlight the potential of ligand L for applications in the construction of "thicker" 2D coordination polymeric networks with well-defined metallomacrocyclic cage units capable of hosting various guest species.

Several long-wavelength (365 nm) photoactivatable diaryltetrazoles were discovered by screening a series of substituted diaryltetrazoles and subsequently showed excellent reactivity in the photoactivated 1,3-dipolar cycloaddition reactions toward electron-deficient and conjugated alkenes in organic solvents as well as an alkene-containing protein in the aqueous buffer.