It is highly desirable, while still challenging, to obtain noble metal nanocrystals with custom capping ligands, because their colloidal synthesis relies on specific capping ligands for the shape control while conventional ligand exchange processes suffer from “the strong replaces the weak” limitation, which greatly hinders their applications. Herein, we report a general and effective ligand exchange approach that can replace the native capping ligands of noble metal nanocrystals with virtually any type of ligands, producing flexibly tailored surface properties. The key is to use diethylamine with conveniently switchable binding affinity to the metal surface as an intermediate ligand. As a strong ligand, it in its original form can effectively remove the native ligands; while protonated, it loses its binding affinity and facilitates the adsorption of new ligands, especially weak ones, onto the metal surface. By this means, the irreversible order in the conventional ligand exchange processes could be overcome. The efficacy of the strategy is demonstrated by mutual exchange of the capping ligands among cetyltrimethylammonium, citrate, polyvinylpyrrolidone, and oleylamine. This novel strategy significantly expands our ability to manipulate the surface property of noble metal nanocrystals and extends their applicability to a wide range of fields, particularly biomedical applications.

The contact angle, as a vital measured parameter of wettability of material surface, has long been in dispute whether it is affected by gravity. Herein, we measured the advancing and receding contact angles on extremely low contact angle hysteresis surfaces under different gravities (1-8G) and found that both of them decrease with the increase of the gravity. The underlying mechanism is revealed to be the contact angle hysteresis and the deformation of the liquid-vapor interface away from the solid surface caused by gradient distribution of the hydrostatic pressure. The real contact angle is not affected by gravity and cannot measured by an optical method. The measured apparent contact angles are angles of inclination of the liquid-vapor interface away from the solid surface. Furthermore, a new equation is proposed based on the balance of forces acting on the three-phase contact region, which quantitatively reveals the relation of the apparent contact angle with the interfacial tensions and gravity. This finding can provide new horizons for solving the debate on whether gravity affects the contact angle and may be useful for the accurate measurement of the contact angle and the development of a new contact angle measurement system.

The effects of V and Ce concentrations (each varying in the 0–100% range) in vanadia–ceria multiphase systems are investigated for synthesis gas production via thermochemical redox cycles of CO₂ and H₂O splitting coupled to methane partial oxidation reactions. The oxidation of prepared oxygen carriers is performed by separate and sequential CO₂ and H₂O splitting reactions. Structural and chemical analyses of the mixed-metal oxides revealed important information about the Ce and V interactions affecting their crystal phases and redox characteristics. Pure CeO₂ and pure V₂O₅ are found to offer the lowest and highest oxygen exchange capacities and syngas production performance, respectively. The mixed-oxide systems provide a balanced performance: their oxygen exchange capacity is up to 5 times higher than that of pure CeO₂ while decreasing the extent of methane cracking. The addition of 25% V to CeO₂ results in an optimum mixture of CeO₂ and CeVO₄ for enhanced CO₂ and H₂O splitting. At higher V concentrations, cyclic carbide formation and oxidation result in a syngas yield higher than that for pure CeO₂.

The direct catalytic oxidation of alcohols to esters is very appealing, but the economical-friendly catalysis systems are not yet well established. Herein, we show that a pure inorganic ligand-supported single-atomic cobalt compound, (NH₄)₃[CoMo₆O₁₈(OH)₆] (simplified as CoMo₆), could be used as a heterogeneous catalyst and effectively promote this type of reaction in the presence of 30% H₂O₂ using KCl as an additive. The oxidative cross-esterification of various alcohols (aromatic and aliphatic) could be achieved under mild conditions in nearly all cases, affording the corresponding esters in high yields, including several drug molecules and natural products. Detailed studies have revealed that chloride ion is able to bind to the CoMo₆ to form a supramolecular dimer 2(CoMo₆∙Cl), which can effectively catalyze the reaction via a synergistic effect from chloride ion and CoMo₆. Mechanism studies and control reactions demonstrate that the esterification proceeds via the key oxidative immediate of aldehydes.

The solubility range of interstitial Ni in the ZrNi{}_{1+x}Sn half-Heusler phase is a controversial issue, but it has an impact on the thermoelectric properties. In this study, two isothermal section phase diagrams of the Zr-Ni-Sn ternary system at 973 K and 1173 K were experimentally constructed based on the binary phase diagrams of Zr-Ni, Zr-Sn, and Ni-Sn. The thermodynamic equilibrium phases were obtained after a long time of heating treatment on the raw alloys prepared by levitation melting. Solubilities of at 973 K and at 1173 K were clearly indicated. An intermediate-Heusler phase with a partly filled Ni void was observed, which is believed to be beneficial to the lowered lattice thermal conductivity. The highest \text{ZT}\text{value}\text{~}0.71 at 973 K was obtained for ZrNi_1.11Sn_1.04. The phase boundary mapping provides an important instruction for the further optimization of ZrNiSn-based materials and other systems.

The general approach for fabricating solid-state materials showing circularly polarized luminescence (CPL) is still in its challenge. In this work, chiral metal-organic frameworks (MOFs) with full-color and white-color circularly polarized light emission are firstly achieved through a host-guest emitter-loading strategy. Chiral zeolitic imidazolate frameworks (ZIFs, a class of MOFs) are fabricated by a facile and simple mixed-ligand coassembly pathway. Meantime, achiral dyes, quantum dots (QDs), and upconversion nanoparticles (UCNPs) are easily loaded into the chiral ZIFs during the synthetic process. Size-matched dyes can be solely encapsulated into the chiral cages of ZIF, resulting in induced CPL and enhanced luminescence efficiency in solid-state \text{ZIF}\supset \text{dye} composites. Large-sized QDs, after embedding into the gap of the ZIF particles, also exhibited intense CPL activity. Furthermore, through modulating the blending ratio of colored dyes or QDs in chiral ZIFs, white light-emitting ZIFs with circular polarization could be constructed in a solid state. In addition, through loading rare earth element-based upconversion nanoparticles (UCNPs) into chiral ZIFs, upconverted CPL (UC-CPL) could be achieved with a high dissymmetry factor (g_{\text{lum}}). Thus, various achiral luminophores were endowed with CPL upon coupling with chiral ZIFs, which significantly deepened and enlarged the research scope of the chiroptical materials in a solid state.

Recent advances in the field of two-dimensional (2D) materials have led to new electronic and photonic devices enabled by their unique properties at atomic thickness. Structuring 2D materials into desired patterns on substrates is often an essential and foremost step for the optimum performance of the functional devices. In this regard, optical patterning of 2D materials has received enormous interest due to its advantages of high-throughput, site-specific, and on-demand fabrication. Recent years have witnessed scientific reports of a variety of optical techniques applicable to patterning 2D materials. In this minireview, we present the state-of-the-art optical patterning of 2D materials, including laser thinning, doping, phase transition, oxidation, and ablation. Several applications based on optically patterned 2D materials will be discussed as well. With further developments, optical patterning is expected to hold the key in pushing the frontiers of manufacturing and applications of 2D materials.

The tomato is the most important vegetable globally. In England, outdoor tomatoes are widely grown by amateur gardeners, with the number of their allotment plots exceeding 150000. For instance, in Germany, only about 16% of tomato plants are cultivated according to organic standards, although these rates are expected to increase. Breeding for yield and fruit quality can increase resource efficiency. Therefore, we need to evaluate the variability of yield and fruit quality parameters, to calculate the heritability of these traits and to identify superior genotypes for organic outdoor tomato production and breeding. With these aims, we grew 24 tomato genotypes of diverse origins in a two-year field trial. The heritability of quality traits such as glucose, fructose, organic acid, and lycopene was high. The medium heritability for yield suggests that trials with a larger number of locations are needed for the reliable selection of this character. Negative correlations of sugar concentrations with fruit weight and of organic acid concentration with fruit weight and yield suggest trade-offs in breeding for larger fruits and higher yields. Breeding for increased lycopene content is not subject to these challenges; the concentrations of the primary metabolite sugars and organic acids are positively correlated.

Maximizing band degeneracy and minimizing phonon relaxation time are proven to be successful for advancing thermoelectrics. Alloying with monotellurides has been known to be an effective approach for converging the valence bands of PbTe for electronic improvements, while the lattice thermal conductivity of the materials remains available room for being further reduced. It is recently revealed that the broadening of phonon dispersion measures the strength of phonon scattering, and lattice dislocations are particularly effective sources for such broadening through lattice strain fluctuations. In this work, a fine control of MnTe and EuTe alloying enables a significant increase in density of electron states near the valence band edge of PbTe due to involvement of multiple transporting bands, while the creation of dense in-grain dislocations leads to an effective broadening in phonon dispersion for reduced phonon lifetime due to the large strain fluctuations of dislocations as confirmed by synchrotron X-ray diffraction. The synergy of both electronic and thermal improvements successfully leads the average thermoelectric figure of merit to be higher than that ever reported for p-type PbTe at working temperatures.

Reducing the capacitive opening between subwavelength metallic objects down to atomic scales or bridging the gap by a conductive path reveals new plasmonic spectral features, known as charge transfer plasmon (CTP). We review the origin, properties, and trending applications of this modes and show how they can be well-understood by classical electrodynamics and quantum mechanics principles. Particularly important is the excitation mechanisms and practical approaches of such a unique resonance in tailoring high-response and efficient extreme-subwavelength hybrid nanophotonic devices. While the quantum tunneling-induced CTP mode possesses the ability to turn on and off the charge transition by varying the intensity of an external light source, the excited CTP in conductively bridged plasmonic systems suffers from the lack of tunability. To address this, the integration of bulk plasmonic nanostructures with optothermally and optoelectronically controllable components has been introduced as promising techniques for developing multifunctional and high-performance CTP-resonant tools. Ultimate tunable plasmonic devices such as metamodulators and metafilters are thus in prospect.