Generating New Cross‐Relaxation Pathways by Coating Prussian Blue on NaNdF4 To Fabricate Enhanced Photothermal Agents

Cross‐relaxation among sensitizers is commonly regarded as deleterious in fluorescent materials, although favorable in photothermal agents. Herein, we coated Prussian blue (PB) on NaNdF₄ nanoparticles to fabricate core–shell nanocomplexes with new cross relaxation pathways between the ladder‐like energy levels of Nd³⁺ ions and continuous energy band of PB. The photothermal conversion efficiency was improved exceptionally and the mechanism of the enhanced photothermal effect was investigated. In vivo photoacoustic imaging and photothermal therapy demonstrated the potential of the enhanced photothermal agents. Moreover, the concept of generating new cross‐relaxation pathways between different materials is proposed to contribute to the design of all kinds of enhanced photothermal agents.     

Super-efficiency measurement under variable return to scale: an approach based on a new directional distance function

A modified super-efficiency model based on the directional distance function (DDF) has recently been developed in order to tackle the infeasibility issue in the two exceptions of the Nerlove–Luenberger (N–L) super-efficiency model under variable return to scale (VRS). However, we find that model does not fully eliminate the infeasibility issue. This paper chooses an appropriate reference bundle in the DDF so that the resulting DDF-based VRS super-efficiency model is always feasible. The proposed new model successfully addresses the infeasibility issue of conventional VRS super-efficiency models and fully eliminates the infeasibility issue in the two exceptions of the VRS N–L super-efficiency model. Additional advantages of the new model include: it is unit-invariant and does not need to predetermine any parameter. Theoretical analyses and numerical examples support the practicality and superiority of our model when compared with other super-efficiency models.     

Optical vortices in the Ginzburg–Landau equation with cubic–quintic nonlinearity

In a dissipative system with cubic–quintic nonlinearity, the curious evolution of optical vortex beams characterized by different topological charges (TCs) is simulated numerically and presented their evolution profiles. We find that new vortices will be induced during propagation, and the behavior of vortices, as affected by the TC and the number of beads of the incident beam, as well as its size, is also discussed. Common rules associated with the initial conditions coming from various incident beams are developed to determine the number of induced vortices and the corresponding rotation direction. Attributed to the nonlinearity, during propagation we see the beams slowly expand to induce new vortices, which commonly appear in oppositely charged pairs, while the net topological charge of the vortex is conserved. Our results not only deepen the understanding of optical vortices, but also widen their potential applications.     

Spiropyran-azobenzene-DBU system as solvent indicator

A dyad bearing azobenzene and spiropyran units was synthesized and its applications in indicating the polarity and protic or aprotic properties of a solvent were explored. The spiropyran-azobenzene derivative (SPAB) can be induced to different forms in different miscellaneous solvents accompanied with different color changes and spectral characteristics at the presence of organic base DBU. In a nonpolar or low-polar solvent, SPAB exists in thermostable spiropyran form with yellow color output. While in an aprotic polar solvent, the spiropyran part isomerized to merocyanine form giving a blue color. When SPAB is subjected to a protic solvent, the alkylation reaction occurs at the oxygen generating the alkylated-SPAB with red color. This solvent-dependent property can be used for discriminating solvent type.     

Ambient Electrosynthesis of Ammonia: Electrode Porosity and Composition Engineering

Ammonia, a key precursor for fertilizer production, convenient hydrogen carrier, and emerging clean fuel, plays a pivotal role in sustaining life on Earth. Currently, the main route for NH₃ synthesis is by the heterogeneous catalytic Haber–Bosch process (N₂+3 H₂→2 NH₃), which proceeds under extreme conditions of temperature and pressure with a very large carbon footprint. Herein we report that a pristine nitrogen‐doped nanoporous graphitic carbon membrane (NCM) can electrochemically convert N₂ into NH₃ in an acidic aqueous solution under ambient conditions. The Faradaic efficiency and rate of production of NH₃ on the NCM electrode reach 5.2 % and 0.08 g m^?2 h^?1, respectively. Functionalization of the NCM with Au nanoparticles dramatically enhances these performance metrics to 22 % and 0.36 g m^?2 h^?1, respectively. As this system offers the potential to be scaled to industrial levels it is highly likely that it might displace the century‐old Haber–Bosch process.     

Cluster carbonyls of the [Re(6)(mu(3)-Se)(8)](2+) core: synthesis, structural characterization, and computational analysis

The reactions of the previously reported cluster complexes [Re(6)(mu(3)-Se)(8)(PEt(3))(5)I]I, trans-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)I(2)], and cis-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)I(2)] with the [Re(6)(mu(3)-Se)(8)](2+) core with CO in the presence of AgSbF(6) afforded the corresponding cluster carbonyls [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(CO)][SbF(6)](2) (), trans-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)(CO)(2)][SbF(6)](2) (), and cis-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)(CO)(2)][SbF(6)](2) (). Infrared spectroscopy indicated weakening of the bond in CO, suggesting the existence of backbonding between the cluster core and the CO ligand(s). Electrochemical studies focusing on the reversible, one-electron oxidation of the cluster core revealed a large increase in the oxidation potential upon going from the acetonitrile derivatives to their carbonyl analogs, consistent with the depleted electron density of the cluster core upon CO ligation. Disparities between the IR spectra and oxidation potential between and indicate that electronic differences exist between sites trans and cis to the location of a ligand of interest. The active role played by the Se atoms in influencing the cluster-to-CO bonding interactions is suggested through this result and density functional (DF) computational analysis. The computations indicate that molecular orbitals near the HOMO account for backbonding interactions with a high percentage of participation of Se orbitals.     

Chemo-, Stereo- and Regioselective Fluoroallylation/Annulation of Hydrazones with gem-Difluorocyclopropanes via Tunable Palladium/NHC Catalysis

Defluorinative manipulation of polyfluorinated molecules has shown great promise due to its granting of synthetic versatility to inert C−F bonds. The development of chemo-, stereo- and regioselective strategies to realize highly efficient formation of either the linear/branched or E/Z products from gem-difluorocyclopropanes (gem-F₂CPs) is a challenging task. Herein, we have realized palladium/NHC-catalyzed fluoroallylation/annulation of hydrazones with gem-F₂CPs that incorporate the hydrazone N₂ moiety into the products. The thermodynamically unstable fluorinated E-allylation products with aryl ketone hydrazones were obtained for the first time, while the di-alkyl ketone hydrazones yielded the monofluorinated products with branched selectivity under similar reaction conditions. With aldehyde hydrazones, two kinds of pyrazoles were obtained via a defluorinative allylation/annulation cascade, in which different carbon atoms of gem-F₂CPs could be incorporated into the pyrazole rings regiospecifically. DFT calculations revealed that the divergent selectivity was kinetically controlled and the final C−C bond formation proceeded through a 7-membered TS.     

Dual shell-like magnetic clusters containing Ni(II) and Ln(III) (Ln = La, Pr, and Nd) ions

Dual shell-like nanoscopic magnetic clusters featuring a polynuclear nickel(II) framework encapsulating that of lanthanide ions (Ln = La, Pr, and Nd) were synthesized using Ni(NO3)(2).6H2O, Ln(NO3)(3).6H2O, and iminodiacetic acid (IDA) under hydrothermal conditions. Structurally established by crystallographic studies, these clusters are [La20Ni30(IDA)30(CO3)6(NO3)6(OH)30(H2O)12](CO3)(6).72H2O (1), [Ln20Ni21(C4H5NO4)21(OH)24(C2H2O3)6(C2O4)3(NO3)9(H2O)12](NO3)9.nH2O [C2H2O3 is the alkoxide form of glycolate; Ln = Pr (2), n = 42; Nd (3), n = 50], and {[La4Ni5Na(IDA)5(CO3)(NO3)4(OH)5(H2O)5][CO3].10H2O} infinity (4). Carbonate, oxalate, and glycolate are products of hydrothermal decomposition of IDA. Compositions of these compounds were confirmed by satisfactory elemental analyses. It has been found that the cluster structure is dependent on the identity of the lanthanide ion as well as the starting Ln/Ni/IDA ratio. The cationic cluster of 1 features a core of the Keplerate type with an outer icosidodecahedron of Ni(II) ions encaging a dodecahedral kernel of La(III). Clusters 2 and 3, distinctly different from 1, are isostructural, possessing a core of an outer shell of 21 Ni(II) ions encapsulating an inner shell of 20 Ln(III) ions. Complex 4 is a three-dimensional assembly of cluster building blocks connected by units of Na(NO3)/La(NO3)3; the structure of the building block resembles closely that of 1, with a hydrated La(III) ion internalized in the decanuclear cage being an extra feature. Magnetic studies indicated ferromagnetic interactions in 1, while overall antiferromagnetic interactions were revealed for 2 and 3. The polymeric, three-dimensional cluster network 4 displayed interesting ferrimagnetic interactions.     

Self-Assembling Behavior of Polyglyceryl-Modified Silicone Surfactant in Aqueous Solution

We report interesting self-assembly behavior of a polyglyceryl-modified silicone surfactant in the aqueous solution; the sample has been characterized through measurements of surface tension, transmission electron microscopy (TEM), dynamic light scattering (DLS), and small-angle x-ray scattering (SAXS). Aqueous solutions of this surfactant had a low critical aggregation concentration (CAC) and surface tension (21.5 mN · m^?1), substantially lower than those reported for polyether-modified silicone surfactants with a similar molecular architecture. DLS and TEM revealed self-assembled spherical micelles with a narrow size distribution. At higher concentrations (10 wt%), linear packing of micelles was observed, while the micelle size distribution remained similar (50–90 nm). SAXS data could be fitted through the use of a core–shell model and implied that the core radius remained roughly 4.3–6.0 nm for all solutions of the surfactant analyzed. The origin of its curious aggregates behavior is attributed to hydrogen bonding, steric effects, and the directionality of bond angle from the polyglyceryl block of this novel class of silicone surfactant. This type of surfactant coupling lipophilic segments assembles the cores of the micelles in water which may find positive factors for potential applications such as microreaction compartmentalization.