Optical Activity in the Near‐IR Region: The λ=980 nm Multiplet of Chiral Yb3+ Complexes

We used a very simplified electrostatic model based on charge and polarizability of atoms and groups on an organic ligand around a lanthanide ion to predict the near‐infrared electronic circular dichroism (NIR ECD) spectra of Yb³⁺ (a monoelectronic ion). We tuned our method by using two widely different complexes. The first was the heterobimetallic species CsYb(hfbc)₄ [hfbc=(?)‐3‐heptafluorobutyrylcamphorate], in which the ligand is a diketonate and, as such, is endowed with a chromophore with strong UV absorption (π–π^*). Its oxygen atoms define a square antiprism, which provides a symmetric coordination polyhedron. The second system was Yb DOTMA [DOTMA=(1R,4R,7R,10R)‐α,α′,α′′,α′′′‐tetramethyl‐1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid], a chiral Yb analogue of Gd DOTA (DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid), in which the ligand lacks relevant electronic transitions and provides a dissymmetric cage. The relative weights of dynamic (ligand polarization) and static contributions to Yb NIR ECD were evaluated, and the spectra appear to have been well predicted by theory through the introduction of a heuristic weight factor. To validate the approach and to confirm the value of the weight factor, we applied it to two other compounds, namely, Na₃Yb(BINOLate)₃ and Yb(BINOLAM)₃ [BINOLate=2,2′‐dihydroxy‐1,1′‐binaphthyl; BINOLAM=3,3′‐bis(diethylaminomethyl)‐1‐1′‐bi‐2‐naphthol].     

Photochromic Metal–Organic Frameworks: Reversible Control of Singlet Oxygen Generation

The controlled generation of singlet oxygen is of great interest owing to its potential applications including industrial wastewater treatment, photochemistry, and photodynamic therapy. Two photochromic metal–organic frameworks, PC‐PCN and SO‐PCN, have been developed. A photochromic reaction has been successfully realized in PC‐PCN while maintaining its single crystallinity. In particular, as a solid‐state material which inherently integrates the photochromic switch and photosensitizer, SO‐PCN has demonstrated reversible control of ¹O₂ generation. Additionally, SO‐PCN shows catalytic activity towards photooxidation of 1,5‐dihydroxynaphthalene.     

Separation and concentration of sulfonylurea herbicides in milk by ionic‐liquid‐based foam flotation solid‐phase extraction

The ultrasound‐assisted ionic liquid foam flotation solid‐phase extraction of sulfonylurea herbicides in milk was developed and validated. The proteins and lipids were isolated from the sample matrix by adding salt and adjusting the pH value. The target analytes eluted from the solid‐phase extraction cartridge were determined by high‐performance liquid chromatography. Some experimental parameters, including the pH value of sample solution, amount of NaCl, ionic liquid type, extraction time, flow rate of carrier gas, flotation time, and solid‐phase extraction cartridge type were investigated and optimized. Under the optimized experimental conditions, the limits of detection for metsulfuron, pyrazosulfuron, chlorimuron‐ethyl, and nicosulfuron were 1.3, 0.6, 0.7, and 1.1 μg/L, respectively. When the present method was applied to the analysis of milk samples the recoveries of the analytes ranged from 84.3 to 105.2% and relative standard deviations were >5.7%.     

Integration of an anti-tumor drug into nanocrystalline assemblies for sustained drug release

Delicate mesoscopic architectures, bearing complex forms with multiple hierarchy levels, lead to significant functions in biogenic minerals. Herein, a bio-inspired approach was developed to fabricate comet-shaped assemblies of an anti-tumor drug – 10-hydroxycamptothecin (HCPT). The anti-solvent co-precipitation of HCPT and the excipient – PEG-b-PLGA – within the emulsifier leads to the immediate nucleation of comet bundles, followed by a secondary nucleation to generate the comet head, which is an assembly of nanofibers aligned almost in parallel. The continuous manufacturing furnishes drug–excipient hybrid particles with high drug-loading and a sustained drug release profile. This simple and efficient bio-inspired approach led to a promising sustained local drug delivery system, and could be extended to the fabrication of other functional organic materials bearing mesoscopic structural units.     

Capping nanoparticles with graphene quantum dots for enhanced thermoelectric performance

Graphene quantum dots (GQDs) are shown to serve as phase transfer agents to transfer various types of nanoparticles (NPs) from non-polar to polar solvents. Thorough characterization of the NPs proves complete native ligand exchange. Pellets of this GQD–NP composite show that the GQDs limit the crystal size during spark plasma sintering, yielding enhanced thermoelectric performance compared with NPs exchanged with inorganic ions. A photoluminescence study of the GQD–NP composite also suggests energy transfer from GQDs to NPs.     

Enhanced nonlinear effects in pulse propagation through epsilon‐near‐zero media

In recent years, unconventional metamaterial properties have triggered a revolution of electromagnetic research which has unveiled novel scenarios of wave‐matter interaction. A very small dielectric permittivity is a leading example of such unusual features, since it produces an exotic static‐like regime where the electromagnetic field is spatially slowly‐varying over a physically large region. The so‐called epsilon‐near‐zero metamaterials thus offer an ideal platform where to manipulate the inner details of the “stretched” field. Here we theoretically prove that a standard nonlinearity is able to operate such a manipulation to the point that even a thin slab produces a dramatic nonlinear pulse transformation, if the dielectric permittivity is very small within the field bandwidth. The predicted non‐resonant releasing of full nonlinear coupling produced by the epsilon‐near‐zero condition does not resort to any field enhancement mechanism and opens novel routes to exploiting matter nonlinearity for steering the radiation by means of ultra‐compact structures.

     

Loss of PEG chain in routine SDS‐PAGE analysis of PEG‐maleimide modified protein

SDS‐PAGE represents a quick and simple method for qualitative and quantitative analysis of protein and protein‐containing conjugates, mostly pegylated proteins. PEG‐maleimide (MAL) is frequently used to site‐specifically pegylate therapeutic proteins via free cysteine residue by forming a thiosuccinimide structure for pursuing homogeneous products. The C–S linkage between protein and PEG‐MAL is generally thought to be relatively stable. However, loss of intact PEG chain in routine SDS‐PAGE analysis of PEG‐maleimide modified protein was observed. It is a thiol‐independent thioether cleavage and the shedding of PEG chain exclusively happens to PEG‐MAL modified conjugates although PEG‐vinylsulfone conjugates to thiol‐containing proteins also through a C–S linkage. Cleavage kinetics of PEG40k‐MAL modified ciliary neurotrophic factor showed this kind of degradation could immediately happen even in 1 min incubation at high temperature and could be detected at physiological temperature and pH, although the rate was relatively slow. This may provide another degradation route for maleimide‐thiol conjugate irrespective of reactive thiol, although the specific mechanism is still not very clear for us. It would also offer a basis for accurate characterization of PEG‐MAL modified protein/peptide by SDS‐PAGE analysis.