High throughput disassembly of cellulose nanoribbons and colloidal stabilization of gel-like Pickering emulsions.

We introduce a strategy to disintegrate cellulose microfibrils present in the cell walls of plant fibers. The process includes impregnation and mild oxidation followed by ultrasonication, which loosens the hydrophilic planes of crystalline cellulose while preserving the hydrophobic ones. The resultant molecularly-sized cellulose structures (cellulose ribbons, CR) retain a length of the order of a micron (1.47 ± 0.48 µm, AFM). A very high axial aspect ratio is determined (at least 190), considering the CR height (0.62 ± 0.38 nm, AFM), corresponding to 1-2 cellulose chains, and width (7.64 ± 1.82 nm, TEM). The new molecularly-thin cellulose proposes excellent hydrophilicity and flexibility, enabling a remarkable viscosifying effect when dispersed in aqueous media (shear-thinning, zero shear viscosity of 6.3 × 105 mPa·s). As such, CR suspensions readily develop into gel-like Pickering emulsions in the absence of crosslinking, suitable for direct ink writing at ultra-low solids content.

Enhanced electrochemiluminescent brightness and stability of porphyrins by supramolecular pinning and pinching for sensitive zinc detection.

Ultrasensitive electrochemiluminescence (ECL) detection can benefit substantially from the rational configuration of emitter-enhancer stereochemistry. Here, using zinc(II) meso-5,10,15,20-tetra(4-sulfonatophenyl)porphyrin (ZnTSPP) as a model, we demonstrate that both the ECL intensity and the photostability of this emitter were significantly improved when it was trapped in pyridyl-bridged ß-cyclodextrin dimer (Py(CD)2); a synthetic enhancer that is ECL inactive. Through NMR characterization, we confirmed that ZnTSPP formed a clam-like inclusion complex involving pinning and pinching forces from the biocompatible container Py(CD)2. Up to a threefold increase in the ECL brightness of ZnTSPP was witnessed when it was encapsulated in ß-CD. Absorption and emission spectroscopic data revealed that both the extended excitation lifetime and the restricted mobility of the guest contributed to the observed improvement in signal transduction within the host molecule. This bioinspired entrapment also led to a marked boost in ECL stability. With the aid of the newly identified coreactant H2O2, the hollow TSPP@Py(CD)2 system was employed to create a Zn2+-selective probe that was capable of sensitive and accurate zinc detection. The observed increase in ECL conversion and enhanced photophysical properties of this compact supramolecular assembly render it a novel template for enhancing ECL in analytical applications. Graphical abstract ᅟ.

In situ formed copper nanoparticles templated by TdT-mediated DNA for enhanced SPR sensor-based DNA assay.

For the efficient surface plasmon resonance (SPR)-based DNA assay researching, signal amplification tactics were absolutely necessary. In this work, a sensitive SPR-DNA sensor was developed by employing in situ synthesis of copper nanoparticles (CuNPs) templated by poly-T sequences DNA from terminal deoxynucleotidyl transferase (TdT)-mediated extension, and synergistically with nano-effect deposition as the mass relay. The objective of this strategy was manifold: firstly, tDNA hybridized with the optimal designed probes to active the TdT-mediated DNA extension onto the surface of SPR chip, resulted a long poly-T sequences ssDNA chain in dsDNA terminal onto surface of gold chip and characterized by SPR signal amplitudes. Secondly, copper ion (Cu2+) adsorbed into the skeleton of poly-T sequences DNA, with the aid of ascorbic acid (VC) to achieve the Cu2+ reduction, copper nanostructures (CuNPs) was synchronously generated onto the single nucleotide chain anchoring in dsDNA derivatives and the formation was featured by transmission electron micrographs (TEM) and electrochemistry. Lastly, dsDNA-complexed CuNPs (CuNPs@dsDNA) triggered the final signal amplification via real-time conversion of the additive catechol violet (CV) into oligomer or chelation precipitation by CuNPs-tagged reporters. With the proposed setups, a precise and replicable DNA sensing platform for specific target oligo was obtained with a detection limit down to 3.21 femtomolar, demonstrating a beneficial overlapping exploitation of nanomaterials and biochemical reaction as unique SPR infrastructure. Such triple-amplification strategic setups, the possibility of various methods abutment and biocompatibility weight reactor was amassed and adapted to more biological detection field.

Electro-Photodynamic Visualization of Singlet Oxygen Induced by Zinc Porphyrin Modified Microchip in Aqueous Media.

A porphyrin-based electro-photodynamic imaging system was fabricated for monitoring the concentration of oxygen. Distinct from the electrochemiluminescent (ECL) inability of numerous organic species in aqueous solutions, a strong and stable red irradiation at 634 nm could be stimulated electrochemically on zinc(II) meso-tetra(4-carboxyphenyl) porphine (ZnTCPP)/tetraoctylammonium bromide (TOAB) in the physiological condition. In terms of in situ electron paramagnetic resonance and ECL spectroscopies, the nature of ECL was thoroughly investigated, being exactly the chemiluminescence from singlet oxygen (1O2) produced during the successive electro-reduction of ZnTCPP. Meanwhile, the excellent film-making capacity of amphiphilic TOAB as a potent ion barrier granted the luminophores a micro-order and patternable electrode modification. Such platform was exceptionally tolerant of pH variation, facilitating a durable solid-state ECL visualization under potentiostatic electrolysis and time exposure in the charge-coupled device (CCD) camera. For flow-injection and real-time detection, a chip-mounted microfluidic cell was customized and manufactured. A sensitive and simple vision-sensing of O2 was further achieved with a real determination limit as low as a few micromolar level. The developed ECL imaging system is a good prototype and an eco-friendly technique in the cathodic range, and thus, it would supplement the primary anodic imaging library, showing great promise for multiplexed and colorimetric assays as well as oxygen-involved activity studies in the future.

Contribution of Aggregate States and Energetic Disorder to a Squaraine System Targeted for Organic Photovoltaic Devices.

Squaraine dyes have significant potential for use in organic photovoltaic devices because their chemical and packing structure tunability leads to a broad solid state panchromaticity. Nevertheless, broadening of the spectrum does not always give rise to increasing power conversion efficiencies. Furthermore, the same processing strategy used to make devices from different squaraines does not lead to the same optimized performance. In this work, by varying the environmental conditions of a set of anilinic squaraines, we demonstrate that spin-cast thin films are made up of a complex set of states, with each state contributing differently to the overall device efficiency. We demonstrate crystallochromy in that small changes in the packing structure give rise to dramatically different absorption spectra. Through a remarkable comparison between squaraines in poly(methyl methacrylate) solid solution and squaraine:PC60BM blends, we also show long-range and orientational disorder broadening, which distorts the ability to correlate qualitative spectroscopic assessment with an understanding of the device mechanism. We conclude that a full quantitative assessment of the populations of each excited state must be carried out in order to make progress toward an improved understanding of each state's contribution to charge transfer at the bulk heterojunction interface.