SERS-Based Hydrogen Bonding Induction Strategy for Gaseous Acetic Acid Capture and Detection.

Surface-enhanced Raman scattering (SERS) can overcome the existing technological limitations, such as complex processes and harsh conditions in gaseous small-molecule detection, and advance the development of real-time gas sensing at room temperature. In this study, a SERS-based hydrogen bonding induction strategy for capturing and sensing gaseous acetic acid is proposed for the detection demands of gaseous acetic acid. This addresses the challenges of low adsorption of gaseous small molecules on SERS substrates and small Raman scattering cross sections and enables the first SERS-based detection of gaseous acetic acid by a portable Raman spectrometer. To provide abundant hydrogen bond donors and acceptors, 4-mercaptobenzoic acid (4-MBA) was used as a ligand molecule modified on the SERS substrate. Furthermore, a sensing chip with a low relative standard deviation (RSD) of 4.15% was constructed, ensuring highly sensitive and reliable detection. The hydrogen bond-induced acetic acid trapping was confirmed by experimental spectroscopy and density functional theory (DFT). In addition, to achieve superior accuracy compared to conventional methods, an innovative analytical method based on direct response hydrogen bond formation (IO-H/Iref) was proposed, enabling the detection of gaseous acetic acid at concentrations as low as 60 ppb. The strategy demonstrated a superior anti-interference capability in simulated breath and wine detection systems. Moreover, the high reusability of the chip highlights the significant potential for real-time sensing of gaseous acetic acid.

Manipulation of Conducting Polymer Hydrogels with Different Shapes and Related Multifunctionality.

Maneuver of conducting polymers (CPs) into lightweight hydrogels can improve their functional performances in energy devices, chemical sensing, pollutant removal, drug delivery, etc. Current approaches for the manipulation of CP hydrogels are limited, and they are mostly accompanied by harsh conditions, tedious processing, compositing with other constituents, or using unusual chemicals. Herein, a two-step route is introduced for the controllable fabrication of CP hydrogels in ambient conditions, where gelation of the shape-anisotropic nano-oxidants followed by in-situ oxidative polymerization leads to the formation of polyaniline (PANI) and polypyrrole hydrogels. The method is readily coupled with different approaches for materials processing of PANI hydrogels into varied shapes, including spherical beads, continuous wires, patterned films, and free-standing objects. In comparison with their bulky counterparts, lightweight PANI items exhibit improved properties when those with specific shapes are used as electrodes for supercapacitors, gas sensors, or dye adsorbents. The current study therefore provides a general and controllable approach for the implementation of CP into hydrogels of varied external shapes, which can pave the way for the integration of lightweight CP structures with emerging functional devices.

Site-selective sulfur anchoring produces sintering-resistant intermetallic ORR electrocatalysts for membrane electrode assemblies.

Intermetallic compounds are emerging as promising oxygen reduction reaction (ORR) catalysts for fuel cells due to their typically higher activity and durability compared to disordered alloys. However, the preparation of intermetallic catalysts often requires high-temperature annealing, which unfortunately leads to adverse sintering of the metal nanoparticles. Herein, we develop a scalable site-selective sulfur anchoring strategy that effectively suppresses alloy sintering, ensuring the formation of efficient intermetallic electrocatalysts with small sizes and high ordering degrees. The alloy-support interactions are precisely modulated by selectively modifying the alloy-support interfaces with oxidized sulfur species, thus simultaneously blocking both the nanoparticle migration and Oswald ripening pathways for sintering. Using this strategy, sub-5 nm PtCo intermetallic electrocatalysts enclosed by two atomic layers of Pt shells have been successfully prepared even at a metal loading higher than 30 wt%. The intermetallic catalysts exhibit excellent ORR performances in both rotating disk electrode and membrane electrode assembly conditions with a mass activity of 1.28 A mgPt-1 at 0.9 V (vs. RHE) and a power density of 1.0 W cm-2 at a current density of 1.5 A cm-2. The improved performances result from the enhanced Pt-Co electronic interactions and compressive surface strain generated by the highly ordering structure, while the atomic Pt shells prevent the dissolution of Co under highly acidic conditions. This work provides new insights to inhibit the sintering of nanoalloys and would promote the scalable synthesis and applications of platinum-based intermetallic catalysts.

Manipulating the light-matter interactions in plasmonic nanocavities at 1 nm spatial resolution.

The light-matter interaction between plasmonic nanocavity and exciton at the sub-diffraction limit is a central research field in nanophotonics. Here, we demonstrated the vertical distribution of the light-matter interactions at ~1 nm spatial resolution by coupling A excitons of MoS2 and gap-mode plasmonic nanocavities. Moreover, we observed the significant photoluminescence (PL) enhancement factor reaching up to 2800 times, which is attributed to the Purcell effect and large local density of states in gap-mode plasmonic nanocavities. Meanwhile, the theoretical calculations are well reproduced and support the experimental results.

In situ SERS study of surface plasmon resonance enhanced photocatalytic reactions using bifunctional Au@CdS core-shell nanocomposites.

Surface plasmon resonance (SPR) has been utilized in many fields, such as surface-enhanced Raman spectroscopy (SERS) and solar energy conversion. Here we developed an Au@CdS core-shell nanostructure, a bifunctional nanoparticle, used as an efficient catalyst for SPR enhanced photocatalytic degradation, and as a substrate for in situ SERS detection of methylene blue (MB) and p-nitrophenol (pNTP). With integration of an Au nanoparticle into a CdS shell, the degradation process was significantly accelerated under 500 nm long-pass (λ > 500 nm) visible light irradiation, which was caused by the injection of hot electrons. Moreover, a highly uniform, monolayer film of Au@CdS nanoparticles (NPs) has been prepared and used as both a SERS substrate and catalyst. The decomposition of MB molecules and nitrogen coupling reaction of pNTP were observed during the 638 nm laser illumination. We demonstrate that a plasmonic core-semiconductor shell nanocomposite can be a promising material for photocatalysis and in situ SERS study.

Correction: Shell-isolated nanoparticle-enhanced Raman spectroscopy study of the adsorption behaviour of DNA bases on Au(111) electrode surfaces.

Correction for 'Shell-isolated nanoparticle-enhanced Raman spectroscopy study of the adsorption behaviour of DNA bases on Au(111) electrode surfaces' by Bao-Ying Wen et al., Analyst, 2016, DOI: 10.1039/c6an00180g.

Shell-isolated nanoparticle-enhanced Raman spectroscopy study of the adsorption behaviour of DNA bases on Au(111) electrode surfaces.

For the first time, we used the electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) technique to in situ characterize the adsorption behaviour of four DNA bases (adenine, guanine, thymine, and cytosine) on atomically flat Au(111) electrode surfaces. The spectroscopic results of the various molecules reveal similar features, such as the adsorption-induced reconstruction of the Au(111) surface and the drastic Raman intensity reduction of the ring breathing modes after the lifting reconstruction. As a preliminary study of the photo-induced charge transfer (PICT) mechanism, the in situ spectroscopic results obtained on single crystal surfaces are excellently illustrated with electrochemical data.

"Smart" theranostic lanthanide nanoprobes with simultaneous up-conversion fluorescence and tunable T1-T2 magnetic resonance imaging contrast and near-infrared activated photodynamic therapy.

The current work reports a type of "smart" lanthanide-based theranostic nanoprobe, NaDyF4:Yb(3+)/NaGdF4:Yb(3+),Er(3+), which is able to circumvent the up-converting poisoning effect of Dy(3+) ions to give efficient near infrared (980 nm) triggered up-conversion fluorescence, and offers not only excellent dark T2-weighted MR contrast but also tunable bright and T1-weighted MR contrast properties. Due to the efficient up-converted energy transfer from the nanocrystals to chlorin e6 (Ce6) photosensitizers loaded onto the nanocrystals, cytotoxic singlet oxygen was generated and photodynamic therapy was demonstrated. Therefore, the current multifunctional nanocrystals could be potentially useful in various image-guided diagnoses where bright or dark MRI contrast could be selectively tuned to optimize image quality, but also as an efficient and more penetrative near-infrared activated photodynamic therapy agent.

Anti-cAngptl4 Ab-conjugated N-TiO(2) /NaYF(4) :Yb,Tm nanocomposite for near infrared-triggered drug release and enhanced targeted cancer cell ablation.

Nanomedicine: NIR-active N-TiO(2) /NaYF(4) :Yb,Tm nanocomposites (NCs) were synthesized for the first time and its potential applications in drug release and targeted cancer cell ablation are explored. Upon 980 nm laser irradiation, the anti-cAngptl4 Ab-conjugated N-TiO(2) /NaYF(4) :Yb,Tm NCs shows a significant increase in apoptotic A-5RT3 cells when compared with that of the unconjugated NCs. The mechanisms for NIR-induced photocatalysis, drug release and targeted cancer cell killing are proposed.

A three-way synergy of triple-modified Bi2WO6/Ag/N-TiO2 nanojunction film for enhanced photogenerated charges utilization.

We demonstrate a general strategy to prepare Bi(2)WO(6)/Ag/N-TiO(2) film with double visible-light-active components bridged by Ag nanoparticles as an electron shuttle, which exhibits enhanced photocatalytic activity and photoelectrochemical performance under visible light.

Enhanced photocatalytic activity of C-N-codoped TiO2 films prepared via an organic-free approach.

An organic-free sol-gel method was developed to synthesize crack-free, high surface roughness and visible-light-active C-N-codoped TiO(2) films. These films were subsequently evaluated for its photodegradation efficient using stearic acid as the model pollutant compound. The current approach avoids the use of hazardous organic solvents and employs carbon black as the carbon source as well as a template to increase the surface roughness. The presence of carbon and nitrogen species in TiO(2) was studied and discussed. The concentrations of carbon and nitrogen dopants in the TiO(2) films were affected by calcination temperature and the concentration of carbon black. Optimal visible light photocatalytic activity was observed for C-N-codoped TiO(2) film at 10.0 wt.% C, which was more than double that of the N-doped TiO(2) film. The enhancement in visible light photocatalytic activities of the C-N-codoped TiO(2) films was attributed to the synergistic effects of carbon and nitrogen dopants, and high surface roughness of the prepared films.

Superhydrophilicity-assisted preparation of transparent and visible light activated N-doped titania film.

A novel and environmental friendly method was developed to prepare transparent, uniform, crack-free and visible light activated nitrogen doped (N-doped) titania thin films without the use of organic Ti precursors and organic solvents. The N-doped titania films were prepared from heating aqueous peroxotitanate thin films deposited uniformly on superhydrophilic uncoated glass substrates. The pure glass substrates were superhydrophilic after being heated at 500 degrees C for 1 h. Nitrogen concentrations in the titania films were adjusted by changing the amount of ammonia solution. The optimal photocatalytic activity of the N-doped titania films was about 14 times higher than that of a commercial self-cleaning glass under the same visible light illumination. The current reported preparative technique is generally applicable for the preparation of other thin films.

Synthesis and characterization of sub-10 nm Platinum Hollow Spheres as electrocatalyst of direct methanol fuel cell.

Platinum Hollow Spheres (PHSs) with diameters less than 10 nm were successfully synthesized by using Co as a sacrificial template and H2PtCl6 as an oxidizing agent at 95 degrees C. The formation of PHSs at this temperature was not affected by citrate reduction and mainly depended on the pH. The results of transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analysis demonstrated that the platinum hollow sphere was mainly constructed by fcc (face cubic center) platinum with tiny crystallites on the shell. The performance of PHSs for methanol electro-oxidation was evaluated and compared with commercial E-TEK platinum black. Electrochemical measurement by cyclic voltammetry (CV) demonstrated that the electrochemical surface area of PHSs was about twice higher than E-TEK platinum black. Therefore, the synthesized PHSs had higher electrocatalytic activity for methanol electro-oxidation.