Raman Scattering Enhancement through Pseudo-Cavity Modes.

Raman spectroscopy plays a pivotal role in spectroscopic investigations. The small Raman scattering cross-section of numerous analytes, however, requires enhancement of the signal through specific structuring of the electromagnetic and morphological properties of the underlying surface. This enhancement technique is known as surface-enhanced Raman spectroscopy (SERS). Despite the existence of various proposed alternatives, the approach involving Fabry-Pérot cavities, which constitutes a straightforward method to enhance the electromagnetic field around the analyte, has not been extensively utilized. This is because, for the analyte to experience the maximum electric field, it needs to be embedded within the cavity. Consequently, the top mirror of the cavity will eventually shield it from the external laser source. Recently, an open-cavity configuration has been demonstrated to exhibit properties similar to the classic Fabry-Pérot configuration, with the added advantage of maintaining direct accessibility for the laser source. This paper showcases how such a simple yet innovative configuration can be effectively utilized to achieve remarkable Raman enhancement. The simple structure, coupled with its inexpensive nature and versatility in material selection and scalability, makes it an ideal choice for various analytes and integration into diverse Raman apparatus setups.

Thiol-functionalized cellulose for mercury polluted water remediation: Synthesis and study of the adsorption properties.

Mercury pollution poses a global health threat due to its high toxicity, especially in seafood where it accumulates through various pathways. Developing effective and affordable technologies for mercury removal from water is crucial. Adsorption stands out as a promising method, but creating low-cost materials with high selectivity and capacity for mercury adsorption is challenging. Here we show a sustainable method to synthesize low-cost sulfhydrylated cellulose with ethylene sulfide functionalities bonded glucose units. Thiol-functionalized cellulose exhibits exceptional adsorption capacity (1325 mg g-1) and selectivity for Hg(II) over other heavy metals (Co, Cu, Zn, Pb) and common cations (Ca++, Mg++) found in natural waters. It performs efficiently across a wide pH range and different aqueous matrices, including wastewater, and can be regenerated and reused multiple times without significant loss of performance. This approach offers a promising solution for addressing mercury contamination in water sources.

Development of Electrochromic Devices, Based on Polymeric Gel, for Energy Saving Applications.

In this work, the implementation of an electrochromic device (10 cm × 10 cm in size) for energy saving applications has been presented. As electrochromic system has been used with an electrochromic solution (ECsol) made by ethyl viologen diperchlorate [EV(ClO4)2], 1,1'-diethyl ferrocene (DEFc) and propylene carbonate (PC), as solvent. The final system has been obtained by mixing the ECsol, described above, with a polymeric system made by Bisphenol-A glycerolate (1 glycerol/phenol) diacrylate (BPA) and 2,2-Dimethoxy-2-phenylacetophenone (Irgacure 651) in a weight percentage equal to 60:40% w/w, respectively. Lithography has been used to make a spacer pattern with a thickness of about 15-20 µm between the two substrates. Micro-Raman spectroscopy confirmed the presence of the EV•+ as justified by the blue color of the electrochromic device in the ON state. Electrochemical and optical properties of the electrochromic device have been studied. The device shows reversible electrochromic behavior as confirmed by cyclic color variation due to the reduction and oxidation process of the EV2+/EV•+ couple. The electrochromic device shows a variation of the % transmittance in the visible region at 400 nm of 59.6% in the OFF state and 0.48% at 3.0 V. At 606 nm the transmittance in the bleached state is 84.58% in the OFF state and then decreases to 1.01% when it is fully colored at 3.0 V. In the NIR region at 890 nm, the device shows a transmittance of 74.3% in the OFF state and 23.7% at 3.0 V while at 1165 nm the values of the transmittance changed from 83.21% in the OFF state to 1.58% in the ON state at 3.0 V. The electrochromic device shows high values of CCR% and exhibits excellent values of CE in both visible and near-infrared regions when switched between OFF/ON states. In the NIR region at 890 nm, electrochromic devices can be used for the energy-saving of buildings with a promising CE of 120.9 cm2/C and 420.1 cm2/C at 1165 nm.

Effect of the Combination of Gold Nanoparticles and Polyelectrolyte Layers on SERS Measurements.

In this study, polyelectrolyte (PE) layers are deposited on substrates made by glass covered with an array of gold nanoparticles (GNPs). In particular, the samples studied have 0 PE layers (GGPE0), 3 PE layers (GGPE3), 11 PE layers (GGPE11), and 21 PE layers (GGPE21). All samples have been studied by micro-Raman spectroscopy. An acetic acid solution (10% v/v) has been used as a standard solution in order to investigate the SERS effect induced by different numbers of PE layers in each sample. The Surface Enhancement Raman Spectroscopy (SERS) effect correlating to the number of PE layers deposited on the samples has been shown. This effect is explained in terms of an increase in the interaction between the photon of the laser source and the plasmonic band of the GNPs due to a change of the permittivity of the surrounding medium around the GNPs. The trends of the ratios of the intensities of the Raman bands of the acetic acid solution (acetic acid and water molecules) on the band at 1098 cm-1 ascribed to the substrates increase, and the number of PE layers increases.

New Zinc-Based Active Chitosan Films: Physicochemical Characterization, Antioxidant, and Antimicrobial Properties.

The improvement of the antioxidant and antimicrobial activities of chitosan (CS) films can be realized by incorporating transition metal complexes as active components. In this context, bioactive films were prepared by embedding a newly synthesized acylpyrazolonate Zn(II) complex, [Zn(QPhtBu)2(MeOH)2], into the eco-friendly biopolymer CS matrix. Homogeneous, amorphous, flexible, and transparent CS@Znn films were obtained through the solvent casting method in dilute acidic solution, using different weight ratios of the Zn(II) complex to CS and characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR), Raman, and scanning electron microscopy (SEM) techniques. The X-ray single-crystal analysis of [Zn(QPhtBu)2(MeOH)2] and the evaluation of its intermolecular interactions with a protonated glucosamine fragment through hydrogen bond propensity (HBP) calculations are reported. The effects of the different contents of the [Zn(QPhtBu)2(MeOH)2] complex on the CS biological proprieties have been evaluated, proving that the new CS@Znn films show an improved antioxidant activity, tested according to the DPPH method, with respect to pure CS, related to the concentration of the incorporated Zn(II) complex. Finally, the CS@Znn films were tried out as antimicrobial agents, showing an increase in antimicrobial activity against Gram-positive bacteria (Staphylococcus aureus) with respect to pure CS, when detected by the agar disk-diffusion method.

Plasticizers and Salt Concentrations Effects on Polymer Gel Electrolytes Based on Poly (Methyl Methacrylate) for Electrochemical Applications.

This work describes the electrochemical properties of a type of PMMA-based gel polymer electrolytes (GPEs). The gel polymer electrolyte systems at a concentration of (20:80) % w/w were prepared from poly (methyl methacrylate), lithium perchlorate LiClO4 and single plasticizer propylene carbonate (PMMA-Li-PC) and a mixture of plasticizers made by propylene carbonate and ethylene carbonate in molar ratio 1:1, (PMMA-Li-PC-EC). Different salt concentrations (0.1 M, 0.5 M, 1 M, 2 M) were studied. The effect of different plasticizers (single and mixed) on the properties of gel polymer electrolytes were considered. The variation of conductivity versus salt concentration, thermal properties using DSC and TGA, anodic stability and FTIR spectroscopy were used in this study. The maximum ionic conductivity of σ = 0.031 S/cm were obtained for PMMA-Li-PC-EC with a salt concentration equal to 1 M. Ion-pairing phenomena and all ion associations were observed between lithium cations, plasticizers and host polymers through FTIR spectroscopy. The anodic stability of the PMMA-based gel polymer electrolytes was recorded up to 4 V. The glass temperatures of these electrolytes were estimated. We found they were dependent on the plasticization effect of plasticizers on the polymer chains and the increase of the salt concentration. Unexpectedly, it was determined that an unreacted PMMA monomer was present in the system, which appears to enhance ion conduction. The presence and possibly the addition of a monomer may be a technique for increasing ion conduction in other gel systems that warrants further study.

In situ polarized micro-Raman investigation of periodic structures realized in liquid-crystalline composite materials.

In situ polarized micro-Raman Spectroscopy has been utilized to determine the liquid crystal configuration inside a periodic liquid crystalline composite structure made of polymer slices alternated to films of liquid crystal. Liquid crystal, Norland Optical Adhesive (NOA-61) monomer and its polymerized form have been investigated separately. The main Raman features, used as markers for the molecular orientation estimation, have been identified. In situ polarized Raman spectra indicate that the orientation of the liquid crystal director inside the structure is perpendicular to its polymeric slices. Results show the usefulness of in situ polarized micro-Raman spectroscopy to investigate liquid crystalline composite structures.

Polymorphism and phase control in titanyl phthalocyanine thin films grown by supersonic molecular beam deposition.

Polymorphism in the growth of titanyl phthalocyanine films on dielectric substrates has been systematically studied by UV absorption and micro-Raman analyses, correlating structure and optical properties. We explored different growth regimes as a function of substrate temperature and growth rate using hyperthermal seeded supersonic beams. We identify and discuss specific signatures in micro-Raman spectra specifically correlated to the different phases and demonstrate the unprecedented ability of growing crystalline films and controlling the relative abundance of the different phases (amorphous, phase I, and phase II) by the beam parameters. We envisage the very promising perspective of controlling polymorphism at low temperatures via supersonic beam growth, paving the way for better performing devices.