Crystal Violet Molecules Research Articles

Constructing recyclable SERS platform based on peroxidase-like Cu2O/g-C3N4/Ag composites for sensitive sensing of fungicides

In this work, we proposed a straightforward self-assembly and in-situ deposition protocol to construct Cu2O/g-C3N4/Ag composites, which demonstrated peroxidase-like attribute and exceptional SERS activity. These composites proved to be an effective SERS analysis tool for detecting organic fungicides like malachite green (MG) and crystal violet (CV). Remarkably, they achieved detection limits as low as 10−9 M in DI water as well as fish pond water, and exhibited a strong linear correlation between logarithmic concentrations and SERS intensities (R2 ≥ 0.97). Beyond that, with the aid of hydrogen peroxide (H2O2), the peroxidase-like Cu2O/g-C3N4/Ag composites rapidly degraded MG and CV molecules within just 5 min. Furthermore, their practical reusability based on the peroxidase-like reaction was proved by high SERS performance across 5 detection cycles. These results emphasize the immense potential of Cu2O/g-C3N4/Ag in SERS-based trace fungicide detection and suggest future applications in ecological restoration through peroxidase-like reactions.

Low-cost Ag/ZnO nanosheets arrays as sensitive and recyclable surface-enhanced Raman scattering substrates

The development of surface-enhanced Raman scattering (SERS) substrate based on metal/semiconductor nanostructured platforms has emerged as a promising technique for achieving highly sensitive and recyclable detection across various fields, including environmental monitoring, food safety, biomedical diagnostics, and the preservation of cultural heritage. However, the design and fabrication of cost-effective metal/semiconductor nanostructures suitable for SERS substrates remain a formidable challenge. In this study, a low-cost, recyclable SERS substrate based on Ag nanoparticle decorated ZnO nanosheets (Ag/ZnO NSs) arrays was developed using hydrothermal growth and photochemical reduction approaches. The optimized Ag/ZnO NSs arrays demonstrated local electric field enhancement and multi-path charge transfer, ensuring an enhancement factor of 107 and a detection limit of 10−10 mol/L for crystal violet molecules. This research not only sheds light on the economical production of metal/semiconductor SERS substrates but also paves the way for a broader spectrum of SERS-based detection applications in diverse fields.

A semiconductor SERS sensor of corrosion-resistant PPy/GO composite film by electrochemical growth for detecting crystal violet residues in fresh fish tissue

Crystal violet (CV) residues in Marine food have produced a severe health threat in human life. In this study, we proposed a semiconductor surface-enhanced Raman scattering (SERS) sensor of corrosion-resistant Polyaniline/Graphene oxide (PPy/GO) film by electrochemical growth method to detect CV residues in fresh fish tissue. A PPy/GO dispersion solution was one-step deposited on a stainless steel sheet surface by electrochemical polymerization process to form a PPy/GO composite film acting as a semiconductor SERS substrate. Since the substrate of PPy/GO film was mainly composed of GO sheet without other metals, it had a good corrosion resistance. The SERS enhancement factor and charge transfer intensity PCT of PPy/Go SERS substrate for CV molecules were up to 1.18 × 106 and 0.903, respectively. Furthermore, the limit of detection (LOD) of PPy/GO SERS substrate could reach 1.58 nM. In addition, SERS sensor of PPy/GO film could identify CV residues in fresh fish tissues, and its recovery rate was 91.8 %–107 %. This preparing method and detecting method we proposed PPy/GO SERS substrate provide a new pathway for detecting CV residues in Marine food.

Enhancement mechanism of copper ions doped TiO2 substrates based on surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) is considered as one of the most attractive analytical tools, and it is necessary to develop more semiconductor substrates. Herein, copper ions-doped TiO2 (Cu-TiO2) nanoparticles (NPs) with different doping ratios were synthesized by a sol-hydrothermal method and used as semiconductor SERS substrates to explore the possible enhancement mechanisms. The synthesized Cu-TiO2 NPs show a cubic crystalline structure of anatase with a small particle size at 8 nm. We discussed the SERS enhancement ability of Cu-TiO2 substrates using crystal violet (CV) used as a probe. It can be found that there is a charge transfer (CT) effect between CV molecules and Cu-TiO2 substrates. In addition, Cu-TiO2 substrates exhibit the most SERS enhancement with an enhancement factor (EF) up to 2.4 × 104 at the Cu2+ doping ratio of 3 %, with a detection limit of 5 × 10–7 M. The experiments demonstrated that Cu-TiO2 NPs can be used as SERS substrates because of the CT route among the valence band, the surface state energy level, and the lowest unoccupied molecular orbital, which facilitates the development of semiconductor SERS substrates and provides a new perspective in exploring SERS enhancement mechanisms.

Laser-induced periodic surface structures on Fe ion doped LN crystal for pyroelectric SERS analysis

We proposed a sensor architecture for surface-enhanced Raman scattering (SERS) based on Fe ion doped LN (FLN) crystal, which was modified by large-area laser-induced periodic surface structures (LIPSS) and subsequently decorated with Ag nanoparticles (Ag NPs). Based on such a FLN/LIPSS/Ag substrate, strikingly boosted SERS enhancement was obtained at constant temperature owing to the LIPSS-related hot spot improvement. Benefiting from the pyroelectric effect of the FLN crystal, further enhanced SERS was achieved under heating and cooling processes, which can be ascribed to the additional charge transfer between molecules and Ag NPs triggered by pyroelectric potential. The experimental results highlight the high fabrication efficiency, ultrasensitivity, high uniformity, and high universality of the substrate, integrating the advantages of both LIPSS and the FLN crystal. More interestingly, selective suppression of Raman signals under cooling processes was observed, which further extends the applications of the FLN/LIPSS/Ag substrate for the detection of molecule complexes such as lake water polluted by crystal violet and 4-aminothiophenol molecules.

Flexible Multicavity SERS Substrate Based on Ag Nanoparticle-Decorated Aluminum Hydrous Oxide Nanoflake Array for Highly Sensitive In Situ Detection.

Flexible surface-enhanced Raman scattering (SERS) substrates are very promising to meet the needs for real-time and on-field detection in practical applications. However, high-performance flexible SERS substrates often suffer from complexity and high cost in fabrication, limiting their widespread applications. Herein, we developed a facile method to fabricate a flexible multicavity SERS substrate composed of a silver nanoparticle (AgNP)-decorated aluminum hydrous oxide nanoflake array (NFA) grown on a polydimethylsiloxane (PDMS) membrane. Strong plasmon couplings promoted by multiple nanocavities afford high-density hotspots within such a flexible AgNPs@NFA/PDMS film, boosting high SERS sensitivity with an enhancement factor (EF) of ∼1.54 × 109, and a limit of detection (LOD) of ∼7.4 × 10-13 M for rhodamine 6G (R6G) molecules. Furthermore, benefiting from the high sensitivity, high mechanical stability, and transparency of this substrate, in situ SERS detections of trace thiram and crystal violet (CV) molecules on the surface of cherry tomatoes and fish have been realized, with LODs much lower than the maximum allowable limit in food, demonstrating the great potential of such a flexible substrate in food safety monitoring. More importantly, the preparation processes are very simple and environmentally friendly, and the techniques involved are completely compatible with well-established silicon device technologies. Therefore, large-area fabrication with low cost can be readily realized, enabling the extensive applications of SERS sensors in daily life.

Improved Surface-Enhanced Raman Scattering Performance of 2D Ti3C2Tx MXene Embedded in PVDF Film Enabled by Photoinduction and Electric Field Modulation.

In this study, we introduce a synergistic approach to enhance the surface-enhanced Raman scattering (SERS) signal in two-dimensional (2D) MXene through photo-irradiation and electric field modulation. Our methodology involves the integration of 2D Ti3C2Tx MXene with piezoelectric polyvinylidene fluoride (PVDF) polymer, resulting in the creation of a free-standing, flexible composite film. On this composite film, a thin layer of Au was deposited. Our flexible substrate was able to sense methylene blue (MB), crystal violet (CV), 4-aminothiophenol (ATP), and melamine. The SERS substrate exhibits low detection limit of 10-8 M MB with a 6.7 × 106 enhancement factor (EF). The SERS substrate enables picomolar (pM) detection sensitivity for CV molecules with an EF of 9.2 × 109. Furthermore, the introduction of photo-irradiation leads to an additional ∼3.5-fold enhancement in the SERS signal, which is attributed to the altered work function and defects. The application of mechanical force to the piezoelectric PVDF/Ti3C2Tx film results in a ∼4.5-fold boost in SERS signal due to mechanical force-induced electrical energy. The fabrication strategy employed here for producing a flexible piezoelectric PVDF/Ti3C2Tx film holds significant promise for expanding the potential application of 2D MXene in rapid, on-site sensing scenarios.

Observation of reversible and irreversible charge transfer processes in dye-monolayer graphene systems using Raman spectroscopy as a tool

Herein, we report the Raman spectroscopy of crystal violet (CV) and IR-780 Iodide molecules dispersed on the monolayer graphene film (MGF). In the CV-MGF system, the enhancement in the Raman scattering of CV molecules is observed irrespective of the location probed during the spectral measurements. This enhancement is due to the charge transfer from the MGF to CV molecules. However, in the case of the IR-780 Iodide – MGF system, the enhancement of Raman scattering of dye molecules or MGF is observed strongly depending upon the probed location. These observations indicate that the charge transfer is irreversible and reversible in the CV-MGF and IR-780 Iodide–MGF systems, respectively. Importantly, for the first time, this experimental study revealed that enhancing the Raman scattering of MGF is possible through the “chemical mechanism” with suitable dye molecules apart from the “electromagnetic mechanism” with plasmonic hot spots of the metal nanoparticles and photonic nanojets of single dielectric microparticles.

Surface-Assisted Laser Desorption/Ionization Mass Spectrometry with a Two-Dimensional Au Nanoparticle Array for Soft Ionization.

Surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) is a valuable technique for detecting small molecules in environmental and medicinal studies. We investigated dot-like and 2D-array gold nanoparticle-based SALDI-MS substrates that excite surface plasmons and enhance the desorption/ionization of sample molecules via charge transfer between the substrate and sample molecules. We aimed to optimize the nondissociative detection of sample molecules by efficiently transferring energy while suppressing excess internal energy. SALDI-MS measurements using crystal violet (CV) molecules revealed ion intensity and spectral pattern differences between the dot-like and 2D-array substrates. SALDI-MS measurements using dot-like substrates suggested two desorption/ionization processes: internal energy supply and charge transfer between the substrate and sample molecules. However, SALDI-MS measurements using 2D-array substrates suggested that the internal energy supply was suppressed. As a result, the dot-like substrate provided higher desorption/ionization efficiency but increased fragmentation, whereas the 2D-array substrate was suitable for highly sensitive and nondissociative SALDI-MS measurements. This study contributes to the optimization of SALDI-MS measurements and advances our understanding of energy transfer and sample molecule dissociation.

Silver Sulfide Anchored Anatase TiO2 Nanoparticles for Ultrafast Degradation of Selective Textile Dyes

AbstractThe surface modification of the TiO2 with selective narrow band gap of metal or metal sulfide is an attractive attention in recent years. Herein, tiny Ag2S nanoparticles are well anchored on the TiO2 surface by a cost‐effective chemical precipitation method for efficient photocatalytic activity. The decoration of Ag2S nanoparticles is clearly identified through electron microscopy studies. The UV‐Vis diffuse reflection spectra (DRS) revealed that TiO2/Ag2S composites absorbed broad spectrum in the visible region. The reduced band‐gap of 2.41 eV by anchored the Ag2S on TiO2 may boosted the photocatalytic activity. Particularly, incorporation of Ag2S nanoparticles increased charge separation efficiency, lowering recombination, and improving photocatalytic performance. Because of their unique structural and optical properties, TiO2/Ag2S composites have increased photocatalytic activity. The photocatalytic performance of the pristine Ag2S and Ag2S anchored TiO2 are Crystal violet (CV) and Methyl orange (MO) dye molecules under same experimental condition. As expected, the TiO2/Ag2S showed highest photocatalytic degradation efficiency than alone TiO2.

Fabrication of complexed nanostructure using AAO template for ultrasensitive SERS detection

In the study of surface-enhanced Raman scattering (SERS) processes, a simple and fast approach is needed to ensure the large-scale preparation of SERS substrates. This article uses anodic aluminum oxide (AAO) as a template to assemble gold nanoparticles (Au NPs) into an ordered array. By changing the pore size of AAO and silanizing the pores, the number and density of Au NPs entering the pores through liquid–liquid two-phase self-assembly (LLSA) can be effectively regulated. Using Rh6G (Rhodamine 6G) and CV (Crystal Violet) molecules as probe molecules, substrate sensitivity was evaluated with an enhancement factor of up to 6.34 × 107. In addition, the uniformity of the substrate is good, with a relative standard deviation (RSD) of 9.94%, and the logarithmic concentration and the Raman signal presented significant linear correlations R2 was 0.997 and 0.985, respectively. The detection limit of the substrate for APM (aspartame) as a solvent is as low as 0.0078 g/L. Finally, the substrate was subjected to high sensitivity testing on two types of beverages containing APM sold, proving the practicality of the substrate. It is expected to achieve simple and rapid detection in food additive trace detection in the future.

Tuning d-Orbital Electronic Structure via Au-Intercalated Two-Dimensional Fe3GeTe2 to Increase Surface Plasmon Activity.

While extensive research has been dedicated to plasmon tuning within non-noble metals, prior investigations primarily concentrated on markedly augmenting the inherently low concentration of free carriers in materials with minimal consideration given to the influence of electron orbitals on surface plasmons. Here, we achieve successful intercalation of Au atoms into the layered structure of Fe3GeTe2 (FGT), thereby exerting control over the orbital electronic states or structure of FGT. This intervention not only amplifies the charge density and electron mobility but also mitigates the loss associated with interband transitions, resulting in increased two-dimensional FGT surface plasmon activity. As a consequence, Au-intercalated FGT detects crystal violet molecules as a surface-enhanced Raman scattering substrate, and the detection lines are 3 orders of magnitude higher than before Au intercalation. Our work provides insight for further studies on plasmon effects and the relation between surface plasmon resonance behavior and electronic structures.

Large-scale fabrication of flexible macroscopic SERS substrates with high sensitivity and long-term stability by wet-spinning technique: Uniform encapsulation of plasmon in graphene oxide fibers

Graphene oxide has attracted wide interest for theoretical research and application exploration in surface enhancement Raman scattering (SERS). However, how to break the geometric limitations of the nanoscale and extend its properties to the macroscopic level remains an urgent problem. Here, we prepared flexible graphene oxide/Au nanoparticles (GO/AuNP) fibers with high sensitivity and reproducibility for SERS sensing using wet spinning method. Benefitting from the plasmonic coupling of GO/AuNP fibers in vertical direction and uniform adsorption of the target molecules, the limit of detection for fiber was as low as 5 × 10-11 M for rhodamine 6G (R6G) and crystal violet (CV) molecules. In addition, due to the optimal distribution of AuNP in the macroscopic assembly of GO/AuNP hybrid, the fiber substrates provided uniform and stable signals for both temporal (6 months) and spatial (RSD = 8.18 %) scales, exhibited excellent reliability and durability. Moreover, an ultra-low concentrations of the pesticide thiram residues could be rapidly traced by direct sampling from the apple peel with a sensitivity of 5 × 10-9 M, which is much lower than the residue limit set by the US environmental protection agency. We envision that this work could provide new insights into the large-scale and economical fabrication of high-performance flexible SERS sensors for real world applications.

Application of Raman spectroscopy in relative blue ballpoint pen ink dating for forensic document analysis – a case report

In this case report, blue ballpoint ink on a questioned document was investigated using a newly developed Raman model devoted for dating of documents via writing inks. The majority of blue ballpoint pen inks contain crystal violet - a triarylmethane dye which displays a typical “molecular fingerprint” type of Raman spectrum, of which most intense peaks at 749 cm−1 and 1542 cm−1 (under 785 nm laser excitation) represents the least and the most stable bonds of crystal violet molecules, respectively. The ratios of peak intensities at above mentioned Raman shifts are utilized to estimate the relative dating of the questioned blue ballpoint pen ink in practice, results of which agreed with estimations using other traditional relative dating methods. ® 2023 Journal of Science and Technology - NTTU

White light-activated bactericidal coating using acrylic latex, crystal violet, and zinc oxide nanoparticles

A white light-activated bactericidal coating consisting of acrylic latex, Zinc oxide nanoparticles (ZnO NPs) and crystal violet (CV) was produced through a two-step dipping process.

Resonance-Assisted Surface-Enhanced Raman Spectroscopy Amplification on Hierarchical Rose-Shaped MoS2/Au Nanocomposites.

Surface-enhanced Raman spectroscopy (SERS) has emerged as a highly sensitive trace detection technique in recent decades, yet its exceptional performance remains elusive in semiconductor materials due to the intricate and ambiguous nature of the SERS mechanism. Herein, we have synthesized MoS2 nanoflowers (NFs) decorated with Au nanoparticles (NPs) by hydrothermal and redox methods to explore the size-dependence SERS effect. This strategy enhances the interactions between the substrate and molecules, resulting in exceptional uniformity and reproducibility. Compared to the unadorned Au nanoparticles (NPs), the decoration of Au NPs induces an n-type effect on MoS2, resulting in a significant enhancement of the SERS effect. This augmentation empowers MoS2 to achieve a low limit of detection concentration of 2.1 × 10-9 M for crystal violet (CV) molecules and the enhancement factor (EF) is about 8.52 × 106. The time-stability for a duration of 20 days was carried out, revealing that the Raman intensity of CV on the MoS2/Au-6 substrate only exhibited a reduction of 24.36% after undergoing aging for 20 days. The proposed mechanism for SERS primarily stems from the synergistic interplay among the resonance of CV molecules, local surface plasma resonance (LSPR) of Au NPs, and the dual-step charge transfer enhancement. This research offers comprehensive insights into SERS enhancement and provides guidance for the molecular design of highly sensitive SERS systems.

A novel core-shell heterostructure of zinc oxide/metal-organic frameworks anchored silver nanoparticles for enhanced SERS and photocatalytic performance

Here, a novel well-ordered ZnO rod-flower/zeolitic imidazolate framework-M (ZIF-M, using 5-mercapto-1-methyltetrazole as ligand) core-shell heterostructure (Al/ZnO/ZIF-M, AZZ*) is induced by aluminum (Al) sheet. Subsequently, Ag nanoparticles (AgNPs) are tightly attached to the ZIF-M layer in AZZ* through the strong Ag-N and Ag-S bonds, and a portable bifunctional substrate of Al/ZnO/ZIF-M/Ag (AZZ*Ag) is constructed. The finite difference time domain (FDTD) analysis shows that the AZZ*Ag substrate generates the stronger electromagnetic field intensity than the AZAg. Also, there is a strong synergistic effect among Al, ZnO, ZIF-M and Ag which can effectively facilitate the electron transfer. Importantly, the AZZ*Ag substrate exhibits outstanding SERS response with high sensitivity and selectivity for crystal violet (CV) molecules. The low detection limit (LOD) of CV molecule is 2.81 × 10−11 mol·L−1 with high analysis enhancement factor (AEF) of 1.93 × 106. In addition, AZZ*Ag substrate shows good photocatalytic performance for CV molecules with high degradation efficiency of 97.35% within 105 min, which is 4.72 times that of AZAg. Importantly, the SERS and photocatalytic performance of AZZ*Ag are 4.4 times and 3.09 times those of the Al/ZnO/ZIF-8/Ag (AZZ#Ag, using 2-methylimidazole as ligand), respectively. Moreover, the AZZ*Ag substrate displays excellent stability, good reproducibility, recyclability and uniformity. Thus, the designed portable bifunctional composite exhibits great potential for SERS detection and photocatalytic degradation of other pollutants in environmental wastewater.

Novel mesoporous nanocomposite of WS2/ZIF-9 for efficient adsorption of textile dyes from wastewater

In this work, novel mesoporous nanocomposite of tungsten disulphide (WS2) and zeolite imidazole framework-9 (ZIF-9) has been successfully synthesized for the adsorption of carcinogenic textile dyes. Various characterization techniques revealed that the modification of WS2 nanosheets with ZIF-9, improved surface chemistry, textural properties, morphological features, surface area, and surface charge of synthesized nanocomposite. Field-Emission Scanning Electron Microscopy (FESEM) and High-Resolution Transmission Electron Microscopy (HRTEM) were used for the morphological details and analysis of size of polyhedrons with diameter of (∼1030 nm), length of each side of polyhedron (∼580 nm) and area of polyhedron ∼ 750 µm2, uniformly distributed on the surface of WS2 nanosheets. The enhanced specific surface area (∼114 m2/g) and micropores of as-synthesized nanocomposite as compared to pristine samples were confirmed by using Brunauer-Emmett-Teller (BET) analysis. A comparative adsorption study was performed using cationic and anionic dyes for determining the adsorption efficiency of pristine WS2 and ZIF-9 (WZF) nanocomposite. The adsorption capacity of as-synthesized materials was studied as a function of concentrations (2, 3 and 5 mg) for Malachite Green (MG) and Crystal violet (CV), textile dyes. The obtained higher adsorption capacity of WZF nanocomposite for CV (∼2124 mg/g) than MG (∼911 mg/g) is due to more electrostatic interactions between CV molecules and adsorbent because of having higher nitrogen groups in CV as compared to MG. The attained higher adsorption efficiency for MG and CV using synthesized WZF nanocomposite as compared to the pristine WS2 was explained on the basis of optimized surface charge (zeta potential study), large specific surface area (BET analysis) and lower recombination rate (TRPL study). The point of zero charge (PZC) was also analyzed by zeta potential studies at diversified values of pH for understanding the adsorption mechanism. The Langmuir isotherm provides best fit for the adsorption process with high value of R2: 0.99 and 0.97 (∼1) for both MG and CV dyes, respectively. The efficiency achieved throughout the four cycles of reusability study confirms the stability and regeneration ability of materials. Such novel nanocomposite has not been previously reported and opens the new pathways to highly efficient, affordable and highly mesoporous material for wastewater treatment.

Three-Phase Catassembly of 10 nm Au Nanoparticles for Sensitive and Stable Surface-Enhanced Raman Scattering Detection.

Interfacial self-assembly with the advantage of providing large-area, high-density plasmonic hot spots is conducive to achieving high sensitivity and stable surface-enhanced Raman scattering (SERS) sensing. However, rapid and simple assembly of highly repeatable large-scale multilayers with small nanoparticles remains a challenge. Here, we proposed a catassembly approach, where the "catassembly" means the increase in the rate and control of nanoparticle assembly dynamics. The catassembly approach was dropping heated Au sols onto oil chloroform (CHCl3), which triggers a rapid assembly of plasmonic multilayers within 15 s at the oil-water-air (O/W/A) interface. A mixture of heated sol and CHCl3 constructs a continuous liquid-air interfacial tension gradient; thus, the plasmonic multilayer film can form rapidly without adding functional ligands. Also, the dynamic assembly process of the three-phase catassembly ranging from cluster to interfacial film formation was observed through experimental characterization and COMSOL simulation. Importantly, the plasmonic multilayers of 10 nm Au NPs for SERS sensing demonstrated high sensitivity with the 1 nM level for crystal violet molecules and excellent stability with an RSD of about 10.0%, which is comparable to the detection level of 50 nm Au NPs with layer-by-layer assembly, as well as breaking the traditional and intrinsic understanding of small particles of plasmon properties. These plasmonic multilayers of 10 nm Au NPs through the three-phase catassembly method illustrate high SERS sensitivity and stability, paving the way for small-nanoparticle SERS sensing applications.

Real-Time Monitoring of a Single Molecule in Sub-nanometer Space by Dynamic Surface-Enhanced Raman Spectroscopy.

In biology and chemistry, the ultimate goal is to monitor single molecules without labels. However, long-term monitoring of label-free molecules remains a challenge. Here, on the basis of the photothermal effect of gold nanorods (GNRs), we developed a platform for monitoring of a single molecule employing surface-enhanced Raman spectroscopy (SERS). Laser re-irradiation forms 1.0 nm gaps between GNRs, allowing us to observe single crystal violet (CV) molecules blinking for up to 4 min with dynamic surface-enhanced Raman spectroscopy (D-SERS). Bianalyte experiments confirm single-molecule features at CV concentrations of 10-14 M. Combining density functional theory (DFT) calculations with a free CV molecule observed in millisecond D-SERS, we propose that CV molecules can be confined to sub-nanometer space and the orientation of an individual CV moving in the range of 50-90° can be dynamically captured by D-SERS. This will provide a novel idea for effective exploration of the temporal and spatial dynamic processes of different reactions.