Faculty Publications
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Item Highly fluorescent materials derived from ortho-vanillin: Structural, photophysical electrochemical and theoretical studies(Elsevier B.V., 2019) Poojary, S.; Acharya, M.; Abdul Salam, A.A.; Kekuda, D.; Nayek, U.; Madan Kumar, S.; Vasudeva Adhikari, A.V.; Dhanya, D.Small-molecule organic fluorophores are highly in demand attributed to their extensive prospective in material and biomedical applications. Particularly, luminescent ?-conjugated organic molecules that possess an efficient solid-state emission are excellent candidates for optoelectronic devices. Focusing on high demand of organic fluorophores, we herein report the synthesis of three organic fluorescent materials derived from o?vanillin, viz. an ester (F1), an azine (F2) and an azo dye (F3). Interestingly, F2 exhibited very intense luminescence in its aggregate phase due to the restriction in intra-molecular rotation (RIR), as demonstrated by solution thickening studies. Further, its Single Crystal X-ray Crystallography (SCXRD) study suggested the existence of various intra and inter molecular interactions and gave evidences for locked intra-molecular rotations of the benzene rings in the rigid conformation of the molecule. The bathochromic shift in fluorescence from solution to solid phase was confirmed by its thin-film emission spectrum, which evidences the formation of J-aggregates. The observed RIR, development of J-aggregates and high conjugation in F2 impart an excellent fluorescence in its aggregated state. Thin films of both F2 and F3 on ITO plates exhibited a bathochromic shift with a deep orange to red photoluminescence on UV excitation. Furthermore, the morphological characterization revealed the presence of clear dense grains in case of F2 and F3, while the DSC analysis indicated phase transitions of all the derivatives. As seen from dielectric measurement studies, the azo dye F3 exhibited the highest dielectric constant among the three derivatives. The electronic and photophysical data based on Density Functional Theory (DFT) and Time Dependent-DFT (TD-DFT) calculations are in agreement with the experimental results. All the above data clearly advocate that, the synthesized fluorophoric o?vanillin derivatives are excellent candidates for electro-optical devices. © 2018 Elsevier B.V.Item Dual emissive water-based flexo ink from tapioca-derived carbon dots for anti-counterfeiting applications(Elsevier B.V., 2022) Ullal, N.; Lewis, P.M.; Dhanya, D.; Kulkarni, S.D.; P.j, A.; K, U.B.Counterfeiting of high-value items is a challenging menace worldwide, and luminescent nanoparticles-based security inks have promising applications while addressing this global issue. As Carbon dots (CDs) show attractive functional properties, hydrophilic CDs were prepared through hydrothermal approach from tapioca starch as an eco-friendly precursor. CDs with bluish-green fluorescence emission under 365 nm UV light illumination was obtained using column chromatography technique. TCSPC studies indicated the presence of blue and green emitters with average lifetimes of 1.12 and 1.61 ns, respectively. The graphitic and polycrystalline nature of CDs (~9 nm) with negatively charged surface groups was confirmed through ATR-IR, XPS, RS, XRD, SAED, DLS and TEM. An eco-friendly water-based security ink for flexography printing was formulated, and the influence of the ink components on the fluorescence of CDs were studied. The prints on UV dull paper displayed good abrasion resistance, densitometry and colorimetric values. The letters written using the invisible ink exhibited good security features including excellent covertness under daylight, and a bluish-green emission under 365 nm UV light. Moreover, a yellow emission was perceived using a yellow-orange pass filter under the same light source. The surface morphology and electrical property investigations suggested the use of flexo-ink in flexible printed electronics for anti-counterfeiting. These results propose that Tapioca-derived CDs can enable unique optical features in its eco-friendly ink formulation to demonstrate promising security applications. © 2022 Elsevier B.V.Item Pistachio shell-derived carbon dots and their screen-printing formulation for anticounterfeiting applications(Springer, 2024) Chinmayi, H.D.; Ullal, N.; Dhanya, D.; Kulkarni, S.D.; Anand, P.J.; Udaya Bhat, K.In synergy with constructing a sustainable environment, facile reuse of carbon-rich biowastes as inexpensive precursors for the synthesis of value-added functional carbon dots (CDs) has garnered fruitful outcomes. Pistachio shells comprising cellulose, hemicellulose, and lignin were successfully utilized as a carbon source for the synthesis of CDs through carbonization and subsequent hydrothermal method. The methanolic fraction with desirable fluorescence in the visible region obtained after column purification of CDs was further characterized using TEM, EDS, SAED, FTIR, XPS, RS, XRD, and TCSPC techniques. The blue and green emitting CDs were used as colorants to prepare a water-based ink for screen printing. The screen prints on UV dull paper substrate exhibited good colorimetric and density values. The UV-induced yellow fluorescence of the ink film can be used as a security feature to authenticate genuine document/products and data storage. Graphical abstract: (Figure presented.). © American Coatings Association 2024.Item Yellow emissive and high fluorescence quantum yield carbon dots from perylene-3,4,9,10-tetracarboxylic dianhydride for anticounterfeiting applications(Royal Society of Chemistry, 2024) Ullal, N.; Sahoo, B.; Dhanya, D.; Kulkarni, S.D.; Bhat K, U.; Anand, P.J.Forged products are widespread in the market and there is an immediate need to counter this growing menace. Anti-counterfeit techniques using fluorescent materials with covert features that appear hidden under daylight and display characteristic fluorescence upon specific source irradiation have gained popularity. Carbon dots (CDs) that can be prepared through facile synthesis from various raw materials are a class of fluorescent materials that provide tremendous opportunities to combat counterfeiting. This work focuses on the fabrication of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) derived CDs via the solvothermal approach and their subsequent purification using column chromatography. The fifth fraction obtained exhibited remarkable yellow emission (λem = 540 nm) with a high fluorescence quantum yield of 53.22% and a lifetime of 4 ns. The CDs appeared quasi-spherical during TEM imaging with an average diameter of 1-3 nm and appeared polycrystalline from the SAED pattern. The XPS and TEM-EDS results suggested carbon as the major element along with oxygen and nitrogen as the other heteroatoms. The water-based ecofriendly ink formulated using the CDs was printed on UV dull paper using the flexography technique. The print-proof paper samples appeared pale pink under daylight and fluorescent yellow upon 365 nm UV illumination. Moreover, the stability of the print was confirmed upon exposure to strong UV radiation cycles and abrasion resistance. Besides, the fluorescence emission remained unaltered even after 5 months of storage under room temperature conditions. The ink was used to print on PVC sheets and FBB boards with good stability against scuffing, suggesting its applicability in the packaging industry. The CDs could also serve as fluorescent markers for identifying post-consumer plastic packaging for a circular economy. © 2024 The Royal Society of Chemistry.Item 5,10,15,20-Tetrakis(p-tolyl)porphyrin derived carbon dots as colorant in flexo and screen inks with multi-level covert features for security printing(Elsevier B.V., 2024) Ullal, N.; Sahoo, B.; Dhanya, D.; Kulkarni, S.D.; Sinha, R.K.; Anand, P.J.; Udaya, B.K.Fluorescent inks with covert security features, which make it difficult for forgers to replicate, are highly sought after among the array of anti-counterfeit technologies. The present study focuses on the synthesis of Carbon dots (CDs) from 5,10,15,20-tetrakis(p-tolyl)porphyrin (TTP) via a solvothermal approach. The prepared CDs exhibit attractive emissive characteristics with an absolute fluorescence quantum yield of 38.85 %. Time-resolved fluorescence studies reveal the multiple exponential decay nature of the emitters, which could be due to the diverse chemical environment on the surface of the CDs. XPS analysis proves oxygen as the major element, along with carbon, sulfur, and nitrogen as minor elements. DFT studies on four optimized structures of CDs along with their respective UV and FT-IR plots are conducted. The theoretically derived photoluminescence plots corresponding to the 25-30th excited states coincide with the experimental emission peak. CDs demonstrate characteristic variations in fluorescence in the presence of water, attributed to ?-? stacking induced aggregation. Aggregate formation is also influenced by pH changes, affecting the surface functional groups in proximity to the solvent medium. CDs are used as colorants in the fabrication of both flexo and screen inks. Flexo ink retains the fluorescence features of the CDs, while screen ink offers multilevel security features. Exposing UV-dull paper to 365 nm UV light allows the ink inscribed letters to appear fluorescent blue, whereas the use of UV/green optical filters facilitates the visualization of green/yellow emissions. The introduction of multilevel features makes the duplication of the print difficult, protecting the integrity of the product and could be used for real-life applications. © 2024 The Author(s)Item Pyrene carbaldehyde derived carbon dots for detecting water in alcohol and security printing(Elsevier B.V., 2024) Ullal, N.; Sahoo, B.; Dhanya, D.; Kulkarni, S.D.; Bhat K, U.; AnandThis study focuses on preparing Carbon dots (CDs) from Pyrene-1-carbaldehyde (PCA) using a solvothermal method and further purification using column chromatography. The aggregation-induced emission (AIE) of CDs was systematically investigated in a THF/water medium. The CDs showed red shifts in their photoluminescence (PL) spectra upon increase in water content. Scanning electron microscopic (SEM) images revealed the formation of aggregates, while X-ray diffraction (XRD) confirmed that the d-spacing values remains unchanged. The NMR spectrum of the CDs displayed peaks corresponding to aromatic carbon, which disappeared upon addition of water due to ?-? stacking, indicating aggregate formation. Based on the aggregation-induced fluorescence emission mechanism, detection of water content in alcohol is demonstrated. Moreover, the synthesized CDs were used as fluorescent colorant in screen inks along with polyvinyl alcohol (PVA) and hydroxyethyl cellulose (HEC) as binders. The print proofs obtained on UV-dull paper using PVA-based screen ink exhibited fluorescence emission at longer wavelengths and showcased desirable photostability under prolonged UV exposure compared to the prints obtained using HEC-based ink. Moreover, though the PVA based print appeared blue or cyan fluorescent, the actual yellow emissions from the CDs can be visualised using UV block filter. Such features, masked to the forger, but known to the user can be utilised in checking the authenticity of the print. © 2024 The AuthorsItem Fluorene-vanillin hybrid: A multifunctional fluorophore for latent fingerprint detection and sustainable offset security ink development(Elsevier B.V., 2025) K Jain, R.; P.j, A.; Dhanya, D.; Bhagavath, P.; Vatti, A.K.; Mahadeva Prasad, M.P.; K, U.B.; Alex, A.Fluorophores play a pivotal role in forensic science and anticounterfeit applications due to their unique and distinct emission features, which enable visualization and authentication. In the pursuit for advanced fluorescent pigments, ortho vanillin-fluorene Schiff base (OAF) with bright orange fluorescence was synthesized using a cost-effective, simple, and one-step method. This fluorophore was highly effective in developing latent fingerprints (LFPs), enabling visualization of level 1–3 features on nonporous glass and semi-porous leather under 365 nm UV light. The interaction between glycine in the fingerprint residue on glass substrate and OAF was analyzed through computational studies and further validated using ATR-FTIR analysis. The FESEM images of the latent prints revealed detailed surface morphology and particle distribution on the ridges of the fingermarks. Further, fluorescent images of LFPs were successfully developed on sticky paint, moist glass, multicolored compact disc, and uneven leaf surface, demonstrating the material's versatility on challenging substrates. Moreover, the powder dusting of composite powder of OAF and JUP-AS120, a commercially available pigment enabled enhanced LFP visualization on glass under both 365 and 980 nm light sources for better contrast and minimal background fluorescence, while minimising degradation of fingerprint residues over time. In addition, an OAF spray was formulated using nitrocellulose resin, ethyl acetate and carbitol for broader forensic application, which facilitated LFP visualization down to fine minutiae details on porous, semi-porous and non-porous substrates. Furthermore, to address the growing rates of counterfeited products/banknotes/security documents, an ecofriendly composite security ink was formulated using OAF and JUP-AS120 to obtain offset prints with excellent resistance to photobleaching and scuffing on paper substrate. The ink film exhibited multilevel authentication features: orange fluorescence under a 365 nm light source, and green and red emissions without and with a 610 nm band pass filter, respectively under 980 nm laser source, enhancing security and making forgery more challenging. Additionally, biocompatible OAF can be incorporated in ink pads to offer a dual layer of validation for fingerprints on security documents: optical authentication by leveraging the ink's fluorescence properties and biometric recognition through fingerprint patterns. © 2025 The Author(s)