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Meso -β, β-β' trifused porphyrins incorporating two distinct active methylene groups (MN = malononitrile and IND = 1,3-indanedione) and their corresponding metal complexes with Cu(II) and Zn(II) have been synthesized with good to excellent yields and characterized by various spectroscopic techniques and spectrometric methods. Single crystal X-ray analysis of the Zn(II) complex ZnTFPMB(MN) 2 (where TFP = trifused porphyrin and MB = mono benzo) revealed a ruffled nonplanar 'armchair' type conformation with a twist angle of 24.10°. The absorption spectra showed a significant bathochromic shift in both the B- and Q-bands, extending into the near-infrared (NIR) region, particularly for π-extended trifused porphyrins. The cyclic voltammograms of MN-appended trifused porphyrins revealed unusual redox behavior, likely due to chemical reactions occurring at the electrode surface during electroreduction. The HOMO-LUMO energy gap for the π-extended porphyrins (MTFPMB(VCN) 2 ) was effectively reduced to ≤1.5 V, compared to ∼2.23 V for the parent porphyrins. Additionally, the femtosecond third-order nonlinear optical properties of the synthesized trifused porphyrins and reported Ni(II) complexes were investigated using the Z -scan technique. Most of the studied porphyrins exhibited promising three-photon absorption coefficients and cross-section values, suggesting their potential applications in optical limiting, bio-imaging, and advanced optoelectronics.

Heterostructures comprise two or more different semiconducting materials stacked either as co-assemblies or self-sorted based on their dynamics of aggregates. However, self-sorting in heterostructures is rather significant in improving the short exciton diffusion length and charge separation. Despite small organic molecules being known for their self-sorting nature, macrocyclic are hitherto unknown owing to unrestrained assemblies from extended π-conjugated systems. Herein, two near infrared region (NIR) active molecules comprised of porphyrin appended D-π-D (1) and A-π-A (2) have been reported to show the self-assembled 0D and 2D nanostructures via J-aggregates. Interestingly, the mixture of 1 and 2 reveals self-sorting at the molecular level promoting nanosphere and sheet structures which further rolled over to spheres through π-π stacking leading to core-shell type heterostructure. Consequently, electrical conductivity is 10 times higher than the individual assemblies due to excited state electron transfer from 1 to 2 in a mixture, confirmed by femto second-transient absorption spectroscopy and electrochemical impedance spectroscopy. These results suggest that controlling the self-sorted heterostructures fosters refining the electronic properties which pave the way for designing novel NIR-absorbed molecules for organic solar cells (OSCs)., (© 2025 Wiley‐VCH GmbH.)

This work presents a unique and straightforward method to synthesise hafnium oxide (HfO 2 ) and hafnium carbide (HfC) nanoparticles (NPs) and to fabricate hafnium nanostructures (NSs) on a Hf surface. Ultrafast picosecond laser ablation of the Hf metal target was performed in three different liquid media, namely, deionised water (DW), toluene, and anisole, to fabricate HfO 2 and HfC NPs along with Hf NSs. Spherical HfO 2 NPs and nanofibres were formed when Hf was ablated in DW. Hf ablated in toluene and anisole demonstrated the formation of core-shell NPs of HfC with a graphitic shell. All NPs exhibited novel optical reflectance properties. Reflectance measurements revealed that the fabricated NPs had a very high and broad optical absorption throughout the UV-vis-NIR range. The NPs synthesised in toluene exhibited the best absorption. The successful fabrication of Hf NSs with the formation of laser-induced periodic surface structures (LIPSS) with low spatial frequency (LSFL) and high spatial frequency (HSFL) orthogonal to each other was also demonstrated. The LSFL and HSFL both exhibited quasi-periodicity. This work presents a simple way to fabricate HfO 2 and HfC NPs and provides insight into their morphological and optical characteristics paving way for their applications in future., (Copyright © 2024, Das et al.)

Plasmonic nanoparticles (NPs) have played a significant role in the evolution of modern nanoscience and nanotechnology in terms of colloidal synthesis, general understanding of nanocrystal growth mechanisms, and their impact in a wide range of applications. They exhibit strong visible colors due to localized surface plasmon resonance (LSPR) that depends on their size, shape, composition, and the surrounding dielectric environment. Under resonant excitation, the LSPR of plasmonic NPs leads to a strong field enhancement near their surfaces and thus enhances various light-matter interactions. These unique optical properties of plasmonic NPs have been used to design chemical and biological sensors. Over the last few decades, colloidal plasmonic NPs have been greatly exploited in sensing applications through LSPR shifts (colorimetry), surface-enhanced Raman scattering, surface-enhanced fluorescence, and chiroptical activity. Although colloidal plasmonic NPs have emerged at the forefront of nanobiosensors, there are still several important challenges to be addressed for the realization of plasmonic NP-based sensor kits for routine use in daily life. In this comprehensive review, researchers of different disciplines (colloidal and analytical chemistry, biology, physics, and medicine) have joined together to summarize the past, present, and future of plasmonic NP-based sensors in terms of different sensing platforms, understanding of the sensing mechanisms, different chemical and biological analytes, and the expected future technologies. This review is expected to guide the researchers currently working in this field and inspire future generations of scientists to join this compelling research field and its branches.

Triarylboron compounds have been established as promising candidates in optoelectronic applications. However, realizing multi-functional properties in triaryl boron-based materials remains challenging. Herein, we present two regioisomers, 1 and 2, designed judiciously by connecting a dimethylamino donor and a dimesitylboryl acceptor at 1,4 and 2,6-positions of the naphthalene spacer, respectively. Both compounds 1 and 2 display simultaneous, delayed fluorescence and persistent room-temperature phosphorescence (580 nm, τ av = 168 ms, Φ = 76% for 1; 550 nm, τ av = 129 ms, Φ = 88% for 2 in 1 wt% PMMA), with the delayed fluorescence bands being sensitive to doping concentration (in PMMA). Notably, compound 1 in 1 wt% PMMA films demonstrates a reversibly switchable single-molecule phosphorescence from orange (580 nm) to green ( λ Ph = 550 nm, τ av = 42 ms) in response to pH, which can be utilized for anti-counterfeiting applications. These results were further corroborated by studying the respective cationic salts 1-OTF and 2-OTF. Moreover, 1 and 2 exhibited blue-shifted fluorescence in response to mechanical pressure. Compound 2 also showed three-photon (σ3P) absorption properties which were better compared to those of compound 1., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We report on the formation of SiC nanoparticles coated with graphene oxide layers by femtosecond (fs) laser ablation of 6H-SiC (n-type and semi-insulating V-doped) in deionized water. Distinct structural features were observed in the surrounding matrix of colloidal spherical nanoparticles. This corresponds to the formation of micro-nanostructures of silicene sheets in the colloidal suspension. Further, the formation of subwavelength (∼λ/8) high spatial frequency laser-induced periodic surface structures (HSFL) is noticed on the ablated SiC surface. The variation in the size and periodicity of LIPSS is noted among two SiC targets with different resistivities. The study continued to investigate the morphology of furnace annealed (FA) and rapid thermal annealed (RTA) Au-deposited LIPSS towards sensing applications based on the surface-enhanced Raman scattering (SERS) technique. The formation of fine spherical Au nanoparticles is observed in the case of RTA samples, which exhibited predominant SERS enhancement in trace detection of the explosive analyte, Tetryl. This study on SiC using fs laser pulses unveils the uniqueness of SiC material in the ablation process, especially in producing the LIPSS and silicon-carbon-based nanoparticles/nanostructures that can be tailored for diverse applications.

The present study investigates the effects of input wavelength (1064, 532, and 355 nm) and surrounding liquid environment (distilled water and aqueous NaCl solution) on the picosecond laser ablation on silver (Ag), gold (Au), and Ag/Au alloy targets. The efficacy of the laser ablation technique was meticulously evaluated by analyzing the ablation rates, surface plasmon resonance peak positions, and particle size distributions of the obtained colloids. The nanoparticles (NPs) were characterized using the techniques of UV-visible absorption, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Furthermore, NPs of various sizes ranging from 6 to 35 nm were loaded onto a filter paper by a simple and effective drop-casting approach to achieve flexible surface-enhanced Raman spectroscopy (SERS) substrates/sensors. These substrates were tested using a simple, portable Raman device to identify various hazardous chemicals (malachite green, methyl salicylate, and thiram). The stability of the substrates was also systematically investigated by determining the decay percentages in the SERS signals over 60 days. The optimized SERS substrate was subsequently employed to detect chemical warfare agent (CWA) simulants such as methyl salicylate (a CWA simulant for sulfur mustard) and dimethyl methyl phosphonate (has some structural similarities to the G-series nerve agents) at different laser excitations (325, 532, and 633 nm). A notably higher SERS efficiency for CWA simulants was observed at a 325 nm Raman excitation. Our findings reveal that a higher ablation yield was observed at IR irradiation than those obtained at the other wavelengths. A size decrease of the NPs was noticed by changing the liquid environment to an electrolyte. These findings have significant implications for developing more efficient and stable SERS substrates for chemical detection applications., Competing Interests: The authors declare no conflicts of interest., (Copyright © 2024, Moram et al.)

This study employs femtosecond transient absorption spectroscopy to investigate the rapid dynamics of excited state carriers in three metalated porphyrin-naphthalimide (PN) molecules and one free-base molecule. The dynamics of electron injection, from PN to mesoporous titania (TiO 2 ), in PN adsorbed TiO 2 films (Ti-PN), were carefully investigated and compared to PN adsorbed ZrO 2 films (Zr-PN). In addition, we examined the self-assembled PN films and found that, in their self-assembled state, these molecules exhibited a longer relaxation time than Zr-PN monomeric films, where the charge injection channel was insignificant. The ground-state bleach band in the Ti-PN films gradually shifted to longer wavelengths, indicating the occurrence of the Stark effect. Faster electron injection was observed for the metalated PN systems and the electron injection times from the various excited states to the conduction band of TiO 2 (CB-TiO 2 ) were obtained from the target model analysis of the transient absorption spectra data matrix. In these metal-organic complexes, hot electron injection from PN to CB-TiO 2 occurred on a time scale of <360 fs. Importantly, Cu(II)-based PN complexes exhibited faster injection and longer recombination times. The injection times have been estimated to result from a locally excited state at ≈280 fs, a hot singlet excited state at 4.95 ps, and a vibrationally relaxed singlet excited state at 97.88 ps. The critical photophysical and charge injection processes seen here provide the potential for exploring the underlying factors involved and how they correlate with photocatalytic performance.

The present work demonstrates the ultrafast carrier dynamics and third-order nonlinear optical properties of electrochemically fabricated free-standing porous silicon (FS-PSi)-based optical microcavities via femtosecond transient absorption spectroscopy (TAS) and single-beam Z-scan techniques, respectively. The TAS (pump: 400 nm, probe: 430-780 nm, ∼70 fs, 1 kHz) decay dynamics are dominated by the photoinduced absorption (PIA, lifetime range: 4.7-156 ps) as well as photoinduced bleaching (PIB, 4.3-324 ps) for the cavity mode (λ c ) and the band edges. A fascinating switching behavior from the PIB (-ve) to the PIA (+ve) has been observed in the cavity mode, which shows the potential in ultrafast switching applications. The third-order optical nonlinearities revealed an enhanced two-photon absorption coefficient (β) in the order of 10 -10 mW -1 along with the nonlinear refractive index ( n 2 ) in the range of 10 -17 m 2 W -1 . Furthermore, a real-time sensing application of such FS-PSi microcavities has been demonstrated for detecting organic solvents by simultaneously monitoring the kinetics in reflection and transmission mode.

β-Heptasubstituted porphyrins [MTPP(NO 2 )X 6 ; M = 2H, Ni II , Cu II , and Zn II ; X = Br, Ph, and PE] were synthesized and their third-order nonlinear optical (NLO) properties explored using the single-beam Z -scan technique with femtosecond, MHz pulses in the visible range. The three-photon absorption ( γ ), third-order nonlinear optical susceptibility ( χ 3 ), three-photon absorption cross-section ( σ 3 ), and nonlinear refractive index ( n 2 ) have been determined from theoretical fits with experimental results. The sign and magnitude of the nonlinear refractive index ( n 2 ) have been obtained from the closed-aperture experiment while the three-photon absorption coefficient and three-photon absorption cross-section were determined from the open-aperture experiment. The magnitudes of the 3PA and σ 3 extended in the range of (2.7-3.4) × 10 -23 cm 3 W -2 and (5.5-7.0) × 10 -78 cm 6 s 2 , respectively. The higher magnitude of the NLO coefficients ensures their utility in optical and photonic applications.

We report a study of the role of material's conductivity in determining the morphology of nanoparticles and nanostructures produced by ultrafast laser ablation of solids. Nanoparticles and textured surfaces formed by laser ablation display a wide variation in size and morphology depending on the material. In general, these qualities can be grouped as to material type, insulator, semiconductor, or metal; although each has many other different material properties that make it difficult to identify the critical material factor. In this report, we study these nanoparticle/surface structural characteristics as a function of silicon (Si) resistivity, thus honing-in on this critical parameter and its effects. The results show variations in morphology, optical, and nonlinear properties of Si nanoparticles. The yield of colloidal Si nanoparticles increased with an increase in the conductivity of Si. Laser-induced periodic surface structures formed on ablated substrates are also found to be sensitive to the initial conductivity of the material. Further, the laser ablation of Gamma-irradiated Si has been investigated to verify the influence of altered conductivity on the formation of Si nanoparticles. These observations are interpreted using the basic mechanisms of the laser ablation process in a liquid and its intricate relation with the initial density of states and thermal conductivities of the target material., (© 2024 IOP Publishing Ltd.)

Metal nanoparticles (MNPs) are synthesized using various techniques on diverse substrates that significantly impact their properties. However, among the substrate materials investigated, the major challenge is the stability of MNPs due to their poor adhesion to the substrate. Herein, it is demonstrated how a newly developed H-glass can concurrently stabilize plasmonic gold nanoislands (GNIs) and offer multifunctional applications. The GNIs on the H-glass are synthesized using a simple yet, robust thermal dewetting process. The H-glass embedded with GNIs demonstrates versatility in its applications, such as i) acting as a room temperature chemiresistive gas sensor (70% response for NO 2 gas); ii) serving as substrates for surface-enhanced Raman spectroscopy for the identifications of Nile blue (dye) and picric acid (explosive) analytes down to nanomolar concentrations with enhancement factors of 4.8 × 10 6 and 6.1 × 10 5 , respectively; and iii) functioning as a nonlinear optical saturable absorber with a saturation intensity of 18.36 × 10 15 W m -2 at 600 nm, and the performance characteristics are on par with those of materials reported in the existing literature. This work establishes a facile strategy to develop advanced materials by depositing metal nanoislands on glass for various functional applications., (© 2023 Wiley-VCH GmbH.)

This study reveals the possibility of distinct ablation mechanisms at different radial positions of the ablated track on GaAs when ablated with femtosecond pulses in distilled water. From the center to the edges of the ablated track, fascinating features such as micron-sized cones, nano-pores, and nano-ripple trenches (average size of 60-70 nm) were observed. The requirement for simulations incorporating the variations in a Gaussian beam fluence and dynamics of the melt flow/surrounding media is discussed. Deep-subwavelength structures, i.e., nano-ripple trenches with a ripple size of ∼λ/11 are achieved on the GaAs surface in this study. Further, these GaAs surface structures acted as excellent hybrid surface-enhanced Raman spectroscopy platforms upon gold coating.

We present a simple, fast, and single-step approach for fabricating hybrid semiconductor-metal nanoentities through liquid-assisted ultrafast (∼50 fs, 1 kHz, 800 nm) laser ablation. Femtosecond (fs) ablation of Germanium (Ge) substrate was executed in (i) distilled water (ii) silver nitrate (AgNO 3 -3, 5, 10 mM) (iii) Chloroauric acid (HAuCl 4 -3, 5, 10 mM), yielding the formation of pure Ge, hybrid Ge-silver (Ag), Ge-gold (Au) nanostructures (NSs) and nanoparticles (NPs). The morphological features and corresponding elemental compositions of Ge, Ge-Ag, and Ge-Au NSs/NPs have been conscientiously studied using different characterization techniques. Most importantly, the deposition of Ag/Au NPs on the Ge substrate and their size variation were thoroughly investigated by changing the precursor concentration. By increasing the precursor concentration (from 3 mM to 10 mM), the deposited Au NPs and Ag NPs' size on the Ge nanostructured surface was increased from ∼46 nm to ∼100 nm and from ∼43 nm to ∼70 nm, respectively. Subsequently, the as-fabricated hybrid (Ge-Au/Ge-Ag) NSs were effectively utilized to detect diverse hazardous molecules (e.g. picric acid and thiram) via the technique of surface-enhanced Raman scattering (SERS). Our findings revealed that the hybrid SERS substrates achieved at 5 mM precursor concentration of Ag (denoted as Ge-5Ag) and Au (denoted as Ge-5Au) had demonstrated superior sensitivity with the enhancement factors of ∼2.5 × 10 4 , 1.38 × 10 4 (for PA), and ∼9.7 × 10 5 and 9.2 × 10 4 (for thiram), respectively. Interestingly, the Ge-5Ag substrate has exhibited ∼10.5 times higher SERS signals than the Ge-5Au substrate., (© 2023 IOP Publishing Ltd.)

Lead-free halide double perovskite nanocrystals (DPNCs) are emerging materials, recently explored as potential candidates in light-emitting, photovoltaic, and other optoelectronic applications. This Letter reveals unusual photophysical phenomena and nonlinear optical (NLO) properties of Mn-doped Cs 2 AgInCl 6 nanocrystals (NCs) via temperature-dependent photoluminescence (PL) and femtosecond Z-scan measurements. The PL emission measurements suggest that self-trapped excitons (STEs) are present, and more than one STE state is possible for this doped double perovskite. We observed enhanced NLO coefficients, owing to the improved crystallinity arising from the Mn doping. From the closed aperture Z-scan data, we have calculated two fundamental parameters, Kane energy (29 eV) and exciton reduced mass (0.22m 0 ). We further obtained the optical limiting onset (1.84 mJ/cm 2 ) and figure of merit as a proof-of-concept application to demonstrate the potential in optical limiting and optical switching applications. Highlighting the self-trapped excitonic emission and NLO applications, the multifunctionality of this material system is demonstrated. This investigation provides an avenue to design novel photonic and nonlinear optoelectronic devices.

The technique of ultrafast laser ablation in liquids has evolved and matured over the past decade, with several impending applications in various fields such as sensing, catalysis, and medicine. The exceptional feature of this technique is the formation of nanoparticles (colloids) and nanostructures (solids) in a single experiment with ultrashort laser pulses. We have been working on this technique for the past few years, investigating its potential using the surface-enhanced Raman scattering (SERS) technique in hazardous materials sensing applications. Ultrafast laser-ablated substrates (solids and colloids) could detect several analyte molecules at the trace levels/mixture form, including dyes, explosives, pesticides, and biomolecules. Here, we present some of the results achieved using the targets of Ag, Au, Ag-Au, and Si. We have optimized the nanostructures (NSs) and nanoparticles (NPs) obtained (in liquids and air) using different pulse durations, wavelengths, energies, pulse shapes, and writing geometries. Thus, various NSs and NPs were tested for their efficiency in sensing numerous analyte molecules using a simple, portable Raman spectrometer. This methodology, once optimized, paves the way for on-field sensing applications. We discuss the protocols in (a) synthesizing the NPs/NSs via laser ablation, (b) characterization of NPs/NSs, and (c) their utilization in the SERS-based sensing studies.

Cs 2 AgInCl 6 double perovskite (DP) nanocrystals (NCs) are an emerging class of materials with promising application potential in photonics/optoelectronics owing to their nontoxicity, direct bandgap, and high thermal and moisture stability. These NCs are, however, rarely explored for nonlinear optical (NLO) applications. Herein, we present a comprehensive investigation of the photophysical and nonlinear optical properties of erbium- (Er) and ytterbium (Yb)-doped Cs 2 AgInCl 6 nanocrystals (denoted as Er-DP and Yb-DP, respectively). Temperature-dependent photoluminescence of these NCs was analyzed to estimate their exciton binding energy, Huang-Rhys parameter ( S ), and electron-phonon coupling strength, which are of fundamental interest to gain an in-depth understanding of the material systems. Femtosecond Z -scan experiments with 800 nm excitation revealed the reverse saturable absorption (RSA) behavior owing to three-photon absorption (3PA). The obtained values of the 3PA coefficients were 1.35 × 10 -4 and 1.64 × 10 -4 cm 3 GW -2 , respectively, and the nonlinear refractive indices were estimated to be 1.02 × 10 -15 and 1.15 × 10 -15 cm 2 W -1 , respectively, for Er-DP and Yb-DP. These values are superior to those obtained in undoped Cs 2 AgInCl 6 NCs. The physical parameter, Kane energy, which is closely related to the magnitude of the oscillator strength, was estimated to be 25 eV and 26 eV for Er-DP and Yb-DP, respectively. As a proof-of-concept application, we further obtained the optical limiting onset and figure of merit to reveal their prospect as an optical limiter and in photonic switching application. With such emission and nonlinear optical properties, we anticipate that lanthanide-doped Cs 2 AgInCl 6 NCs can be used for designing eco-friendly nonlinear optoelectronic/photonic devices.

Asymmetrically substituted porphyrins possessing ethyl acetoacetate or acetylacetone (EAA or acac) with six bromine atoms at β-positions were synthesized and then characterized by various spectroscopic techniques, such as UV-Vis, fluorescence and NMR, and also by CV, DFT, MALDI-TOF-MS and elemental analysis. The mechanistic pathway followed the nucleophilic substitution reaction (nucleophile: EAA and acac) with MTPP(NO 2 )Br 6 (M = 2H, Cu(II), and Ni(II)), and the resultant β-heptasubstituted porphyrins exhibited keto-enol tautomerism, as supported by 1 H NMR spectroscopy. The six bulky bromo and EAA/acac groups made the macrocyclic ring highly electron deficient and nonplanar such that the quantum yield and fluorescence intensity for H 2 TPP[EAA]Br 6 and H 2 TPP[acac]Br 6 were severely reduced in contrast to those values for H 2 TPP. The poor electron density and nonplanarity over the porphyrin ring shifted the first oxidation potential from 11 to 521 mV anodically for MTPP[X]Br 6 [M = 2H, Cu(II), and Ni(II); X = EAA or acac] as compared to corresponding MTPPs. Notably, density functional theory proved the nonplanarity of the synthesized porphyrins as Δ24 spans from ±0.546 to ± 0.559 Å while Δ C β stretches from ±0.973 to ±1.162 Å. The third-order nonlinear optical measurements were performed using the femtosecond pulsed laser Z -scan technique at 800 nm and 1 kHz repetition rate to acquire insights into nonlinear absorption and nonlinear refraction of the porphyrins. The three-photon absorption coefficients ( γ ) are in the range of 2.2 × 10 -23 -2.8 × 10 -23 cm 3 W -2 and the nonlinear refractive index values were in the range of 3.7 × 10 -16 -5.1 × 10 -16 cm 2 W -1 . The higher-order nonlinear absorption exhibited by porphyrins helps improve resolution at depth for various photonic and optoelectronic applications.

Surface-enhanced Raman spectroscopy (SERS) is an improved Raman spectroscopy technique to identify the analyte under study uniquely. At the laboratory scale, SERS has realised a huge potential to detect trace analytes with promising applications across multiple disciplines. However, onsite detection with SERS is still limited, given the unwanted glitches of signal reliability and blinking. SERS has inherent signal fluctuations due to multiple factors such as analyte adsorption, inhomogeneous distribution of hotspots, molecule orientation etc. making it a stochastic process. Given these signal fluctuations, validating a signal as a representation of the analyte often relies on an expert's knowledge. Here we present a neural network-aided SERS model (NNAS) without expert interference to efficiently identify reliable SERS spectra of trace explosives (tetryl and picric acid) and a dye molecule (crystal violet). The model uses the signal-to-noise ratio approach to label the spectra as representative (RS) and non-representative (NRS), eliminating the reliability of the expert. Further, experimental conditions were systematically varied to simulate general variations in SERS instrumentation, and a deep-learning model was trained. The model has been validated with a validation set followed by out-of-sample testing with an accuracy of 98% for all the analytes. We believe this model can efficiently bridge the gap between laboratory and on-site detection using SERS., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Surface-enhanced Raman spectroscopy/scattering (SERS) has evolved into a popular tool for applications in biology and medicine owing to its ease-of-use, non-destructive, and label-free approach. Advances in plasmonics and instrumentation have enabled the realization of SERS's full potential for the trace detection of biomolecules, disease diagnostics, and monitoring. We provide a brief review on the recent developments in the SERS technique for biosensing applications, with a particular focus on machine learning techniques used for the same. Initially, the article discusses the need for plasmonic sensors in biology and the advantage of SERS over existing techniques. In the later sections, the applications are organized as SERS-based biosensing for disease diagnosis focusing on cancer identification and respiratory diseases, including the recent SARS-CoV-2 detection. We then discuss progress in sensing microorganisms, such as bacteria, with a particular focus on plasmonic sensors for detecting biohazardous materials in view of homeland security. At the end of the article, we focus on machine learning techniques for the (a) identification, (b) classification, and (c) quantification in SERS for biology applications. The review covers the work from 2010 onwards, and the language is simplified to suit the needs of the interdisciplinary audience., Competing Interests: The authors declare no conflict of interest.

We have developed simple and cost-effective surface-enhanced Raman scattering (SERS) substrates for the trace detection of pesticide (thiram and thiabendazole) and dye (methylene blue and Nile blue) molecules. Surface patterns (micro/nanostructures) on silicon (Si) substrates were fabricated using the technique of femtosecond (fs) laser ablation in ambient air. Different surface patterns were achieved by tuning the number of laser pulses per unit area (4200, 8400, 42 000, and 84 000 pulses per mm 2 ) on Si. Subsequently, chemically synthesized gold (Au) nanostars were embedded in these laser-patterned areas of Si to achieve a plasmonic active hybrid SERS substrate. Further, the SERS performance of the as-prepared Au nanostar embedded Si substrates were tested with different probe molecules. The as-prepared substrates allowed us to detect a minimum concentration of 0.1 ppm in the case of thiram, 1 ppm in the case of thiabendazole (TBZ), 1.6 ppb in the case of methylene blue (MB), and 1.8 ppb in case of Nile blue (NB). All these were achieved using a simple, field-deployable, portable Raman spectrometer. Additionally, the optimized SERS substrate demonstrated ∼21 times higher SERS enhancement than the Au nanostar embedded plain Si substrate. Furthermore, the optimized SERS platform was utilized to detect a mixture of dyes (MB + NB) and pesticides (thiram + TBZ). The possible reasons for the observed additional enhancement are elucidated., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A series of three novel tetrabenzotriazacorroles (TBCs) designed with an alkyl substituent tert -butyl group (TBC-tert), an electron donor phenothiazine group (TBC-PTZ) and an energy donor carbazole group (TBC-CBZ) on the peripheral position with phosphorus metal in the cavity have been synthesized. All three compounds were characterized using various spectroscopic techniques and we assessed their femtosecond third-order nonlinear optical (NLO) properties. TBCs exhibit the properties of both phthalocyanines and corroles as they are derived from parent phthalocyanines. The optical studies revealed a new band at ∼450 nm, which was absent in the parent phthalocyanine molecules, and all three compounds obeyed Beer-Lambert's law. Singlet-state quantum yields were measured in different solvents and were found to be in the range of 0.3 to 0.6 for TBC-tert, 0.21 to 0.25 in the case of TBC-PTZ and 0.31 to 0.41 for TBC-CBZ. Time-resolved fluorescence studies revealed lifetimes in the ns regime (typically few ns). The redox properties of the TBCs suggest that they are easier to oxidize and harder to reduce and exhibit multiple oxidation and reduction potentials. Using the Z -scan technique, the third-order NLO properties were investigated with kilohertz and megahertz repetition rate femtosecond pulses at 800 nm. We report the first observation of strong three-photon absorption in these molecules with coefficients of ∼10 -22 cm 3 W -2 (∼10 -13 cm 3 W -2 ) with kHz (MHz) repetition rate fs pulse excitation.

The nonlinear optical properties of pure ZnO and Ni-doped ZnO thin films are explored using the Z-scan technique at different input laser intensities and an excitation wavelength of 750 nm by 100 fs laser pulses. The pure ZnO and Ni-doped ZnO thin films were prepared by radio frequency magnetron sputtering at room temperature. A scanning electron microscope equipped with energy-dispersive x-ray spectroscopy was used to measure the thickness and composition of the thin films, while a UV-visible spectrophotometer was used to measure the linear optical properties. The structure of the thin films was measured using x-ray diffraction. Saturable absorption (SA) was observed in the pure ZnO thin film, while Ni-doped ZnO illustrated a combination of SA and reverse SA (RSA). The nonlinear absorption coefficient ( β ) and nonlinear refractive index ( n 2 ) of both pure ZnO and Ni-doped ZnO thin films were found to be input laser intensity dependent. As the input laser intensity increased, the nonlinear absorption coefficient and the nonlinear refractive index of both samples increased. An enhancement of two times in the nonlinear refractive index was observed for the Ni-doped ZnO thin film compared to the pure ZnO thin film. The optical limiting behavior of pure ZnO and Ni-doped ZnO thin films was investigated, and the data demonstrated that Ni-doped ZnO thin film is a good candidate for optical limiter applications due to the presence of strong RSA.

Recently, filter paper (FP)-based surface-enhanced Raman scattering (SERS) substrates have stimulated significant attention owing to their promising advantages such as being low-cost, easy to handle, and practically suitable for real-field applications in comparison to the solid-based substrates. Herein, a simple and versatile approach of laser-ablation in liquid for the fabrication of silver (Ag)-gold (Au) alloy nanoparticles (NPs). Next, the optimization of flexible base substrate (sandpaper, printing paper, and FP) and the FP the soaking time (5−60 min) was studied. Further, the optimized FP with 30 min-soaked SERS sensors were exploited to detect minuscule concentrations of pesticide (thiram-50 nM), dye (Nile blue-5 nM), and an explosive (RDX-1,3,5-Trinitroperhydro-1,3,5-triazine-100 nM) molecule. Interestingly, a prominent SERS effect was observed from the Au NPs exhibiting satisfactory reproducibility in the SERS signals over ~1 cm2 area for all of the molecules inspected with enhancement factors of ~105 and relative standard deviation values of <15%. Furthermore, traces of pesticide residues on the surface of a banana and RDX on the glass slide were swabbed with the optimized FP substrate and successfully recorded the SERS spectra using a portable Raman spectrometer. This signifies the great potential application of such low-cost, flexible substrates in the future real-life fields.

A zeroth-order, non-diffracting Bessel beam, generated by picosecond laser pulses (1064 nm, 10 Hz, 30 ps) through an axicon, was utilized to perform pulse energy-dependent (12 mJ, 16 mJ, 20 mJ, 24 mJ) laser ablation of silver (Ag) substrates in air. The fabrication resulted in finger-like Ag nanostructures (NSs) in the sub-200 nm domain and obtained structures were characterized using the FESEM and AFM techniques. Subsequently, we employed those Ag NSs in surface-enhanced Raman spectroscopy (SERS) studies achieving promising sensing results towards trace-level detection of six different hazardous materials (explosive molecules of picric acid (PA) and ammonium nitrate (AN), a pesticide thiram (TH) and the dye molecules of Methylene Blue (MB), Malachite Green (MG), and Nile Blue (NB)) along with a biomolecule (hen egg white lysozyme (HEWL)). The remarkably superior plasmonic behaviour exhibited by the AgNS corresponding to 16 mJ pulse ablation energy was further explored. To accomplish a real-time application-oriented understanding, time-dependent studies were performed utilizing the AgNS prepared with 16 mJ and TH molecule by collecting the SERS data periodically for up to 120 days. The coated AgNSs were prepared with optimized gold (Au) deposition, accomplishing a much lower trace detection in the case of thiram (~50 pM compared to ~50 nM achieved prior to the coating) as well as superior EF up to ~10 8 (~10 6 before Au coating). Additionally, these substrates have demonstrated superior stability compared to those obtained before Au coating.

In this study, we report a novel, to the best of our knowledge, instrumentation procedure in the automation of laser beam steering for raster/spiral scanning of the samples used in standoff femtosecond laser-induced breakdown spectroscopy (LIBS) experiments. We have used a readily available and easy-to-handle Arduino-based computerized numerical control (CNC) shield along with the free software, universal G-code sender, for the automation. Standoff femtosecond filamentation-induced breakdown spectra (St-Fs-FIBS) of metals, three compositions of Ag-Au alloy, and polyvinyl chloride, unplasticized polyvinyl chloride, and chlorinated polyvinyl chloride plastic samples were recorded using the developed automated experimental setup. The St-Fs-FIBS spectra were recorded at a standoff distance of ∼5 m utilizing a simple hand-held spectrometer. Furthermore, principal component analysis technique was utilized for the successful classification of three compositions of Au-Ag alloy spectra using their St-Fs-FIBS spectral data.

Given the intrinsic nature of low reproducibility and signal blinking in the surface enhanced Raman scattering (SERS) technique, especially while detecting trace/ultra-trace amounts, it remains a major challenge to quantify the analyte under study. Here we present a simple and economically viable, flexible hydrophobic plasmonic filter paper-based SERS substrate for the quantification of two trace analytes [crystal violet (CV) and picric acid (PA)] using machine learning techniques and SERS data. The wettability of the substrate was modified with an easy and low-cost technique of coating it with silicone oil. Gold nanoparticles were synthesized using a femtosecond laser ablation in water technique. The prepared nanoparticles were characterized using UV, TEM, and SEM techniques and subsequently loaded onto filter papers before using them for SERS studies. We have considered the SERS intensities of the analytes at different concentrations with over 900 spectra to train the model. Principal component analysis (PCA) was used to reduce the dimensionality and, hence, the complexity of the model. Furthermore, support vector regression was used to quantify the analyte molecules and we achieved an R 2 error of 0.9629 for CV and 0.9472 for PA. In conjunction with a portable Raman spectrometer and a computation time of less than <10 s, we believe that this is an affordable and rapid method for quantification of analytes using the SERS technique.

We report the fabrication and performance evaluation of hybrid surface-enhanced Raman scattering (SERS) substrates involving laser ablation and chemical routes for the trace-level detection of various analyte molecules. Initially, picosecond laser ablation experiments under ambient conditions were performed on pure silver (Ag) and gold (Au) substrates to achieve distinct nanosized features on the surface. The properties of the generated surface features on laser-processed portions of Ag/Au targets were systematically analyzed using UV-visible reflection and field emission scanning electron microscopy studies. Later, hybrid-SERS substrates were achieved by grafting the chemically synthesized Au nanostars on the plain and laser-processed plasmonic targets. Subsequently, we employed these as SERS platforms for the detection of a pesticide (thiram), a molecule used in explosive compositions [ammonium nitrate (AN)], and a dye molecule [Nile blue (NB)]. A comparative SERS study between the Au nanostar-decorated bare glass, silicon, Ag, Au, and laser-processed Ag and Au targets has been established. Our studies and the obtained data have unambiguously determined that laser-processed Ag structures have demonstrated reasonably good enhancements in the Raman signal intensities for distinct analytes among other substrates. Importantly, the fabricated hybrid SERS substrate of "Au nanostar-decorated laser-processed Ag" exhibited up to eight times enhancement in the SERS intensity compared to laser-processed Ag (without nanostars), as well as up to three times enhancement than the Au nanostar-loaded plain Ag substrates. Additionally, the achieved detection limits from the Au nanostar-decorated laser-processed Ag SERS substrate were ∼50 pM, ∼5 nM, and ∼5 μM for NB, thiram, and AN, respectively. The estimated enhancement factors accomplished from the Au nanostar-decorated laser-processed Ag substrate were ∼10 6 , ∼10 6 , and ∼10 4 for NB, thiram, and AN, respectively., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

We report results from our extensive studies on the fabrication of ultra-thin, flexible, and cost-effective Ag nanoparticle (NP) coated free-standing porous silicon (FS-pSi) for superior molecular sensing. The FS-pSi has been prepared by adopting a simple wet-etching method. The deposition time of AgNO 3 has been increased to improve the number of hot-spot regions, thereby the sensing abilities are improved efficiently. FESEM images illustrated the morphology of uniformly distributed AgNPs on the pSi surface. Initially, a dye molecule [methylene blue (MB)] was used as a probe to evaluate the sensing capabilities of the substrate using the surface-enhanced Raman scattering (SERS) technique. The detection was later extended towards the sensing of two important explosive molecules [ammonium nitrate (AN), picric acid (PA)], and a pesticide molecule (thiram) clearly demonstrating the versatility of the investigated substrates. The sensitivity was confirmed by estimating the analytical enhancement factor (AEF), which was ∼10 7 for MB and ∼10 4 for explosives and pesticides. We have also evaluated the limit of detection (LOD) values in each case, which were found to be 50 nM, 1 µM, 2 µM, and 1 µM, respectively, for MB, PA, AN, and thiram. Undeniably, our detailed SERS results established excellent reproducibility with a low RSD (relative standard deviation). Furthermore, we also demonstrate the reasonable stability of AgNPs decorated pSi by inspecting and studying their SERS performance over a period of 90 days. The overall cost of these substrates is attractive for practical applications on account of the above-mentioned superior qualities.

A new series of non-aqueous phthalocyanines having 3,4,5-trimethoxy phenyl group at peripheral positions in which the central cavity possessing Cu(II), Zn(II), and without metals has been synthesized, and its absorption, fluorescence (steady-state and excited state lifetimes), electrochemical, and third-order nonlinear optical (NLO) properties were evaluated. Absorption studies data suggest that all three phthalocyanines obey Beer-Lambert's law, and the redox properties indicate that both oxidation and reduction reactions are macrocyclic centered. The singlet quantum yields were measured in different solvents and were found to be in the range of 0.2-0.5 in the case of free-base, whereas it was in the range of 0.1-0.5 in zinc derivative, while the time-resolved fluorescence data revealed lifetimes of typically a few ns. The third-order NLO properties were investigated using the Z-scan technique with kilohertz (for retrieving true electronic nonlinearities) and megahertz repetition rate femtosecond pulses at 800 nm. Intensity-dependent Z-scan studies revealed robust NLO coefficients for solutions and thin films (two-photon absorption cross-sections of 9,300-57,000 GM) of these molecules suggesting a strong potential for optical switching, imaging, and optical limiting applications., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Srivishnu, Banerjee, Ramnagar, Rathod, Giribabu and Soma.)

A new series of "push-pull"meso-substituted trans-A 2 BC porphyrins, where A = mesityl, B = phenothiazine (push) and C = o/p-nitrophenyl moiety (pull) and M = 2H, Ni(ii), Cu(ii), and Zn(ii), were synthesized. These trans-A 2 BC porphyrins were characterized by various techniques viz. UV-Vis, fluorescence and NMR spectroscopy, matrix assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry, cyclic voltammetry, single-crystal X-ray diffraction analysis and density functional theory (DFT) studies. The single crystal structure of the newly synthesized free base trans-H 2 A 2 BC porphyrin (2) revealed the orientation of meso-substituents and the planar conformation of the porphyrin core. All newly synthesized free base trans-H 2 A 2 BC porphyrins (1 or 2) and their metal complexes exhibited a sharp Soret band. The first reduction potential of all synthesized trans-MA 2 BC porphyrins showed an anodic shift as compared with that of meso-tetraphenylporphyrins (MTPPs) due to the strong electron withdrawing nature of the nitrophenyl group. In general, the first oxidation potential of trans-MA 2 BC porphyrins shows a cathodic shift due to the electron donating phenothiazine moiety as compared to that of MTPPs. p-Nitrophenyl appended trans-A 2 BC porphyrins exhibited large ground state dipole moment values (8.59-9.64 D) as compared to MTPPs (0.0013-0.052 D) owing to the polarized "push-pull" effect of meso-substituents such as phenothiazine (push) and nitrophenyl (pull) moieties. Femtosecond nonlinear optical (NLO) studies performed with kHz pulses at 800 nm revealed strong two-photon absorption coefficients (∼0.082-0.0953 cm GW -1 ) and cross-sections (∼1.71-1.95 × 10 3 GM) for these "push-pull" porphyrins. We have also attempted to understand the NLO coefficients in terms of the structural changes in these porphyrin derivatives. A comparison that has been accomplished with similar porphyrin molecules and under similar experimental conditions revealed the superior performance of the title molecules. Furthermore, femtosecond transient absorption studies demonstrated several ultrafast processes from various excited states in these porphyrins, useful for identifying the processes relevant to optical switching applications.

The structural, thermal, linear, and femtosecond third-order nonlinear optical (NLO) properties of two pyridine-based anthracene chalcones, (2 E )-1-(anthracen-9-yl)-3-(pyridin-2-yl)prop-2-en-1-one ( 2PANC ) and (2 E )-1-(anthracen-9-yl)-3-(pyridin-3-yl)prop-2-en-1-one ( 3PANC ), were investigated. These two chalcones were synthesized following the Claisen-Schmidt condensation method. Optically transparent single crystals were achieved using a slow evaporation solution growth technique. The presence of functional groups in these molecules was established by Fourier transform infrared and NMR spectroscopic data. The detailed solid-state structure of both chalcones was determined from the single-crystal X-ray diffraction data. Both crystals crystallized in the centrosymmetric triclinic space group P 1̅ with the nuance of unit cell parameters. The crystals (labeled as 2PANC and 3PANC ) have been found to be transparent optically [in the entire visible spectral region] and were found to be thermally stable up to 169 and 194 °C, respectively. The intermolecular interactions were investigated using the Hirshfeld surface analysis, and the band structures (highest occupied molecular orbital-lowest unoccupied molecular orbital, excited-state energies, global chemical reactivity descriptors, and molecular electrostatic potentials) were studied using density functional theory (DFT) techniques. The ultrafast third-order NLO properties were investigated using (a) Z -scan and (b) degenerate four-wave mixing (DFWM) techniques using ∼50 fs pulses at 800 nm (1 kHz, ∼4 mJ) from a Ti:sapphire laser amplifier. Two-photon-assisted reverse saturable absorption, self-focusing nonlinear refraction, optical limiting, and optical switching behaviors were witnessed from the Z -scan data. 3PANC demonstrated a stronger two-photon absorption coefficient, while 2PANC depicted a stronger nonlinear refractive index among the two. The time-resolved DFWM data demonstrated that the decay times of 2PANC and 3PANC were ∼162 and ∼180 fs, respectively. The second hyperpolarizability (γ) values determined by DFT, Z -scan, and DFWM were found to be in good correlation (with a magnitude of ∼10 -34 esu). The ultrafast third-order NLO response, significant NLO properties, and thermal stability of these chalcones brands them as potential candidates for optical power limiting and switching applications.

We demonstrate the detection of dipicolinic acid, (DPA), a biomarker of bacterial spores for Bacillus anthracis, 2,4-Dinitrotoluene (DNT) and picric acid (PA) nitroaromatic hazardous chemicals on ultra-sensitive, reusable femtosecond laser textured Au nanostructures decorated with hierarchical AuNPs as a SERS substrate. The AuNPs were achieved by ablating an Au sheet using two different laser scan speeds (1 and 0.1 mm/s) in linear and crossed patterns. The morphological studies revealed dense hierarchical nanostructures decorated with spherical AuNPs possessing 30-40 nm in size in 0.1 mm/s laser scan. The limits of detection (LOD) of the sensor were determined from the detailed SERS measurements and were estimated to be 0.83 pg/L, 3.6 pg/L and 2.3 pg/L for DPA, DNT, and PA, respectively. To the best of our knowledge, the achieved sensitivity is nearly 2 orders improved for DPA when compared with the currently reported LODs using other techniques and 1 order in the case of SERS. Moreover, for DNT and PA the LODs were found to be either superior or comparable with recent reports. We have also demonstrated the competence of our SERS substrates by testing a few real samples (water spiked with these analytes) and again obtained very good sensitivity., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Increasingly, two-dimensional (2D) materials are being investigated for their potential use as surface-enhanced Raman spectroscopy (SERS) active substrates. Hexagonal Boron Nitride (hBN), a layered 2D material analogous to graphene, is mostly used as a passivation layer/dielectric substrate for nanoelectronics application. We have investigated the SERS activity of few-layer hBN film synthesized on copper foil using atmospheric pressure chemical vapor deposition. We have drop casted the probe molecules onto the hBN substrate and measured the enhancement effect due to the substrate using a 532 nm excitation laser. We observed an enhancement of ≈10 3 for malachite green and ≈10 4 for methylene blue and rhodamine 6G dyes, respectively. The observed enhancement factors are consistent with the theoretically calculated interaction energies of MB > R6G > MG with a single layer of hBN. We also observed that the enhancement is independent of the film thickness and surface morphology. We demonstrate that the hBN films are highly stable, and even for older hBN films prepared 7 months earlier, we were able to achieve similar enhancements when compared to freshly prepared films. Our detailed results and analyses demonstrate the versatility and durability of hBN films for SERS applications.

We report the fabrication and performance evaluation of cost-effective, reproducible silver nanodendrite (AgND) substrates, possessing high-density trunks and branches, achieved by a simple electroless etching process and subsequently utilized them for the trace detection of 1,3,5-trinitroperhydro-1,3,5-triazine (Research Development Explosive, RDX) and Ammonium Nitrate (AN). The intricate structural features in AgNDs offer high-density hotspots for effective molecular detection based on the surface enhanced Raman scattering (SERS) technique. The active SERS-substrate was initially tested with standard Rhodamine 6G (R6G) molecules at 1 nM concentration, which established an effective enhancement factor (EF) of ∼10 8 . The AgNDs were subsequently utilized in the detection of the explosives RDX and AN, down to concentrations of 1 μM. The typical EF achieved in the case of RDX and AN was ∼10 4 . The sensitivity of 1 μM R6G was further enhanced by two-fold through the deposition of Au nanoparticles on the AgNDs. The reproducibility of the low-cost substrate was also demonstrated, with a ∼9% RSD value in the measurements., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We report the fabrication of silver nanoribbons by picosecond laser ablation of bulk silver (Ag) targets submerged in double distilled water (DDW) using a cylindrical focusing geometry. The laser ablation was performed by ∼2 picosecond laser pulses and the corresponding light sheet engendered by a cylindrical lens of focal length ∼4.5 cm. The input pulse energies employed at a wavelength ∼800 nm in the experiments were ∼1000 μJ, ∼1200 μJ, and ∼1400 μJ. In contrast to the case of ablation with spherical lenses, cylindrical lens ablation produced nanoparticles (NPs) and nanostructures (NSs) in 20% less time. The data obtained from the optical characterizations exemplify that localized surface plasmon resonance (LSPR) was observed at 406 nm, 408 nm, and 410 nm for the input energies of ∼1000 μJ, ∼1200 μJ, and ∼1400 μJ, respectively. Interestingly, it was observed that the ablation performed at an input energy of ∼1200 μJ demonstrated the fabrication of Ag nanoribbons rather than the formation of Ag NPs. Selected area electron diffraction (SAED) data of the nanoribbons recorded revealed their crystalline phase and linear morphology. Ag nanomaterials (NPs and ribbons) synthesized in these experiments were employed to detect the explosive molecules of 2,4,6-trinitrotoluene (TNT) at a concentration 25 nM using the technique of surface enhanced Raman scattering. The enhancement factor in the case of Ag nanoribbons (width of ∼20-30 nm, length of ∼0.6-2 μm), obtained using the cylindrical focussing geometry at input pulse energies of ∼1200 μJ, was estimated to be ∼10 7 for the 1362 cm -1 mode, corresponding to the symmetric NO 2 stretch of TNT., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Two new series of β-triphenylamine-appended porphyrins (MTPP(TPA) 2 X, (where M = 2H, Co(ii), Ni(ii), Cu(ii), Zn(ii) and X = NO 2 /CHO) have been synthesized and characterized by various spectroscopic techniques, namely, UV-vis, fluorescence, NMR spectroscopy, mass spectrometry, cyclic voltammetry, density functional theory and ultrafast nonlinear optical (NLO) studies. They exhibited 16-22 nm and 39-58 nm red-shifts in the Soret and Q x (0,0) bands, respectively, as compared to MTPPs due to the resonance and inductive effects of β-substituents on the porphyrin π-system. The first reduction potential of CuTPP(TPA) 2 NO 2 and CuTPP(TPA) 2 CHO exhibited an anodic shift by 0.44 and 0.36 V, respectively, as referenced to CuTPP, due to the electronic nature of β-substituents (NO 2 and CHO), which led to their easier reduction compared with CuTPP. H 2 TPP(TPA) 2 NO 2 and H 2 TPP(TPA) 2 CHO exhibited the largest resultant dipole moments (7.66 D and 4.55 D, respectively) as compared to H 2 TPP (0.052 D) due to the cross-polarized push-pull effect of β-substituents (NO 2 /CHO and triphenylamino groups) and the nonplanarity of the macrocyclic core. Third-order nonlinear optical properties of MTPP(TPA) 2 NO 2 and MTPP(TPA) 2 CHO (M = 2H and Zn(ii)) were investigated in a broad spectral range (680-850 nm) using the Z-scan technique with femtosecond 80 MHz pulses. These materials demonstrate strong nonlinear optical coefficients, endowing them with potential for prominent photonic applications.

The development of recyclable surface enhanced Raman scattering (SERS) based sensors has been in huge demand for trace level explosives detection. A simple, hybrid Silicon (Si) nanotextured target-based SERS platform is fabricated through patterning micro square arrays (MSA) on Si using femtosecond (fs) laser ablation technique at different fluences. Using the hybrid target Si MSA substrate loaded/decorated with Ag-Au alloy NPs (obtained using femtosecond ablation in liquids) we demonstrate the trace level detection of organic nitro-explosives [picric acid (PA), 2,4-dinitrotoluene (DNT), and 1, 3, 5-trinitroperhydro-1, 3, 5-triazine (RDX)] and their mixtures. The microstructures/nanostructures of MSA fabricated at an input fluence of 9.55 J/cm 2 , and decorated with Ag-Au alloy NPs, exhibited exceptional SERS enhancement factors (EFs) up to ∼10 10 for MB, ∼10 6 for PA, and ∼10 4 for RDX with the detection limits obtained being ∼5 pM, ∼36 nM, and ∼400 nM for MB, PA and RDX respectively. Furthermore, we demonstrate these SERS substrates possess good reproducibility (RSD values < 15%) and a superior performance compared to a commercial Ag substrate (SERSitive, Poland). Three binary mixtures, i.e. MB-PA, MB-DNT, PA-DNT at different concentrations, were also investigated using the same SERS substrate to test the efficacy. Further, the SERS spectra of dyes, explosives, and complex mixtures were utilized for discrimination/classification using principal component analysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

While the unabated race persists in achieving record efficiencies in solar cells and other photonic/optoelectronic devices using lead halide perovskite absorbers, a comprehensive picture of the correlated third-order nonlinear optical (NLO) properties is yet to be established. The present study is aimed at deciphering the role of dopants in multiphoton absorption properties of intentionally engineered CsPbBr 3 colloidal nanocrystals (NCs). The charge separation of the plasmon-semiconductor conduction band owing to the hot electron transfer at the interface was demystified using the dynamics of the bleached spectral data from femtosecond (fs) transient absorption spectroscopy with broadband capabilities. The NLO properties studied through the fs Z-scan technique revealed that Ni-doped CsPbBr 3 NCs exhibited strong third-order NLO susceptibility of ∼10 -10 esu. The exotic photophysical phenomena in these pristine and Ni-doped CsPbBr 3 colloidal two-dimensional (2D) NCs reported herein are believed to provide the avenues to address the critical variables involved in the structural differences and their correlated optoelectronic properties.

Surface enhanced Raman spectroscopy (SERS) is a cutting edge analytical tool for trace analyte detection due to its highly sensitive, non-destructive and fingerprinting capability. Herein, we report the detection of multiple analytes from various mixtures using gold nanoparticles (NPs) and nanostructures (NSs) as SERS platforms. NPs and NSs were achieved through the simple approach of laser ablation in liquids (LAL) and their morphological studies were conducted with a UV-Visible absorption spectrometer, a high resolution transmission electron microscope (HRTEM) and a field emission scanning electron microscope (FESEM). The fabricated NPs/NSs allowed the sensitive and selective detection of different mixed compounds containing (i) rhodamine 6G (Rh6G) and methylene blue (MB), (ii) crystal violet (CV) and malachite green (MG), (iii) picric acid (explosive) and MB (dye), (iv) picric acid and 3-nitro-1,2,4- triazol-5-one (explosive, NTO) and (v) picric acid and 2,4-dinitrotoluene (explosive, DNT) using a portable Raman spectrometer. Thus, the obtained results demonstrate the capability of fabricated SERS substrates in identifying explosives and dyes from various mixtures. This could pave a new way for simultaneous detection of multiple analytes in real field applications.

Fabrication of reproducible and versatile surface-enhanced Raman scattering (SERS) substrates is crucial for real-time applications such as explosive detection for human safety and biological imaging for cancer diagnosis. However, it still remains a challenging task, even after several methodologies were developed by various research groups, primarily due to (a) a lack of consistency in detection of a variety of molecules (b) cost-effectiveness of the SERS substrates prepared, and (c) byzantine preparation procedures, etc. Herein, we establish a procedure for preparing reproducible SERS-active substrates comprised of laser-induced nanoparticle-embedded periodic surface structures (LINEPSS) and metallization of silicon (Si) LINEPSS. LINEPSS were fabricated using the technique of femtosecond laser ablation of Si in acetone. The versatile SERS-active substrates were then achieved by two ways, including the drop casting of silver (Ag)/gold (Au) nanoparticles (NPs) on Si LINEPSS and Ag plating on the Si LINEPSS structures. By controlling the LINEPSS grating periodicity, the effect of plasmonic nanoparticles/plasmonic plating on the Si NPs embedded periodic surface structures enormously improved the SPR strength, resulting in the consistent and superior Raman enhancements. The reproducible SERS signals were achieved by detecting the molecules of Methylene Blue (MB), 2,4-dinitrotoluene (DNT), and 5-amino-3-nitro-l,2,4-triazole (ANTA). The SERS signal strength is determined by the grating periodicity, which, in turn, is determined by the input laser fluence. The SERS-active platform with grating periodicity of 130 ± 10 nm and 150 ± 5 nm exhibited strong Raman enhancements of ∼10 8 for MB and ∼10 7 for ANTA molecules, respectively, and these platforms are demonstrated to be capable, even for multiple usages., Competing Interests: The authors declare no competing financial interest.

The femtosecond filament-induced breakdown spectroscopy (FIBS) technique coupled with principal component analysis (PCA) is demonstrated for standoff (ST) analysis of metals, alloys (Al, Cu, brass, stainless steel), and bimetallic strips (Ag@Cu, Ag@Au with varying weight percentages). The experiments were performed by analyzing the filament-produced plasma at ∼6.5  m from the laser. The plasma emissions were collected using a Schmidt-Cassegrain telescope (6″ f/10) at ∼8  m away. The variations in intensities of persistent atomic transitions in the FIBS spectra clearly reflected the varying weight percentage in bimetallic strips. Furthermore, PCA was successfully utilized to discriminate the metals, alloys, and bimetallic strips batch wise and altogether. Our results demonstrate the capability of femtosecond ST-FIBS for ST analytical applications.

We present a systematic study on the fabrication, characterization of versatile, and low-cost filter paper-based surface-enhanced Raman spectroscopy (SERS) substrates loaded with salt-induced aggregated Ag/Au nanoparticles (NPs). These were demonstrated as efficient SERS substrates for the detection of multiple explosive molecules such as picric acid (5 μM), 2,4-dinitrotoluene (1 μM), and 3-nitro-1,2,4-triazol-5-one (10 μM) along with a common dye molecule (methylene blue, 5 nM). The concentrations of the dye and explosive molecules in terms of mass represent 31.98 pg, 11.45 ng, 1.82 ng, and 13.06 ng, respectively. Silver (Ag) and gold (Au) colloidal NPs were prepared by femtosecond laser (∼50 fs, 800 nm, 1 kHz) ablation of Ag/Au-target immersed in distilled water. Subsequently, the aggregated nanoparticles were achieved by mixing the pure Ag and Au NPs with different concentrations of NaCl. These aggregated NPs were characterized by UV-visible absorption and high-resolution transmission electron microscopy techniques. The SERS substrates were prepared by soaking the filter paper in aggregated NPs. The morphologies of the paper substrates were investigated using field-emission scanning electron microscopy technique. We have achieved superior enhancements with high reproducibility and sensitivity for filter paper substrates loaded with Ag/Au NPs mixed for an optimum concentration of 50 mM NaCl., Competing Interests: The authors declare no competing financial interest.

We report the standoff (up to ~2 m) and remote (~8.5 m) detection of novel high energy materials/explosive molecules (Nitroimidazoles and Nitropyrazoles) using the technique of femtosecond laser induced breakdown spectroscopy (LIBS). We utilized two different collection systems (a) ME-OCT-0007 (commercially available) and (b) Schmidt-Cassegrain telescope for these experiments. In conjunction with LIBS data, principal component analysis was employed to discriminate/classify the explosives and the obtained results in both configurations are compared. Different aspects influencing the LIBS signal strength at far distances such as fluence at target, efficiency of collection system etc. are discussed.

Picric acid (PA) is a severe environmental and security risk due to its unstable, toxic, and explosive properties. It is also challenging to detect in trace amounts and in situ because of its highly acidic and anionic character. Here, we assess sensing of PA under nonlaboratory conditions using surface-enhanced Raman scattering (SERS) silver nanopillar substrates and hand-held Raman spectroscopy equipment. The advancing elasto-capillarity effects are explained by molecular dynamics simulations. We obtain a SERS PA detection limit on the order of 20 ppt, corresponding attomole amounts, which together with the simple analysis methodology demonstrates that the presented approach is highly competitive for ultrasensitive analysis in the field.

Contrast-associated nephropathy (CaN) has become a major cause of iatrogenic acute renal failure, especially with the increasing use of radiographic contrast media in both diagnostic and interventional procedures. CaN is the third most common cause of iatrogenic acute renal failure, and is associated with increased morbidity and in-hospital mortality. CaN typically presents as an acute rise in serum creatinine levels, usually within 48 hours after exposure to contrast media. Renal medullary ischemia secondary to contrast-induced vasoconstriction is now believed to be the most likely cause of CaN, although direct renal tubular cytotoxicity does appear to play a role. The occurrence of CaN is directly related to the number of coexisting clinical risk factors. Among the many risk factors, preexisting renal impairment, the presence of diabetes mellitus and the volume of the contrast agent administered are the most important. The most effective means of reducing the incidence of CaN is through prevention, by first identifying the risk factors and then attempting to correct for them before the administration of contrast material. Although the earliest and most well-tested preventive measure, namely intravenous hydration, continues to be the most effective way to prevent CaN, recent studies have provided many new preventive modalities. The growing use of these new agents, such as acetylcysteine, endothelin blockers, and most recently fenoldopam, has increased the options available for the prevention of CaN.