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Gliomas of the brain are characterised by high aggressiveness, high postoperative recurrence rate, high morbidity and mortality, posing a great challenge to clinical treatment. Traditional treatments include surgery, radiotherapy and chemotherapy; they also have significant associated side effects, leading to difficulties in tumour resection and recurrence. Photodynamic therapy has been shown to be a promising new strategy to help treat malignant tumours of the brain. It irradiates the tumour site at a specific wavelength to activate a photosensitiser, which selectively accumulates at the tumour site, triggering a photochemical reaction that destroys the tumour cells. It has the advantages of being minimally invasive, highly targeted and with few adverse reactions, and is expected to be well used in anti-tumour therapy. However, the therapeutic effect of traditional PDT is limited by the weak tissue penetration ability of photosensitiser, hypoxia and immunosuppression in the tumour microenvironment. This paper reviews the current research status on the therapeutic principle of photodynamic therapy in glioma and the mechanism of tumour cell injury, and also analyses the advantages and disadvantages of the current application in glioma treatment, and clarifies the analysis of ideas to improve the tissue penetration ability of photosensitizers. It aims to provide a feasible direction for the improvement of photodynamic therapy for glioma and a reference for the clinical treatment of deep brain tumours.

A novel water-soluble substituted pyridine dicarboxylate containing a quaternary ammonium ion with potential applications in fluorescence cell imaging was synthesized and characterized. Remarkably, this compound exhibited water solubility in the absence of additional solubilizers, enabling direct dissolution in phosphate-buffered saline for cell studies. No obvious cytotoxicity was observed in 4T1 cells (mouse breast cancer cells) within the concentration range of 0.2–25 μmol L−1, with a cell survival rate above 89%. Furthermore, the compound exhibited a maximum two-photon absorption cross-section of 86 GM at an excitation wavelength of 780 nm, demonstrating high cell permeability, effective distribution in the cytoplasm, and preferential targeting of organelles. Single- and two-photon fluorescence imaging of cells revealed a distinctive blue emission and strong bright green emission, respectively. The newly synthesized substituted pyridine dicarboxylate exhibited low cytotoxicity and strong fluorescence imaging properties, demonstrating its potential in cell imaging applications.

It is shown that the two-photon absorption (TPA)-induced losses in a non-centrosymmetric crystal reduce considerably when the angle θ between the polarization vector of incident radiation and the optical c-axis is 45°. In such a geometry of interaction in a Ca3(VO4)2 crystal, the effective TPA coefficient for 300 fs laser pulses at θ = 45° is 3.5 ± 0.5 times lower than its maximum at θ = 0°, which is more than two times higher than reported earlier in the literature.

In the continuation of our sustained interest in porphyrin-based dendrimers and their use as luminescent photosensitizers for two-photon photodynamic therapy (2P-PDT), we wondered about the effect of changing the connectors in our macromolecular structures. We also wanted to initiate preliminary studies on meso-tetraarylporphyrins decorated with more electron-releasing arms. Thus, various meso-tetrafluorenylporphyrin-cored star-shaped and dendrimeric derivatives have been synthesized and characterized, as well as their zinc(II) complexes. In the new dendrimeric derivatives, the peripheral fluorenyl units of the dendrons are linked to the inner core either by N-phenylcarbazole (CCbz) or triphenylamine (CTpa) connectors instead of the more classic 1,3,5-phenylene (CPh) linkers previously used by us. Selected linear and non-linear optical (LO and NLO) properties were then determined for these compounds via absorption or emission studies and by two-photon excited fluorescence (TPEF) measurements. It was found that the CCbz-containing dendrimer, which has the most rigid structure, exhibits a significantly lower two-photon absorption (2PA) cross-section than its CTpa analog, presenting a more flexible structure while rather similar luminescence and singlet oxygen activation quantum yields are found for both. The origin of this unexpected discrepancy is briefly discussed based on our photophysical data. It is then demonstrated that the latter dendrimer also outperforms several closely related dendrimers in terms of 2PA action cross-section and 2PA-oxygen sensitization, making its molecular architecture quite appealing for developing new 2PA photosensitizers suited to theranostic uses.

The crystal structure of the title compound, C13H9Br2N [systematic name: (E)-N,1-bis(4-bromophenyl)methanimine], is a second polymorph (Form II) crystallizing in the orthorhombic space group Pccn. The first polymorph (Form I) crystallizes in the monoclinic space group P21/c [Bernstein & Izak (1975). J. Cryst. Mol. Struct. 5, 257–266; Marin et al. (2013). J. Mol. Struct. 1049, 377–385]. The molecule is disordered about an inversion center situated in the middle of the C=N bond, similar to the situation in the monoclinic polymorph: the C=N bond length is 1.243 (7) Å. In the crystal, molecules stack along the b-axis direction and are linked by C—H...π interactions. The interatomic contacts in the crystal for both polymorphs were studied by Hirshfeld surface analysis and have notable differences. The solid-state fluorescence spectrum of Form II shows an emission peak at ca 469 nm. The two-photon absorption coefficient measured from the open aperture Z-scan technique is 1.3 × 10 −11 m W−1, hence, Form II shows optical limiting behaviour.

Simultaneous interrogation of pump and probe beams interacting in ZnO nanostructures of a two-wave mixing is proposed for dual-path data processing of optical signals by nonlinear optical effects. An enhancement in third-order nonlinear optical properties was exhibited by Al-doped ZnO thin films. Multiphoton absorption and nonlinear refraction were explored by the z-scan technique at 532 nm with nanosecond pulses. The evolution of the optical Kerr effect in the ZnO thin films was analyzed as a function of the incorporation of Al in the sample by a vectorial two-wave mixing method. Electrical and photoconductive effects were evaluated to further characterize the influence of Al in the ZnO solid samples. Potential applications of nonlinear optical parameters for encoding and encrypting information in light can be envisioned.

This review describes the two-photon absorption properties of dendrimers, which are arborescent three-dimensional macromolecules differing from polymers by their perfectly defined structure. The two-photon absorption process is a third order non-linear optical property that is attractive because it can be used in a wide range of applications. In this review, dendrimers that were studied for their two-photon absorption properties are first described. Then, the use of dendritic TPA chromophores for light harvesting, photopolymerization, optical power limitation, cell imaging, singlet oxygen generation, and photodynamic therapy is described. This review thus proposes an overview of the properties and possible applications of two-photon absorbing dendrimers.

The donor-acceptor interaction of a charge-coupled heterostructure encompassing a metal and an amorphous semiconductor subjected to a laser field has many potential applications in the realm of nonlinear optics. In this work, we fabricate an electron donor gold nanoparticle (AuNP) and acceptor amorphous Ge24Se76 heterostructure on a quartz substrate using a sequential thermal evaporation technique. In this charge coupled heterostructure, we demonstrate the ultrafast third-order nonlinear absorptive and refractive response, and their sign reversal compared to pristine Ge24Se76. Enhanced optical nonlinearity in these heterostructures of varying plasmonic wavelengths is due to charge transfer, verified by the Raman spectroscopy. Further, the ultrafast transient absorption measurements support the thesis of charge transfer in the AuNP/Ge24Se76 heterostructure. These findings open up exciting opportunities for developing novel device technologies with far-reaching applications in nonlinear optics.

The linear and nonlinear optical properties of two quadrupolar bithiophenes and two quadrupolar cyclopentadithiophenes have been investigated. At the 5,5′ positions of the central bi/dithiophene units, the molecules possess 1,4-phenylalkynyl groups that bear either electron-donating (NPh2) or electron-withdrawing (SO2CF3) groups. The optical properties were experimentally studied and modelled via quantum chemistry computations of key configurations and conformations. All the compounds show good light harvesting efficiency due to their strong absorption in the visible range. These fluorescent compounds are also good two-photon absorbers in the NIR range that can photosensitize oxygen in toluene. DFT calculations reveal that the mixtures of conformers in a solution show similar linear optical properties. TD-DFT calculations reproduce the experimental spectroscopic data fairly well, including vibronic couplings in the fluorescence spectra. The lowest excited state for two-photon absorption corresponds to the S2 state. The roles of the SO2CF3 and NPh2 terminal groups on the nonlinear response were analyzed for possible bio-oriented applications, with the cyclopentadithiophenes showing the most promising figures of merit.

This article reports three new two-photon absorption (TPA) materials that are quinolinium-carbazole derivates. They are 3-(N-methyl-4-ethylquinolinium iodide)-9-ethylcarbazole (M4), 3-(N-methyl-4-ethylquinolinium iodide)-9-ethylcarbazole (H2), and 3-(N-methyl-4-ethylquinolinium iodide)-9-ethylcarbazole (H4). Their TPA cross-sections are 491, 515, and 512 GM, respectively. Under the excitation of near-infrared light, their fluorescence emission is about 650 nm. The compounds can stain nucleic acid DNA with the same level of nuclear localization as Hoechst 33342. Under continuous irradiation with a near-infrared laser, the three new compounds showed less fluorescence decay than DAPI, and the average fluorescence decay rates were 0.016%/s, 0.020%/s, and 0.023%/s. They are expected to become new two-photon fluorescent probes of nucleic acid DNA because of their excellent performance.

Micro/nano structures with morphological gradients possess unique physical properties and significant applications in various research domains. This study proposes a straightforward and precise method for fabricating micro/nano structures with morphological gradients utilizing single-voxel synchronous control and a nano-piezoelectric translation stage in a two-photon laser direct writing technique. To address the defocusing issue in large-scale fabrication, a methodology for laser focus dynamic proactive compensation was developed based on fluorescence image analysis, which can achieve high-precision compensation of laser focus within the entire range of the nano-piezoelectric translation stage. Subsequently, the fabrication of micro/nano dual needle structures with morphological gradients were implemented by employing different writing speeds and voxel positions. The minimum height of the tip in the dual needle structure is 80 nm, with a linewidth of 171 nm, and a dual needle total length reaching 200 μm. Based on SEM (scanning electron microscope) and AFM (atomic force microscope) characterization, the dual needle structures fabricated by the method proposed in this study exhibit high symmetry and nanoscale gradient accuracy. Additionally, the fabrication of hexagonal lattice periodic structures assembled from morphological gradient needle structures and the size gradient Archimedean spiral structures validate the capability of the single voxel-based fabrication and proactive focus compensation method for complex gradient structure fabrication.

Nonlinear optical materials, especially two-dimensional materials, are anticipated to reveal broadband optical nonlinearity for future miniaturized photonic applications. Herein, we report a physical vapor deposition method to produce β-In _2 Se _3 thin film and investigate the broadband nonlinear absorption ( β ) and refraction (n _2 ) characteristics. The β-In _2 Se _3 semiconductor shows an excellent optical nonlinearity with large β in 10 ^2 cm GW ^−1 scale and n _2 in 10 ^−12 cm ^2 W ^−1 scale from visible to NIR wavelengths, which are superior to those of metal carbides and nitrides (MXenes) and metal-organic frameworks. This excellent optical nonlinearity makes β-In _2 Se _3 a promising candidate for advanced nanophotonic devices and beyond.

Abstract Organic–inorganic hybrid perovskites carry unique semiconducting properties and advanced flexible crystal structures. These characteristics of organic–inorganic hybrid perovskites create a promising candidacy for circularly polarized light (CPL) detection. However, CPL detections based on chiral perovskites are limited to UV and visible wavelengths. The natural quantum well structures of layered hybrid perovskites generate strong light–matter interactions. This makes it possible to achieve near‐infrared (NIR) CPL detection via two‐photon absorption in the sub‐wavelength region. In this study, cooperative strategies of dimension increase and mixed spacer cations are used to obtain a pair of chiral multilayered perovskites (R‐β‐MPA)EA2Pb2Br7 and (S‐β‐MPA)EA2Pb2Br7 (MPA = methylphenethylammonium and EA = ethylammonium). The distinctive bi‐cations interlayer and multilayered inorganic skeletons provide enhanced photoconduction. Moreover, superior photoconduction leads to the prominent NIR CPL response with a responsivity up to 8.1 × 10−5 A W−1. It is anticipated that this work can serve as a benchmark for the fabrication and optimization of efficient NIR CPL detection by simple chemical design.

Abstract Molecules with strong two‐photon absorption (TPA) are important in many advanced applications such as upconverted laser and photodynamic therapy, but their design is hampered by the high cost of experimental screening and accurate quantum chemical (QC) calculations. Here a systematic study is performed by collecting an experimental TPA database with ≈900 molecules, analyzing with interpretable machine learning (ML) the key molecular features explaining TPA magnitudes, and building a fast ML model for predictions. The ML model has prediction errors of similar magnitude compared to experimental and affordable QC methods errors and has the potential for high‐throughput screening as additionally validated with the new experimental measurements. ML feature analysis is generally consistent with common beliefs which is quantified and rectified. The most important feature is conjugation length followed by features reflecting the effects of donor and acceptor substitution and coplanarity.

The first-, second-, and third-order molecular nonlinear optical properties, including two-photon absorption of a series of derivatives, involving two dithienylethene (DTE) groups connected by several molecular linkers (bis(ethylene-1,2-dithiolato)Ni- (NiBDT), naphthalene, quasilinear oligothiophene chains), are investigated by employing density functional theory (DFT). These properties can be efficiently controlled by DTE switches, in connection with light of appropriate frequency. NiBDT, as a linker, is associated with a greater contrast, in comparison to naphthalene, between the first and second hyperpolarizabilities of the “open–open” and the “closed–closed” isomers. This is explained by invoking the low-lying excited states of NiBDT. It is shown that the second hyperpolarizability can be used as an index, which follows the structural changes induced by photochromism. Assuming a Förster type transfer mechanism, the intramolecular excited-state energy transfer (EET) mechanism is studied. Two important parameters related to this are computed: the electronic coupling (VDA) between the donor and acceptor fragments as well as the overlap between the absorption and emission spectra of the donor and acceptor groups. NiBDT as a linker is associated with a low electronic coupling, VDA, value. We found that VDA is affected by molecular geometry. Our results predict that the linker strongly influences the communication between the open–closed DTE groups. The sensitivity of the molecular nonlinear optical properties could assist with identification of molecular isomers.

The search for fluorescent proteins with large two-photon absorption (TPA) cross-sections and improved brightness is required for their efficient use in bioimaging. Here, we explored the impact of a single-point mutation close to the anionic form of the GFP chromophore on its TPA activity. We considered the lowest-energy transition of EGFP and its modification EGFP T203I. We focused on a methodology for obtaining reliable TPA cross-sections for mutated proteins, based on conformational sampling using molecular dynamics simulations and a high-level XMCQDPT2-based QM/MM approach. We also studied the numerical convergence of the sum-over-states formalism and provide direct evidence for the applicability of the two-level model for calculating TPA cross-sections in EGFP. The calculated values were found to be very sensitive to changes in the permanent dipole moments between the ground and excited states and highly tunable by internal electric field of the protein environment. In the case of the GFP chromophore anion, even a single hydrogen bond was shown to be capable of drastically increasing the TPA cross-section. Such high tunability of the nonlinear photophysical properties of the chromophore anions can be used for the rational design of brighter fluorescent proteins for bioimaging using two-photon laser scanning microscopy.

In this article, we report on an optical real-time autocorrelator readout with a 5 Hz refresh rate, equipped with a transimpedance amplified photodetector based on the two-photon absorption (TPA) of semiconductor photodiodes (PDs) for ultrashort (1 < ps) pulse measurement. By replacing the GaP PD of a commercial TPA detector with GaAsP and Si PD elements, we demonstrated that the spectral response based on the TPA of each photodetector followed the linear response of the corresponding semiconductor PD within accessible wavelength regions. The TPA spectral response of the GaAsP detector exhibited a peak at 1200 nm and a long wavelength limit near 1300 nm. The TPA spectral response of the Si detector exhibited a short wavelength limit near 1170 nm and a linear response up to 1300 nm. The two types of PD were compared with the characteristics of the GaP photodiode. These photoconductive detectors are efficient, compact, and robust sensors and can be used to diagnose the pulse characteristics of ultrafast fiber lasers and light sources near IR wavelengths.

Since its inception in 1984, 3D printing has revolutionized manufacturing by leveraging the additivity principle and simple material–energy coupling. Stereolithography, as the pioneering technology, introduced the concept of photopolymerization with a single photon. This groundbreaking approach not only established the essential criteria for additive processes employing diverse localized energies and materials, including solid, pasty, powdery, organic, and mineral substances, but also underscored the significance of light–matter interactions in the spatial and temporal domains, impacting various critical aspects of stereolithography’s performance. This review article primarily focuses on exploring the intricate relationship between light and matter in stereolithography, aiming to elucidate operational control strategies for fabrication processes, encompassing voxel size manipulation. Furthermore, advancements in light excitation modes, transitioning from one-photon to two-photon mechanisms, have unlocked new material and creative possibilities. Notable advantages include the elimination of layering (true 3D printing) and the ability to fabricate objects using silica glass. Although these volumetric 3D printing methods deviate from conventional additive manufacturing concepts and possess narrower application scopes, they offer reduced manufacturing and design timeframes along with enhanced spatial resolution in select cases. These complex light–matter interactions form the cornerstone of this comprehensive review, shedding light on operational control strategies and considerations in stereolithography. By comprehensively analyzing the impact of light–matter interactions, including the novel two-photon excitation, this review highlights the transformative potential of stereolithography for rapid and precise fabrication. While these techniques may occupy a smaller niche within the broader spectrum of 3D printing technologies, they serve as valuable additions to the array of 3D devices available in the market.

Intercalation has been demonstrated to be a powerful tool for tuning the physical and chemical properties of two-dimensional (2D) materials, providing the highest possible doping level and an ideal system to study various electronic states. In this work, we demonstrate that the nonlinear absorption effect of few-layer graphene (about 6–8 layers) is changed from saturable absorption (SA) to reverse saturable absorption (RSA) after lithium intercalation. This is attributed to the increase of Fermi energy owing to the charge transfer from Li to graphene layers in intercalated compounds (LiC6). And the change of nonlinear absorption effect is revisable after deintercalation. In addition, the modulation depth of RSA in lithiated graphene is found to rise with the decrease of incident laser wavelength, different from that of pristine graphene. Besides, the dispersion relationships of degenerate and nondegenerate two-photon absorption are analyzed from the results of nonlinear absorption and transient dynamics of lithiated graphene, indicating the 1.91–2.21 eV upshift of the Fermi surface. Our findings of the intercalation-tunable nonlinear optical absorption effect pave the way for the construction of nonlinear optical devices based on 2D intercalation compounds.

Laser Fault Injection (LFI) is considered to be the most powerful semiinvasive fault injection method for implementation attacks on security devices. In this work we discuss for the first time the application of the nonlinear Two-Photon Absorption (TPA) effect for the purpose of LFI. Though TPA is an established technique in other areas, e.g. fluorescence microscopy, so far it did not receive any attention in the field of physical attack methods on integrated circuits. We show that TPA has several superior properties over the regular linear LFI method. The TPA effect allows to work on non-thinned devices without increasing the induced energy and hence the stress on the device. In contrast to regular LFI, the nonlinearity of the TPA effect leads to increased precision due to the steeper descent in intensity and also a vertically restricted photoelectric effect. By practical experiments, we demonstrate the general applicability of the method for a specific device and that unlike a regular LFI setup, TPA-LFI is capable to inject faults without triggering a latch-up effect. In addition we discuss the possible implications of TPA-LFI on various sensor-based countermeasures.

Laser Fault Injection (LFI) is considered to be the most powerful semiinvasive fault injection method for implementation attacks on security devices. In this work we discuss for the first time the application of the nonlinear Two-Photon Absorption (TPA) effect for the purpose of LFI. Though TPA is an established technique in other areas, e.g. fluorescence microscopy, so far it did not receive any attention in the field of physical attack methods on integrated circuits. We show that TPA has several superior properties over the regular linear LFI method. The TPA effect allows to work on non-thinned devices without increasing the induced energy and hence the stress on the device. In contrast to regular LFI, the nonlinearity of the TPA effect leads to increased precision due to the steeper descent in intensity and also a vertically restricted photoelectric effect. By practical experiments, we demonstrate the general applicability of the method for a specific device and that unlike a regular LFI setup, TPA-LFI is capable to inject faults without triggering a latch-up effect. In addition we discuss the possible implications of TPA-LFI on various sensor-based countermeasures.

Carbon dots (CDs) provide ideal platforms for applications in bioimaging, sensing, and photocatalysis. Herein, a new type of red fluorescent carbon dot (RCD) is successfully synthesized, and its broadband nonlinear optical (NLO) properties are systematically characterized. The nonlinear absorption coefficient (αNL) values of the RCDs at 580, 630, 650, 1064 nm are − 0.65, −3.09, −4.02, and 0.14 cm/GW, respectively. The nonlinear absorption transforms from saturable absorption to two-photon absorption in the near-infrared domain. We demonstrate the application of the RCDs for imaging Hela cells. Our results indicate that the synthesized RCDs with a broadband NLO response exhibit potential applications in saturable absorbers and deep-tissue imaging.

The way in which photons travel through biological tissues and subsequently become scattered or absorbed is a key limitation for traditional optical medical imaging techniques using visible light. In contrast, near-infrared wavelengths, in particular those above 1000 nm, penetrate deeper in tissues and undergo less scattering and cause less photo-damage, which describes the so-called “second biological transparency window”. Unfortunately, current dyes and imaging probes have severely limited absorption profiles at such long wavelengths, and molecular engineering of novel NIR-II dyes can be a tedious and unpredictable process, which limits access to this optical window and impedes further developments. Two-photon (2P) absorption not only provides convenient access to this window by doubling the absorption wavelength of dyes, but also increases the possible resolution. This review aims to provide an update on the available 2P instrumentation and 2P luminescent materials available for optical imaging in the NIR-II window.

Palcewska et al. first demonstrated near infrared (NIR) visual response in human volunteers upon two-photon absorption (TPA), in a seminal work of 2014, and assessed the process in terms of wavelength- and power-dependence on murine \textit{ex-vivo} retinas. In the present study, ex-vivo electroretinography (ERG) is further developed to perform a complete characterization of the effect of NIR pulse duration, energy, and focal spot size on the response. The same set of measurements is successively tested on living mice. We discuss how the nonlinear intensity dependence of the photon absorption process is transferred to the amplitude of the visual response acquired by ERG. Finally, we show that the manipulation of the spectral phase of NIR pulses can be translated to predictable change in the two-photon induced response under physiological excitation conditions.

Abstract Organic phosphorescence materials have received wide attention in bioimaging for bio‐low toxicity and large Stokes. Herein, a design strategy to achieve near‐infrared (NIR) excitation and emission of organic room‐temperature phosphorescence through two‐stage confinement supramolecular assembly is presented. Via supramolecular macrocyclic confinement, the host–guest complexes exhibit phosphorescence with two‐photon absorption (excitation wavelength up to 890 nm) and NIR emission (emission wavelength up to 800 nm) in aqueous solution, and further nano‐confinement assembly significantly strengthens phosphorescence. Moreover, the nano‐assemblies possess color‐tunable luminescence spanning from the visible to NIR regions under different excitation wavelengths. Intriguingly, the prepared water‐soluble assemblies maintain two‐photon absorption and multicolor luminescence in cells or vivo.

Two-photon absorption has been systematically studied in Ca3(VO4)2 and Ca2.7Sr0.3(VO4)2 crystals, both of which are prospective nonlinear optical and laser host materials. A strong dependence of the two-photon absorption coefficients on the orientation of the laser beam polarization with respect to the optical c-axis of the crystals is revealed. The measured coefficients for perpendicular and parallel orientations were 50 ± 10 cm/TW and 19 ± 4 cm/TW in Ca3(VO4)2, and 18 ± 3 cm/TW and 10 ± 2 cm/TW in Ca2.7Sr0.3(VO4)2, respectively. Thus, to minimize optical losses caused by two-photon absorption, an orientation of Ca2.7Sr0.3(VO4)2 crystals with the laser beam polarization parallel to the crystal optical c-axis is preferred.

Entangled photons are promising candidates for a variety of novel spectroscopic applications. In this paper, we simulate two-photon absorption (TPA) of entangled photons in a molecular ensemble with inhomogeneous broadening. We compare our results with a homogeneously broadened case and comment on the consequences for the possible quantum enhancement of TPA cross sections. We find that, while there are differences in the TPA cross section, this difference always remains small and of the order unity. We further consider the impact of the polarization degrees of freedom and carry out the orientational average of a model system Hamiltonian. We find that certain molecular geometries can give rise to a substantial polarization dependence of the entangled TPA rate. This effect can increase the TPA cross section by up to a factor of five.

The title compound DBNB, C24H20N2O6, has been crystallized and studied by X-ray diffraction, spectroscopic and computational methods. In the title molecule, which is based on a 1,4-distyryl-2,5-dimethoxybenzene core with p-nitro-substituted terminal benzene rings, the dihedral angle between mean planes of the central fragment and the terminal phenyl ring is 16.46 (6)°. The crystal packing is stabilized by π–π interactions. DFT calculations at the B3LYP/6–311 G(d,p) level of theory were used to compare the optimized structures with the experimental data. Energy parameters, including HOMO and LUMO energies, their difference, and vertical excitation and emission energies were obtained.

A colorimetric two-photon multianalyte sensor with spirobifluorene motif was developed. Along with the addition of hypochlorite/hydrazine to a solution of the probe, a colorimetric change from yellow to colorless and a fluorescence enhancement (Under 365 nm UV light) can be observed by ‘naked-eye’. The detection limits are 28 nM for hypochlorite and 12 nM for hydrazine, respectively. The molecule has large two-photon cross-section value of 220GM and has been successfully applied to two-photon imaging of hypochlorite / hydrazine in live cells. As far as we know, a two-photon fluorescent probe capable of detecting reactive oxygen species and reducing agent, and a colorimetric two-photon fluorescent probe for hypochlorite is reported for the first time. In addition, the detection limit for hydrazine is much lower than those of most hydrazine fluorescent probes reported in the literature.

Polymers are well-recognized carriers useful for delivering therapeutic drug and imaging probes to the target specified in the defined pathophysiological site. The functional drug molecules and imaging agents were chemically attached or physically loaded in the carrier polymer matrix via cleavable spacers. Using appropriate targeting moieties, these polymeric carriers (PCs) loaded with functional molecules were designed to realize target-specific delivery at the cellular level. The biodistribution of these carriers can be tracked using imaging agents with suitable imaging techniques. The drug molecules can be released by cleaving the spacers either by endogenous stimuli (e.g., pH, redox species, glucose level and enzymes) at the targeted physiological site or exogenous stimuli (e.g., light, electrical pulses, ultrasound and magnetism). Recently, two-photon absorption (2PA)-mediated drug delivery and imaging has gained significant attention because TPA from near-infrared light (700–950 nm, NIR) renders light energy similar to the one-photon absorption from ultraviolet (UV) light. NIR has been considered biologically safe unlike UV, which is harmful to soft tissues, cells and blood vessels. In addition to the heat and reactive oxygen species generating capability of 2PA molecules, 2PA-functionalized PCs were also found to be useful for treating diseases such as cancer by photothermal and photodynamic therapies. Herein, insights attained towards the design, synthesis and biomedical applications of 2PA-activated PCs are reviewed. In particular, specific focus is provided to the imaging and drug delivery applications with a special emphasis on multi-responsive platforms.

In this study, the up-conversion luminescence for aqueous suspensions of carbon dots with polyfunctional and carboxylated surfaces synthesized by a hydrothermal method was investigated. The obtained quadratic dependence of the luminescence intensity on the power of the exciting radiation indicates that the up-conversion luminescence of these carbon dots is caused by two-photon absorption. The optimal wavelength of the exciting radiation was determined for the studied samples. The dependences of the signal for the up-conversion luminescence of carbon dots on the pH value of the suspension were obtained. It was shown that these carbon dots can be used as the nanosensor of pH of liquid media in a wide range of pH values. The advantage of this nanosensor is that the excitation of the up-conversion luminescence of carbon dots does not entail excitation of autoluminescence of the biological medium. It expands the possibilities of using this sensor in biomedical applications.

Lead halide perovskite nanoplatelets (NPls) attract significant attention due to their exceptional and tunable optical properties. Doping is a versatile strategy for modifying and improving the optical properties of colloidal nanostructures. However, the protocols for B-site doping have been rarely reported for 2D perovskite NPls. In this work, we investigated the post-synthetic treatment of CsPbBr3 NPls with different Cd2+ sources. We show that the interplay between Cd2+ precursor, NPl concentrations, and ligands determines the kinetics of the doping process. Optimization of the treatment allows for the boosting of linear and nonlinear optical properties of CsPbBr3 NPls via doping or/and surface passivation. At a moderate doping level, both the photoluminescence quantum yield and two-photon absorption cross section increase dramatically. The developed protocols of post-synthetic treatment with Cd2+ facilitate further utilization of perovskite NPls in nonlinear optics, photonics, and lightning.

Carbon nanomaterials endowed with significant luminescence have been synthesized for the first time from an abundant, highly localized waste, the wet pomace (WP), a semi-solid by-product of industrial olive oil production. Synthetic efforts were undertaken to outshine the photoluminescence (PL) of carbon nanoparticles through a systematic search of the best reaction conditions to convert the waste biomass, mainly consisting in holocellulose, lignin and proteins, into carbon dots (CDs) by hydrothermal carbonization processes. Blue-emitting CDs with high fluorescence quantum yields were obtained. Using a comprehensive set of spectroscopic tools (FTIR, Raman, XPS, and 1H/13C NMR) in combination with steady-state and time-resolved fluorescence spectroscopy, a rational depiction of WP-CDs structures and their PL properties was reached. WP-CDs show the up-conversion of PL capabilities and negligible cytotoxicity against two mammalian cell lines (L929 and HeLa). Both properties are excellent indicators for their prospective application in biological imaging, biosensing, and dynamic therapies driven by light.

The pulsed laser has gradually become the standard method of studying the single-event effects of micro-nano devices, and it is a powerful supplement to heavy ion experiments on single-event effects. In particular, with the continuous improvement of the technological range and operating frequency of electronic devices, the femtosecond pulse laser has the potential for broad applications and practical value in the single-event effects testing and radiation hardness evaluations of devices. The single-event effects of single-photon and two-photon absorption were studied with a laser of 1064 nm and 1260 nm, and the influences of SPA (single-photon absorption) and TPA (two-photon absorption) on the single-event transient voltage under different pulse laser energies were analyzed. The test results of the TPA SEE (single-event effect) were basically consistent with those of the SPA SEE, and the trend of the change in the transient voltage pulse was consistent. These results lay a foundation for the application of the femtosecond pulse laser in the performance evaluation and screening of space electronic devices and the radiation hardness evaluation of satellite electronic systems.

This work reports a detailed study of the synthesis, characterization and third-order nonlinear optical properties of Ag and Al2O3 nanoparticles and their polymer nanocomposites. Ag and Al2O3 nanoparticles were prepared by the chemical precipitation method. The X-ray diffraction studies confirmed the purity and the crystalline nature of the sample and revealed the crystallite size. The linear optical properties and the structural morphology of the nanoparticles were confirmed using UV–visible spectroscopy and SEM analysis. The prepared nanoparticles were introduced into the polymer matrix by the spin-coating technique. Open-aperture and closed-aperture Z-scan technique was used to study the nonlinear absorption and nonlinear refraction of the samples under a Q-switched Nd:YAG laser at 532 nm. The observed third-order nonlinear optical susceptibility (χ(3)) was on the order of 10−6 esu, which indicates that these materials are potential candidates for photonic applications.

The visual method is used to theoretically discuss the influence of different external electric fields on the photo-induced charge transfer of the donor-bridge-acceptor (D-B-A) system in the two-photon absorption (TPA). We dynamically observe the transition process in different spatial dimensions. The final results show that the external electric field can manipulate the orientation and type of intermolecular charge transfer in the TPA process of the D-B-A system. The changes in the proportions of sequential charge transfer and super-exchange charge transfer in TPA provide a strong proof for the conclusion. This non-monotonic change has theoretically deepened our understanding of the charge transfer characteristics in TPA, and we have a further understanding of the optical properties of the D-B-A system.

Photon frequency conversion using optical materials is a common strategy for light generation and utilization. Materials capable of visible‐to‐ultraviolet (UV) light conversion have attracted particular attention due to their potential applications in nonlinear optics, biophotonics, as well as environmental sciences. There are four main mechanisms of visible‐to‐UV light conversion processes, including second‐harmonic generation, two‐photon absorption, lanthanide‐based upconversion, and triplet–triplet annihilation. Herein, recent developments in visible‐to‐UV light conversion materials are collectively reviewed and the emerging applications are presented. The prospects and challenges for further development in this field are also highlighted.

Different types of two-photon absorbing (TPA) fluorophores have been synthesized and specifically functionalized to be incorporated in the structure of phosphorus dendrimers (highly branched macromolecules). The TPA fluorophores were included in the periphery as terminal functions, in the core, or in the branches of the dendrimer structures, respectively. Also the functionalization in two compartments (core and surface, or branches and surface) was achieved. The consequences of the location of the fluorophores on the fluorescence and TPA properties have been studied. Several of these TPA fluorescent dendrimers have water-solubilizing functions as terminal groups, and fluorophores at the core or in the branches. They have been used as fluorescent tools in biology for different purposes, such as tracers for imaging blood vessels of living animals, for determining the phenotype of cells, for deciphering the mechanism of action of anticancer compounds, and for safer photodynamic therapy.

Optical pulling forces exerted on small particles can be achieved by tailoring the properties of the electromagnetic field, the particles themselves, or the surrounding environment. However, the nonlinear optical effect of the surrounding environment has been largely neglected. Herein, we report the optical pulling forces on a Rayleigh particle immersed in a nonlinear optical liquid using high-repetition-rate femtosecond laser pulses. The analytic expression of time-averaged optical forces allows us to better understand the underlying mechanism of the particle transportation. It is shown that the two-photon absorption of the surrounding liquid gives rise to a negative radiation force. Transversely confined Rayleigh particles can be continuously dragged towards the light source during a pulling process.

Co-crystal materials formed by stacking different molecules with weak interactions are a hot research topic. In this work, we theoretically investigate the intermolecular interactions and charge transfer properties of the supramolecular BDBT-TCNB co-crystal (BTC). The π-π bonds, hydrogen bonds, and S-N bonds in the BTC bind the BDBT and TCNB molecules together to form a highly ordered co-crystal and lead to the co-crystal’s excellent two-photon absorption (TPA) properties. The intermolecular interactions of the BTC are discussed in detail by the independent gradient model based on Hirshfeld partition (IGMH), atoms in molecules (AIM), electrostatic overlay diagram, and symmetry-adapted perturbation theory (SAPT) energy decomposition; it is found that there is a strong interaction force along the stacking direction. The charge transfer properties of the one-photon absorption (OPA) and TPA of the BTC were investigated by charge density difference (CDD) and transition density matrix (TDM). It is found that the dominant charge transfer mode is the cross-space charge transfer along the stacking direction. Therefore, strong intermolecular interactions will promote intermolecular cross-space charge transfer. This work is of great significance for the design of organic optoelectronic supramolecular materials.

Evaluating candidates for novel materials with high nonlinear absorption properties for applications as biomarkers is a very important field of research. In this context, experimental and computational information on the two-photon absorption (TPA) properties of the dye IR780 is shown. The two-photon absorption data from 850 to 1000 nm for IR780 and other two well-known dyes, taken as reference, are presented. The experimental data were collected via an implementation of the two-photon induced fluorescence technique, while the quantum chemical data were produced by implementing DFT (Density-functional theory) methods. The data presented here supplement the paper “Two-photon absorption spectrum and characterization of the upper electronic states of dye IR780” by Guarin et al. (2021).

Genetically encoded probes with red-shifted absorption and fluorescence are highly desirable for imaging applications because they can report from deeper tissue layers with lower background and because they provide additional colors for multicolor imaging. Unfortunately, red and especially far-red fluorescent proteins have very low quantum yields, which undermines their other advantages. Elucidating the mechanism of nonradiative relaxation in red fluorescent proteins (RFPs) could help developing ones with higher quantum yields. Here we consider two possible mechanisms of fast nonradiative relaxation of electronic excitation in RFPs. The first, known as the energy gap law, predicts a steep exponential drop of fluorescence quantum yield with a systematic red shift of fluorescence frequency. In this case the relaxation of excitation occurs in the chromophore without any significant changes of its geometry. The second mechanism is related to a twisted intramolecular charge transfer in the excited state, followed by an ultrafast internal conversion. The chromophore twisting can strongly depend on the local electric field because the field can affect the activation energy. We present a spectroscopic method of evaluating local electric fields experienced by the chromophore in the protein environment. The method is based on linear and two-photon absorption spectroscopy, as well as on quantum-mechanically calculated parameters of the isolated chromophore. Using this method, which is substantiated by our molecular dynamics simulations, we obtain the components of electric field in the chromophore plane for seven different RFPs with the same chromophore structure. We find that in five of these RFPs, the nonradiative relaxation rate increases with the strength of the field along the chromophore axis directed from the center of imidazolinone ring to the center of phenolate ring. Furthermore, this rate depends on the corresponding electrostatic energy change (calculated from the known fields and charge displacements), in quantitative agreement with the Marcus theory of charge transfer. This result supports the dominant role of the twisted intramolecular charge transfer mechanism over the energy gap law for most of the studied RFPs. It provides important guidelines of how to shift the absorption wavelength of an RFP to the red, while keeping its brightness reasonably high.

In this Letter, we report the second harmonic generation (SHG) in a colloidal solution of CdSe/CdS nanoplatelets (NPLs) in the case of two-photon excitation in the region of exciton transition from the light holes sub-band to the conduction sub-band (549 nm, 1lh-1e) by femtosecond laser pulses (1064 nm, 100 kHz). Discovery of the SHG in colloidal solutions of NPLs opens up new perspectives for their use as biomarkers or for optical imaging, since in contrast to two-photon photoluminescence the SHG can increase both spectral and temporal resolution by several orders of magnitude. The SHG is also extremely important to consider when designing two-photon pumping lasers.

We applied time-domain Brillouin scattering (TDBS) for the characterization of porogen-based organosilicate glass (OGS) films deposited by spin-on-glass technology and cured under different conditions. Although the chemical composition and porosity measured by Fourier-transform infrared (FTIR) spectroscopy and ellipsometric porosimetry (EP) did not show significant differences between the films, remarkable differences between them were revealed by the temporal evolution of the Brillouin frequency (BF) shift of the probe light in the TDBS. The observed modification of the BF was a signature of the light-induced modification of the films in the process of the TDBS experiments. It correlated to the different amount of carbon residue in the samples, the use of ultraviolet (UV) femtosecond probe laser pulses in our optical setup, and their intensity. In fact, probe radiation with an optical wavelength of 356 nm appeared to be effective in removing carbon residue through single-photon absorption processes, while its two-photon absorption might have led to the breaking of Si-CH3 bonds in the OSG matrix. The quantum chemical calculations confirmed the latter possibility. This discovery demonstrates the possibility of local modifications of OSG films with a nanometric resolution via nonlinear optical processes, which could be important, among other applications, for the creation of active surface sites in the area-selective deposition of atomic layers.

An innovative two-photon microscope exploiting a line-shaped illumination has been recently devised and then implemented. Such configuration allows to carry out a real-time detection by means of standard CCD cameras and is able to maintain the same resolution as commonly used point-scanning devices, thus overcoming what is usually regarded as the main limitation of line-scanning microscopes. Here, we provide an overview of the applications in which this device has been tested and has proved to be a flexible and efficient tool, namely imaging of biological samples, in-depth sample reconstruction, two-photon spectra detection, and dye cross-section measurements. These results demonstrate that the considered setup is promising for future developments in many areas of research and applications.

The linear and nonlinear optical properties of two BODIPY derivatives, 1,7-Diphenyl-3,5-bis(9,9-dimethyl-9H-fluoren-2-yl)-boron-diuoride-azadipyrromethene (ZL-61) and 1,7-Diphenyl-3,5-bis(4-(1,2,2-triphenylvinyl)phenyl)-boron-diuoride-azadipyrromethene (ZL-22), were comprehensively investigated based on experimental and theoretical studies. It was found that both compounds show a strong two-photon absorption response in the near-infrared regime, and the two-photon-absorption cross-section values of ZL-61 and ZL-22 were determined to be 8321 GM and 1864 GM at 800 nm, respectively. The improvement of the two-photon absorption cross section in ZL-61 was attributed to the enhancement of the donor group, which was confirmed by transient absorption measurements and DFT calculation. Our results indicate that these BODIPY derivatives are a promising candidate for optical limiting and two-photon imaging applications.

We have presented a theoretical investigation of exciton and biexciton states for the ground and excited levels in a strongly oblate ellipsoidal quantum dot made from GaAs. The variational trial wave functions for the ground and excited states of the exciton and biexciton are constructed on the base of one-particle wave functions. The energies for the ground and excited levels, depending on the ellipsoidal quantum dot’s geometrical parameters, are depicted in the framework of the variational method. The oscillator strength of the transition from exciton to biexciton states for ground and excited levels is investigated as a function of the ellipsoidal quantum dot’s small and large semiaxes. The third-order optical susceptibilities of ground and excited biexcitons around one-photon and two-photon resonances are calculated as a function of the photon energy. The dependences of third-order optical susceptibilities for the ground and excited levels on the photon energy for different values of the ellipsoidal quantum dot’s semiaxis are revealed. The absorption coefficients in the ellipsoidal quantum dot, both for ground and excited states of exciton and biexciton, are calculated. The absorption coefficients for the ground level of exciton and biexciton for the fixed value of the large semiaxis and for the different values of the small semiaxis are determined. Finally, the two-photon absorption coefficient of the biexciton in the GaAs ellipsoidal quantum dot is computed.

A dynamical system defined by a metriplectic structure is a dissipative model characterized by a specific pair of tensors, which defines a Leibniz bracket; and a free energy, formed by a “Hamiltonian” and an entropy, playing the role of dynamics generator. Generally, these tensors are a Poisson bracket tensor, describing the Hamiltonian part of the dynamics, and a symmetric metric tensor, that models purely dissipative dynamics. In this paper, the metriplectic system describing a simplified two-photon absorption by a two-level atom is disclosed. The Hamiltonian component is sufficient to describe the free electromagnetic radiation. The metric component encodes the radiation–matter coupling, driving the system to an asymptotically stable state in which the excited level of the atom is populated due to absorption, and the radiation has disappeared. First, a description of the system is used, based on the real–imaginary decomposition of the electromagnetic field phasor; then, the whole metriplectic system is re-written in terms of the phase–amplitude pair, named Madelung variables. This work is intended as a first result to pave the way for applying the metriplectic formalism to many other irreversible processes in nonlinear optics.

Multi-photon absorption properties, particularly two-photon absorption (2PA), of fluorescent proteins (FPs) have made them attractive tools in deep-tissue clinical imaging. Although the diversity of photophysical properties for FPs is wide, there are some caveats predominant among the existing FP variants that need to be overcome, such as low quantum yields and small 2PA cross-sections. From a computational perspective, Salem et al. (2016) suggested the inclusion of non-canonical amino acids in the chromophore of the red fluorescent protein DsRed, through the replacement of the tyrosine amino acid. The 2PA properties of these new non-canonical chromophores (nCCs) were determined in vacuum, i.e., without taking into account the protein environment. However, in the computation of response properties, such as 2PA cross-sections, the environment plays an important role. To account for environment and protein–chromophore coupling effects, quantum mechanical/molecular mechanical (QM/MM) schemes can be useful. In this work, the polarizable embedding (PE) model is employed along with time-dependent density functional theory to describe the 2PA properties of a selected set of chromophores made from non-canonical amino acids as they are embedded in the DsRed protein matrix. The objective is to provide insights to determine whether or not the nCCs could be developed and, thus, generate a new class of FPs. Results from this investigation show that within the DsRed environment, the nCC 2PA cross-sections are diminished relative to their values in vacuum. However, further studies toward understanding the 2PA limit of these nCCs using different protein environments are needed.

In this work we describe the linear and non-linear (chiro)optical properties of an enantiopure bis-perylenediimide (PDI) cyclohexane derivative. This compound exhibits upconversion based on a two-photon absorption (TPA) process with a cross-section value of 70 GM together with emission of circularly polarized luminescence (CPL), showing a glum in the range of 10−3. This simple structure represents one of the scarce examples of purely organic compounds combining both TPA and CPL responses, together with large values of molar absorptivity and fluorescence quantum yield with emission in the 500–600 nm. Self-assembly induced by introduction of a poor solvent allows for a spectacular shift of the emission into the near-infrared (NIR, 650–750 nm) by formation of well-defined rotationally displaced dimers. Therefore, we are here presenting a versatile platform whose optical properties can be simply tuned by self-assembly or by functionalization of the electron-deficient aromatic core of PDIs.