Two-photon Chromophores Research Articles

Rhodamine-Sensitized Two-Photon Activation of a Red Light-Absorbing BODIPY Photocage.

Two-photon (2P) activatable probes are of high value in biological and medical chemistry since near infrared (NIR) light can penetrate deeply even in blood-perfused tissue and due to the intrinsic three-dimensional activation properties. Designing two-photon chromophores is challenging. However, the two-photon absorption qualities of a photocage can be improved with an intramolecular sensitizer, which transfers the absorbed light onto the cage. We herein present the synthesis and photophysical characterization of a 2P-sensitive uncaging dyad based on rhodamine 101 as donor fluorophore and a redshifted BODIPY as acceptor photocage. Liberation of p-nitroaniline (PNA) upon one-photon photolysis was confirmed by HPLC analysis. The photoreaction was found to be accompanied by a considerable change of the fluorescence properties of the chromophores. The possibility of a fluorescent read-out enabled the detection of two-photon induced uncaging by confocal fluorescence microscopy.

System for psychophysical measurements of two-photon vision

Two-photon absorption occurring in photoreceptors of human eye is responsible for perception of pulsed infrared laser beams. Color of perceived light corresponds to about half of wavelength of stimulating beam. This recently discovered phenomenon is called two-photon vision. However it is yet not clear how such phenomena could impact an ophthalmic diagnosis and therefore further studies are required. In this paper we present the system that enables future psychophysical experiments to extend knowledge about two-photon vision and its diagnostic value by identifying differences between two-photon and single-photon vision. Full Text: PDF ReferencesD. A. Atchison, G. Smith, Optics of the human eye (Butterworth-Heinemann 2000) CrossRef G. Palczewska et al. "Human infrared vision is triggered by two-photon chromophore isomerization", Proceedings of the National Academy of Sciences 111, 1428 (2014). CrossRef P. Artal, S. Manzanera, K. Komar, A. Gambín-Regadera, M. Wojtkowski, "Visual acuity in two-photon infrared vision", Optica 4, 1488 (2017). CrossRef K. Komar et al. "Posterior Eye Shape Measurement With Retinal OCT Compared to MRI", Investigative Ophthalmology & Visual Science 57, 196 (2016). CrossRef K. Komar et al. "Two-photon visual sensitivity of human cones - a psychophysical study", Investigative Ophthalmology & Visual Science 59, 4049 (2018). DirectLink S. A. Burns,R.H. Webb, Handbook of optics 28 (New York, McGraw Hill 1994) DirectLink R. W. Nygaard, T. E. Frumkes, "Calibration of the retinal illuminance provided by maxwellian views", Vision Research (1982) CrossRef P. Melillo et al. "Pupillometric analysis for assessment of gene therapy in Leber Congenital Amaurosis patients", Biomedical engineering online 11, 40 (2012) CrossRef P. A. Stanley, A. K. Davies, "The effect of field of view size on steady-state pupil diameter", Ophthalmic and Physiological Optics, 15, 601 (1995) CrossRef S. Mathôt, "Pupil mimicry is the result of brightness perception of the iris and pupil" Journal of Cognition 1 (2018) CrossRef M. M. Thomas, T. D. Lamb, "Light adaptation and dark adaptation of human rod photoreceptors measured from the a‐wave of the electroretinogram", The Journal of physiology 518, 479 (1999) CrossRef

Stepwise dual stimuli triggered dual drug release by a single naphthalene based two-photon chromophore to reverse MDR for alkylating agents with dual surveillance in uncaging steps.

In this work, we depleted glutathione (GSH) by releasing SO2 with internal stimulus GSH itself, and also selectively marked the cancer cells followed by release of anticancer drug using another orthogonal stimulus i.e., two-photon (TP) NIR light by a single naphthalene based chromophore (TP absorbance 77 GM and uncaging cross-section 21 GM). We demonstrated the improved therapeutic efficacy of chlorambucil by the stepwise dual stimuli approach and dual surveillance of both the drug uncaging process in real-time using in vitro studies.

Two-photon actuation of crosslinked liquid-crystalline polymers utilizing energy transfer system

ABSTRACTWe prepared crosslinked azotolane liquid-crystalline polymer (LCP) films doped with a stilbene derivative (two-photon chromophore) utilizing an interpenetrating polymer network (IPN) structure. The IPN films bend toward the light source upon irradiation with femtosecond laser pulses at 600 nm, which can excite the stilbene derivative by two-photon absorption. The bending speed of the IPN films increases with the square of the laser pulse intensity, which is compelling evidence for the two-photon processes.

Synthesis and Characterization of Two-Photon Active Chromophores Based on Tetrathienoacene (TTA) and Dithienothiophene (DTT).

Three new donor-π-donor (D-π-D) tetrathienoacene (thieno[2',3':4,5]thieno[3,2-b]thieno[2,3-d]thiophene (TTA))-cored chromophores, end-functionalized with electron-donating triphenylamine (TPA) groups, were developed and characterized for their two-photon-related properties by using both nano- and femtosecond laser pulses as the probing tools. TTA-based chromophores exhibit stronger and more widely dispersed two-photon absorption (2PA) than those of dithienothiophene (DTT)-based congeners. As a consequence, the bithiophene-conjugated TTA chromophore exhibits the highest maximum 2PA cross-section value (up to 2500 GM) with good thermal stability, and thus, it is the best performing two-photon chromophore among the studied model compounds. The bithiophene-conjugated DTT analogue exhibits the second highest maximum two-photon absorptivity of 1950 GM, which is nearly 7 times larger than that of previously reported DTT-based chromophores.

Synthesis and characterization of novel symmetrical two-photon chromophores derived from bis(triphenylaminotetrathienoacenyl) and fused-thiophene units

Four new donor–π–donor (D–π1–π2–π1–D) fused-thiophene-based chromophores, end-functionalized with electron-donating triphenylamine (TPA) groups, were developed and characterized for a two-photon absorption study.

Human infrared vision is triggered by two-photon chromophore isomerization.

Vision relies on photoactivation of visual pigments in rod and cone photoreceptor cells of the retina. The human eye structure and the absorption spectra of pigments limit our visual perception of light. Our visual perception is most responsive to stimulating light in the 400- to 720-nm (visible) range. First, we demonstrate by psychophysical experiments that humans can perceive infrared laser emission as visible light. Moreover, we show that mammalian photoreceptors can be directly activated by near infrared light with a sensitivity that paradoxically increases at wavelengths above 900 nm, and display quadratic dependence on laser power, indicating a nonlinear optical process. Biochemical experiments with rhodopsin, cone visual pigments, and a chromophore model compound 11-cis-retinyl-propylamine Schiff base demonstrate the direct isomerization of visual chromophore by a two-photon chromophore isomerization. Indeed, quantum mechanics modeling indicates the feasibility of this mechanism. Together, these findings clearly show that human visual perception of near infrared light occurs by two-photon isomerization of visual pigments.

Synthesis and photophysical properties of two-photon chromophores containing 1H-benzimidazole residue

The non-centrosymmetric, trans,trans-2-{4-[2-(1H-benzimidazol-2-yl)ethenyl]-styryl}-1,3-dimethylbenzimidazole iodide and centrosymmetric, trans,trans-1,4-bis[4-(2-(1H-benzimidazol-2-yl)ethenyl)]benzene polymethine compounds based on 1H-benzimidazole residue were synthesized and characterized. Their photophysical properties in solvents of different polarity were thoroughly studied by means of absorption, emission and fluorescence quantum yield measurements. Analysis of the results clearly indicates that the compounds have strong one-photon absorption bands in the near ultraviolet region, relatively high fluorescence quantum yields and large Stokes' shifts due to the charge transfer effect.The one- and two-photon absorption properties of a selected non-centrosymmetric dye were compared to those of a centrosymmetric polymethine dye. Their two-photon absorption cross-sections in DMF were determined to be ∼330 GM and ∼380 GM at ca. 650 nm for the centrosymmetric and non-centrosymmetric polymethine compounds, respectively.Density functional theory calculations of one- and two-photon absorption electronic spectra of the tested compounds using CAM-B3LYP, LC-BLYP and LC-ωPBE functionals were carried out to support the experimental data.

Synthesis and characterization of two-photon chromophores based on a tetrasubstituted tetraethynylethylene scaffold.

A new series of model dye molecules composed of three multibranched analogues based on the tetrasubstituted tetraethynylethylene structural motif have been synthesized and experimentally shown to possess strong and widely dispersed two-photon absorption (2PA) in the near-IR region. It was found that the spectral position of the major 2PA band could be tuned by the electronic nature of the selected substitution units. The studied model fluorophores also exhibited fairly low photodegradation of their fluorescence intensity even under prolonged UV-light irradiation, which is beneficial for the development of fluorescence probes that are needed for long-term light exposure. Furthermore, representative chromophores were selected to demonstrate the power-control properties within the femtosecond and nanosecond time domains.

Chemical control of channel interference in two-photon absorption processes.

The two-photon absorption (TPA) process is the simplest and hence the most studied nonlinear optical phenomenon, and various aspects of this process have been explored in the past few decades, experimentally as well as theoretically. Previous investigations have shown that the two-photon (TP) activity of a molecular system can be tuned, and at present, performance-tailored TP active materials are easy to develop by monitoring factors such as length of conjugation, dimensionality of charge-transfer network, strength of donor-acceptor groups, polarity of solvents, self-aggregation, H-bonding, and micellar encapsulation to mention but a few. One of the most intriguing phenomena affecting the TP activity of a molecule is channel interference. The phrase "channel interference" implies that if the TP transition from one electronic state to another involves more than one optical pathway or channel, characterized by the corresponding transition dipole moment (TDM) vectors, the channels may interfere with each other depending upon the angles between the TDM vectors and hence can either increase (constructive interference) or decrease (destructive interference) the overall TP activity of a system to a significant extent. This phenomenon was first pointed out by Cronstrand, Luo, and Ågren [Chem. Phys. Lett. 2002, 352, 262-269] in two-dimensional systems (i.e., only involving two components of the transition moment vectors). For three-dimensional molecules, an extended version of this idea was required. In order to fill this gap, we developed a generalized model for describing and exploring channel interference, valid for systems of any dimensionality. We have in particular applied it to through-bond (TB) and through-space (TS) charge-transfer systems both in gas phase and in solvents with different polarities. In this Account, we will, in addition to briefly describing the concept of channel interference, discuss two key findings of our recent work: (1) how to control the channel interference by chemical means, and (2) the role of channel interference in the anomalous solvent dependence of certain TP chromophores. For example, we will show that simple structurally induced changes in certain dihedral angles of the well-known betaine dye (TB type) will help fine-tune the constructive channel interference and hence increase the overall TP activity of molecules with this general TP channel structure. Another intriguing result we will discuss is observed for a tweezer-trinitrofluorinone complex (TS type) where, on moving from polar to essentially nonpolar solvents, the nature of the channel interference switches from destructive to constructive, leading to a net abnormal solvent dependence of the TP activity of the system. The present Account highlights the usefulness of the channel interference effect and establishes it as a new and unique way of controlling the TP transition probability in different types of three-dimensional molecules.

Biocompatible well-defined chromophore–polymer conjugates for photodynamic therapy and two-photon imaging

A versatile approach is introduced for the synthesis of well-defined, biocompatible conjugates combining two-photon chromophores and hydrophilic multifunctional polymers synthesized by RAFT controlled radical polymerization. As an illustration, two different classes of conjugates carrying multiple fluorophores (based on an anthracene moiety, Anth) or photosensitizers (based on a dibromobenzene moiety, DBB) along the polymer chain were elaborated for bioimaging and photodynamic therapy (PDT) applications, respectively. In both cases, the polymer greatly improved the solubility in biorelevant media as well as the cell uptake. Anth conjugates provided high quality fluorescence microscopy images using both one- and two-photon excitation. DBB conjugates potently induced the death of cancer cells upon photoactivation.

Optical Properties of a Two-Photon Chromophore in a Polymeric Nanostructure

Optical properties of a cationic two-photon absorption (TPA) chromophore, 1,4-bis{4′-[N,N-bis(6″-trimethylammoniumhexyl)amino]styryl}benzene tetrabromide (C1) upon complexation with an anionic diblock copolymer, poly[(ethylene oxide)-block-(sodium 2-acrylamido-2-methyl-1-propane sulfonate)] (Em -An ) and a cationic surfactant, cetyltrimethylammonium bromide (CTAB) have been studied. Electrostatic interaction among C1, cationic CTAB and anionic (Em -An ) forms a vesicular polymeric nanostructure (containing C1 in a core), which is soluble in water. Incorporation of C1 into the nonpolar microenvironment inside the nanostructure successfully modulated its optical properties in aqueous medium. In water, fluorescence quantum yield (η) of C1 (0.32) was increased up to 0.55 accompanied with 30∼40 nm PL photoluminescence (PL) spectral shifts by forming the self-assembled nanostructure. This vesicular nanostructure may have a potential application as a two-photon molecular tag for biological imaging by two-photon microscopy.

Synthesis, optical properties and singlet oxygen generation of a phthalocyanine derivative containing strong two-photon-absorbing chromophores in the periphery

A phthalocyanine derivative containing two-photon chromophores which are based on pyrimidine was designed and synthesized. Its light-emission property was studied in detail, and a strong energy transfer from peripheral chromophores to the phthalocyanine core was observed. The compound exhibited strong two-photon absorption responses with a two-photon absorption cross-section up to 1153 GM when irradiated with a picosecond laser in the wavelength range of 800-870 nm, and gave good singlet oxygen generation.

Photophysical Properties of a Series of Electron-Donating and -Withdrawing Platinum Acetylide Two-Photon Chromophores

To explore spectroscopic structure-property relationships in platinum acetylides, we synthesized a series of complexes having the molecular formula trans-bis(tributylphosphine)-bis(4-((9,9-diethyl-7-ethynyl-9H-fluoren-2-yl)ethynyl)-R)-platinum. The substituent, R = NH(2), OCH(3), N(phenyl)(2), t-butyl, CH(3), H, F, benzothiazole, CF(3), CN, and NO(2), was chosen for a systematic variation in electron-donating and -withdrawing properties as described by the Hammett parameter σ(p). UV/vis, fluorescence, and phosphorescence spectra, transient absorption spectra on the fs-ps time scale, and longer time scale flash photolysis on the ns time scale were collected. DFT and TDDFT calculations of the T(1) and S(1) energies were performed. The E(S) and E(T) values measured from linear spectra correlate well with the calculated results, giving evidence for the delocalized MLCT character of the S(1) state and confinement of the T(1) exciton on one ligand. The calculated T(1) state dipole moment ranges from 0.5 to 14 D, showing the polar, charge-transfer character of the T(1) state. The ultrafast absorption spectra have broad absorption bands from 575 to 675 nm and long wavelength contribution, which is shown from flash photolysis measurements to be from the T(1) state. The T(1) energy obtained from phosphorescence, the T(1)-T(n) transition energy obtained from flash photolysis measurements, and the triplet-state radiative rate constant are functions of the calculated spin density distribution on the ligand. The calculations show that the triplet exciton of chromophores with electron-withdrawing substituents is localized away from the central platinum atom, red-shifting the spectra and increasing the triplet-state lifetime. Electron-donating substituents have the opposite effect on the location of the triplet exciton, the spectra, and the triplet-state lifetime. The relation between the intersystem crossing rate constant and the S(1)-T(1) energy gap shows a Marcus relationship with a reorganization energy of 0.83 eV. The calculations show that intersystem crossing occurs by conversion from a nonpolar, delocalized S(1) state to a polar, charge-transfer T(1) state confined to one ligand, accompanied by conformation changes and charge transfer, supporting the experimental evidence for Marcus behavior.

Water-Soluble Two-Photon Absorbing Nitrosyl Complex for Light-Activated Therapy through Nitric Oxide Release

A water-soluble nitrosyl complex with large two-photon absorption was synthesized by incorporating a two-photon absorbing chromophore with tetra(ethylene glycol) units, into the Roussin's red salt. The nitrosyl complex exhibits quenched emission due to energy transfer from the two-photon chromophore to the Roussin's red salt. The nitric oxide (NO) release induced by one- or two-photon irradiation was detected by EPR spectroscopy with a chemical probe, the Fe(II)- N-(dithiocarbamoyl)- N-methyl- d-glucamine (Fe-MGD) complex. Increased one- or two-photon excited fluorescence, with a concomitant photochemical release of NO, was observed upon one- or two-photon light irradiation. With the observed light-dependent cytotoxicity against cancer cells of the water-soluble nitrosyl complex, it was demonstrated that two-photon-functionalized nitrosyl complexes can be effective NO donors for light-activated treatment.

Effects of conjugation length and resonance enhancement on two-photon absorption in phenylene–vinylene oligomers

Two-photon excitation spectra have been recorded over the large spectral range of 540-1000 nm for five phenylene-vinylene oligomers that differ in the length of the conjugated pi system. The significant changes observed in the two-photon excitation spectra and absorption cross sections as a function of this systematic change in the chromophore are discussed in light of (1) the corresponding one-photon absorption spectra and (2) high-level density functional response theory calculations performed on analogues of these systems. The results obtained illustrate one way to exploit parameters that influence nonlinear optical properties in large organic molecules. Specifically, data are provided to indicate that when the frequency of the laser used in the two-photon experiment is nearly-resonant with an allowed one-photon transition, significant increases in the two-photon absorption cross section can be realized. This phenomenon of the so-called resonance enhancement allows for greater control in obtaining an optimal response when using existing two-photon chromophores, and provides a much-needed guide for the systematic development and efficient use of two-photon singlet oxygen sensitizers.

Study of the absorption and emission spectroscopy of “A–B” type photosensitive compounds including two-photon chromophore and benzophenone moiety

“A–B” type photosensitive compounds including two-photon chromophore and benzophenone moiety have been designed, synthesized and characterized. The UV–vis absorption and fluorescence emission of the compounds have been extensively studied in various solvents. The results show that the absorption of “A–B” type compounds displays obvious double absorption bands, one of which at short-wavelength is related to the benzophenone moiety, the other at long-wavelength is mainly contributed by chromophore. The emission of “A–B” type compounds at 500–700 nm shows an “unexpected” blue-shift comparing with that of the sole chromophore. The photosensitive compounds with amino group display strong emission in apolar solvents and have a low fluorescence quantum yields in polar solvents. In contrast, the compounds without amino group exhibit strong fluorescence emission in polar solvents, and low fluorescence quantum yields in apolar solvents. The fluorescence quantum yields of “A–B” type compounds are higher than those of the sole chromophore. The discoveries suggest that charge redistribution induced by the introduction of benzophenone moiety plays a key role on the absorption and emission spectroscopy.

A modular approach to two-photon absorbing organic nanodots: brilliant dendrimers as an alternative to semiconductor quantum dots?

Nanoscopic fluorescent dendrimers having up to 96 two-photon chromophores and showing very large two-photon absorption cross-sections (up to 56 000 GM) were designed as a complementary "organic" alternative to quantum dots.

Dependence of the Two-Photon Absorption Cross Section on the Conjugation of the Phenylacetylene Linker in Dipolar Donor−Bridge−Acceptor Chromophores

The nonlinear optical properties of four isomeric dipolar two-photon chromophores are compared. The chromophores consist of a carbazole electron donor coupled to a naphthalimide electron acceptor by a phenylacetylene bridge. By variation of the connectivity of the bridge at the phenyl groups, four compounds with 0, 1, and 2 meta linkages are synthesized. The linear and nonlinear optical properties of these compounds are measured. Despite similar linear absorption cross sections, the two-photon absorption cross section delta of the all-meta compound is almost a factor of 10 lower than the all-para compound. By taking the detailed molecular conformations into account in order to calculate accurate dipole moment changes, we find that the decrease in delta results largely from the decreased charge transfer ability with increasing number of meta linkages. We find that a two-state model can be used to predict semiquantitatively the observed trend in delta on the basis of the linear optical properties of the molecules. This work illustrates the dramatic effect the ground-state polarizability can have on the nonlinear optical response of organic compounds and also provides a way to quantify the ability of meta linkages to inhibit charge transfer in their ground-state configuration.

Two-photon absorption in solution by means of time-dependent density-functional theory and the polarizable continuum model

We present the first study of two-photon absorption (TPA) of solvated molecules based on direct evaluation of TPA cross sections from the quadratic response of time-dependent perturbations. A set of prototypical two-photon (TP) chromophores has been selected and analyzed: a pure pi system (t-stilbene) and its substituted homologs obtained employing a donor (D) and an acceptor (A) group to probe the solvent effects along the series pi, D-pi-D, A-pi-D, and A-pi-A. For the selected systems we have calculated the TPA cross sections in different environments by means of the polarizable continuum model. The data have been analyzed to evaluate how the structural and environmental parameters contribute to the final two-photon absorption cross section. These include molecular structure, geometry relaxation in solution, polarity, and refractive index of the solvent. The performances of the three common functionals SVWN, BLYP, and B3LYP have been compared. The results show a significant solvent dependence of the TPA cross section and an unusual trend when passing from cyclohexane to water. The data have also been rationalized in terms of the main orbital excitations leading to the transitions. Finally, trends along the series have been described and comparison with experiments and previous calculations has been drawn.