Low Two-photon Absorption Research Articles

Combining Two-Photon-Activated Fluorescence Resonance Energy Transfer and Near-Infrared Photothermal Effect of Unimolecular Micelles for Enhanced Photodynamic Therapy.

Recent years have witnessed significant progress in the field of two-photon-activated photodynamic therapy (2P-PDT). However, the traditional photosensitizer (PS)-based 2P-PDT remains a critical challenge in clinics due to its low two-photon absorption (2PA) cross sections. Here, we propose that the therapeutic activity of current PSs can be enhanced through a combination of two-photon excited fluorescence resonance energy transfer (FRET) strategy and photothermal effect of near-infrared (NIR) light. A core-shell unimolecular micelle with a large two-photon-absorbing conjugated polymer core and thermoresponsive shell was constructed as a high two-photon light-harvesting material. After PSs were grafted onto the surface of a unimolecular micelle, the FRET process from the conjugated core to PSs could be readily switched "on" to kill cancer by the collapsed thermoresponsive shell due to the photothermal effect of NIR light. Such NIR-triggered FRET leads to an enhanced 2PA activity of the traditional PSs and, in turn, amplifies their cytotoxic singlet oxygen generation. Eventually, both in vitro and in vivo PDT efficiencies treated with the thermoresponsive micelles were dramatically enhanced under NIR light irradiation, as compared to pure PSs excited by traditional visible light. Such a facile and simple methodology for the enhancement of the photodynamic antitumor effect holds great promises for cancer therapy with further development.

Strong Modulation Instability in a Silicon–Organic Hybrid Slot Waveguide

In this paper, we investigate the strong modulation instability (MI) at telecommunication band in a silicon–organic hybrid slot waveguide. The organic material of polymer poly (bis para-toluene sulfonate) of 2, 4-hexadiyne 1, 6 diol (PTS), which has high third-order nonlinear refractive index and very low two-photon absorption, is used to fill the slot of the waveguide. The optical gain can be up to $\sim$ 3600 ${\rm m}^{-1} $ with a low pump peak power of 300 mW. By using Gaussian pulses with width of 10 ps and peak power of 250 mW, deep modulation of the pump is achieved, and the ultrashort pulse trains with the periods of 27 and 24 fs are obtained in the anomalous and normal group-velocity dispersion regions, respectively.

Highly efficient and excitation tunable two-photon luminescence platform for targeted multi-color MDRB imaging using graphene oxide.

Multiple drug-resistance bacteria (MDRB) infection is one of the top three threats to human health according to the World Health Organization (WHO). Due to the large penetration depth and reduced photodamage, two-photon imaging is an highly promising technique for clinical MDRB diagnostics. Since most commercially available water-soluble organic dyes have low two-photon absorption cross-section and rapid photobleaching tendency, their applications in two-photon imaging is highly limited. Driven by the need, in this article we report extremely high two-photon absorption from aptamer conjugated graphene oxide (σ2PA = 50800 GM) which can be used for highly efficient two-photon fluorescent probe for MDRB imaging. Reported experimental data show that two-photon photoluminescence imaging color, as well as luminescence peak position can be tuned from deep blue to red, just by varying the excitation wavelength without changing its chemical composition and size. We have demonstrated that graphene oxide (GO) based two-photon fluorescence probe is capable of imaging of multiple antibiotics resistance MRSA in the first and second biological transparency windows using 760–1120 nm wavelength range.

Stent bioactivo de titanio y óxido nítrico, ¿más seguro y eficaz que los stents farmacoactivos de segunda generación?

Photodynamic therapy (PDT) is a promising cancer treatment that can be implemented using various agents. The conventional photosensitizer Al (III) phthalocyanine chloride tetrasulfonic acid (Pc) has limitations of selectivity in tumor targeting, low affinity to cancer cells, and low two-photon absorption. This study presents a novel photosensitizer FA-TiO2-Pc, which has the TiO2 nanoparticle conjugated with a tumor targeting agent of folic acid (FA), and Pc. FA-TiO2-Pc possessed high targeted photodynamic therapeutic activity and excellent biocompatibility. This promising photosensitizer showed high therapeutic drug efficiency in vitro at a low concentration dose and short incubation time under one-photon excitation (OPE). In vivo, when treated with a low dose of FA-TiO2-Pc and low light irradiation, the tumor growth was depressed in mice bearing HeLa xenograft tumors with minimal side effects. In addition, the two-photon absorption of FA-TiO2-Pc was also enhanced compared to Pc, proving that FA-TiO2-Pc system has a great potential to be used for the therapy of the folate receptor positive cancer cells in both OPE-PDT and two-photon excitation (TPE)-PDT agents.

Production of orientation-patterned GaP templates using wafer fusion techniques

Nonlinear optical frequency conversion is an effective technique for generating infrared (IR) and terahertz (THz) wavelengths not readily available from existing laser sources. Birefringent materials such as LiNbO 3 are often used to generate wavelengths where gaps exist, but are unsuitable in the mid-IR, far-IR, and THz regions as these materials are often opaque in these regions. As an alternative, GaAs has been employed for frequency conversion in these regions using quasi-phase-matching (QPM) to overcome the material’s lack of birefringence. QPM has been successfully demonstrated in GaAs using fused stacks of thin alternately oriented layers or inverted orientation patterned (OP) grating templates overgrown with thick columnar GaAs layers. Although GaAs has a high nonlinear coefficient d 14 = 170 pm/V at 1.064 μm and good thermal conductivity (52 W/m K), it suffers from strong two-photon absorption below 1.7 μm making it inefficient when pumped with a source less than or equal to this wavelength. GaP also has a high nonlinear coefficient d 14 = 71 pm/V at 1.064 μm, better thermal conductivity (110 W/m K) and much lower two-photon absorption in the 1 μm region. Therefore, OPGaP is desirable for NLO applications in the mid-IR and THz that use commercially available pump lasers in the 1.06–1.55 μm wavelength range. In this work the fabrication of OPGaP templates suitable for thick columnar hydride vapor phase epitaxial growth of GaP is reported using a commercially viable wafer fusion technique.

Synthesis, characterization, and large two-photon absorption cross-sections of solid red-emitting 1,4-diketo-3,6-diphenylpyrrolo [3,4-c ]pyrrole/3,6-carbazole/terfluorene copolymers

The synthesis, one- and two-photon absorption (TPA) and emission properties of three novel 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP)/3,6-carbazole (Cz)/terfluorene (TF) copolymers are reported. The molar ratios of DPP versus TF are 15:85 (TCP15), 25:75 (TCP25), and 50:50 (TCP50) under Cz:(TF + DPP) = 1. Two distinguished one-photon absorption and emission bands observed in solutions imply that the electronic states of Cz–DPP–Cz and Cz–TF–Cz are not well mixed and the energy transfer from TF segments to DPP units is incomplete. However, in film states, all three copolymers are monochromatic red emitting with the peak wavelengths at 617, 621, and 631 nm for TCP15, TCP25, and TCP50, respectively, indicating that the interchain interactions also have played an important role in the energy transfer. In two-photon measurement, the copolymer solutions still exhibit two distinguished emission bands but the relative intensities at short-wavelength region are obviously decreased, implying that Cz–TF–Cz segment is high one-photon active but low TPA active, whereas Cz–DPP–Cz unit is low one-photon active but high TPA active. All the copolymers show large δ over the range of measured wavelengths and the δ values of TCP15, TCP25, and TCP50 increase with DPP contents and are up to 530, 770, and 850 GM per repeating unit, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Twisted π-System Chromophores for All-Optical Switching

Molecular chromophores with twisted π-electron systems have been shown to possess unprecedented values of the quadratic hyperpolarizability, β, with very large real parts and much smaller imaginary parts. We report here an experimental and theoretical study which shows that these twisted chromophores also possess very large values of the real part of the cubic hyperpolarizability, γ, which is responsible for nonlinear refraction. Thus, for the two-ring twisted chromophore TMC-2 at 775 nm, relatively close to one-photon resonance, n(2) extrapolated to neat substance is large and positive (1.87 × 10(-13) cm(2)/W), leading to self-focusing. Furthermore, the third-order response includes a remarkably low two-photon absorption coefficient, which means minimal nonlinear optical losses: the T factor, α(2)λ/n(2), is 0.308. These characteristics are attributed to closely spaced singlet biradical and zwitterionic states and offer promise for applications in all-optical switching.

Octave spanning supercontinuum in an As_2S_3taper using ultralow pump pulse energy

An octave spanning spectrum is generated in an As₂S₃ taper via 77 pJ pulses from an ultrafast fiber laser. Using a previously developed tapering method, we construct a 1.3 μm taper that has a zero-dispersion wavelength around 1.4 μm. The low two-photon absorption of sulfide-based chalcogenide fiber allows for higher input powers than previous efforts in selenium-based chalcogenide tapered fibers. This higher power handling capability combined with input pulse chirp compensation allows an octave spanning spectrum to be generated directly from the taper using the unamplified laser output.

Photosensitive and thermal nonlinear effects in chalcogenide photonic crystal cavities

We investigate the photosensitive and thermo-optic nonlinear properties of chalcogenide glass photonic crystal (PhC) cavities at telecommunications wavelengths. We observe a photosensitive refractive index change in AMTIR-1 (Ge(33)As(12)Se(55)) material in the near-infrared, which is enhanced by light localization in the PhC cavity and manifests in a permanent blue-shift of the nanocavity resonance. Thermo-optic non-linear properties are thoroughly investigated by i) carrying out thermal bistable switching experiments, from which we determined thermal switching times of 63 μs and 93 μs for switch on and switch off respectively and ii) by studying heating of the cavity with a high peak power pulsed laser input, which shows that two-photon absorption is the dominant heating mechanism. Our measurements and analysis highlight the detrimental impact of near-infrared photosensitivity and two-photon absorption on cavity based nonlinear optical switching schemes. We conclude that glass compositions with lower two-photon absorption and more stable properties (reduced photosensitivity) are therefore required for nonlinear applications in chalcogenide photonic crystal cavities.

Two-photon high-resolution measurement of partial pressure of oxygen in cerebral vasculature and tissue

The ability to measure oxygen partial pressure (pO2) with high temporal and spatial resolution in three dimensions is crucial for understanding oxygen delivery and consumption in normal and diseased brain. Among existing pO2 measurement methods, phosphorescence quenching is optimally suited for the task. However, previous attempts to couple phosphorescence with two-photon laser scanning microscopy have faced substantial difficulties because of extremely low two-photon absorption cross-sections of conventional phosphorescent probes. Here, we report the first practical in vivo two-photon high-resolution pO2 measurements in small rodents’ cortical microvasculature and tissue, made possible by combining an optimized imaging system with a two-photon-enhanced phosphorescent nanoprobe. The method features a measurement depth of up to 250 µm, sub-second temporal resolution and requires low probe concentration. Most importantly, the properties of the probe allowed for the first direct high-resolution measurement of cortical extravascular (tissue) pO2, opening numerous possibilities for functional metabolic brain studies.

A new approach to dual-color two-photon microscopy with fluorescent proteins

BackgroundTwo-photon dual-color imaging of tissues and cells labeled with fluorescent proteins (FPs) is challenging because most two-photon microscopes only provide one laser excitation wavelength at a time. At present, methods for two-photon dual-color imaging are limited due to the requirement of large differences in Stokes shifts between the FPs used and their low two-photon absorption (2PA) efficiency.ResultsHere we present a new method of dual-color two-photon microscopy that uses the simultaneous excitation of the lowest-energy electronic transition of a blue fluorescent protein and a higher-energy electronic transition of a red fluorescent protein.ConclusionOur method does not require large differences in Stokes shifts and can be extended to a variety of FP pairs with larger 2PA efficiency and more optimal imaging properties.

Nonlinear optical properties of 2,4,5-Trimethoxy-4ʹ-nitrochalcone: observation of two-photon-induced excited-state nonlinearities

We report experimental investigations of optical nonlinearities and nonlinear dynamics in acetone solution of 2,4,5-Trimethoxy-4- nitrochalcone. By performing Z-scans with femtosecond laser pulses at low excitation intensity, two-photon absorption (2PA) and third-order nonlinear refraction are measured. As laser excitation intensity exceeds a critical value, however, the interplay between third- and fifth-order nonlinearities is observed. It is also confirmed that fifth-order processes mainly originate from 2PA-induced excited-state nonlinearities by conducting femtosecond time-resolved degenerate pump-probe measurements. All the nonlinear parameters are determined unambiguously in the near infrared region of the 2PA cross-section, second-order hyperpolarizability, excited-state absorption cross-section, excited-state refraction cross-section, lifetime of excited states induced by 2PA, and critical population of the excited states in 2,4,5-Trimethoxy-4-nitrochalcone molecule.

Large two photon absorption cross section of asymmetric Zn(II) porphyrin complexes substituted in the meso or β pyrrolic position by –C [tbnd]C–C 6H 4X moieties (X = NMe 2, NO 2)

A large two photon absorption (TPA) cross section of about 4000 GM is measured by Z-scan technique for a push–pull A–π–D Zn(II) porphyrin complex disubstituted in the meso position with strong donor and acceptor moieties. This result is compared to the lower TPA cross section of Zn(II) porphyrinates mono-substituted in the meso or β pyrrolic position with the same donor or acceptor substituents. The origin of such trend is discussed in terms of charge transfer processes, π delocalisation and resonance pathways.

Optical and structural properties of new chalcohalide glasses

New class of chalcohalide glasses has been prepared in the GeS2–In2S3–CsI system with regard to their potential non-linear properties. The study of glass-forming region was undertaken to select glassy compositions, which present high non-linear (NL) optical properties with a low two-photon absorption. Thermal analyses, structural examination by Raman spectroscopy, non-linear optical measurements were investigated as a function of CsI contents. Introduction of CsI has shifted the band-gap edge towards the blue region of the absorption optical spectrum and therefore has limited the two-photon absorption. Their NL refractive index n2 are 60 times higher than silica glasses without any NL absorption. Moreover, second harmonic signal was observed in thermally poled samples similar to silica glass. However, this second order non-linearity is not temporally stable.

Optical linearity and nonlinearity of ZnSe nanocrystals embedded in epoxy resin matrix investigated by Z-scan technique

The ZnSe nanocrystals were synthesized by hydrothermal method. Through mixed with epoxy resin in vacuum at high temperature environment, the nanocrystals embedded in an epoxy resin matrix structure were obtained. This nanocomposite sample was characterized by transmission electron microscope (TEM) and electron beam diffraction, showing the nanocrystals were dispersed homogeneously and their structures were zinc blende structure. The nanocomposite structure was also confirmed by the blue-shift of the absorption edge. The nonlinear refraction index and two-photon absorption (TPA) coefficient were measured by the Z-scan technique, using a single Gaussian beam of Nd:YAG laser (532 nm). The result shows that ZnSe nanocrystals embedded in epoxy resin matrix have higher nonlinear refraction index and lower TPA coefficient than that of bulk ZnSe.

Ultrafast all-optical chalcogenide glass photonic circuits

<p> <a href="http://oe.osa.org/virtual_issue.cfm?vid=36">Focus Serial: Frontiers of Nonlinear Optics</a> </p>Chalcogenide glasses offer large ultrafast third-order nonlinearities, low two-photon absorption and the absence of free carrier absorption in a photosensitive medium. This unique combination of properties is nearly ideal for all-optical signal processing devices. In this paper we review the key properties of these materials, outline progress in the field and focus on several recent highlights: high quality gratings, signal regeneration, pulse compression and wavelength conversion.

Theoretical investigation of two-photon absorption allowed excited states in symmetrically substituted diacetylenes by ab initio molecular-orbital method

Symmetrically substituted diacetylene compounds, which shows large two-photon absorption (TPA) cross sections, have been theoretically investigated by the ab initio molecular-orbital method employing several theoretical models including the configuration interaction with single excitation (CIS), random phase approximation (RPA), and time-dependent density-functional theory (TDDFT) methods. The calculated excited energies are overestimated by CIS or RPA, whereas underestimated by TDDFT with the B3LYP parametrization for both one-photon absorption (OPA) and TPA allowed states. The lowest OPA state is well described by the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) transition. On the other hand, lower TPA allowed states can be represented as the superposition of the HOMO-LUMO+1 and HOMO-1-LUMO transitions, giving rise to two TPA allowed states. The absorption intensity for the lower TPA state of the diacetylenes molecules is discussed in terms of the alternancy symmetry and its breaking. The symmetry property is differently manifested for neutral and dicationic diacetylenes. Introduction of charges breaks the alternancy symmetry, which gives rise to an increase in the TPA cross sections at the lower frequency. The upper TPA state is calculated to show huge TPA cross sections, which reproduces the enhancement of the TPA cross section experimentally observed for one of the diacetylenes at the higher-frequency region. The enhancement is discussed employing an index defined as the ratio of the transition polarizability and its static limit, which represents the degree of influence of one-photon resonance on the TPA intensity. The huge TPA cross sections are found to be due to a near-resonance effect. The present theoretical calculation approves the previously proposed assumption based on the four-state (dual three-state) model, which consists of the ground, one OPA allowed, and two TPA allowed states.

Third-order nonlinear optical properties of a cadmiun sulfide-dendrimer nanocomposite

We have investigated the nonlinear optical response of thin films consisting of a poly(propyleneimine) dendrimer matrix having diaminobutane core with and without small 2.2nm diameter CdS quantum dots. Large nonlinear coefficients and low nonlinear absorption losses were observed at 532 and 1064nm. The high nonlinearity and low two-photon absorption yielded promising figures of merit for nonlinear optical switching applications.

Phosphorescent Oxygen Sensor with Dendritic Protection and Two-Photon Absorbing Antenna

Imaging oxygen in 3D with submicron spatial resolution can be made possible by combining phosphorescence quenching technique with multiphoton laser scanning microscopy. Because Pt and Pd porphyrin-based phosphorescent dyes, traditionally used as phosphors in biological oxygen measurements, exhibit extremely low two-photon absorption (2PA) cross-sections, we designed a nanosensor for oxygen, in which a 2P absorbing antenna is coupled to a metalloporphyrin core via intramolecular energy transfer (ET) with the purpose of amplifying the 2PA induced phosphorescence of the metalloporphyrin. The central component of the device is a polyfunctionalized Pt porphyrin, whose triplet state emission at ambient temperatures is strong, occurs in the near infrared and is sensitive to O2. The 2PA chromophores are chosen in such a way that their absorption is maximal in the near infrared (NIR) window of tissue (e.g., 700-900 nm), while their fluorescence is overlapped with the absorption band(s) of the core metalloporphyrin, ensuring an efficient antenna-core resonance ET. The metalloporphyrin-antenna construct is embedded inside the protecting dendritic jacket, which isolates the core from interactions with biological macromolecules, controls diffusion of oxygen and makes the entire sensor water-soluble. Several Pt porphyrin-coumarin based sensors were synthesized and their photophyics studied to evaluate the proposed design.

Effect of low numerical-aperture femtosecond two-photon absorption on (SU-8) resist for ultrahigh-aspect-ratio microstereolithography

We report the quantitative characterization and analysis on the solidification of SU-8, a chemically amplified near-ultraviolet ultrathick resist, based on two-photon-absorbed (TPA) near-infrared photopolymerization. The resolution of TPA photopolymerized SU-8 voxels and lines is studied as a function of laser-pulse energy, single-shot exposure time, and scanning speed. Two-photon microstereolithography using SU-8 as the matrix material was verified by the fabrication of SU-8 photoplastic structures with subdiffraction-limit resolution. We show that the nonlinear velocity dependence of TPA photopolymerization can be used as the shutter mechanism for disruptive three-dimensional (3D) lithography. This mechanism, when combined with low numerical-aperture optics is exploited for the rapid 3D microfabrication of ultrahigh-aspect-ratio (up to 50:1) photoplastic pillars, planes, and cage structures.