Two-photon Absorber Research Articles

Tweezer Dyads for H-Bond Assisted Cooperativity in Tandem Uncaging Systems.

"Tandem" uncaging systems, in which a photolabile protecting group (PPG) is sensitized by an energy-harvesting antenna, may increase the photosensitivity of PPGs by several orders of magnitude for two-photon (2P) photorelease. Yet, they remain poorly accessible because of arduous multi-step synthesis. In this work, we design efficient tandem uncaging systems by (i) using a convenient assembly of the building blocks relying on click chemistry, (ii) introducing H-bonding induced proximity thus facilitating (iii) photoinduced electron transfer (PeT) as a cooperative mechanism. A strong two-photon absorber electron-donating quadrupolar antenna and various electron-accepting PPGs (mDEAC, MNI or MDNI) were clicked stepwise onto a "tweezer-shaped" pyrido-2,6-dicarboxylate platform whose H-bonding and π-stacking abilities were exploited to keep the antenna and the PPGs in close proximity. The different electron-accepting ability of the PPGs led to dyads with wildly different behaviors. Whilst the MDNI and MNI dyads showed poor dark stability or no photo-uncaging ability due to their too high electron-accepting character, the mDEAC dyad benefited from optimum redox potentials to promote PeT and slow down charge recombination, resulting in enhanced uncaging quantum yield (Φu=0.38) compared to mDEAC (Φu=0.014). This unique combination resulted in large 2P photo-sensitivity in the near-infrared window (240 GM at 710 nm).

Two-Photon Light Trigger siRNA Transfection of Cancer Cells Using Non-Toxic Porous Silicon Nanoparticles.

The concept of using two-photon excitation in the NIR for the spatiotemporal control of biological processes holds great promise. However, its use for the delivery of nucleic acids has been very scarcely described and the reported procedures are not optimal as they often involve potentially toxic materials and irradiation conditions. This work prepares a simple system made of biocompatible porous silicon nanoparticles (pSiNP) for the safe siRNA photocontrolled delivery and gene silencing in cells upon two-photon excitation. PSiNP are linked to an azobenzene moiety, which possesses a lysine group (pSiNP@ICPES-azo@Lys) to efficiently complex siRNA. Non-linear excitation of the two-photon absorber system (pSiNP) followed by intermolecular energy transfer (FRET) to trans azobenzene moiety, result in the photoisomerization of the azobenzene from trans to cis and in the destabilization of the azobenzene-siRNA complex, thus inducing the delivery of the cargo siRNA to the cytoplasm of cells. Efficient silencing in MCF-7 expressing stable firefly luciferase with siRNAluc against luciferase is observed. Furthermore, siRNA against inhibitory apoptotic protein (IAP) leads to over 70% of MCF-7 cancer cell death. The developed technique using two-photon light allows a unique high spatiotemporally controlled and safe siRNA delivery in cells in few seconds of irradiation.

Enhanced two-photon excited fluorescence from green fluorescent proteins by ultrafast fluctuations in intense light pulse

The parametric down-conversion process in optical parametric generators causes bunching of light due to ultrafast intensity fluctuations, which enhances the efficiency of nonlinear interactions between light and matter. However, the bunching effect in a sufficiently intense light pulse light required for biological nonlinear imaging has not yet been investigated. We demonstrate enhanced two-photon excited fluorescence by ultrafast fluctuations in intense pulse using a wavelength-tunable optical parametric generator consisting of a periodically poled lithium niobate crystal pumped by nanosecond pulses at a wavelength of 532 nm and emitting pulses with a peak power of about 1 kW. The emission wavelength is tuned to about 927 nm, which is optimal for two-photon excitation of green fluorescent protein. The effect of bunching by ultrafast intensity fluctuations in the pulse is evaluated by an autocorrelator using a green fluorescent protein solution as a two-photon absorber. We found an about 1.9-fold enhancement compared with the coherent state of light. Using this calibrated optical parametric generator, we perform two-photon imaging of green fluorescent protein in brain tissue within a timescale of seconds. These experimental results using intense pulses demonstrate that the bunching effect by ultrafast fluctuations can enhance nonlinear imaging in biology and medicine.

Excited-State Symmetry Breaking in a Multiple Multipolar Chromophore Probed by Single-Molecule Fluorescence Imaging and Spectroscopy.

Excited-state symmetry breaking (ESB) has attracted much attention because it is often observed in symmetric multipolar chromophores designed as two-photon absorption/emission materials. Herein, we report an ensemble and single-molecule fluorescence imaging and spectroscopy investigation of ESB in hexakis[4-(p-dioctylaminostyryl)phenylethynyl]benzene(DB6), a two-photon absorber possessing a C6-symmetric π-D6 structure (π = hexaethynylbenzene, D = (p-dioctylaminostyryl)phenyl group) consisting of three equivalent D-π-D moieties. Ensemble and single-molecule measurements and theoretical calculations revealed that DB6 undergoes a photoabsorption process with two orthogonal transition dipole moments, whereas it fluoresces with a single transition dipole moment after one- or two-step ESB upon photoexcitation, depending on the environmental polarity. In nonpolar solvents and polymer films, one of the three D-π-D sites becomes planar, and the excited state is localized on this moiety: a [Dδ+-πδ--Dδ+]* quadrupolar state is formed. In polar solvents, the symmetry is further broken within the planarized D-π-D moiety, and the excited state is localized on one of the two D-π sites; i.e., a D-[πδ--Dδ+]* dipolar state is generated. Hence, DB6 can behave like a multichromophore with multiple emission sites in the molecule, which was demonstrated by stepwise photobleaching under photon antibunching conditions.

Two-photon ratiometric fluorescent probe based on NBD-amine functionalized semiconducting polymer nanoparticles for real-time imaging of hydrogen sulfide in living cells and zebrafish

The thiolysis of 7-nitro-1,2,3-benzoxadiazole amine (NBD-A) paves the way for specific sensing of H2S over biothiols and real-time imaging in living organisms. Rational fabrication of NBD-A-based probe with ratiometric mode and two-photon excitation is highly appealing to achieve high quality bioimaging. In this work, the NBD-A molecules are assembled with poly(9,9-dioctylfluorenyl-2,7-diyl) polymer nanoparticles, defined as NBD@PFO, to construct two-photon ratiometric probes for H2S detection through the fluorescence resonance energy transfer (FRET). For the construction of NBD@PFO nanohybrids, polymer nanoparticles are employed as the NBD-A molecular vehicle, energy donor and two-photon absorber, while NBD-A is served as the response unit and energy acceptor. Taking advantages of NBD-A and polymer nanoparticles, the obtained NBD@PFO probes exhibit high selectivity, fast response (<5 s), ratiometric detection and two-photon excitation. Our results indicate that NBD@PFO nanohybrids are successfully applied for monitoring of H2S concentration in living cells and zebrafish, exhibiting great potential of polymer nanoparticles to improve the imaging capability of an organic small molecular probe.

Diindeno-Fused Dibenzo[a,h]anthracene and Dibenzo[c,l]chrysene: Syntheses, Structural Analyses, and Properties.

Diindeno-fused dibenzo[a,h]anthracene 6 and diindeno-fused dibenzo[c,l]chrysene 9 contain the key moieties 1,4-quinodipropene (1,4-QDP) and 2,6-naphthoquinodipropene (2,6-NQDP), respectively, and they both have an open-shell singlet ground state. The latter compound exhibits a strong biradical character and interesting properties, including a low ΔET-S (2.44 kcal mol-1 ), a small HOMO-LUMO gap (1.06 eV), a wide photoabsorption range (250-1172 nm), and a large two-photon absorption cross-section (σ=1342±56 GM). This work verifies that 6 has a slightly larger HOMO-LUMO gap and ΔET-S than its helical isomer diindeno[2,1-f:1',2'-j]picene (DIP), but is a much stronger two-photon absorber, verifying the important effect of geometry on the photophysical properties.

Er:Yb phosphate glass laser with nonlinear absorber for phase-sensitive optical time domain reflectometry

A novel laser for phase-sensitive optical time-domain reflectometry (Φ-OTDR) is presented. The advantages of a compact solid-state laser are listed, current problems are shown. Experiments with a microchip single-optical-element laser, from setup construction to usage in Φ-OTDR system, are presented. New laser scheme with two-photon intracavity absorber is suggested and its advantages are described.

Large enhancement of optical limiting effects in anisotropic two-photon absorbers by radially polarized beams

We report the large enhancement of optical limiting effects by exploiting the anisotropy of a two-photon absorber and manipulating the polarization distribution of the light field simultaneously. After modeling the polarization-orientation dependence on the two-photon absorption (TPA) coefficient, we demonstrate the enhanced TPA effect on an anisotropic two-photon absorber using radially polarized beams (RPBs) and show its interesting applications through the Z-scan technique and an optical limiter. The numerical results reveal that both the sensitivity of the Z-scan technique and the optical limiting effect on an anisotropic two-photon absorber using RPBs have great enhancement compared with those on an isotropic two-photon absorber and using linearly polarized Gaussian beams. The presented work opens up new avenues for the enhancement of polarization-dependent nonlinear optical effects, which have potential applications in two-photon lithography, polarization-sensitive photodetectors, and multi-photon photoluminescence imaging.

In-phase and antiphase self-intensity regulated dual-frequency laser using two-photon absorption.

A 25 dB reduction of resonant intensity noise spectra is experimentally demonstrated for both the antiphase and in-phase relaxation oscillations of a dual-frequency solid-state laser operating at telecommunication wavelengths. Experimental results demonstrate that incorporation of an intracavity two-photon absorber that acts as a buffer reservoir reduces efficiently the in-phase noise contribution, while it is somewhat ineffective in lowering the antiphase noise contributions. A slight spatial separation of the two modes in the nonlinear two-photon absorber reduces the antiphase resonant intensity noise component. These experimental results provide a new approach in the design of ultra-low noise dual-frequency solid-state lasers.

Enhanced optical limiting effects in a double-decker bis(phthalocyaninato) rare earth complex using radially polarized beams

Optical limiting (OL) effects can be enhanced by exploiting various limiting mechanisms and by designing nonlinear optical materials. In this work, we present the large enhancement of OL effects by manipulating the polarization distribution of the light field. Theoretically, we develop the Z-scan and nonlinear transmission theories on a two-photon absorber under the excitation of cylindrical vector beams. It is shown that both the sensitivity of Z-scan technique and the OL effect using radially polarized beams have the large enhancement compared with that using linearly polarized beams (LPBs). Experimentally, we investigate the nonlinear absorption properties of a double-decker Pr[Pc(OC8H17)8]2 rare earth complex by performing Z-scan measurements with femtosecond-pulsed radially polarized beams at 800 nm wavelength. The observed two-photon absorption process, which originates from strong intramolecular π–π interaction, is exploited for OL application. The results demonstrate the large enhancement of OL effects using radially polarized beams instead of LPBs.

Buffer reservoir approach for cancellation of laser resonant noises.

The introduction of a buffer reservoir mechanism with optimized time-constants and cross sections in a laser system enables breaking any resonant exchange between the population inversion and photon population over an extremely wide bandwidth. The associated noise cancellation, including the excess noise at relaxation oscillations and spontaneous-signal beating, is experimentally evidenced up to 16 GHz in an Er,Yb laser comprising a GaAs two-photon absorber. Such approach is shown to preserve the laser linewidth quality and is advantageously implemented for optical distribution of frequency references.

3D photografting with aromatic azides: A comparison between three-photon and two-photon case

Photografting is a method utilizing light activation for covalent incorporation of functional molecules into a polymer surface or polymer matrix. It has been widely applied as a simple and versatile method for tailoring physical–chemical properties of various surfaces. Grafting induced via multi-photon absorption provides additional advantages of spatial and temporal control of the process. Here, a novel fluoroaryl azide photografting compound (AFA) was synthesized and compared with the commercially available azide BAC-M. Using Z-scan technique, it was determined that AFA is a two-photon absorber at 798nm, whereas BAC-M is a three-photon absorber at this wavelength. Both azides were employed for 3D photografting within a PEG-based matrix using femtosecond laser pulses. Both Z-scan measurements and 3D photografting tests indicated that, the intensity threshold for nonlinear absorption and photografting process is lower for AFA. As a result the processing window of AFA is much broader than that of BAC-M. But on the other hand, since BAC-M is characterized by the three-photon absorption (3PA) process, patterns with finer features can be produced using this molecule. The choice of the appropriate compound for 3D grafting will depend on the final application and the requirements associated with the resolution and post-modification protocol.

Exponential pulse steepening in degenerate two-photon propagation

The resonant propagation of an optical pulse in a two-photon absorber with a coherent initial excitation of the medium may lead to a pulse steepening growing exponentially in space. In addition another example is given wherein the steepening is followed by flattening. These results are new although, principally, they could be obtained from the general solution of the respective Goursat problem of an amplitude-modulated initial wave (H Steudel and D J Kaup 1996 J. Mod. Opt. 43 1851). In addition, we also give a simple theorem whereby it is demonstrated that the spatial derivative of the phase of the electric field will always be bounded. Furthermore, it is also shown that there can be certain critical points at which the atomic state, as well as the electric field, can become stationary in time and the spatial direction.

High-resolution Cs133 6S–6D, 6S–8S two-photon spectroscopy using an intracavity scheme

This Letter presents an intracavity scheme for diode laser based two-photon spectroscopy. To demonstrate generality, three (133)Cs hyperfine transition groups of different wavelengths are shown. For the 6S-6D transitions, we achieved a 10(2) times better signal-to-noise ratio than in previous work [J. Phys. Soc. Jpn. 74, 2487 (2005)] with 10(-3) times less laser power, revealing some previously vague and unobserved spectra. Possible mutual influences between the two-photon absorber and laser cavity were investigated for the first time to our knowledge, which leads to the application of a reliable hand-sized optical frequency reference. Our approach is applicable for most of the two-photon spectroscopy of alkali atoms.

Organometallic Complexes for Nonlinear Optics, 47 – Synthesis and Cubic Optical Nonlinearity of a Stilbenylethynylruthenium Dendrimer

The synthesis of the 1st generation dendrimer 1,3,5-{trans-[Ru(C≡C-3,5-(trans-[Ru(C≡CPh)(dppe)(2) (C≡CC(6) H(4) -4-(E)-CHCH)])(2) C(6) H(3) )(dppe)(2) (C≡CC(6) H(4) -4-(E)-CHCH)]}(3) C(6) H(3) proceeds by a novel route that features Emmons-Horner-Wadsworth coupling of 1,3,5-C(6) H(3) (CH(2) PO(OEt)(2) )(3) with trans-[Ru(C≡CC(6) H(4) -4-CHO)Cl(dppe)(2) ] and 1-I-C(6) H(3) -3,5-(CH(2) PO(OEt)(2) )(2) with trans-[Ru(C≡CPh)(C≡CC(6) H(4) -4-CHO)(dppe)(2) ] as key steps. The stilbenylethynylruthenium dendrimer is much more soluble than its ethynylated analog 1,3,5-{trans-[Ru(C≡C-3,5-(trans-[Ru(C≡CPh)(dppe)(2) (C≡CC(6) H(4) -4-C≡C)])(2) C(6) H(3) )(dppe)(2) (C≡CC(6) H(4) -4-C≡C)]}(3) C(6) H(3) and, in contrast to the ethynylated analog, is a two-photon absorber at telecommunications wavelengths.

Phototriggered release of photolabile drugs via two‐photon absorption‐induced cleavage of polymer‐bound dicoumarin

Abstract7‐(tert‐Butyldimethylsiloxy)‐7′‐(methacryloxy)dicoumarin (TBS‐Cum‐D‐MA) is introduced as a versatile polymerizable and photocleavable linker system for drug attachment to acrylic polymers. Following the copolymerization of the TBS‐Cum‐D‐MA with monomeric methylmethacrylate, a model drug chlorambucil was attached in a simple reaction. Phototriggered drug release via single‐ and two‐photon absorption induced cycloreversion of the cyclobutane of the dicoumarin part was investigated. The bound drug chlorambucil is sensitive to UV light being required for single‐photon induced cleavage of the dicoumarin linker and decomposes upon UV exposure. However, under the conditions of two‐photon absorption induced drug release, no photodegradation of chlorambucil was observed. As the only effective two‐photon absorber in the molecule is the cyclobutane structure, even high energies of visible light do not cause any degradation of the drug. This suggests that two‐photon‐triggered drug release may be successfully accomplished even with UV light sensitive drugs. The concept introduced here may be a powerful strategy in polymer design for photocontrolled drug delivery devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2443–2452, 2007

Quantum states of light produced by a high-gain optical parametric amplifier for use in quantum lithography

We present a theoretical analysis of the properties of an unseeded optical parametic amplifier (OPA) used as the source of entangled photons for applications in quantum lithography. We first study the dependence of the excitation rate of a two-photon absorber on the intensity of the light leaving the OPA. We find that the rate depends linearly on intensity only for output beams so weak that they contain fewer than one photon per mode. We also study the use of an N-photon absorber for arbitrary N as the recording medium to be used with such a light source. We find that the contrast of the interference pattern and the sharpness of the fringe maxima tend to increase with increasing values of N, but that the density of fringes and thus the limiting resolution does not increase with N. We conclude that the output of an unseeded OPA exciting an N-photon absorber provides an attractive system in which to perform quantum lithography.

Generalized theoretical treatment and numerical method of time-resolved radially dependent laser pulses interacting with multiphoton absorbers

We introduce a generalized numerical method to calculate short-pulsed laser propagation in a wide class of multiphoton absorbing materials. The method has no restrictions on the input pulse widths varying from nanosecond to femtosecond, and its numerical solution is both radially and temporarily dependent, enabling us to check numerically the validity of assuming radially constant solutions, which ensures that the true peak intensity falls below the damage causing level. A new feature of our technique enables us to determine quantitatively the contributions to the total absorption due to every electronic energy level. We found excellent agreement between our calculations and experiments using sample materials ranging from reverse saturable absorbers, two-photon absorbers with excited-state absorption to three-photon absorbers. We applied our technique to a two-photon absorber with excited-state absorption and found approximately 1 order of magnitude increase in the absorption when femtosecond pulses were used in place of nanosecond pulses.

Third-Order Nonlinear Optical Properties of Some Electron-Rich Iron Mono- and Trinuclear Alkynyl Complexes

The syntheses of [1,3,5-{(η2-dppe)(η5-C5Me5)FeC⋮C-4-C6H4C⋮C}3C6H3] (1) and [(η2-dppe)(η5-C5Me5)Fe(C⋮C-1,4-C6H4C⋮CPh)] (2) are reported, together with an X-ray diffraction study of 2. The linear optical spectra of these compounds reveal characteristic low-energy transitions at 430 and 436 nm, respectively, significantly red shifted in comparison to those recorded for [1,3,5-{(η2-dppe)(η5-C5Me5)FeC⋮C}3C6H3] (3) and [(η2-dppe)(η5-C5Me5)FeC⋮CPh] (4), respectively. Cubic nonlinear optical response data for 1, 2, and 4 are reported. Cubic molecular nonlinearities by Z-scan at 695 nm reveal an increase in nonlinearities upon introduction of the ligated metal unit and progression from linear monometallic complex to octupolar trimetallic complex. Oxidation of 1 to 13+ results in a change of sign and magnitude of the imaginary (absorptive) part of the third-order nonlinearity; that is, the molecule can be electrochemically cycled between two-photon absorber and saturable absorber states.

Dimethyl-pepep: a DNA probe in two-photon excitation cellular imaging

Dimethyl-pepep (D-pepep), a newly developed and very efficient two-photon absorber, has been tested here for two-photon excitation (TPE) cellular imaging. The spectral characteristics of the dye following one-photon excitation (OPE) and TPE (excitation and emission spectra, fluorescence lifetime, molecular brightness, saturation intensity) are reported. In vitro interaction studies with biomolecules show that dimethyl-pepep has a large affinity for DNA. A comparison with a widely used DNA stainer, 4-6-diamidino-2-phenylindole (DAPI) bound to DNA shows that the D-pepep brightness is one order of magnitude higher than that of DAPI, making this dye suitable for microscopy and imaging applications. TPE images taken from double-stained yeast Saccharomyces cerevisiae cells have revealed that D-pepep localizes mainly in the nucleus, similarly to DAPI, and in mitochondria, although to a minor extent. Preliminary tests have shown that the dye cellular toxicity is negligible.