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1.
Chem Soc Rev ; 48(15): 4087-4117, 2019 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-31292567

RESUMO

This review provides a comprehensive description of nonlinear optical (NLO) properties of gold nanoparticles, which can be used in biological applications. The main focus is placed on two-photon absorption (2PA) and two-photon excited photoluminescence (2PEL) - the processes crucial for multiphoton microscopy, which allows deeper imaging of the material and causes less damage to the biological samples in comparison to conventional (one-photon) microscopy. We present the basics of 2PA measurement techniques and a summary of recent achievements in the understanding of multiphoton excitation and the resulting photoluminescence in gold nanoparticles, both plasmonic ones and small nanoclusters with molecule-like properties. The examples of 2PA applications in bioimaging are also presented, with a comment on future challenges and applications.

2.
Chemistry ; 25(55): 12740-12750, 2019 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-31241793

RESUMO

The biological mediation of mineral formation (biomineralization) is realized through diverse organic macromolecules that guide this process in a spatial and temporal manner. Although the role of these molecules in biomineralization is being gradually revealed, the molecular basis of their regulatory function is still poorly understood. In this study, the incorporation and distribution of the model intrinsically disordered starmaker-like (Stm-l) protein, which is active in fish otoliths biomineralization, within calcium carbonate crystals, is revealed. Stm-l promotes crystal nucleation and anisotropic tailoring of crystal morphology. Intracrystalline incorporation of Stm-l protein unexpectedly results in shrinkage (and not expansion, as commonly described in biomineral and bioinspired crystals) of the crystal lattice volume, which is described herein, for the first time, for bioinspired mineralization. A ring pattern was observed in crystals grown for 48 h; this was composed of a protein-enriched region flanked by protein-depleted regions. It can be explained as a result of the Ostwald-like ripening process and intrinsic properties of Stm-l, and bears some analogy to the daily growth layers of the otolith.


Assuntos
Carbonato de Cálcio/química , Minerais/química , Membrana dos Otólitos/metabolismo , Proteínas Recombinantes/química , Animais , Peixes , Membrana dos Otólitos/química , Proteínas Recombinantes/metabolismo
3.
J Phys Chem B ; 123(19): 4271-4277, 2019 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-30835470

RESUMO

The development of photodynamic therapy (PDT) at depth requires photosensitizers which have both sufficient quantum yield for singlet oxygen generation and strong two-photon absorption. Here, we show that this can be achieved by conjugated linkage of zinc porphyrins to make dimers. We determined the quantum yield of generation of 1O2 , ϕΔ, by measuring emission at 1270 nm using a near-infrared streak camera and found it to increase from 15% for a single porphyrin unit to 27-47% for the dimers with a conjugated linker. Then, we recorded the spectra of two-photon absorption cross section, σ2, by a focus-tunable Z-scan method, which allows for nondestructive investigation of light-sensitive materials. We observed a strong enhancement of the two-photon absorption coefficient in the dimers, especially those with an alkyne linker. These results lead to an excellent figure of merit for two-photon production of singlet oxygen (expressed by the product σ2 × Ï•Δ) in the porphyrin dimers, of around 3700 GM, which is very promising for applications involving treatment of deep tumors by PDT.

4.
ACS Appl Mater Interfaces ; 11(11): 10435-10441, 2019 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-30838852

RESUMO

Lanthanide-based metal-organic frameworks (MOFs) and coordination polymers (CPs) attract much attention as candidates for optical ratiometric thermometry applications. Thus far, excitation of these materials was mainly performed in the ultraviolet that drastically limits their applicability as sensors, e.g., in tissue biological thermometry. As a remedy for this constraint, for the first time, we leverage a nonlinear optical process, the three-photon absorption property of Eu,Tb-CPs to shift the excitation wavelength from ultraviolet into near-infrared region. Experiments demonstrate that three-photon induced thermometric responses of Eu,Tb-CPs follow excellent optical characteristics similar to those determined for one-photon excitation, yet are not identical. The relative sensitivity reaches a very high value of 2.91%K-1 in the physiological temperature region. We put forward a notion that utilizing multiphoton absorption is a general strategy for realizing NIR-to-VIS remote temperature sensing in practically any CP that is designed for UV-to-VIS thermometry.

5.
Phys Chem Chem Phys ; 20(38): 24523-24526, 2018 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-30226238

RESUMO

Atomically-precise chiral gold nanoclusters hold promise for an accurate manipulation of chiro-optical properties, both in linear and nonlinear optics regimes. Here, we present the determination of two-photon linear-circular dichroism and two-photon circular dichroism (TPCD) of Au25[(Capt)18]- (where Capt is captopril). TPCD is found to be two orders of magnitude higher than one-photon circular dichroism.

6.
Chemistry ; 24(61): 16332-16341, 2018 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-30191625

RESUMO

Straightforward syntheses of bis[bis{1,2-bis(diphenylphosphino)ethane}ruthenium]-functionalized 1,3,5-triethynylbenzene-cored complexes via a methodology employing "steric control" permit facile formation of Y-shaped Sonogashira coupling products and distorted-H-shaped homo-coupled quadrupolar products. Cyclic voltammetric data from these products reveal two reversible metal alkynyl-localized oxidation processes for all complexes. The wavelengths of the linear optical absorption maxima are dominated by the nature of the peripheral alkynyl ligand rather than the substituent at the unique arm of the "Y" or at the quadrupolar complex "core". The quadratic optical nonlinearities of the Y-shaped complexes were assessed by the hyper-Rayleigh scattering technique at 800 nm and employing 100 fs light pulses; introduction of donor NEt2 and/or acceptor NO2 to the wedge periphery resulted in non-zero nonlinearities, with the largest ßHRS,800 values being observed for the complexes containing the 4-nitrophenylalkynyl ligands. Depolarization ratios are consistent with substantial off-diagonal first hyperpolarizability tensor components and 2D nonlinear character. Computational studies employing time-dependent density functional theory have been employed to assign the key low-energy transitions in the linear optical spectra and to compute the quadratic nonlinear optical tensorial components. Cubic optical nonlinearities of the quadrupolar complexes were assessed by the Z-scan technique over the range 500-1600 nm and employing 130 fs light pulses; two-photon absorption cross-sections for these distorted-H-shaped complexes are moderate to large in value (up to 5500 GM at 880 nm), while one example displays significant three-photon absorption (1300×10-80  cm6 s2 at 1200 nm).

7.
Phys Chem Chem Phys ; 20(34): 22260-22271, 2018 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-30123919

RESUMO

A three-step synthetic route to a structurally unique π-expanded pyrrolo[3,2-b]pyrrole derived bis-ketone has been developed. In contrast to all previous ladder-type pyrrolopyrroles, the new dye exhibits a low-energy absorption band in the visible region which is responsible for its red-purple color. Interestingly, even though the compound is centrosymmetric, this band coincides with the lowest energy two-photon absorption (TPA) transition. This non-typical behaviour has been computationally rationalized by finding two close lying excited states, one of which (S1) is active for OPA and the other (S2) for TPA processes, which arise from the mixing of two symmetric partial charge-transfer states. The ultrafast excited-state dynamics was characterized by means of transient absorption analysis. A relaxation process involving S1 symmetry breaking occurs in a few ps, leading to the formation of the lowest energy charge-transfer state. This is weakly emitting, with a measured lifetime in the order of tens of picoseconds. Interestingly, two-photon polymerization has been achieved using this new ketone. The high yield of radical photo-initiation upon two-photon excitation was demonstrated by the fabrication of woodpile photonic crystal templates by direct laser writing using a zirconium-silicon hybrid composite.

8.
ChemSusChem ; 2018 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-30134014

RESUMO

Multilayer nanocarriers loaded with optically activated payloads are gaining increasing attention due to their anticipated crucial role for providing new mechanisms of energy transfers in the health-oriented applications, as well as for energy storage and environmental protection. The combination of careful selection of optical components for efficient Förster resonance energy transfer, and surface engineering of the nanocarriers, allowed us to synthesize and characterize novel theranostic nanosystems for diagnosis and therapy of deep-seated tumors. The cargo, constrained within the oil core of the nanocapsules, composed of NaYF4 :Tm+3 , Yb+3 up-converting nanoparticles together with a second-generation porphyrin-based photosensitizing agent-Verteporfin, assured requisite diagnostic and therapeutic functions under near-IR laser excitation. The outer polyaminoacid shell of the nanocapsules was functionalized with a ligand-poly(l-glutamic acid) functionalized by PEG-ylated folic acid-to ensure both a "stealth" effect and active targeting towards human breast cancer cells. The preparation criteria of all nanocarrier building blocks meet the requirements for sustainable and green chemistry practices. The multifunctionality of the proposed nanocarriers is a consequence of both the surface-functionalized organic exterior part, which was accessible for selective accumulation in cancer cells, and the hydrophobic optically active interior, which shows phototoxicity upon irradiation within the first biological window.

9.
Nanoscale ; 10(24): 11302-11306, 2018 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-29892748

RESUMO

We show that the incorporation of chiral bioinspired photochromic compounds into inherently chiral DNA matrices enables the building of smart nanoscale photoswitchable chiroptical assemblies tunable over a wide range of wavelengths. Moreover, the use of light as external trigger affords precise control of the resulting hybrid DNA nanostructures, and their chiroptical activities can be spatially modulated without photochemical fatigue.

10.
Nanoscale ; 10(24): 11335-11341, 2018 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-29713724

RESUMO

Thiolate-protected gold nanoclusters have recently attracted considerable attention due to their size-dependent luminescence characterized by a long lifetime and large Stokes shift. However, the optimization of nanocluster properties such as the luminescence quantum yield is still a challenge. We report here the transformation of Au25Capt18 (Capt labels captopril) nanoclusters occurring at low pH and yielding a product with a much increased luminescence quantum yield which we have identified as Au23Capt17. We applied a simple method of treatment with HCl to accomplish this transformation and we characterized the absorption and emission of the newly created ligated nanoclusters as well as their morphology. Based on DFT calculations we show which Au nanocluster size transformations can lead to highly luminescent species such as Au23Capt17.

11.
J Phys Chem Lett ; 8(23): 5915-5920, 2017 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-29148817

RESUMO

The implication of guanine-rich DNA sequences in biologically important roles such as telomerase dysfunction and the regulation of gene expression has prompted the search for structure-specific G-quadruplex agents for targeted diagnostic and therapeutic applications. Herein, we report on a near-infrared (NIR) two-photon poly(cationic) anthracene-based macromolecule able to selectively target G-quadruplexes (G4s) over genomic double-stranded DNA. In particular, the striking changes in its linear and third-order nonlinear optical properties, combined with the emergence of a strong induced electronic circular dichroism (ECD) signal upon binding to canonical and noncanonical DNA secondary structures allowed for a highly specific detection of several different G4s. Furthermore, through a detailed computational analysis we bring compelling evidence that our probe intercalation within G4s is a thermodynamically favored event, and we fully rationalize the spectroscopic evolution resulting from this complexation event by providing a reasonable explanation regarding the origin of the peculiar ECD effect that accompanies it.


Assuntos
DNA/química , Quadruplex G , Substâncias Macromoleculares , Sequência de Bases , Dicroísmo Circular , Corantes Fluorescentes/química , Guanina/química , Conformação de Ácido Nucleico , Fótons , Termodinâmica
12.
Small ; 13(47)2017 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-29116668

RESUMO

At the core of luminescence color and lifetime tuning of rare earth doped upconverting nanoparticles (UCNPs), is the understanding of the impact of the particle architecture for commonly used sensitizer (S) and activator (A) ions. In this respect, a series of core@shell NaYF4 UCNPs doped with Yb3+ and Ho3+ ions are presented here, where the same dopant concentrations are distributed in different particle architectures following the scheme: YbHo core and YbHo@…, …@YbHo, Yb@Ho, Ho@Yb, YbHo@Yb, and Yb@YbHo core-shell NPs. As revealed by quantitative steady-state and time-resolved luminescence studies, the relative spatial distribution of the A and S ions in the UCNPs and their protection from surface quenching has a critical impact on their luminescence characteristics. Although the increased amount of Yb3+ ions boosts UCNP performance by amplifying the absorption, the Yb3+ ions can also efficiently dissipate the energy stored in the material through energy migration to the surface, thereby reducing the overall energy transfer efficiency to the activator ions. The results provide yet another proof that UC phosphor chemistry combined with materials engineering through intentional core@shell structures may help to fine-tune the luminescence features of UCNPs for their specific future applications in biosensing, bioimaging, photovoltaics, and display technologies.

13.
Angew Chem Int Ed Engl ; 56(46): 14743-14748, 2017 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-28898510

RESUMO

Multi-photon absorption (MPA) is among the most prominent nonlinear optical (NLO) effects and has applications, for example in telecommunications, defense, photonics, and bio-medicines. Established MPA materials include dyes, quantum dots, organometallics and conjugated polymers, most often dispersed in solution. We demonstrate how metal-organic frameworks (MOFs), a novel NLO solid-state materials class, can be designed for exceptionally strong MPA behavior. MOFs consisting of zirconium- and hafnium-oxo-clusters and featuring a chromophore linker based on the tetraphenylethene (TPE) molecule exhibit record high two-photon absorption (2PA) cross-section values, up to 3600 GM. The unique modular building-block principle of MOFs allows enhancing and optimizing their MPA properties in a theory-guided approach by combining tailored charge polarization, conformational strain, three-dimensional arrangement, and alignment of the chromophore linkers in the crystal.

14.
Langmuir ; 33(36): 8993-8999, 2017 09 12.
Artigo em Inglês | MEDLINE | ID: mdl-28800705

RESUMO

We report on two-photon excitation properties of small silver-doped gold nanoclusters (AuAgNCs) and on their three-dimensional arrangement in a hybrid system composed of DNA liquid crystals (LCs) and AuAgNCs. UV-vis and fluorescence spectroscopy, transmission electron microscopy (TEM), and multiphoton excitation spectroscopy were used to characterize the nanoparticles. We show that AuAgNCs exhibit two-photon excited luminescence (2PL) emission and second-harmonic generation (SHG) and that these properties remain the same in liquid crystalline matrix. The results are described in detail and discussed in the context of possible imaging application of AuAgNC and specific AuAgNCs organization induced by liquid crystalline ordering of DNA molecules.

15.
Chem Soc Rev ; 46(16): 4976-5004, 2017 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-28621347

RESUMO

The building block modular approach that lies behind coordination polymers (CPs) and metal-organic frameworks (MOFs) results not only in a plethora of materials that can be obtained but also in a vast array of material properties that could be aimed at. Optical properties appear to be particularly predetermined by the character of individual structural units and by the intricate interplay between them. Indeed, the "design principles" shaping the optical properties of these materials seem to be well explored for luminescence and second-harmonic generation (SHG) phenomena; these have been covered in numerous previous reviews. Herein, we shine light on CPs and MOFs as optical media for state-of-the-art photonic phenomena such as multi-photon absorption, triplet-triplet annihilation (TTA) and stimulated emission. In the first part of this review we focus on the nonlinear optical (NLO) properties of CPs and MOFs, with a closer look at the two-photon absorption property. We discuss the scope of applicability of most commonly used measurement techniques (Z-scan and two-photon excited fluorescence (TPEF)) that can be applied for proper determination of the NLO properties of these materials; in particular, we suggest recommendations for their use, along with a discussion of the best reporting practices of NLO parameters. We also outline design principles, employing both intramolecular and intermolecular strategies, that are necessary for maximizing the NLO response. A review of recent literature on two-, three- and multi-photon absorption in CPs and MOFs is further supplemented with application-oriented processes such as two-photon 3D patterning and data storage. Additionally, we provide an overview of the latest achievements in the field of frequency doubling (SHG) and tripling (third-harmonic generation, THG) in these materials. Apart from nonlinear processes, in the next sections we also target the photonic properties of MOFs that benefit from their porosity, and resulting from this their ability to serve as containers for optically-active molecules. Thus, we survey dye@MOF composites as novel media in which efficient upconversion via triplet energy migration (TEM) occurs as well as materials for stimulated emission and multi-photon pumped lasing. Prospects for producing lasing as an intrinsic property of MOFs has also been discussed. Overall, further development of the optical processes highlighted herein should allow for realization of various photonic, data storage, biomedical and optoelectronic applications.

16.
Chemistry ; 23(35): 8395-8399, 2017 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-28488357

RESUMO

Very large molecular two- and three-photon absorption cross-sections are achieved by appending ligated bis(diphosphine)ruthenium units to oligo(p-phenyleneethynylene) (OPE)-based "stars" with arms up to 7 phenyleneethynylene (PE) units in length. Extremely large three- and four-photon absorption cross-sections, through the telecommunications wavelengths range and beyond, are obtained for these complexes upon optimizing OPE length and the ruthenium-coordinated peripheral ligand. Multi-photon absorption (MPA) cross-sections are optimized with stars possessing arms 2 PE units in length. Peripheral ligand variation modifies MPA merit and, in particular, 4-nitrophenylethynyl ligand incorporation enhances maximal MPA values and "switches on" four-photon absorption (4PA) in these low molecular-weight complexes. The 4-nitrophenylethynyl-ligated 2PE-armed star possesses a maximal four-photon absorption cross-section of 1.8×10-108  cm8 s3 at 1750 nm, and significant MPA activity extending beyond 2000 nm.

17.
J Am Chem Soc ; 139(8): 3095-3105, 2017 03 01.
Artigo em Inglês | MEDLINE | ID: mdl-28170229

RESUMO

New stilbenoid and thiophenic compounds terminally functionalized with donor-donor, acceptor-acceptor, or donor-acceptor moieties and possessing a central [2.2]paracyclophane unit have been prepared, and their properties interpreted in terms of through-bond and through space π-electron delocalization (i.e., π-conjugations). Based on photophysical data, their excited-state properties have been described with a focus on the participation of the central [2.2]paracyclophane in competition with through-bond conjugation in the side arms. To this end, two-photon and one-photon absorption and emission spectroscopy, as a function of temperature, solvent polarity, and pressure in the solid state have been recorded. Furthermore, charge delocalization through the [2.2]paracyclophane in the neutral state and in the oxidized species (radical cations, dications and radical trications) has been investigated, allowing the elucidation of the vibrational Raman fingerprint of through-space charge delocalization. Thus, a complementary approach to both "intermolecular" excitation and charge delocalizations in [2.2]paracyclophane molecules is shown which can serve as models of charge and exciton migration in organic semiconductors.

18.
ACS Omega ; 2(9): 5715-5725, 2017 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-30023750

RESUMO

The binding interaction of a biocompatible water-soluble polycationic two-photon fluorophore (Ant-PIm) toward human serum albumin (HSA) was thoroughly investigated under simulated physiological conditions using a combination of steady-state, time-resolved, and two-photon excited fluorescence techniques. The emission properties of both Ant-PIm and the fluorescent amino acid residues in HSA undergo remarkable changes upon complexation allowing the thermodynamic profile associated with Ant-PIm-HSA complexation to be accurately established. The marked increase in Ant-PIm fluorescence intensity and quantum yield in the proteinous environment seems to be the outcome of the attenuation of radiationless decay pathways resulting from motional restriction imposed on the fluorophore. Fluorescence resonance energy transfer and site-marker competitive experiments provide conclusive evidence that the binding of Ant-PIm preferentially occurs within the subdomain IIA. The pronounced hypsochromic effect and increased fluorescence enhancement upon association with HSA, compared to that of bovine serum albumin (BSA) and other biological interferents, makes the polymeric Ant-PIm probe a valuable sensing agent in rather complex biological environments, allowing facile discrimination between the closely related HSA and BSA. Furthermore, the strong two-photon absorption (TPA) with a maximum located at 820 nm along with a TPA cross section σ2 > 800 GM, and the marked changes in the position and intensity of the band upon complexation definitely make Ant-PIm a promising probe for two-photon excited fluorescence-based discrimination of HSA from BSA.

19.
Biomacromolecules ; 17(11): 3609-3618, 2016 11 14.
Artigo em Inglês | MEDLINE | ID: mdl-27696875

RESUMO

We report the synthesis, spectroscopy, and the DNA binding properties of a biocompatible, water-soluble, polycationic two-photon absorbing anthracenyl derivative (Ant-PIm) specifically designed for biorelated applications. Detailed insights into the Ant-PIm-DNA binding interaction are provided by using several spectroscopic approaches, including UV-vis absorption, circular dichroism (CD), Fourier-transform infrared spectroscopy (FTIR), steady-state, and time-resolved fluorescence techniques. Absorption and fluorescence quantitative data analysis show a strong Ant-PIm-duplex interaction with binding constants of Kf = 4.7 ± 0.2 × 105 M-1, 7.1 ± 0.3 × 105 M-1, and 1.0 ± 0.1 × 106 M-1 at 298, 304, and 310 K, respectively. Spectral changes observed upon DNA binding provide evidence for a complex formation with off-on fluorescence pattern, which can be related to two consecutive binding equilibria. Results of DNA binders displacement and iodide quenching experimental assays unambiguously point to the groove binding mode of Ant-PIm to the DNA-helicate. Thermodynamic and chemical denaturation studies suggest that long-range interactions of hydrophobic nature regulate the association of Ant-PIm with the biopolymer. The ionic strength dependence of the binding constant shows that electrostatic component has an important contribution to the overall Gibbs free energy. FTIR and CD data provide evidence of partial modification of the B-DNA secondary structure, while the increase in the melting temperature clearly indicates the enhancement of the thermal stability of the duplex. Furthermore, the two-photon absorption cross section spectrum determined using the two-photon excited fluorescence (TPEF) technique shows a strong 2PA maximum at 820 nm with a σ2 > 800 GM, which emphasizes the advantageous combination of biological and optical properties possessed by this positively charged bioprobe.


Assuntos
Antracenos/química , DNA/química , Corantes Fluorescentes/química , Cátions/química , Dicroísmo Circular , Interações Hidrofóbicas e Hidrofílicas , Concentração Osmolar , Espectrometria de Fluorescência , Espectroscopia de Infravermelho com Transformada de Fourier
20.
Inorg Chem ; 55(19): 9501-9504, 2016 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-27673339

RESUMO

The nonlinear-optical properties of Prussian Blue nanoparticles have been evaluated with the use of femtosecond Z-scan measurements in the 1350-1750 nm range. This well-known inorganic pigment having interesting magnetic and electrochemical properties was found to be an efficient near-IR three-photon absorber. The maximum of the effective three-photon cross section is as high as 4.5 × 10-78 cm6 s2 at 1375 nm. By a comparison of the three-photon molar-mass-normalized merit factors, σ3/M, we show that this material is a competitive multiphoton absorber, especially in comparison to semiconductor quantum dots.

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