Photomedical Applications Research Articles

Wavelength-Tunable Textile-Based Organic Light-Emitting Diode for Multifunctional Wearable Photomedical Applications and Display with Cool White to Warm White Light

Wavelength-Tunable Textile-Based Organic Light-Emitting Diode for Multifunctional Wearable Photomedical Applications and Display with Cool White to Warm White Light

Wearable quantum dots organic light-emitting diodes patch for high-power near infra-red photomedicene with real-time wavelength control

Wearable photomedical application fields, such as photobiomodulation (PBM), and photoplethysmography (PPG) sensors using organic light-emitting diodes (OLEDs), are promising and attractive due to their flexibility, surface light emission, and ability to apply to various free-form (attachable or implantable) healthcare platforms. However, to maximize the impact on wearable photomedical applications, their spectrum needs to be freely tunable in real-time, and expanded into the near-infrared (NIR) wavelengths which are difficult to achieve in conventional electroluminescent OLED. In this study, we introduce the wavelength selective quantum dots high-power parallel-stacked OLED (QD-OLED) patch. Several NIR QD-OLEDs with 630, 700, and 730 nm peak wavlength were optimized by the high-power (> 100 mW·cm−2 at 6.3 V) parallel-stacked blue OLED with a 465 nm emission peak.The NIR QD-OLED patch platform with multi-functional blue reflective NIR-enhanced (> 60 %) encapsulation film (6 x 10−6 g·m−2·day−1), capable of real-time wavelength control, achieved a high-output NIR power density (>23.28 mW·cm−2). Using this NIR QD-OLED patch, PPG bio-signals were successfully measured. Additionally, this NIR QD-OLED demonstrated that it can increase the proliferation of dermal papilla cells by up to 131 % through NIR wavelength control, thereby optimizing the hair growth effect.

Red Light Absorption of [ReI(CO)3(α-diimine)Cl] Complexes through Extension of the 4,4'-Bipyrimidine Ligand's π-System.

Rhenium(I) complexes of type [Re(CO)3(NN)Cl] (NN = α-diimine) with MLCT absorption in the orange-red region of the visible spectrum have been synthesized and fully characterized, including single crystal X-ray diffraction on two complexes. The strong bathochromic shift of MLCT absorption was achieved through extension of the π-system of the electron-poor bidiazine ligand 4,4'-bipyrimidine by the addition of fused phenyl rings, resulting in 4,4'-biquinazoline. Furthermore, upon anionic cyclization of the twisted bidiazine, a new 4N-doped perylene ligand, namely, 1,3,10,12-tetraazaperylene, was obtained. Electrochemical characterization revealed a significant stabilization of the LUMO in this series, with the first reduction of the azaperylene found at E1/2(0/-) = -1.131 V vs. Fc+/Fc, which is the most anodic half-wave potential observed for N-doped perylene derivatives so far. The low LUMO energies were directly correlated to the photophysical properties of the respective complexes, resulting in a strongly red-shifted MLCT absorption band in chloroform with a λmax = 586 nm and high extinction coefficients (ε586nm > 5000 M-1 cm-1) ranging above 700 nm in the case of the tetraazaperylene complex. Such low-energy MLCT absorption is highly unusual for Re(I) α-diimine complexes, for which these bands are typically found in the near UV. The reported 1,3,10,12-tetraazaperylene complex displayed the [Re(CO)3(α-diimine)Cl] complex with the strongest MLCT red shift ever reported. UV-Vis NIR spectroelectrochemical investigations gave further insights into the nature and stability of the reduced states. The electron-poor ligands explored herein open up a new path for designing metal complexes with strongly red-shifted absorption, thus enabling photocatalysis and photomedical applications with low-energy, tissue-penetrating red light in future.

Efficient CuInS2/ZnS Quantum Dots Light‐Emitting Diodes in Deep Red Region Using PEIE Modified ZnO Electron Transport Layer

In this study, the enhanced device performance of CuInS2/ZnS quantum dots‐based light‐emitting didoes (QLEDs) for photomedical applications using polyethylenimine ethoxylated (PEIE)‐modified ZnO as electron transport layer has been reported. The device enhancement is investigated by applying time‐resolved photoluminescence and transient electroluminescence spectra. The results show that the modification of PEIE on ZnO layer limits the electron injection into quantum dots layer and reduces the accumulation of electrons at ZnO/QD interface. This provides an effective way to suppress the charging processes of quantum dots and thus enhance the device efficiency. As a result, the synergistic effect of PEIE modifying layer leads to a record current efficiency of 2.75 cd A−1 for the CuInS2/ZnS‐based QLEDs with deep red emission at 650 nm.

Flexible quantum dot light‐emitting devices for targeted photomedical applications

Quantum dot light-emitting devices (QLEDs), originally developed for displays, were recently demonstrated to be promising light sources for various photomedical applications, including photodynamic therapy cancer cell treatment and photobimodulation cell metabolism enhancement. With exceptional emission wavelength tunability and potential flexibility, QLEDs could enable wearable, targeted photomedicine with maximized absorption of different medical photosensitizers. In this paper, we report, for the first time, the in vitro study to demonstrate that QLEDs-based photodynamic therapy can effectively kill Methicillin-resistant Staphylococcus aureus, an antibiotic-resistant bacterium. We then present successful synthesis of highly efficient quantum dots with narrow spectra and specific peak wavelengths to match the absorption peaks of different photosensitizers for targeted photomedicine. Flexible QLEDs with a peak external quantum efficiency of 8.2% and a luminance of over 20,000 cd/m2 at a low driving voltage of 6 V were achieved. The tunable, flexible QLEDs could be employed for oral cancer treatment or diabetic wound repairs in the near future. These results represent one fresh stride toward realizing QLEDs' long-term goal to enable the wide clinical adoption of photomedicine.

22‐3: Distinquished Student Paper: Flexible Quantum Dot Light Emitting Devices for Photomedicine

We demonstrate highly efficient quantum dots with narrow spectra and specific peak wavelengths for photomedical applications. Flexible quantum dot light emitting devices with peak EQE of 8.2% and luminance over 20,000 Cd/m2 were achieved which will be employed for treatment of oral cancers or diabetic wounds.

20‐1: Invited Paper: Solution Processable Luminescent Nanomaterials for Display, Lighting and Beyond

Colloidal quantum dots (QDs) and organic‐inorganic hybrid perovskites (OIHPs) represent two key solution processable luminescent nanomaterials. We will report a recent discovery that led to green OIHP ‐ polymer composite films with high photoluminescence efficiency, color purity and unprecedented water and heat stability for LCD backlight and some current developments of ultrabright red QLEDs for lighting, sensing and photomedical applications.

68‐2: Distinguished Student Paper: Quantum Dot Light Emitting Devices (QLEDs) for Photomedical Applications

We demonstrate using an ultra‐bright quantum dot light emitting device for photobiomodulation (PBM) and photodynamic therapy (PDT). In‐vitro study indicates this approach could increase cell metabolism in multiple cell lines by ~12.5%–27.9% over control systems for PBM and kill cancerous cell efficiently for PDT.

Quantum dot light emitting devices for photomedical applications.

While OLEDs have struggled to find a niche lighting application that can fully take advantage of their unique form factors as thin, flexible, lightweight and uniformly large-area luminaire, photomedical researchers have been in search of low-cost, effective illumination devices with such form factors that could facilitate widespread clinical applications of photodynamic therapy (PDT) or photobiomodulation (PBM). Although existing OLEDs with either fluorescent or phosphorescent emitters cannot achieve the required high power density at the right wavelength windows for photomedicine, the recently developed ultrabright and efficient deep red quantum dot light emitting devices (QLEDs) can nicely fit into this niche. Here, we report for the first time the in-vitro study to demonstrate that this QLED-based photomedical approach could increase cell metabolism over control systems for PBM and kill cancerous cells efficiently for PDT. The perspective of developing wavelength-specific, flexible QLEDs for two critical photomedical fields (wound repair and cancer treatment) will be presented with their potential impacts summarized. The work promises to generate flexible QLED-based light sources that could enable the widespread use and clinical acceptance of photomedical strategies including PDT and PBM.

Molecular devices based on reversible singlet oxygen binding in optical and photomedical applications

Latest advances in design and synthesis of molecular systems for reversible singlet oxygen binding and their applications in optical and biomedical research are discussed.

Hydrophilic tetracarboxy bacteriochlorins for photonics applications.

Bacteriochlorins absorb strongly in the near-infrared (NIR, 700-900 nm) region and hence are well suited for photophysical studies and photomedical applications, yet such endeavors heretofore have been largely limited by the intrinsic lipophilicity of the bacteriochlorin macrocycle. Here, a new molecular design is investigated wherein 3,5-dicarboxyphenyl units are appended to the β-pyrrolic positions of the bacteriochlorin. Use of the 3,5-aryl substitution motif places the carboxylic acid groups, which are anionic at neutral pH, above and below the plane of the bacteriochlorin macrocycle. A de novo synthesis has been employed to create five such bacteriochlorins, which uses as intermediates two new 2,12-dibromobacteriochlorin building blocks and a known 3,13-dibromobacteriochlorin. The aryl groups with protected carboxylate moieties were introduced by Suzuki coupling; subsequent deprotection afforded the hydrophilic bacteriochlorins. The latter were characterized by absorption and fluorescence spectroscopy in DMF and in aqueous phosphate buffer (pH 7). In most cases, comparable sharp emission (FWHM of ∼25 nm) and modest fluorescence yields (0.060-0.11) were observed in aqueous phosphate buffer medium and in DMF. Aqueous solubility was examined by absorption spectral interrogation of samples over a 1000-fold concentration range with reciprocal change in pathlength (∼0.5, 5, 50, and 500 μM; 10, 1, 0.1, and 0.01 cm pathlength cuvettes). One hydrophilic bacteriochlorin was prepared that contains a single maleimido-terminated tether for bioconjugation; the tether was installed by the sequence of 15-bromination of the bacteriochlorin, Suzuki coupling, and DCC-mediated amide formation. The maleimido-bacteriochlorin was conjugated to a 48-residue cysteine-containing peptide analogue of a constituent from a bacterial photosynthetic light-harvesting complex. Taken together, the results show a new molecular design and facile de novo synthetic route for obtaining hydrophilic bacteriochlorins including a bioconjugatable group if desired.

It is All About Proteases: From Drug Delivery to In Vivo Imaging and Photomedicine

Clinical studies provide overwhelming evidence for the importance of proteolytic imbalance and the upregulation of diverse protease classes in diseases such as cancer and arthritis. While the complex nature of proteolytic networks has hampered the development of protease inhibitors for these indications, aberrant enzyme activity could be successfully exploited for the development of proteasesensitive drug delivery systems and fluorescent in vivo imaging agents. More recently, these concepts have also been translated into photomedical applications to develop dual modality prodrugs for the simultaneous treatment and imaging of disease. After an introductory overview of proteases and their role in cancer, we present and discuss different strategies to exploit upregulated protease activity for the development of drug delivery systems, fluorescent in vivo reporter probes, and photosensitizer-prodrugs with respect to their potential and limitations. The main approaches used for targeting proteases in all three areas can be roughly divided into peptide-based and macromolecular strategies. Both involve the use of a short, peptide-based protease substrate, which is either directly tagged to the therapeutic agent or dye/quencher pair, or alternatively, serves as a linker between the polymeric carrier and a functional unit. In the latter case, the pharmacokinetic properties of peptide-based protease-sensitive prodrugs and imaging probes can be further ameliorated by the passive targeting capacity of macromolecular drug delivery systems for neoplastic and inflammatory lesions.

30 ORAL LASER APPLICATIONS FOR DECONTAMINATION AND BIOSTIMULATION

We review current clinical applications of photodiagnosis (PD) and photodynamic therapy (PDT) in the head and neck field and highlight the actual status, problems, challenges as well as the future of this emerging treatment modality.In recent years literature presented input from many new developments and their applications. This is due to better awareness and developing knowledge about PD–PDT from the clinical staff, both nurses and doctors. But it is also a result of improved drug and hardware development such as lasers, LEDs and related optical devices. Current photo-medical applications in the head and neck region range from diagnostics, treatment of premalignant and malignant lesions, aesthetic and cosmetic applications to the ever expanding anti-microbial applications.Although treatment of premalignant and early malignant lesions of the oropharyngeal cavity have long been the favourite lesions to treat with PDT patients with unsalvageable tumors have also been responding remarkably well to PDT, adding significant quality of life.There is growing interest in anti-microbiological PDT and recent progress has shown that this application is able to significantly reduce the number or even eradicate specific microbial pathogens. During many surgical treatments better control of microbiological activity through PDT may lead to a better outcome.Despite progressive development in this field a few problems remain: prolonged phototoxicity, limited penetration of the photosensitizer and light, inadequate specificity, PDT-related pain as well as the lack of uniformly accepted protocols both for light application as well as photosensitizers. Recent studies have shown that PDT based pain can be separated from other forms of pain, offering hope that a specific management of pain will be possible. If PDT will become fully accepted by patients and doctors we must care about the negative factors such as pain and prolonged phototoxicity.

Swallowtail Bacteriochlorins. Lipophilic Absorbers for the Near-Infrared

Bacteriochlorins absorb strongly in the near-infrared spectral region and hence are ideally suited for diverse photomedical applications, yet naturally occurring bacteriochlorins have limited stability and synthetic malleability. A de novo route has been exploited to prepare synthetic bacteriochlorins that bear a geminal dimethyl group in each pyrroline ring for stability and a symmetrically branched 1,5-dimethoxypentyl group attached to each pyrrole ring for solubility in lipophilic media.

Ultraviolet photoionization of the photosensitizers khellin and visnagin in aqueous solution and in micelles: one-photon ionization is a minor process

One-photon ionization, leading to formation of hydrated electrons and radical cations, has been proposed as a possible mechanism of action of some sensitizers in photobiology. In this contribution, we have investigated this proposal for the compounds khellin and visnagin, used in photomedical applications. Nanosecond transient absorption spectroscopy covering a wide range of laser pulse energies was employed to measure the formation of radical cations and hydrated electrons in aqueous solution and in cationic (CTAB) as well as anionic (SDS) micellar solutions. A model allowing for simultaneous one- and two-photon processes and fully accounting for the nonlinearity of the pulse energy dependence was used to simulate the data. The results did not support the hypothesis of a significant role of one-photon ionization, the upper limits of the quantum yields of radical cation formation being phi < 0.01 for visnagin and phi < 0.004 for khellin.

Optical properties of rat liver between 350 and 2200 nm

Previous investigators have determined the optical properties of the liver at isolated wavelengths using various models of light propagation. In this study we derived coefficients for absorption, scattering, and anisotropy for rat liver between 350 and 2200 nm using measurements of integrated reflectance, transmittance, and on-axis attenuation and a diffusion approximation algorithm to solve the 1-D transport equation. These results were used to estimate the effective attenuation coefficient, penetration depth, and temperature rise induced by laser irradiation. The data should be of value to investigators in the field of tissue optics and developers of photomedical applications involving the liver.