Selective antibacterial and antibiofilm activity of chlorinated hemicyanine against gram-positive bacteria.

Antibiotic-free therapies are highly needed due to the limited success of conventional approaches especially against biofilm related infections. In this direction, antimicrobial phototherapy, either in the form of antimicrobial photothermal therapy (aPTT) or antimicrobial photodynamic therapy (aPDT), have appeared to be highly promising candidates in recent years. These are local and promising approaches for antibiotic resistant bacterial infections and biofilms. Organic small photosensitizers (PSs) are extensively preferred in antimicrobial phototherapy applications as they offer a great opportunity to combine therapeutic action (aPTT, aPDT or both) with fluorescence imaging on a single molecule. In this study, the bactericidal effect of cationic chlorinated hemicyanine (Cl-Hem)-based type I PS, which can function as a dual aPDT/aPTT agent, was investigated on both planktonic cells and biofilms of different gram-positive (E. faecalis and S. epidermidis) and gram-negative bacteria (P. aeruginosa and K. pneumoniae) with and without 640 nm laser irradiation. Cl-Hem was shown to induce a selective phototheranostic activity against gram-positive bacteria (E. faecalis and S. epidermidis). Cl-Hem exhibited both dose and laser irradiation time dependent bactericidal effect on planktonic and biofilms of S. epidermidis. These results clearly showed that highly potent Cl-Hem can treat resistant microbial infections, while allowing fluorescence detection at the same time. High biofilm reduction observed with combined aPDT/aPTT action of Cl-Hem together with its non-cytotoxic nature points out that Cl-Hem is a promising PS for antibacterial and antibiofilm treatments.

Er3+:YLiF4 channeled waveguide laser near 2.7-2.8†µm fabricated by femtosecond laser inscription.

We report, for the first time to our knowledge, a demonstration of robust waveguide lasing near 2.7-2.8 µm in an erbium-doped fluoride host. Femtosecond laser inscription was employed to fabricate 50- and 70-µm diameter channeled waveguides inside an Er3+:YLiF4 crystal. The best power performance was obtained with the 70-µm diameter waveguide and 16% transmitting output coupler. The propagation loss and refractive index contrast were measured as 0.23 dB/cm and 7.1 × 10-4, respectively, for the 70-µm diameter waveguide. Both self-Q-switched (SQS) and continuous-wave (CW) operations could be obtained. During the SQS operation, as short as 240-ns pulses with average power of 51 mW, repetition rate of 368 kHz, and power slope efficiency of 15.2% were generated at the wavelength of 2717 nm with 465 mW of the pump power. During the CW operation, as high as 66 mW of output power was achieved at 2808 nm by using 460 mW of pump power at 798 nm, with a power slope efficiency of 19.6%.

Broadly tunable continuous wave 2.3-µm Tm3+:tellurite bulk glass laser.

We report, for the first time to the best of our knowledge, a continuous wave trivalent thulium ion (Tm3+)-doped bulk glass near 2.3 µm. In the experiments, a bulk Tm3+-doped tellurite glass with the stoichiometric composition of 74TeO2-12ZnO-4La2O3-10Na2O (Tm3+:TZLN) was used. Lasing operation was achieved by using an x-fold cavity at the free-running wavelength of 2303 nm. The maximum slope efficiency of 6.2% was obtained with respect to the absorbed pump power with a 1% transmitting output coupler. In this case, as high as 100-mW output power was generated with 2.2 W of absorbed pump power. Continuous, broad tuning was achieved from 2233 nm to 2400 nm. The excitation spectrum of the laser was also investigated and 2.3-µm lasing was obtained by varying the pump wavelength over the 773-809-nm range. The absorption cross section was determined to be 4.4 × 10-21 cm2, based on open-aperture z-scan measurement. By using the laser efficiency data, the emission cross section of the Tm3+:TZLN glass was further determined to be 1.3 × 10-20 cm2 at 2.3 µm.

ALA/Ag2S/MnO2 Hybrid Nanoparticles for Near-Infrared Image-Guided Long-Wavelength Phototherapy of Breast Cancer.

The combination of photothermal therapy (PTT) and photodynamic therapy (PDT) based on temperature increase and the formation of reactive oxygen species (ROS), respectively, is an exciting avenue to provide local and improved therapy of tumors with minimal off-site toxicity. 5-Aminolevulinic acid (ALA) is one of the most popular PDT pro-drugs, and its efficiency improves significantly when delivered to tumors with nanoparticles (NPs). But the tumor site's hypoxic environment is a handicap for the oxygen-consuming PDT process. In this work, highly stable, small, theranostic NPs composed of Ag2S quantum dots and MnO2, electrostatically loaded with ALA, were developed for enhanced PDT/PTT combination of tumors. MnO2 catalyzes endogenous H2O2 to O2 conversion and glutathione depletion, enhancing ROS generation and ALA-PDT efficiency. Ag2S quantum dots (AS QDs) conjugated with bovine serum albumin (BSA) support MnO2 formation and stabilization around Ag2S. AS-BSA-MnO2 provided a strong intracellular near-infrared (NIR) signal and increased the solution temperature by 15 °C upon laser irradiation at 808 nm (215 mW, 10 mg/mL), proving the hybrid NP as an optically trackable, long-wavelength PTT agent. In the in vitro studies, no significant cytotoxicity was observed in the absence of laser irradiation in healthy (C2C12) or breast cancer cell lines (SKBR3 and MDA-MB-231). The most effective phototoxicity was observed when AS-BSA-MnO2-ALA-treated cells were co-irradiated for 5 min with 640 nm (300 mW) and 808 nm (700 mW) due to enhanced ALA-PDT combined with PTT. The viability of cancer cells decreased to approximately 5-10% at 50 µg/mL [Ag], corresponding to 1.6 mM [ALA], whereas at the same concentration, individual PTT and PDT treatments decreased the viability to 55-35%, respectively. The late apoptotic death of the treated cells was mostly correlated with high ROS levels and lactate dehydrogenase. Overall, these hybrid NPs overcome tumor hypoxia, deliver ALA to tumor cells, and provide both NIR tracking and enhanced PDT + PTT combination therapy upon short, low-dose co-irradiation at long wavelengths. These agents that may be utilized for treating other cancer types are also highly suitable for in vivo investigations.

Image-Guided Enhanced PDT/PTT Combination Therapy Using Brominated Hemicyanine-Loaded Folate Receptor-Targeting Ag2S Quantum Dots.

Tumor-targeting nanoparticles and phototherapies are the two major trends in tumor-specific, local cancer therapy with minimal side effects. Organic photosensitizers (PSs) usually offer effective photodynamic therapy (PDT) but require enhanced solubility and tumor-targeting, which may be provided by a nanoparticle. Near-infrared (NIR)-emitting Ag2S quantum dots may act as a delivery vehicle for the PS, NIR tracking agent, and as a phototherapy (PTT) agent. A combination of the two provides luminescent dual-phototherapy agents with tumor-specificity and image-guided and enhanced cytotoxicity as a result of synergistic PDT and PTT. In this study, brominated hemicyanine (Hemi-Br), a photosensitizer, was loaded onto folic acid (FA)-tagged, glutathione (GSH)-coated Ag2S quantum dots (AS-GSH QDs) to provide enhanced phototoxicity via a photodynamic and mild photothermal effect in folate receptor(+) cancer cell lines at clinically relevant 640 nm irradiation. Final particles (AS-GSH-FA/Hemi-Br) had a hydrodynamic size of 75.5 nm, dual emission at both 705 and 910 nm, and a 93% light-to-heat conversion efficiency under 640 nm laser irradiation. In vitro cytotoxicity studies were conducted with folate receptor (FR)-positive HeLa and -negative A549 cell lines to differentiate receptor-mediated uptake. Enhanced phototoxicity on HeLa cells was observed with AS-GSH-FA/Hemi-Br compared to free Hemi-Br and AS-GSH-FA QDs due to increased uptake of the photosensitizer via active targeting and combination therapy, which is especially visible at the safe dose of single agents. Upon irradiation with a 640 nm (300 mW, 0.78 W/cm2) laser for 5 min, the viability of the HeLa cells decreased from 64% to 42 and 25% when treated with free Hemi-Br, AS-GSH-FA, and AS-GSH-FA/Hemi-Br, respectively. Overall, AS-GSH-FA/Hemi-Br provides image-guided enhanced PDT/PTT, which may be adopted for different FR(+) tumors.

Development of a cysteine responsive chlorinated hemicyanine for image-guided dual phototherapy.

A cysteine (Cys) activatable chlorinated hemicyanine (Cl-Cys) was introduced as a tumour selective image-guided dual phototherapy agent. Cl-Cys exhibited a significant turn on response in its near-IR emission signal and activated its singlet oxygen generation as well as photothermal conversion potentials upon reacting with Cys. The laser irradiation of Cl-Cys induced significant cell death in cancer cells with high Cys level, while it stayed deactivated and non-emissive in a healthy cell line. A profound synergistic PDT/PTT effect was observed at high doses. Remarkably, Cl-Cys marks the first ever example of Cys-responsive small organic-based therapeutic agent and holds a great promise to develop new activity-based photosensitizers for dual phototherapy action.

Determination of the Wavelength-Dependent Photothermal Conversion Efficiency of Photosensitizers for Photothermal Therapy: Application to Ag2S-Glutathione Quantum Dots.

Nanoparticles have become popular photosensitizers for photothermal therapy (PTT), as they can be targeted to specific cancer tissues and deliver a chemotherapeutic drug, providing a multimodal therapeutic approach. Photothermal conversion efficiency of nanoparticles is critical in the assessment of their therapeutic use in PTT. We describe an accurate calorimetric method for the determination of the photothermal conversion efficiency of nanoparticles in solution. A tightly focused laser beam was used to irradiate a cuvette containing a solution of silver sulfide-glutathione quantum dots (Ag2S-GSH QDs), and the maximum steady-state temperature rise was measured with an infrared camera. The data were analyzed using two different photothermal conversion efficiencies, the intrinsic and external conversion efficiencies, to relate the induced heating power of the nanoparticles to the absorbed and incident optical powers, respectively. Measurements with a tunable Ti3+:sapphire laser showed that the intrinsic photothermal conversion efficiency of Ag2S-GSH QDs exceeded 91% over the 720-810 nm wavelength range. The method was also used to analyze poly(acrylic acid)-coated superparamagnetic iron oxide nanoparticles (PAA/SPIONs), and the intrinsic photothermal conversion efficiency was determined to be 83.4% at 810 nm. This approach is useful for the evaluation of various potential nanoparticles for photothermal therapy applications.

Cetuximab-Ag2S quantum dots for fluorescence imaging and highly effective combination of ALA-based photodynamic/chemo-therapy of colorectal cancer cells.

Colorectal cancer (CRC) has a poor prognosis and urgently needs better therapeutic approaches. 5-Aminolevulinic acid (ALA) induced protoporphyrin IX (PpIX) based photodynamic therapy (PDT) is already used in the clinic for several cancers but not yet well investigated for CRC. Currently, systemic administration of ALA offers a limited degree of tumour selectivity, except for intracranial tumours, limiting its wider use in the clinic. The combination of effective ALA-PDT and chemotherapy may provide a promising alternative approach for CRC treatment. Herein, theranostic Ag2S quantum dots (AS-2MPA) optically trackable in near-infrared (NIR), conjugated with endothelial growth factor receptor (EGFR) targeting Cetuximab (Cet) and loaded with ALA for PDT monotherapy or ALA/5-fluorouracil (5FU) for the combination therapy are proposed for enhanced treatment of EGFR(+) CRC. AS-2MPA-Cet exhibited excellent targeting of the high EGFR expressing cells and showed a strong intracellular signal for NIR optical detection in a comparative study performed on SW480, HCT116, and HT29 cells, which exhibit high, medium and low EGFR expression, respectively. Targeting provided enhanced uptake of the ALA loaded nanoparticles by strong EGFR expressing cells and formation of higher levels of PpIX. Cells also differ in their efficiency to convert ALA to PpIX, and SW480 was the best, followed by HT29, while HCT116 was determined as unsuitable for ALA-PDT. The therapeutic efficacy was evaluated in 2D cell cultures and 3D spheroids of SW480 and HT29 cells using AS-2MPA with either electrostatically loaded, hydrazone or amide linked ALA to achieve different levels of pH or enzyme sensitive release. Most effective phototoxicity was observed in SW480 cells using AS-2MPA-ALA-electrostatic-Cet due to enhanced uptake of the particles, fast ALA release and effective ALA-to-PpIX conversion. Targeted delivery reduced the effective ALA concentration significantly which was further reduced with codelivery of 5FU. Delivery of ALA via covalent linkages was also effective for PDT, but required a longer incubation time for the release of ALA in therapeutic doses. Phototoxicity was correlated with high levels of reactive oxygen species (ROS) and apoptotic/necrotic cell death. Hence, both AS-2MPA-ALA-Cet based PDT and AS-2MPA-ALA-Cet-5FU based chemo/PDT combination therapy coupled with strong NIR tracking of the nanoparticles demonstrate an exceptional therapeutic effect on CRC cells and excellent potential for synergistic multistage tumour targeting therapy.

Cadmium-Free and Efficient Type-II InP/ZnO/ZnS Quantum Dots and Their Application for LEDs.

It is a generally accepted perspective that type-II nanocrystal quantum dots (QDs) have low quantum yield due to the separation of the electron and hole wavefunctions. Recently, high quantum yield levels were reported for cadmium-based type-II QDs. Hence, the quest for finding non-toxic and efficient type-II QDs is continuing. Herein, we demonstrate environmentally benign type-II InP/ZnO/ZnS core/shell/shell QDs that reach a high quantum yield of ∼91%. For this, ZnO layer was grown on core InP QDs by thermal decomposition, which was followed by a ZnS layer via successive ionic layer adsorption. The small-angle X-ray scattering shows that spherical InP core and InP/ZnO core/shell QDs turn into elliptical particles with the growth of the ZnS shell. To conserve the quantum efficiency of QDs in device architectures, InP/ZnO/ZnS QDs were integrated in the liquid state on blue light-emitting diodes (LEDs) as down-converters that led to an external quantum efficiency of 9.4% and a power conversion efficiency of 6.8%, respectively, which is the most efficient QD-LED using type-II QDs. This study pointed out that cadmium-free type-II QDs can reach high efficiency levels, which can stimulate novel forms of devices and nanomaterials for bioimaging, display, and lighting.

Dual laser activatable brominated hemicyanine as a highly efficient and photostable multimodal phototherapy agent.

Dual phototherapy agents have attracted great interest in recent years as they offer enhanced cytotoxicity on cancer cells due to the synergistic effect of photodynamic and photothermal therapies (PDT/PTT). In this study, we demonstrate a brominated hemicyanine (HC-1), which is previously shown as mitochondria targeting PDT agent, can also serve as an effective photosensitizer for PTT for the first time under a single (640 nm or 808 nm) and dual laser (640 nm + 808 nm) irradiation. Generation of reactive oxygen species and photothermal conversion as a function of irradiation wavelength and power were studied. Both single wavelength irradiations caused significant phototoxicity in colon and cervical cancer cells after 5 min of irradiation. However, co-irradiation provided near-complete elimination of cancer cells due to synergistic action. This work introduces an easily accessible small molecule-based synergistic phototherapy agent, which holds a great promise towards the realization of local, rapid and highly efficient treatment modalities against cancer.

Multimodal image-guided folic acid targeted Ag-based quantum dots for the combination of selective methotrexate delivery and photothermal therapy.

Multifunctional quantum dots (QDs) with photothermal therapy (PTT) potential loaded with an anticancer drug and labelled with a targeting agent can be highly effective nano-agents for tumour specific, image-guided PTT/chemo combination therapy of cancer. Ag-chalcogenides are promising QDs with good biocompatibility. Ag2S QDs are popular theranostic agents for imaging in near-infrared with PTT potential. However, theranostic applications of AgInS2 QDs emitting in the visible region and its PTT potential need to be explored. Here, we first present a simple synthesis of small, glutathione (GSH) coated AgInS2 QDs with peak emission at 634 nm, 21% quantum yield, and excellent long-term stability without an inorganic shell. Ag2S-GSH QDs emitting in the near-infrared region (peak emission = 822 nm) were also produced. Both QDs were tagged with folic acid (FA) and conjugated with methotrexate (MTX). About 3-fold higher internalization of FA-tagged QDs by folate-receptor (FR) overexpressing HeLa cells than HT29 and A549 cells was observed. Delivery of MTX by QD-FA-MTX reduced the IC50 of the drug from 10 µg/mL to 2.5-5 µg/mL. MTX release was triggered at acidic pH, which was further enhanced with local temperature increase created by laser irradiation. Irradiation of AgInS2-GSH QDs at 640 nm (300 mW) for 10 min, caused about 10 °C temperature increase but did not cause any thermal ablation of cells. On the other hand, Ag2S-GSH-FA based PTT effectively and selectively killed HeLa cells with 10 min 808 nm laser irradiation via mostly necrosis with an IC50 of 5 µg Ag/mL. Under the same conditions, IC50 of MTX was reduced to 0.21 µg/mL if Ag2S-GSH-FA.

The Fast-Track Water Oxidation Channel on BiVO4 Opened by Nitrogen Treatment.

BiVO4 is one of the most promising photoanode materials for water-splitting systems. Nitrogen incorporation into a BiVO4 surface overcomes the known bottleneck in its charge-transfer kinetics into the electrolyte. We explored the role of nitrogen in the surface charge recombination and charge-transfer kinetics by employing transient photocurrent spectroscopy at the time scale of surface recombination and water oxidation kinetics, transient absorption spectroscopy, and X-ray photoelectron spectroscopy. We attributed the activity enhancement mechanism to the accelerated V5+/V4+ redox process, in which incorporated nitrogen suppresses a limiting surface recombination channel by increasing the oxygen vacancies.

Tunable continuous-wave laser operation of Tm3+:BaY2F8 near 2.3 µm.

We report, for the first time to our knowledge, tunable continuous-wave laser action in the Tm3+:BaY2F8 (BYF) crystal near 2.3 µm. In the experiments, a BYF crystal doped with 3 at. % thulium was end pumped with a narrow-linewidth, tunable Ti3+:sapphire laser with up to 920 mW of incident power. Lasing was achieved for the two pump polarizations of E//x and E//y. The best power performance was obtained in the case of E//x, double-end pumping, where 100 mW of output power was obtained at 2290 nm with 920 mW of pump power and 1% output coupler. The laser could be continuously tuned from 2233 to 2385 nm. Excitation spectra for E//x and E//y pumping were measured in the 760-810 nm range, and the optimum pumping wavelength was determined to be 779 nm for E//x. By using the lifetime and lasing threshold data, the stimulated emission cross section at 2290 nm was further determined to be (0.66±0.06)×10-24m2.

High-Performance, Large-Area, and Ecofriendly Luminescent Solar Concentrators Using Copper-Doped InP Quantum Dots.

Colloidal quantum dots (QDs) are promising building blocks for luminescent solar concentrators (LSCs). For their widespread use, they need to simultaneously satisfy non-toxic material content, low reabsorption, high photoluminescence quantum yield, and large-scale production. Here, copper doping of zinc carboxylate-passivated InP core and nano-engineering of ZnSe shell facilitated high in-device quantum efficiency of QDs over 80%, having well-matched spectral emission profile with the photo-response of silicon solar cells. The optimized QD-LSCs showed an optical quantum efficiency of 37% and an internal concentration factor of 4.7 for a 10 × 10-cm2 device area under solar illumination, which is comparable with the state-of-the-art LSCs based on cadmium-containing QDs and lead-containing perovskites. Synthesis of the copper-doped InP/ZnSe QDs in gram-scale and large-area deposition (3,000 cm2) onto commercial window glasses via doctor-blade technique showed their scalability for mass production. These results position InP-based QDs as a promising alternative for efficient solar energy harvesting.

Advanced Solid-State Lasers 2019: focus issue introduction.

This joint issue of Optics Express and Optical Materials Express features 17 state-of-the art articles written by authors who participated in the international conference Advanced Solid-State Lasers held in Vienna, Austria, from September 29 to October 3, 2019. This introduction provides a summary of these articles that cover numerous areas of solid-state lasers from materials research to sources and from design to experimental demonstration.

Laser-micromachined zebra-patterned graphene as a mode locker with adjustable loss.

In this Letter, we describe a novel, to the best of our knowledge, device based on micro-structured graphene, referred to as zebra-patterned graphene saturable absorber (ZeGSA), which can be used as a saturable absorber with adjustable loss to initiate femtosecond pulse generation. Femtosecond laser micro-machining was employed to ablate monolayer graphene on an infrasil substrate in the form of stripes with a different duty cycle, resulting in the formation of regions with variable insertion loss in the 0.21%-3.12% range. The mode-locking performance of the device was successfully tested using a ${{\rm Cr}^{4 {+} }}{:}\,{\rm forsterite}$Cr4+:forsterite laser, operating near 1250 nm. In comparison with mode locking using non-ablated graphene, the ZeGSA device with regions of decreasing graphene, enabled improved power performance where the mode-locked output power increased from 68 mW to 114 mW, and the corresponding pulse duration decreased from 62 to 48 fs at the same incident pump power of 6.3 W. These experiments indicate that ZeGSA shows great potential as a laser mode locker with adjustable loss and that it should find applications in the development of femtosecond lasers over a broad spectral range.

Upconversion pumping of a 2.3 µm Tm3+:KY3F10 laser with a 1064 nm ytterbium fiber laser.

We report efficient lasing of the isotropic ${{\rm Tm}^{3 + }}\!:\!{{\rm KY}_3}{{\rm F}_{10}}$Tm3+:KY3F10 crystal near 2.3 µm via upconversion pumping with a 1064 nm ytterbium fiber laser as the pump source. When pumped at 1064 nm, an x-cavity ${{\rm Tm}^{3 + }}\!:\!{{\rm KY}_3}{{\rm F}_{10}}$Tm3+:KY3F10 laser operated at the free-running wavelength of 2344 nm. Lasing was obtained with output couplers having transmissions in the range of 1-3%, and as high as 124 mW of continuous-wave (cw) output power was generated with 604 mW of absorbed pump power by using the 3% output coupler. Broadly tunable cw lasing could be obtained in the 2268-2373 nm wavelength range. An analysis of the experimental power efficiency data shows that nearly all of the absorbed pump photons were converted to 2.3 µm laser output after accounting for the quantum defect of the laser transition and resonator losses. We expect that higher lasing efficiency should be possible by using longer crystals to increase the pump absorption.

Graphene mode-locked operation of Tm3+:YLiF4 and Tm3+:KY3F10 lasers near 2.3 µm.

We report experimental demonstration of graphene mode-locked operation of ${{\rm Tm}^{3 + }}\!:\!{{\rm YLiF}_4}$Tm3+:YLiF4 (YLF) and ${{\rm Tm}^{3 + }}\!:\!{{\rm KY}_3}{{\rm F}_{10}}$Tm3+:KY3F10 (KYF) lasers near 2.3 µm. To scale up the intracavity pulse energy, the cavity was extended, and double-end pumping was employed with a continuous-wave, tunable ${{\rm Ti}^{3 + }}\!:\!{\rm sapphire}$Ti3+:sapphire laser delivering up to 1 W near 780 nm. The extended ${{\rm Tm}^{3 + }}\!:\!{\rm KYF}$Tm3+:KYF laser cavity was purged with dry nitrogen to eliminate pulsing instabilities due to atmospheric absorption lines, but this was not needed in the case of the ${{\rm Tm}^{3 + }}\!:\!{\rm YLF}$Tm3+:YLF laser. Once initiated by graphene, stable uninterrupted mode-locked operation could be maintained with both lasers. With the extended cavity ${{\rm Tm}^{3 + }}\!:\!{\rm YLF}$Tm3+:YLF laser, 921 fs pulses were generated at a repetition rate of 17.2 MHz at 2304 nm. 739 fs pulses were obtained at the repetition rate of 54 MHz from the ${{\rm Tm}^{3 + }}\!:\!{\rm KYF}$Tm3+:KYF laser at 2340 nm. The corresponding pulse energy and peak power were 2.4 nJ and 2.6 kW for the ${{\rm Tm}^{3 + }}\!:\!{\rm YLF}$Tm3+:YLF laser, and 1.2 nJ and 1.6 kW for the ${{\rm Tm}^{3 + }}\!:\!{\rm KYF}$Tm3+:KYF laser. We foresee that it should be possible to generate shorter pulses at higher pump levels.

Indocyanine green loaded APTMS coated SPIONs for dual phototherapy of cancer.

Superparamagnetic iron oxide nanoparticles (SPIONs) have been recently recognized as highly efficient photothermal therapy (PTT) agents. Here, we demonstrate, for the first time to our knowledge, dose and laser intensity dependent PTT potential of small, spherical, 3-aminopropyltrimethoxysilane coated cationic superparamagnetic iron oxide nanoparticles (APTMS@SPIONs) in aqueous solutions upon irradiation at 795 nm. Indocyanine green (ICG) which has been recently used for photodynamic therapy (PDT), was loaded to APTMS@SPIONs to improve the stability of ICG and to achieve an effective mild PTT and PDT (dual therapy) combination for synergistic therapeutic effect on cancer cells via a single laser treatment in the near infrared (NIR). Neither APTMS@SPIONs nor ICG-APTMS@SPIONs showed dark toxicity on MCF7 breast and HT29 colon cancer cell lines. A safe laser procedure was determined as 10 min irradiation at 795 nm with 1.8 W/cm2 of laser intensity, at which APTMS@SPION did not cause a significant cell death. However, free ICG reduced cell viability at and above 10 µg/ml under these conditions along with generation of reactive oxygen species (ROS), more effectively in MCF7. ICG-APTMS@SPION treated cells showed 2-fold increase in ROS generation and near complete cell death at and below 5 µg/ml ICG dose, even in less sensitive HT29 cells after a single laser treatment at NIR, which would be safe for the healthy tissue and provide a longer penetration depth. Besides, both components can be utilized for diagnosis and the overall composition may be used for optical-image guided phototherapy in the NIR region.

21 fs Cr:LiSAF laser mode locked with a single-walled carbon nanotube saturable absorber.

We report the shortest femtosecond pulses directly generated from a solid-state laser that is mode locked by using a single-walled carbon nanotube saturable absorber (SWCNT-SA). In the experiments, we used a 660 nm diode-pumped, low-threshold extended-cavity Cr:LiSAF laser operating around 850 nm with a repetition rate of 47.9 MHz. The SWCNT-SA mode-locked Cr:LiSAF laser produced 21 fs pulses with a time-bandwidth product of 0.56 by using only 210 mW of pump power. Pump-probe spectroscopy measurements showed that the SWCNT-SA exhibited saturable absorption with slow and fast decay times of 2.7 ps and 0.4 ps. The single-pass modulation depth and saturation fluence of the SWCNT-SA were further determined as 0.3% and 45 µJ/cm2 at the pump wavelength of 850 nm.