Dye Release from Laser Irradiated Liposomes

The main focus of this paper is to examine the consequence of laser pulses of narrow width impinging on phosphatidylcholine liposomes containing sulforhodamine dye molecules. The release of dye molecules following short-pulsed laser excitation and localized heating was measured and its dependence on laser excitation parameters studied. A characterization of the optimal conditions necessary for release of liposome contents can be applied to the targeted delivery of therapeutic drugs.     

Unusual temperature dependences of the photoconductivity and recombination luminescence of amorphous molecular semiconductors doped with ionic dyes

A nonexponential increase in photoconductivity with increasing temperature is discovered for poly(N-epoxypropylcarbazole) (PEPK) films doped with polymethine dyes. It is postulated that traps for nonequilibrium charge carriers form in these films during irradiation and are destroyed as the temperature is raised. Such traps are manifested by broadening of the high-temperature shoulder on the thermally stimulated luminescence (TSL) curves following the preliminary irradiation of PEPK films doped with polymethine and xanthene ionic dyes in the visible or UV range at 250–320 K and by the appearance of a new narrow TSL maximum near the preliminary irradiation temperature. These TSL features disappear after prolonged storage of the films in the dark or heating to higher temperatures. Fiz. Tverd. Tela (St. Petersburg) 41, 203–209 (February 1999)     

Near‐Infrared‐Light‐Induced Fast Drug Release Platform: Mesoporous Silica‐Coated Gold Nanoframes for Thermochemotherapy

Development of advanced theranostics for personalized medicine is of great interest. Herein, a multifunctional mesoporous silica‐based drug delivery carrier has been developed for efficient chemo/photothermal therapy. The unique Au nanoframes@mSiO₂ spheres are elaborately prepared by utilizing Ag@mSiO₂ yolk–shell spheres as the template through spatially confined galvanic replacement method. Compared with the Ag@mSiO₂ yolk–shell spheres, the resultant Au nanoframes@mSiO₂ spheres show a strong and broad near‐infrared (NIR) absorbance in the 550–1100 nm region, high surface areas, and good biocompatibility. When irradiated with a NIR laser with a power intensity of 1 W cm^?2 at 808 nm, they can become highly localized heat sources through the photothermal effect. Moreover, the photothermal effect of the Au nanoframes can significantly promote the fast release of doxorubicin. The in vitro studies show obvious synergistic effects combining photothermal therapy and chemotherapy in the Au nanoframes@mSiO₂ spheres against Hela cells. It is believed that the as‐obtained multifunctional vehicles provide a promising platform for the combination of hyperthermia and chemotherapy for cancer treatment application.     

Localized rapid heating process for precision chalcogenide glass molding

Precision glass molding is an important process for high volume optical fabrication. However, conventional glass molding is a bulk heating process that usually requires a long thermal cycle, where molding assembly and other mechanical parts are heated and cooled together. This often causes low efficiency and other heating and cooling related problems, such as large thermal expansion in both the molds and molded optics. To cope with this issue, we developed a localized rapid heating process to effectively heat only very small part of the glass. This localized rapid heating study utilized a fused silica wafer coated with a thin graphene layer to heat only the surface of the glass. The graphene coating functions as an electrical resistant heater when a power source was applied across the thin film coating, generating heat on and near the coating. The feasibility of this process was validated by both experiments and numerical simulation. To demonstrate the advantages of the localized rapid heating, both localized rapid heating process and bulk heating process were performed and carefully compared. The uniformity and quality of the molded sample by localized rapid heating process was also demonstrated. In summary, localized rapid heating process by using graphene coated fused silica wafer was characterized and can be readily implemented in replication of micro scale chalcogenide glasses.     

Temperature measurement in a single patterned gold nanorod cluster using laser-induced fluorescence

The ability of photon to thermal conversion on wet chemically synthesized gold nanorods (GNRs) is a unique advantage to explore specific local heating. In this study, we demonstrate the thermal response of a single patterned GNR cluster in aqueous solution under near infrared irradiation. To improve the properties of GNRs, such as solubility, we describe the initiated chemical vapor deposition method by the interaction of poly(2-hydroxyethyl methacrylate). A laser-induced fluorescence technique was utilized as a potential and non-intrusive way to measure the temperature field in and around the highly localized GNR cluster. The correlation between fluorescence intensities and temperature was investigated with two dyes by controlling the near infrared laser intensities to heat up the GNRs. Using this technique, we observed highly localized temperature rise in the GNR cluster and heat transfer to the surrounding medium during the laser irradiation.     

Human‐Serum‐Albumin‐Coated Prussian Blue Nanoparticles as pH‐/Thermotriggered Drug‐Delivery Vehicles for Cancer Thermochemotherapy

Constructing novel multimodal antitumor therapeutic nanoagents has attracted tremendous recent attention. In this work, a new drug‐delivery vehicle based on human‐serum‐albumin (HSA)‐coated Prussian blue nanoparticles (PB NPs) is synthesized. It is demonstrated that doxorubicin (DOX)/HSA is successfully loaded after in situ polymerization of dopamine onto PB NPs, and the PB@PDA/DOX/HSA NPs are highly compatible and stable in various physiological solutions. The NPs possess strong near‐infrared (NIR) absorbance, and excellent capability and stability of photothermal conversion for highly efficient photothermal therapy applications. Furthermore, a bimodal on‐demand drug release sensitively triggered by pH or NIR irradiation has been realized, resulting in a significant chemotherapeutic effect due to the preferential uptake and internalization of the NPs by cancer cells. Importantly, the thermochemotherapy efficacy of the NPs has been examined by a cell viability assay, revealing a remarkably superior synergistic anticancer effect over either monotherapy. Such multifunctional drug‐delivery systems composed of approved materials may have promising biomedical applications for antitumor therapy.     

Intracellular Breakable and Ultrasound‐Responsive Hybrid Microsized Containers for Selective Drug Release into Cancerous Cells

This work reports an efficient and straightforward strategy to fabricate hybrid microsized containers with reduction‐sensitive and ultrasound‐responsive properties. The ultrasound and reductive sensitivity are visualized using scanning electron microscopy, with the results showing structural decomposition upon ultrasound irradiation and in the presence of reducing agent. The ultrasound‐responsive functionalities of hybrid carriers can be used as external trigger for rapid controlled release, while prolonged drug release can be achieved in the presence of reducing agent. To evaluate the potential for targeted drug delivery, hybrid microsized containers are loaded with the anticancer drug doxorubicin (Dox). Such hybrid capsules can undergo structural intracellular degradation after cellular uptake by human cervical cancer cell line (HeLa), resulting in Dox release into cancer cells. In contrast, there is no Dox release when hybrid capsules are incubated with human mesenchymal stem cells (MSCs) as an example of normal human cells. The cell viability results indicate that Dox‐loaded capsules effectively killed HeLa cells, while they have lower cytotoxicity against MSCs as an example of healthy cells. Thus, the newly developed intracellular‐ and ultrasound‐responsive microcarriers obtained via sol‐gel method and layer‐by‐layer technique provide a high therapeutic efficacy for cancer, while minimizing adverse side effect.     

Dynamic and Reversible Accumulation of Plasmonic Core‐Satellite Nanostructures in a Light‐Induced Temperature Gradient for In Situ SERS Detection

A surface‐enhanced Raman spectroscopy (SERS) detection method that allows dynamic on‐demand generation of SERS substrates at locations of interest for in situ molecular sensing is demonstrated. Thermal convection and thermophoresis, which are both generated in a laser‐induced temperature gradient, are used to accumulate suspended plasmonic nanostructures to form 3D SERS substrate. Raman signals of melamine, which is used as a model analyte, increase to ≈117‐fold within 2 min of laser irradiation because of the accumulation. In addition, it is demonstrated that the accumulation of the nanostructures is reversible, and that reproducible SERS effects can be obtained during a repeated heating and cooling process. Because of the capability of on‐demand generation of a high density of SERS hot spots at different locations in solution, this particle manipulation and SERS detection method is applicable to monitor temporal and spatial variations of the concentrations of molecules. The complexity of the detection system remains the same when using this method since all the measurements are performed with a conventional Raman system and simple fluid channels. The required temperature gradient is generated by the laser used to excite Raman signals, and no nanofabricated substrates and complicated microfluidic or optical components are needed.     

A Multifunctional Nanocrystalline CaF2:Tm,Yb@mSiO2 System for Dual‐Triggered and Optically Monitored Doxorubicin Delivery

Daunting challenges in investigating the controlled release of drugs in complicated intracellular microenvironments demand the development of stimuli‐responsive drug delivery systems. Here, a nanoparticle system, CaF₂:Tm,Yb@mSiO₂, made of a mesoporous silica (mSiO₂) nanosphere with CaF₂:Tm,Yb upconversion nanoparticles (UCNPs) is developed, filling its mesopores and with its surface‐modified with polyacrylic acid for binding the anticancer drug molecules (doxorubicin, DOX). The unique design of CaF₂:Tm,Yb@mSiO₂ enables us to trigger the drug release by two mechanisms. One is the pH‐triggered mechanism, where drug molecules are preferentially released from the nanoparticles at acidic conditions unique for the intracellular environment of cancer cells compared to normal cells. Another is the 808 nm near infrared (NIR)‐triggered mechanism, where 808 nm NIR induces the heating of the nanoparticles to weaken the electrostatic interaction between drug molecules and nanoparticles. In addition, luminescence resonance energy transfer occurs from the UCNPs (the energy donor) to the DOX drug (the energy acceptor) in the presence of 980 nm NIR irradiation, allowing us to monitor the drug release by detecting the vanishing blue emission from the UCNPs. This study demonstrates a new multifunctional nanosystem for dual‐triggered and optically monitored drug delivery, which will facilitate the rational design of personalized cancer therapy.     

Core–Shell Bi2Se3@mSiO2‐PEG as a Multifunctional Drug‐Delivery Nanoplatform for Synergistic Thermo‐Chemotherapy with Infrared Thermal Imaging of Cancer Cells

Thermo‐chemotherapy combining photothermal therapy (PTT) with chemotherapy has become a potent approach for antitumor treatment. In this study, a multifunctional drug‐delivery nanoplatform based on polyethylene glycol (PEG)‐modified mesoporous silica‐coated bismuth selenide nanoparticles (referred to as Bi₂Se₃@mSiO₂‐PEG NPs) is developed for synergistic PTT and chemotherapy with infrared thermal (IRT) imaging of cancer cells. The product shows no/low cytotoxicity, strong near‐infrared (NIR) optical absorption, high photothermal conversion capacity, and stability. Utilizing the prominent photothermal effect, high‐contrast IRT imaging and efficient photothermal killing effect on cancer cells are achieved upon NIR laser irradiation. Moreover, the successful mesoporous silica coating of the Bi₂Se₃@mSiO₂‐PEG NPs cannot only largely improve the stability but also endow the NPs high drug loading capacity. As a proof‐of‐concept model, doxorubicin (DOX) is successfully loaded into the NPs with rather high loading capacity (≈50.0%) via the nanoprecipitation method. It is found that the DOX‐loaded NPs exhibit a bimodal on‐demand pH‐ and NIR‐responsive drug release property, and can realize effective intracellular drug delivery for chemotherapy. The synergistic thermo‐chemotherapy results in a significantly higher antitumor efficacy than either PTT or chemotherapy alone. The work reveals the great potential of such core–shell NPs as a multifunctional drug‐delivery nanosystem for thermo‐chemotherapy.     

Near‐room‐temperature photon‐noise‐limited quantum well infrared photodetector

With the modern development of infrared laser sources such as broadly tunable quantum cascade lasers and frequency combs, applications of infrared laser spectroscopy are expected to become widespread. Consequently, convenient infrared detectors are needed, having properties such as fast response, high efficiency, and room‐temperature operation. This work investigated conditions to achieve near‐room‐temperature photon‐noise‐limited performance of quantum well infrared photodetectors (QWIPs), in particular the laser power requirement. Both model simulation and experimental verification were carried out. At 300 K, it is shown that the ideal performance can be reached for typical QWIP designs up to a detection wavelength of 10 µm. At 250 K, which is easily reachable with a thermoelectric Peltier cooler, the ideal performance can be reached up to 12 µm. QWIPs are therefore suitable for detection and sensing applications with devices operating up to or near room temperature.     

Self‐Assembly of Drug–Drug Conjugates as Drug Self‐Delivery System for Tumor‐Specific pH‐Triggered Release

An acid‐labile doxorubicin dimer (D‐DOX) is designed as drug–drug conjugate for tumor intracellular pH‐triggered release, by conjugating doxorubicin (DOX) with adipic acid dihydrazide (ADH). The dimer‐based surfactants modified with polyethylene glycol (PEG), DOX‐ADH‐DOX‐PEG or are synthesized by mono‐PEGylation and bi‐PEGylation, respectively. Then the prodrug nanoparticles are fabricated with different drug contents via dialyzing the mixture solution of D‐DOX and the PEGylated surfactants in dimethyl sulfoxide (DMSO) with different mass ratios against water. It is found that the smaller prodrug nanoparticles (142–163 nm) could be obtained with the mono‐PEGylated surfactant, than those of 157–225 nm with the bi‐PEGylated surfactant. Furthermore, the mono‐PEGylated surfactant results in a higher drug content of 51% due to their lower PEG contents. All prodrug nanoparticles could release DOX completely within 36 h at pH 5.0, with the premature drug leakage of less than 10% at pH 7.4. The 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assays demonstrate the proposed drug self‐delivery system possessed an enhanced anticancer efficacy against HepG2 cells than the free DOX.     

Photothermal/Photodynamic Therapy with Immune‐Adjuvant Liposomal Complexes for Effective Gastric Cancer Therapy

A diagnosis and therapeutic strategy for gastric cancer is developed herein by combining thermosensitive liposomal (TSL)‐based photothermal/photodynamics therapy (PTT/PDT) with chemotherapy and adjuvant immunotherapy. IR820, a photothermal agent, paclitaxel (PTX), an antitumor drug, and imiquimod (R837), a Toll‐like‐receptor‐7 agonist, are coencapsulated into a TSL drug delivery system. These formed PTX‐R837‐IR820@TSL complexes exhibit excellent optical properties, good dispersibility, and stability. Under NIR light irradiation, the measurement of singlet oxygen production and thermal efficiency indicate promising potential of PTX‐R837‐IR820@TSL complexes for PTT and PDT. Confocal microscopy and small animal NIR imaging demonstrate tumor targeting ability of the liposomal complexes to gastric cancer cells. In vitro cell viability assays and in vivo animal experiments show prominent antitumor efficiency of PTX‐R837‐IR820@TSL complexes upon NIR light irradiation. This excellent therapeutic efficacy is attributed to the simultaneous chemotherapy and PTT/PDT. Furthermore, the liposomal complexes under NIR irradiation would ablate tumors to generate a pool of tumor‐associated antigens, which is able to promote strong antitumor immune responses in the presence of those R837‐containing liposomal complexes acted as adjuvant. These results indicate that the multifunctional liposomal complexes could realize a remarkable synergistic therapeutic outcome in gastric carcinoma.     

Radioluminescence of synthetic and natural quartz

The effect of X-ray irradiation and thermal treatments on the radio-luminescence emission spectrum of both a natural pegmatitic quartz and a synthetic one was investigated. All the emission spectra could be deconvolved into the same set of five Gaussian components. Among the identified RL bands, a blue emission at 2.53 eV (480 nm) is enhanced under X-ray irradiation. A strong correlation with the sensitization of the so called “110 °C” TSL peak (in our measurements seen at lower temperature due to the lower heating rate) was proved, suggesting that the recombination centers associated with the 2.53 eV band are produced under X-ray irradiation and are involved in both RL and TSL luminescence mechanisms. When each irradiation was followed by heating up to 500 °C a strong sensitization of the RL band emitting at 3.44 eV and of the 110 °C TSL peak were observed. A perfect correlation between the RL and TSL emissions suggests that the recombination centers involved in the RL and TSL emissions are the same.     

Photothermally Responsive Inks for Inkjet‐Printing Secure Information

2D patterns of photothermally responsive near‐infrared (NIR) absorbing gold nanostars (GNS), coated with multiple charged polymer layers, are inkjet‐printed on a glass surface. The shape of the localized surface plasmon resonance (LSPR) NIR absorption bands in the printed patterns loses its peaked form due to plasmon coupling, unless GNS are enveloped in multiple coating layers, keeping the inter‐GNS distance sufficiently large. In the latter case, the photothermal temperature increase (ΔT) induced by the NIR laser irradiation follows a ΔT versus irradiation wavelength (λ_irr) profile with the same sharply peaked shape of the LSPR bands of the liquid ink. With this result, a new paradigm for inkjet‐writing secure information is introduced, as an alternative to the current methods based on direct visual inspection of printed patterns. While the printed ink patterns of GNS with different coatings are visually indistinguishable despite their different NIR absorption spectrum, their photothermal response changes dramatically with λ_irr. This allows either to write and read simple information using a single λ_irr (YES answer for ΔT > threshold) or to use multiple λ_irr to write and read complex information like thermal bar codes and anti‐counterfeit signatures.     

Generation of continuous-wave 243-nm radiation by sum-frequency mixing

We have generated tunable cw radiation near 243 nm with a linewidth of less than 4 MHz by sum-frequency mixing the 351 nm radiation from an argon-ion laser with the 789 nm radiation from a ring dye laser in a crystal of ammonium dihydrogen phosphate held at moderate temperature. An external ring cavity, resonant with the dye laser, gives a power enhancement of about 12 in the sum-frequency generated radiation. Thermal lensing due to laser heating of the nonlinear crystal, distorded the 351 nm mode structure. This effect could limit the efficiency of the sum frequency mixing process.     

自然对流情形下激光辐照液体贮箱的机理

利用激光辐照靶目标时,被辐照部位可能是液体贮箱。通过实验测量与数值模拟的紧密结合,揭示了液体处于自然对流状态时激光辐照下贮箱侧壁温升及液体速度场的演化规律。结果表明:激光辐照初期,铝板中心温升率较高;随着壁面附近液体温度的升高,光斑附近速度边界层内的最大流速增大,传热强度亦增大,导致铝板温升率降低;当铝板吸收的激光能量能够基本被水的对流带走时,铝板中心的温升率趋于零。     

Ion‐Beam Sculpting of Nanowires

Nanomaterials often undergo unusual mechanical deformations compared to their bulk counterparts when irradiated with ion‐beams. This study visualizes and investigates some of the unusual interactions that can occur in nanomaterials during irradiation with medium‐energy ion‐beams using a helium‐ion microscope (HIM). Ion‐beam sculpting of semiconductor nanowires (NWs) with sub‐10 nm features is demonstrated. Moreover, irradiation‐induced growth of NWs at room‐temperature is discovered. The new concept and possible mechanism of irradiation‐induced VLS (vapor–liquid–solid) growth of NWs is introduced. These results are the basis for further fundamental and technological developments toward manipulation and visualization of ion–matter interactions at the nanoscale.     

Simple method to prepare size‐controllable gold nanoparticles in solutions and their applications on surface‐enhanced Raman scattering

We report here, for the first time, a simple method to prepare size‐controllable Au nanoparticles (NPs) in aqueous solutions from bulk Au substrates. First, chitosan (Ch)‐capped Au‐containing complexes were prepared by electrochemical oxidation–reduction cycles in 0.1 N NaCl and 1 g/l Ch solutions. Then the solutions were heated from room temperature to boiling at different heating rates to synthesize size‐controllable Au NPs. The particle sizes of the prepared Au(111) NPs could be controlled from 5 to 30 nm with an increase of the heating rate during preparation. Experimental results indicate that the prepared Au(111) NPs with diameters ranging from 10 to 30 nm can serve as surface‐enhanced Raman scattering active probes for molecules of rhodamine 6G. Copyright © 2010 John Wiley & Sons, Ltd.     

pH‐Responsive Hybrid Organic–Inorganic Ruthenium Nanoparticles for Controlled Release of Doxorubicin

The current study aims at preparing biocompatible hybrid organic–inorganic ruthenium core–shell nanostructures (RuNPs) coated with polyvinylpyrrolidone (PVP) and polyoxyethylene stearate (POES). Thereafter, the core/shell RuNPs are loaded with doxorubicin (to form RuPDox) with a loading efficiency > 60%. RuPDox possesses exceptional stability and pH‐responsive release kinetics with approx. 50% release of doxorubicin at up to 1 h exposure to an acidic endosomal environment. The cytotoxic effects of RuPDox are tested in vitro against breast cancer (MDA‐MB‐231), ovarian cancer (A2780), and neuroblastoma (UKF‐NB‐4) cells. Notably, although RuNPs have slight cytotoxicity only, RuPDox causes a synergistic enhancement of cytotoxicity when compared to free doxorubicin. Significant increase in free radicals formation, enhanced activity of executioner caspases 3/7, and higher expression of p53 and metallothionein is further identified due to the RuPDox treatment. Single‐cell gel electrophoresis reveals no additional contribution of RuNPs to genotoxicity of doxorubicin. Moreover, RuPDox promotes significantly increased stability of doxorubicin in human plasma and pronounced hemocompatibility assayed on human red blood cells. The results imply a high potential of biocompatible hybrid RuNPs with PVP‐POES shell as versatile nanoplatforms to enhance the efficiency of cancer treatment.