Charge-conversional and pH-sensitive PEGylated polymeric micelles as efficient nanocarriers for drug delivery.

A novel amphiphilic copolymer, poly (ethylene glycol)-graft-polyethyleneimine/amide (PEG-g-PEI/amide), is synthesized by grafting PEG and1,2-cis-Cyclohexanedicarboxylic anhydride onto the PEI. PEGylated polymeric micelles can be assembled from the amphiphilic copolymers with well-defined nano-sizes, and anti-cancer drugs are successfully loaded into micelle core formed by the amide. The amides with neighboring carboxylic acid groups exhibit pH-dependent hydrolysis and can reversibly shield the cationic charge of amine groups on the PEI, giving the micelles a charge-conversion property from negative to positive in acidic tumor tissue environment. Meanwhile, the cleavage of amide bonds at acidic pH also results in the disassembly of the micelle and pH-responsive drug release. These micelles are promising drug delivery systems due to their smart properties: PEGylation, suitable size, charge-conversion, and simultaneous pH-sensitive drug release.

Layer by layer self-assembly of poly[2-(methacryloyloxy) ethyl phosphorylcholine] multilayer via the ionic complexation with zirconium.

Zirconium-phosphonate (Zr-P) ionic complexation chemistry is explored as a new approach to fabricate poly[2-(methacryloyloxy) ethyl phosphorylcholine] (PMPC) multilayer film by layer-by-layer self-assembly method. Quartz crystal microbalance with dissipation (QCM-D) and optical ellipsometry measurements demonstrated that PMPC layer can be fully absorbed on each Zr(4+) layer. The thickness of the multilayer film with a good linear relationship was followed by the ellipsometry in situ adlayer characterization. The influence of pH of the PMPC and Zr(4+) solutions on the multilayer deposition were investigated by optical ellipsometry. QCM-D results indicated that the multilayer film is stable in a PBS flowing chamber at a high flow rate of 5.2×10(-3)m/s. The ellipsometry data demonstrated that 67.2% of the film still remained on the silicon wafer after being strong shaken in PBS at 80 rpm for 12h. The adsorption of bovine serum albumin (BSA) and fetal bovine serum (FBS) on the PMPC surface was monitored by the QCM-D and spectroscopic ellipsometry, and the results showed the multilayer film have excellent protein resistance.

Aggregation-induced emission of tetraphenylethene derivative as a fluorescence method for probing the assembling/disassembling of amphiphilic molecules.

The aggregation-induced emission (AIE) of a 1,2-diphenyl-1,2-di(p-tolyl)ethene (TPE) was explored as a novel fluorescence method for probing the assembling/disassembling of amphiphilic molecules. The fluorescence intensity was able to monitor the formation of micelles and determine the critical micelle concentration (CMC) of surfactants. The temperature-dependent micellization of the pharmaceutically important PEO-PPO-PEO copolymer, Pluronic F127, was further studied by using the TPE fluorescence spectrum intensity. Our results showed good agreement with those reported in the literature by using other methods. The special advantage of the AIE probe method was further explored to determine the assembling/disassembling process of the colored amphiphilic molecule, 1-[4-(3-phenylazophenoxy)butyl]triethylamine bromide (AzoC4), whose CMC value has not previously been described. Since the TPE fluorescence signal mainly comes from the aqueous phase, not from the inside of hydrophobic core, it provides a possible platform to study the CMC of those colored surfactants. Based on the novel fluorescence properties of TPE in the aggregated and dispersed states, one can conclude that the TPE method is a promising method for the determination of the CMC and critical micellization temperature (CMT), particularly having a special advantage to determine the assembling/disassembling process of colored amphiphilic molecules.

Biocompatible micelles based on comb-like PEG derivates: formation, characterization, and photo-responsiveness.

A novel comb-like derivative CPEG-g-DNQ was prepared by incorporating light responsive 2-diazo-1,2-naphthoquinone (DNQ) groups into the structure of comb-like poly(ethylene glycol) (CPEG). DLS and TEM results showed that CPEG-g-DNQ self-assembled into spherical micelles with an average size of about 135 nm in water. Upon exposure to light, the micelles could be disrupted because of the conversion of hydrophobic DNQ to hydrophilic 3-indenecarboylic acid. Additionally, hydrophobic coumarin 102 was successfully loaded into the micelles and photo-induced ON-OFF release was demonstrated by fluorescence spectroscopy. MTT assay revealed that the micelles are biocompatible. These photo-responsive micelles might have great potential for controlled release of hydrophobic drugs.

Enhanced broadband near-infrared luminescence from transparent Yb3+/Ni2+ codoped silicate glass ceramics.

The near-infrared emission intensity of Ni(2+) in Yb(3+)/Ni(2+) codoped transparent MgO-Al(2)O(3)-Ga(2)O(3)-SiO(2)-TiO(2) glass ceramics could be enhanced up to 4.4 times via energy transfer from Yb(3+) to Ni(2+) in nanocrystals. The best Yb(2)O(3) concentration was about 1.00 mol%. For the Yb(3+)/Ni(2+) codoped glass ceramic with 1.00 mol% Yb(2)O(3), a broadband near-infrared emission centered at 1265 nm with full width at half maximum of about 300 nm and lifetime of about 220 mus was observed. The energy transfer mechanism was also discussed.

Energy transfer between Cr3+ and Ni2+ in transparent silicate glass ceramics containing Cr3+/Ni2+ co-doped ZnAl2O4 nanocrystals.

The emission intensity of Ni(2+) at 1200 nm in transparent ZnO-Al(2)O(3)-SiO2 glass ceramics containing ZnAl(2)O(4) nanocrystals is improved approximately 8 times by Cr(3+) codoping with 532 nm excitation. This enhanced emission could be attributed to an efficient energy transfer from Cr(3+) to Ni(2+), which is confirmed by time-resolved emission spectra. The energy transfer efficiency is estimated to be 57% and the energy transfer mechanism is also discussed.

Three-photon-excited upconversion luminescence of Ce(3+): YAP crystal by femtosecond laser irradiation.

Infrared to ultraviolet and visible upconversion luminescence was demonstrated in trivalent cerium doped YAlO(3) crystal (Ce(3+): YAP) under focused infrared femtosecond laser irradiation. The fluorescence spectra show that the upconverted luminescence comes from the 5d-4f transitions of trivalent cerium ions. The dependence of luminescence intensity of trivalent cerium on infrared pumping power reveals that the conversion of infrared radiation is dominated by three-photon excitation process. It is suggested that the simultaneous absorption of three infrared photons pumps the Ce(3+) ion into upper 5d level, which quickly nonradiatively relax to lowest 5d level. Thereafter, the ions radiatively return to the ground states, leading to the characteristic emission of Ce(3+).

Superbroadband 1310 nm emission from bismuth and tantalum codoped germanium oxide glasses.

Near-infrared broadband emission from bismuth-tantalum-codoped germanium oxide glasses was observed at room temperature when the glasses were pumped by an 808 nm laser diode. The emission band covered the O, E, S, C, and L bands (1260-1625 nm), with a maximum peak at approximately 1310 nm, a FWHM broader than 400 nm, and a lifetime longer than 200 micros. The observed broadband luminescence was attributed to bismuth clusters in the glasses. Bismuth-tantalum-codoped germanium oxide glass might be promising as amplification media for broadly tunable lasers and wideband amplifiers in optical communications.

Rare-earth-doped silica microchip laser fabricated by sintering nanoporous glass.

We report a new method for fabricating rare-earth-doped silica glasses for laser materials obtained by sintering nanoporous silica glasses impregnated with rare-earth-doped ions. The fabricated materials have no residual pores and show good optical and mechanical properties. Good performance from a Nd3+ -doped silica microchip laser operating at 1.064 microm is successfully demonstrated, suggesting that the fabricated silica glasses have potential for use as active materials for high-power solid-state lasers.

Near infrared broadband emission of bismuth-doped aluminophosphate glass.

Near infrared broadband emission characteristics of bismuth-doped aluminophosphate glass have been investigated. Broad infrared emissions peaking at 1210nm, 1173nm and 1300nm were observed when the glass was pumped by 405nm laser diode (LD), 514nm Ar+ laser and 808nm LD, respectively. The full widths at half maximum (FWHMs) are 235nm, 207nm and 300nm for the emissions at 1210nm, 1173nm and 1300nm, respectively. Based on the energy matching conditions, it is suggested that the infrared emission may be ascribed to 3P1? 3P0 transition of Bi+. The broadband infrared luminescent characteristics of the glasses indicate that they are promising for broadband optical fiber amplifiers and tunable lasers.

Infrared broadband emission of bismuth-doped barium-aluminum-borate glasses.

We report near infrared broadband emission of bismuth-doped barium-aluminum-borate glasses. The broadband emission covers 1.3microm window in optical telecommunication systems. And it possesses wide full width at half maximum (FWHM) of ~200nm and long lifetime as long as 350micros. The luminescent properties are quite sensitive to glass compositions and excitation wavelengths. Based on energy matching conditions, we suggest that the infrared emission may be ascribed to 3P1? 3P0 transition of Bi+. The broad infrared emission characteristics of this material indicate that it might be a promising candidate for broadband optical fiber amplifiers and tunable lasers.

Direct writing computer-generated holograms on metal film by an infrared femtosecond laser.

Writing computer-generated holograms have been achieved by using a near infrared femtosecond laser selective ablation of metal film deposited on glass substrate. The diffraction features with data reconstruction of the fabricated computer-generated holograms were evaluated. Both transmission and reflection holograms can be fabricated in a single process. The process requires no mask, no pre- or post-treatment of the substrate.

Optical transfer of periodic microstructures by interfering femtosecond laser beams.

We report on an optical interference method for transferring periodic microstructures of metal film from a supporting substrate to a receiving substrate by means of five-beam interference of femtosecond laser pulses. Scanning electron microscopy and optical microscopy revealed microstructures with micrometer-order were transferred to the receiving substrate. In the meanwhile, a negative copy of the transferred structures was induced in the metal film on the supporting substrate. The diffraction characteristics of the transferred structures were also evaluated. The present technique allows one-step realization of functional optoelectronic devices.

Broadband infrared luminescence from Li2O-Al2O3-ZnO-SiO2 glasses doped with Bi2O3.

The broadband emission in the 1.2~1.6mum region from Li2O-Al2O3-ZnO-SiO2 ( LAZS ) glass codoped with 0.01mol.%Cr2O3 and 1.0mol.%Bi2O3 when pumped by the 808nm laser at room temperature is not initiated from Cr4+ ions, but from bismuth, which is remarkably different from the results reported by Batchelor et al. The broad ~1300nm emission from Bi2O3-containing LAZS glasses possesses a FWHM ( Full Width at Half Maximum ) more than 250nm and a fluorescent lifetime longer than 500mus when excited by the 808nm laser. These glasses might have the potential applications in the broadly tunable lasers and the broadband fiber amplifiers.

Bismuth- and aluminum-codoped germanium oxide glasses for super-broadband optical amplification.

Broadband infrared luminescence from bismuth-doped germanium oxide glasses prepared by a conventional melting-quenching technique was discovered. The absorption spectrum of the glasses covered a wide range from the visible to the near-infrared wavelength regions and consisted of five broad peaks below 370, 500, 700, 800, and 1000 nm. The fluorescence spectrum exhibited broadband characteristics (FWHM) greater than 300 nm with a maximum at 1300 nm pumped by an 808-nm laser. The fluorescence lifetime at room temperature decreased with increasing Bi2O3 concentration in the glass. Codoping of aluminum and bismuth was indispensable for the broadband infrared luminescence in GeO2:Bi, Al glass.

One-off writing of multimicrogratings on glass by two interfered femtosecond laser pulses.

Multimicrogratings are one-off written on silicate glass by two interfered femtosecond pulsed laser beams with the aid of a mask. The period and depth of the multimicrogratings are revealed by optical microscopy and atomic force microscopy. The depth is dependent on both the colliding angle between the two interfered laser beams and the laser pulse energy, but the period relies on the colliding angle only. We also observe a series of grooves formed at the middle of each bulge of the multimicrogratings and attribute it to the higher-order modulation arising from second-harmonic generation of the femtosecond laser pulse during the one-off writing processes.

Optical properties of structurally modified glasses doped with gold ions.

We report on the optical properties of a structurally modified silicate glass doped with Au ions. The area in the vicinity of the focal point of an 800-nm femtosecond laser in a glass sample became gray as a result of the formation of color centers after laser irradiation and turned red because of precipitation of Au nanoparticles after further annealing at 550 degrees C for 30 min. When the glass was excited by UV light at 365 nm, yellowish-white and orange-yellow emissions were observed in the laser-irradiated and the Au-nanoparticle-precipitated area, respectively. An optical Kerr shutter experiment showed that the Au nanoparticle-precipitated glass had an ultrafast nonlinear optical response, and the third-order nonlinear susceptibility was estimated to be approximately 10(-11) esu.

Fabrication of internal diffraction gratings in calcium fluoride crystals by a focused femtosecond laser.

We report the fabrication of internal diffraction gratings in calcium fluoride crystals by a focused near-IR 800 nm femtosecond laser. The diffraction efficiency and refractive index change were evaluated after femtosecond laser irradiation and subsequent annealing. The maximum refractive index change was estimated to be 3.57x10(-4). Optical absorption spectra, measured for the crystals before and after the laser irradiation and subsequent annealing, indicate that the absorbance increase after femtosecond laser irradiation and decrease with increasing annealing temperature. The mechanisms of refractive index change are proposed. The results may be useful for fabrication of three-dimensional integrated optics devices in the crystals.

Controllable precipitation and dissolution of silver nanoparticles in ultrafast laser pulses irradiated Ag+-doped phosphate glass.

We report a controllable process of recipitation and dissolution of silver nanoparticles in ultrashort laser pulses irradiated Ag+-doped phosphate glass. Absorption spectra, transmission electron microscopy and refractive index measurement revealed that metallic silver nanoparticles were precipitated in the glass sample after irradiation by an 800-nm femtosecond laser and subsequent annealing at 300 degrees C, and dissolved after further annealing at 450 degrees C. We discuss a mechanism that combines the formation and decoloration of color centers, precipitation and dissolution of silver nanoparticles.