Low-Dose Near-Infrared Light-Activated Mitochondria-Targeting Photosensitizers for PDT Cancer Therapy

Phthalocyanines (Pcs) are promising candidates for photodynamic therapy (PDT) due to their absorption in the phototherapeutic window. However, the highly aromatic Pc core leads to undesired aggregation and decreased reactive oxygen species (ROS) production. Therefore, short PEG chain functionalized A₃B type asymmetric Pc photosensitizers (PSs) were designed in order to decrease aggregation and increase the aqueous solubility. Here we report the synthesis, characterization, optical properties, cellular localization, and cytotoxicity of three novel Pc-based agents (LC31, MLC31, and DMLC31Pt). The stepwise functionalization of the peripheral moieties has a strong effect on the distribution coefficient (logP), cellular uptake, and localization, as well as photocytotoxicity. Additional experiments have revealed that the presence of the malonic ester moiety in the reported agent series is indispensable in order to induce photocytotoxicity. The best-performing agent, MLC31, showed mitochondrial targeting and an impressive phototoxic index (p.i.) of 748 in the cisplatin-resistant A2780/CP70 cell line, after a low-dose irradiation of 6.95 J/cm². This is the result of a high photocytotoxicity (IC₅₀ = 157 nM) upon irradiation with near-infrared (NIR) light, and virtually no toxicity in the dark (IC₅₀ = 117 μM). Photocytotoxicity was subsequently determined under hypoxic conditions. Additionally, a preliminarily pathway investigation of the mitochondrial membrane potential (MMP) disruption and induction of apoptosis by MLC31 was carried out. Our results underline how agent design involving both hydrophilic and lipophilic peripheral groups may serve as an effective way to improve the PDT efficiency of highly aromatic PSs for NIR light-mediated cancer therapy.     

NIR light-triggered gelling in situ of porous silicon nanoparticles/PEGDA hybrid hydrogels for localized combinatorial therapy of cancer cells

Porous silicon-based nanocomposite hydrogels were readily constructed with the gelation of poly(ethylene glycol) double acrylates (PEGDA) macromers, due to the initiation of singlet oxygen photosensitized with porous silicon nanoparticles (PSiNPs) under near-infrared (NIR) light irradiation. Multifunctional PSiNPs/PEGDA nanocomposite hydrogels showed strong fluorescence, excellent biodegradability, significant photothermal effect, and sustained drug release with high efficiency (>80%). Finally, in situ growth of PSiNPs/PEGDA hybrid hydrogels on cancer cells was also achieved by NIR light, and then their biodegradation, drug release and synergistic chemo-phototherapeutic efficacy were further demonstrated, which could provide a significant localized inhibition for the viability, adherence, and migration of cancer cells in vitro. Thus, we suggested that these resultant hybrid hydrogels would have important potential on local cancer therapy in future clinical practice. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47443.     

Hollow PUA/PSS/Au microcapsules with interdependent near‐infrared/pH/temperature multiresponsiveness

In this work, smart hollow microcapsules made of thermal‐/pH‐dual sensitive aliphatic poly(urethane‐amine) (PUA), sodium poly(styrenesulfonate) (PSS), and Au nanoparticles (AuNPs) for interdependent multi‐responsive drug delivery have been constructed by layer‐by‐layer (LbL) technique. The electrostatic interactions among PUA, PSS, and AuNPs contribute to the successful self‐assembly of hollow multilayer microcapsules. Thanks to the shrinkage of PUA above its lower critical solution temperature (LCST) and the interaction variation between PUA and PSS at different pH conditions, hollow microcapsules exhibit distinct pH‐ and thermal‐sensitive properties. Moreover, AuNPs aggregates can effectively convert light to heat upon irradiation with near‐infrared (NIR) laser and endow the hollow microcapsules with distinct NIR‐responsiveness. More importantly, the NIR‐responsive study also demonstrates that the microcapsule morphology and the corresponding NIR‐responsive drug release are strongly dependent on the pH value and temperature of the media. The results indicate that the prepared hollow PUA/PSS/Au microcapsules have the great potential to be used as a novel smart drug carrier for the remotely controllable drug delivery. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43008.     

Novel photo-crosslinkable polymeric electrolyte system based on poly(ethylene glycol) and trimethylolpropane triacrylate for dye-sensitized solar cell with long-term stability

Polyethylene glycol (PEG) and trimethylolpropane triacrylate (TMPTA) were used as photo-crosslinkable polymer electrolytes for dye-sensitized solar cells (DSSCs). PEG and trifunctional TMPTA formed a crosslinked structure upon light illumination, as confirmed by the solubility test and FTIR spectroscopy. In order to make close contact with the TiO₂ porous film, the polymeric electrolyte was prepared by photo-polymerization after injecting the monomer electrolyte solution into the porous film. The cross-sectional FE-SEM images showed the penetration of the electrolyte into the porous TiO₂ layer. Under AM 1.5 (100 mW/cm²) light irradiation for up to 30 min, a maximum 21% increase in the photo-conversion efficiency (η%) was observed. The electrolyte containing PEG and 20 wt% TMPTA showed a maximum increase in the photo-conversion efficiency from 2.75% to 3.35% with 30 min of light illumination. Also, the DSSCs with the novel crosslinkable PEG/TMPTA based polymer electrolyte showed improved long-term stability in comparison to those with electrolytes containing only PEG.     

Preparation and drug‐release behavior of minocycline‐loaded poly[hydroxyethyl methacrylate‐co‐poly(ethylene glycol)–methacrylate] films

In this work, biocompatible hydrogel matrices for wound‐dressing materials and controlled drug‐release systems were prepared from poly[hydroxyethyl methacrylate‐co‐poly(ethylene glycol)–methacrylate] [p(HEMA‐co‐PEG–MA] films via UV‐initiated photopolymerization. The characterization of the hydrogels was conducted with swelling experiments, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis (differential scanning calorimetry), and contact‐angle studies. The water absorbency of the hydrogel films significantly changed with the change of the medium pH from 4.0 to 7.4. The thermal stability of the copolymer was lowered by an increase in the ratio of poly(ethylene glycol) (PEG) to methacrylate (MA) in the film structure. Contact‐angle measurements on the surface of the p(HEMA‐co‐PEG–MA) films demonstrated that the copolymer gave rise to a significant hydrophilic surface in comparison with the homopolymer of 2‐hydroxyethyl methacrylate (HEMA). The blood protein adsorption was significantly reduced on the surface of the copolymer hydrogels in comparison with the control homopolymer of HEMA. Model antibiotic (i.e., minocycline) release experiments were performed in physiological buffer saline solutions with a continuous flow release system. The amount of minocycline release was shown to be dependent on the HEMA/PEG–MA ratio. The hydrogels have good antifouling properties and therefore are suitable candidates for wound dressing and other tissue engineering applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of venlafaxine hydrochloride‐loaded chitosan nanoparticles and in vitro release of drug

The venlafaxine hydrochloride (VHL)‐loaded chitosan nanoparticles were prepared by ionic gelation of chitosan (CS) using tripolyphosphate (TPP). The nanoparticles were characterized using FTIR, differential scanning calorimetry, X‐ray diffraction, dynamic light scattering, transmission electron microscopy, and X‐ray photoelectron spectroscopy. The effect of concentration of CS, polyethylene glycol (PEG), VHL and CS/TPP mass ratio on the particle size and zeta potential of nanoparticles was examined. The particle size of CS/TPP nanoparticles and VHL‐loaded CS/TPP nanoparticles was within the range of 200–400 nm with positive surface charge. In the case of VHL‐loaded nanoparticles and PEG‐coated CS/TPP nanoparticles, the particle size increases and surface charge decreases with increasing concentration of VHL and PEG. Both placebo and VHL‐loaded CS/TPP nanoparticles were observed to be spherical in nature. PEG coating on the surface of CS/TPP nanoparticles was confirmed by XPS analysis. Maximum drug entrapment efficiency (70%) was observed at 0.6 mg/mL drug concentration. In vitro drug release study at 37°C ± 0.5°C and pH 7.4 exhibited initial burst release followed by a steady release. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Spray‐dried microparticles composed of cinnamoyl poly(N‐isopropylacrylamide‐co‐hydroxyethylacrylate) and gold nanoparticle

Temperature‐ and NIR irradiation‐responsive microparticles composed of cinnamoyl poly(N‐isopropylacrylamide‐co‐hydroxyethylacrylate) [CinP(NIPAM‐HEA)] and gold nanoparticle (GNP) were prepared by a spray‐drying method. According to the cloud points determined by an optical method, the HEA content in P(NIPAM‐HEA) had no marked effect on the lower critical solution temperature (LCST). However, the cinnamoyl group content in CinP(NIPAM‐HEA) had a significant effect on the LCST. The LCSTs determined by a calorimetric method was in agreement with those determined by an optical method. The hydrodynamic mean diameter of gold nanoparticle (GNP) prepared by reducing gold ions was about 30 nm and it seemed to be a nanosphere on TEM photo. Spray‐dried CinP(NIPAM‐HEA) microparticles containing GNP was 1.5 μm to 12 μm in diameter on SEM photo. Gold was detected on the energy‐dispersive X‐ray spectrum of the microparticles. The amount of FITC‐dextran released for 12 h from the microparticles was much higher at temperatures above the LCST (at 37 °C and 45 °C) than below the LCST (at 20 °C and 25 °C). The cumulative release amount in 12 h was only about 3% without NIR irradiation, whereas the value was about 26.5% when NIR was irradiated to the microparticle suspension. The photothermal energy generated by GNP was believed to render the thermosensitive copolymers de‐swollen and hydrophobic, allowing for the active release of dye from the microparticles. The NIR irradiation‐responsive GNP‐loaded microparticles could be applied to the development of NIR‐responsive drug carriers which release their contents in response to an external stimulus (i.e., NIR irradiation). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44141.     

Effect of modified graphene quantum dots on photocatalytic degradation property

The effective use of solar energy in sewage disposal has been extensively investigated. This work focuses on the photocatalytic property of graphene quantum dots (GQDs) and polymer-modified GQDs under visible light. A hydrothermal synthesis route to GQDs was developed by using citric acid as a carbon precursor. The GQDs were modified with polyethylenimine (PEI) and polyethylene glycol (PEG). The obtained GQDs, GQDs-PEIs, and GQDs-PEGs were characterized and their structural information was determined through Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), photoluminescence spectroscopy, and UV–Vis absorption spectroscopy. Results revealed that the GQDs were uniform in size (2–5 nm) and rich in oxygen-containing groups. The GQDs exhibited a strong blue and excitation-independent photoluminescent behavior under excitation wavelengths of 320–420 nm. The photocatalytic performance of these samples was demonstrated on the basis of methylene blue (MB) degradation. The photocatalytic rates of GQDs, GQDs-PEIs, and GQDs-PEGs decreased successively. The polymer-modified GQDs could qualitatively control the degradation rate of MB. Free radical species were generated to oxidize MB under light irradiation. Thus, photocatalytic organic matter degradation, sustained drug release, and tracking can be combined to implement proper sewage disposal.Prime noveltyThe main object of this work is to find out a novel property of graphene quantum dots (GQDs) as efficient nanomaterials for degradation of organic pollutant dyes under visible light irradiation. And, the GQDs exhibited a strong blue and excitation-independent photoluminescent behavior under excitation wavelengths of 320–420 nm. Moreover, the degradation rate could be qualitatively controlled by using different polymer-modified GQDs. Thus, photocatalytic organic matter degradation, sustained drug release, and tracking can be combined to implement proper sewage disposal. Also, the degradation mechanism is discussed.     

Er3+ ‐Doped Y2O3 Nanophosphors for Near‐Infrared Fluorescence Bioimaging Applications

Rare‐earth‐doped ceramic nanophosphor (RED‐CNP) materials are promising near‐infrared (NIR) fluorescence bioimaging (FBI) agents that can overcome problems of currently used organic dyes including photobleaching, phototoxicity, and light scattering. Here, we report a NIR–NIR bioimaging system by using NIR emission at 1550 nm under 980 nm excitation which can allow a deeper penetration depth into biological tissues than ultraviolet or visible light excitation. In this study, erbium‐doped yttrium oxide nanoparticles (Er³⁺:Y₂O₃) with an average particle size of 100 and 500 nm were synthesized by surfactant‐assisted homogeneous precipitation method. NIR emission properties of Er³⁺:Y₂O₃ were investigated under 980 nm excitation. The surface of Er³⁺:Y₂O₃ was electrostatically PEGylated using poly (ethylene glycol)‐b‐poly(acrylic acid) (PEG‐b‐PAAc) block copolymer to improve the chemical durability and dispersion stability of Er³⁺:Y₂O₃ under physiological conditions. In vitro cytotoxic effects of bare and PEG‐b‐PAAc‐modified Er³⁺:Y₂O₃ were investigated by incubation with mouse macrophage cells (J774). Microscopic and macroscopic FBI were demonstrated in vivo by injection of bare or PEG‐b‐PAAc‐modified Er³⁺:Y₂O₃ into C57BL/6 mice. The NIR fluorescence images showed that PEG‐b‐PAAc modification significantly reduced the agglomeration of Er³⁺:Y₂O₃ in mice and enhanced the distribution of Er³⁺:Y₂O₃.     

Tuning the Hydrophobicity of a Mitochondria‐Targeted NO Photodonor

A few compounds in which the nitric oxide (NO) photodonor N‐[4‐nitro‐3‐(trifluoromethyl)phenyl]propane‐1,3‐diamine is joined to the mitochondria‐targeting alkyltriphenylphosphonium moiety via flexible spacers of variable length were synthesized. The lipophilicity of the products was evaluated by measuring their partition coefficients in n‐octanol/water. The obtained values, markedly lower than those calculated, are consistent with the likely collapsed conformation assumed by the compounds in solution, as suggested by molecular dynamics simulations. The capacity of the compounds to release NO under visible light irradiation was evaluated by measuring nitrite production by means of the Griess reaction. The accumulation of compounds in the mitochondria of human lung adenocarcinoma A549 cells was assessed by UPLC–MS. Interestingly, compound 13 [(9‐((3‐((4‐nitro‐3‐(trifluoromethyl)phenyl)amino)propyl)amino)‐9‐oxononyl) triphenylphosphonium bromide] displayed both the highest accumulation value and high toxicity toward A549 cells upon irradiation‐mediated NO release in mitochondria.     

Modified microwave method for the synthesis of visible light-responsive TiO2/MWCNTs nanocatalysts

Recently, TiO₂/multi-walled carbon nanotube (MWCNT) hybrid nanocatalysts have been a subject of high interest due to their excellent structures, large surface areas and peculiar optical properties, which enhance their photocatalytic performance. In this work, a modified microwave technique was used to rapidly synthesise a TiO₂/MWCNT nanocatalyst with a large surface area. X-ray powder diffraction, field-emission scanning electron microscopy, transmission electron microscopy and Brunauer-Emmett-Teller measurements were used to characterise the structure, morphology and the surface area of the sample. The photocatalytic activity of the hybrid nanocatalysts was evaluated through a comparison of the degradation of methylene blue dye under irradiation with ultraviolet and visible light. The results showed that the TiO₂/MWCNT hybrid nanocatalysts degraded 34.9% of the methylene blue (MB) under irradiation with ultraviolet light, whereas 96.3% of the MB was degraded under irradiation with visible light.     

Light-Triggered Covalent Coupling of Gold Nanoparticles for Photothermal Cancer Therapy

Manipulating the cross-coupling of gold nanoparticles (AuNPs) to maximize the photothermal effect is a promising strategy for cancer therapy. Here, by taking advantage of the well-known tetrazole/alkene photoclick chemistry, we have demonstrated for the first time that small AuNPs (23 nm) decorated with both 2,5-diphenyltetrazole and methacrylic acid on their surfaces can form covalently crosslinked aggregates upon laser irradiation (λ=405 nm). In vitro studies indicated that the light-triggered assembling shifted the surface plasmon resonance of AuNPs significantly to near-infrared (NIR) regions, which as a consequence effectively enhanced the efficacy of photothermal therapy for 4T1 breast cancer cells. We thus believe that this new light-triggered cross-coupling approach might offer a valuable tool for cancer treatment.     

Near‐Infrared Light‐Triggered Dual Drug Release Using Gold Nanorod‐Embedded Thermosensitive Nanogel‐Crosslinked Hydrogels

Gold nanorod (AuNR)‐embedded poly(N‐isopropylacrylamide) (PNIPAM) hydrogels offer the possibility of achieving near‐infrared (NIR) light‐triggered drug release. In addition, using nanoparticles as a crosslinker can enhance the mechanical properties of PNIPAM hydrogels, and nanoparticle‐crosslinked hydrogels provide an important approach for dual drug release. Here, NIR light‐triggered dual drug release using AuNR‐embedded thermosensitive nanogel‐crosslinked hydrogels is reported for the first time. Two kinds of drugs are encapsulated, one in the nanogel and the other in the hydrogel. The volume phase transition of the PNIPAM hydrogels is induced by NIR light by utilizing the photothermal effect of AuNRs. By changing the number of embedded AuNRs and the intensity of NIR light, the release rate and drug quantity can be adjusted for on‐demand release. Because of its NIR light‐triggering and nanoparticle‐crosslinking capabilities, AuNR‐embedded thermosensitive nanogel‐crosslinked hydrogels may expand the application scope of hydrogels and provide enhanced properties in their applications.     

Electrocapillary wave studies of different poly(dimethyl siloxane)s

The monolayer behavior of different end-functionalized poly(dimethyl siloxane)s (PDMSs) and a block copolymer, poly(dimethyl siloxane-co-ethylene oxide) (PDMS-co-EO) spread on an oligomeric poly(ethylene glycol) (PEG) substrates, were studied by means of electrocapillary wave diffraction (ECWD). Over a relatively small temperature range (40–70°C), the damping constant was more dependent on temperature than on the wave vector. Different surface layer properties were observed for two PDMS: one terminated with a methyl group (PDMS-CH₃) and the one terminated with a hydroxy group (PDMS-OH). PDMS-OH showed a larger reduction in surface tension compared to PDMS-CH₃ because of a higher interfacial affinity with PEG, which indicated that its monolayer surface activity was weaker. A lower surface elasticity of PDMS-OH than that of PDMS-CH₃ supported that conclusion. The block copolymer showed no surface activity, since the short siloxane moiety did not repel the strong interaction between PEG and the ethylene oxide.     

Photo/pH dual‐responsive biocompatible poly(methacrylic acid)‐based particles for triggered drug delivery

A novel dual‐responsive (light and pH) particle based on poly(methacrylic acid), poly(methacrylic acid)–poly[1‐(2‐nitrophenyl)ethane‐1,2‐diyl bis(2‐methylacrylate)]was prepared with the facile method of two‐step homogeneous radical polymerization with methacrylic acid as the monomer and 1‐(2‐nitrophenyl)ethane‐1,2‐diyl bis(2‐methylacrylate) as a photodegradable crosslinker. Photolytic assessments were conducted upon irradiation with a UV lamp; this led to particle disintegration caused by cleavage of the photolabile crosslinking points. The light‐dependent degradation was investigated through particle size changes, absorption spectra variations, surface morphology changes, Fourier transform infrared spectroscopy, and the release of Nile red from the particles after irradiation. The pH dependence of the particle systems induced by the protonation and deprotonation of poly(methacrylic acid) was also confirmed by fluorescence spectroscopy. The triggered release of fluorescein diacetate was investigated to demonstrate that the release behavior in cells was light dependent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44003.     

Photo‐induced protonation and conductivity of polyaniline/poly(ethylene glycol) and polyaniline/[poly(ethylene glycol)‐grafted polyaniline] composites

Composites of polyaniline in its emeraldine base form (PANI‐EB) and photo‐acid generators (PAG) show an increase in conductivity upon photo‐irradiation due to the protonation of PANI‐EB. Such materials may be utilized to fabricate conducting patterns by photo‐irradiation. However, the conductivity obtained by direct irradiation of PANI‐EB/PAG composites was normally quite low (<10^?3 S/cm) due to aggregation of highly loaded PAG. In this work, poly(ethylene glycol) (PEG), which is a proton transfer polymer, was added to PANI‐EB/PAG. Results showed that addition of low M_w (550) PEG significantly enhance the photo‐induced conductivity. Conductivities as high as 10^?1–10⁰ S/cm were observed after photo‐irradiation. This conductivity is comparable to that of PANI‐salt synthesized by oxidizing aniline in the presence of an acid. High M_w (8000) PEG is much less effective than PEG 550, which is attributed to its lower compatibility with PANI. PEG‐grafted PANI (N‐PEG‐PANI) was also studied as an additive. Composites of PANI‐EB and N‐PEG‐PANI showed conductivity as high as 10² S/cm after treatment with HCl vapor. The photo‐induced conductivity of the N‐PEG‐PANI/PANI‐EB/PAG composite reached 10^?2–10^?1 S/cm. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enzymatic preparation of polyethylene glycol esters of castor oil fatty acids and their surface-active properties

This study concerns the preparation and evaluation of nonionic surfactants prepared from polyethylene glycol (PEG) esters of castor oil fatty acid, a source of hydroxy fatty acid. A lipase-catalyzed esterification reaction has been employed to prepare PEG esters of hydroxy acid to overcome problems associated with chemical processes. Castor oil fatty acid (85% ricinoleic acid) was mixed with PEG of different molecular weight. Rhizomucor miehei lipase was added as catalyst (10% level) and the reaction was continued at 60°C under 2 mm Hg pressure for 360 min. Conversion of PEG to esters was in the range of 86–94%, depending on the molecular size of PEG. The products were isolated and examined for surface activity by surface tension measurement. Surface tension values measured at 25°C were about 36–37 dynes/cm.     

Polychromophoric metal complexes for generating the bioregulatory agent nitric oxide by single- and two-photon excitation

In order to deliver a bioactive agent to a physiological location, it is important to be able to regulate precisely the location and the dosage. Such exquisite control can easily be envisioned for a photochemical drug that is active toward release of the desired bioactive agent upon irradiation of a specific tissue site. These materials should be thermally stable but reactive under excitation at visible (vis) or near-infrared (NIR) wavelengths where tissue transmission is optimal. Two photon excitation (TPE) is of special interest, since the use of focused laser pulses to activate release could provide 3D spatial control in therapeutic applications. This Account describes the preparation and photochemistry of a series of transition metal complexes designed to release the simple bioregulatory compound nitric oxide upon vis or NIR excitation. In order to enhance the light gathering capability of such compounds, we have attached chromophores with high single- or two-photon absorption cross sections to several photochemical NO precursors. For example, the iron nitrosyl clusters Fe2(mu-SR)2(NO)4 (Roussin's red esters) have been prepared with various chromophores as pendant groups, an example being the protoporphyrin XI derivative illustrated here. Direct excitation into the vis absorbing Q bands of the porphyrin leads to enhanced rates of NO generation from the Fe/S/NO cluster owing to the larger rate of light absorption by that antenna. Furthermore, femtosecond pulsed laser NIR excitation of the same compound at 810 nm (a spectral region where no absorption bands are apparent) leads to weak emission at approximately 630 nm and generation of NO, both effects providing evidence of a TPE mechanism. Roussin's red esters with other chromophores described here are even more effective for TPE-stimulated NO release. Another photochemical NO precursor discussed is the Cr(III) complex trans-Cr(L)(ONO)2(+) where L is a cyclic tetraamine such as cyclam. When L includes a chromophore tethered to the ligand backbone, excitation of that functionality results in energy transfer to the spin-forbidden ligand field double states and light-stimulated release of NO. We are working to develop systems where L is attached to a semiconductor nanoparticle as the antenna. In this context, we have shown that electrostatic assemblies are formed between the anionic surface of water-soluble CdSe/ZnS core/shell quantum dots (QDs) and Cr(L)(ONO)2(+) cations via an ion-pairing mechanism. Photoexcition of such modified QDs leads to markedly enhanced NO generation and suggests promising applications of such nanomaterials as photochemical drugs.     

Introducing small cationic groups into 4-armed PLLA–PEG copolymers leads to preferred micellization over thermo-reversible gelation

Starting from bis-MPA, PEG–PLLA triblock copolymers (bis-MPA-(PLLA–PEG)₂), comprising a central N-hydroxysuccinimide active ester, were synthesized. Reacting the corresponding active ester with α,ω-diamines afforded four-armed (PEG–PLLA)₂–R–(PLLA–PEG)₂ copolymers with central α,ω-diamide groups (R). Applying the α,ω-diamines, hexamethylene-diamine, spermine or norspermidine none, one or two secondary amine groups, respectively, were introduced into the linking moiety R. Whereas a copolymer containing no secondary amine groups showed fully thermo-reversible gelation behavior, copolymers comprising a central moiety containing one or two secondary amine groups retained the ‘sol’ state after a few heating and cooling cycles. Dynamic light scattering revealed that the copolymer containing no secondary amine groups showed a thermo-reversible shift in micellar size and small aggregates (57 and 877 nm at 25 °C and 40 and 152 nm at 50 °C). Conversely, copolymers comprising a central moiety containing secondary amine groups show a temperature independent distribution mainly consisting of micelles. It is proposed that the protonated amine groups preferably are located at the corona of the micelles and micellar aggregates and/or shielded by the PEG blocks, hindering the formation of hydrogels by PEG entanglements upon a change in temperature.     

Micropatterning of polymethacrylates by single‐ or two‐photon irradiation using π‐conjugated o‐nitrobenzyl ester phototrigger as side chains

A new single‐/two‐photon sensitive monomer, (E)‐5‐(4‐ethoxystyryl)?2‐nitrobenzyl methacrylate (ENbMA), was synthesized and copolymerized with methyl methacrylate (MMA) to form a series of photosensitive copolymers P(ENbMA–MMA)s that were well characterized by ¹H NMR and GPC. The photochemical and photophysical properties of both photosensitive monomer and copolymers upon visible light irradiation were studied by UV–Vis, FTIR, and HPLC spectra, which confirmed that 5‐(4‐ethoxystyryl)‐2‐nitrobenzyl ester can be photolyzed effectively with generation of the corresponding 5‐(4‐ethoxystyryl)‐2‐nitrosobenzaldehyde and carboxylic acid groups. The successful photocleavage endowed the optimized copolymers with excellent micropatterning property due to the effective generation of alkaline‐soluble carboxylic acid groups. Moreover, the high two‐photon absorption cross‐sections (over 20 GM at 800 nm) and the comparable photolysis upon two‐photon NIR light irradiation of the chromophores provided the copolymers with significant application in two‐photon microfabrication. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4099–4106, 2013