Dual‐curable fluorinated poly(methacrylate) copolymers for optical adhesives

In pursuit of photo‐curable adhesive for optical communication, dual‐curable acrylic oligomers (AOs) having alkoxy silane group, fluorine atoms and vinyl group as a pendent group were synthesized by two‐stage reactions. The isocyanate group containing oligomers were firstly synthesized via radical polymerization of acrylic monomers, and followed by urethane reaction with 2‐hydroxy ethyl methacrylate. The dual curing behaviors, e.g. thermal and photo‐cure, were studied by using photo‐differential scanning calorimetry (DSC) and real‐time IR. An optimum adhesive formulation, based on AO (15 g), epoxy acrylate (80 g), isobonyl methacrylate (17 g) and photo‐initiator (3 g), was obtained. As the content of AO was increased in the optical adhesive formulation, refractive index decreased but transmittance increased due to the increase in fluorine content. The optical transmittance at the range of 1.3 to 1.55 μm was higher than 90%. The addition of colloidal silica with the earlier mentioned formulation was helpful in decreasing crosslinking volume shrinkage and the increasing of glass fiber adhesion. The required properties for the optical adhesive, including chemical resistance and thermal resistance, dimension stability, etc. were also investigated. Copyright © 2005 John Wiley & Sons, Ltd.     

Dual Photo‐functionalized Amphiphile for Photo‐reversible Liquid Crystal Alignments

Without the conventional polymer‐based liquid crystal (LC) alignment process, a newly synthesized dual photo‐functionalized amphiphile (abbreviated as ADMA₁) was successfully applied as a robust photo‐reversible LC alignment layer by self‐assembly and photo‐polymerization. The LC alignment layer constructed by directly adding dual photo‐functionalized amphiphiles into LC media significantly cuts the manufacturing cost as well as opens new doors for the fabrication of novel electro‐optical devices.     

Photo‐aligning of polyimide layers for liquid crystals

A series of soluble and highly transparent semi‐alicyclic polyimides (PIs) with designed flexible linkages have been synthesized derived from an alicyclic aromatic dianhydride (1,2,3,4‐cyclobutanetetracarboxylic dianhydride, CBDA) and various aromatic ether‐bridged diamines. The semi‐alicyclic PIs were evaluated as the photo‐alignment layers of liquid crystal (LC) molecules in liquid crystal display (LCD). Experimental results indicate that the photo‐alignment characteristics of LC molecules induced by the photo‐aligned PI layers and the electro‐optical (EO) properties of the LC cell devices are closely related with PI backbone structures. The retardation of the photo‐aligned PI layers is correlated with the ultraviolet (UV) absorption intensity of PI at 220 to approximately 330 nm. The higher UV absorption intensity PI has, the higher retardation and lower pre‐tilt angle the photo‐aligned PI layer exhibits. The defect‐free and photo‐aligned PI layer could result into the uniform LC texture, which is highly desired for in‐plane switching (IPS) mode LCD devices. In comparison, PI layer containing trifluoromethyl moiety shows poor photo‐aligning performance because of the strong electronic withdrawing effect of the fluorinated linkage.     

A concept for bifocal contact‐ or intraocular lenses: liquid single crystal hydrogels (“LSCH”)

The synthesis of liquid single crystal hydrogels (“LSCH”) in suitable molds offers an innovative concept to realize bifocal contact‐ or intraocular‐lenses. LSCH combine the properties required for applications as bifocal ophthalmic lenses: the soft and water‐containing hydrogel enables oxygen permeation and exhibits high birefringence due to the liquid crystalline phase structure built up by rigid rod‐like amphiphiles. Via a photo‐initiated crosslinking reaction of aqueous solutions of monomeric lyotropic liquid crystalline amphiphiles in the macroscopically ordered liquid crystalline state, we obtain optically uniaxially ordered and transparent LSCH. The orientation process and the phase structure of the anisotropic hydrogel is analyzed by deuterium NMR‐spectroscopy. Copyright © 2002 John Wiley & Sons, Ltd.     

An Isoindigo‐Based “Double‐Cable” Conjugated Polymer for Single‐ Component Polymer Solar Cells

An isoindigo‐based “double‐cable” conjugated polymer bearing perylene bisimide side units was developed via Stille polymerization for application in single‐component polymer solar cells, in which a power conversion efficiency of 1% with broad photo‐response from 300 nm to 800 nm was achieved. There is no evidence of large phase separation confirmed by AFM images and photoluminescence (PL) spectra. The space charge limit current measurements and light intensity dependence measurements indicate that the low electron mobility and the significant recombination of photogenerated charge carriers in active layer mainly account for the low performance of our solar cells. Our results suggest that these “double‐cable” are promising candidates for use in single‐component polymer solar cells with NIR photoresponse.     

Electro‐optical characteristics in phase separated liquid crystal/photo‐curable acrylic monomer mixture system

One of the main objectives of the experiment was to achieve the vertical aligned (VA) effect. To accomplish this, we employed liquid crystal (LC)/photo‐curable acrylic monomers mixture systems to prepare vertical alignment copolymer film (VACOF) for LC molecules with the photo‐polymerization induce phase separation (PIPS) process. From previous experimental results, we successfully fabricated LC devices without the micro‐protrusion structure. After the application of a saturated voltage, the LC molecules actually exhibited such interesting phenomena as uniaxial orientation, uniform single‐domain display state, etc. In this study, to obtain VACOF with smooth surface, we similarly controlled appropriate experimental conditions such as UV light exposure intensity and curing temperature, and altered process parameters such as the cell thickness, chemical structure length of the main chain type biphenol acrylic monomer [to simulate the main chain function of the traditional vertical alignment type polyimide (PI)], etc. During the experiment, we discovered that regardless of the cell thickness, this photo‐alignment system would yield the VACOF instead of the polymer disperse liquid crystal (PDLC) film morphology. Another notable finding was that the contrast ratio was heavily influenced by the length of the main chain type acrylic monomer structure for LC/monomer mixture systems, with enhancement of up to ～56%. Therefore, we further investigated the display effects, electro‐optical properties, etc. for these two main chain type acrylic monomer systems with different lengths and cell thicknesses. Copyright © 2011 John Wiley & Sons, Ltd.     

Photo‐stimulated “turn‐on/off” molecularly imprinted polymers based on magnetic mesoporous silicon surface for efficient detection of sulfamerazine

In this study, novel photo‐stimulated molecularly imprinted polymers based on magnetic mesoporous carrier surface were developed for selective identification and intelligent separation of sulfamerazine in complex samples. The photosensitive monomer of the molecularly imprinted polymers was azobenzene derivative 5‐[(4‐(methacryloyloxy)phenyl) diazenyl] isophthalic acid with stimulus reaction mechanisms, which has photoisomerization between trans and cis for N=N bonds. Further, the properties of the photo‐stimulated molecularly imprinted polymers were further evaluated through several sets of adsorption experiments. It illustrated that the maximum adsorption amount is 0.45 mmol/L. By ultraviolet spectrophotometry, the material reaches typical characteristic peaks of photo sensitivity, and the cycle time is 16 min. Three adsorption and desorption processes were repeated, the adsorption rate reached 34.4%. Overall, the photo‐stimulated molecularly imprinted polymers can enrich and separate determine sulfamerazine with high selectivity, which have good recovery for real samples.     

Investigation of the tensile properties of “epoxy resin‐monomer” systems using cationic UV‐crosslinkable blends

The compatibility of cycloaliphatic and aromatic multifunctional epoxides with several epoxide resins allows the development of a wide range of cationic radiation‐curable formulations. The influence of different “epoxide resin‐monomer” systems UV‐cured in the presence of suitable cationic photoinitiators on the resulting physicochemical film properties was studied, and the results are stated. Copyright © 2004 John Wiley & Sons, Ltd.     

Thermally enhanced photoinduced in‐plane reorientation in photo‐cross‐linkable polymer liquid crystalline films and its application to linear polarizer

Thermally enhanced photoinduced in‐plane molecular reorientation in new photo‐cross‐linkable polymer liquid crystalline (PPLC) films comprising 4‐[ω‐(4‐methoxycinnamoyloxy)alkyloxy]biphenyl side groups is explored using linearly polarized ultraviolet (LPUV) light exposure and subsequent annealing. The influence of the alkylene spacer length between the photo‐cross‐linkable group and the biphenyl mesogenic moiety is investigated. The straight‐line characteristics of the photoreactive mesogenic side group and the 4‐methoxycinnamoyl group play important roles in the high photoreactivity and the large thermally enhanced molecular reorientation, where the in‐plane order and the birefringence of the reoriented film are 0.61 and 0.18 are obtained. Finally, cooperative molecular reorientation of dichroic dyes doped in PPLC films is also achieved to fabricate a linear polarizer. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4712–4718, 2008     

Bright, “Clickable” Porphyrins for the Visualization of Oxygenation under Ambient Light

A new group of “clickable” and brightly emissive metalloporphyrins has been developed for the visualization of oxygenation under ambient light with the naked eye. These alkynyl‐terminated compounds permit the rapid and facile synthesis of oxygen‐sensing dendrimers through azide–alkyne click chemistry. With absorption maxima overlapping with the wavelengths of common commercial laser sources, they are readily applicable to biomedical imaging of tissue oxygenation. An efficient synthetic methodology, featuring the stable trimethylacetyl (pivaloyl) protecting group, is described for their preparation. A paint‐on liquid bandage containing a new, click‐synthesized porphyrin dendrimer has been used to map oxygenation across an ex vivo porcine skin burn model.     

“Synthetic Metals”: A Novel Role for Organic Polymers (Nobel Lecture)

Since the initial discovery in 1977, that polyacetylene (CH)_x, now commonly known as the prototype conducting polymer, could be p‐ or n‐doped either chemically or electrochemically to the metallic state, the development of the field of conducting polymers has continued to accelerate at an unexpectedly rapid rate and a variety of other conducting polymers and their derivatives have been discovered. Other types of doping are also possible, such as “photo‐doping” and “charge‐injection doping” in which no counter dopant ion is involved. One exciting challenge is the development of low‐cost disposable plastic/paper electronic devices. Conventional inorganic conductors, such as metals, and semiconductors, such as silicon, commonly require multiple etching and lithographic steps in fabricating them for use in electronic devices. The number of processing and etching steps involved limits the minimum price. On the other hand, conducting polymers combine many advantages of plastics, for example, flexibility and processing from solution, with the additional advantage of conductivity in the metallic or semiconducting regimes; however, the lack of simple methods to obtain inexpensive conductive polymer shapes/patterns limit many applications. Herein is described a novel, simple, and cheap method to prepare patterns of conducting polymers by a process which we term, “Line Patterning”.     

The “Green” Electrochemical Synthesis of Periodate

High‐grade periodate is relatively expensive, but is required for many sensitive applications such as the synthesis of active pharmaceutical ingredients. These high costs originate from using lead dioxide anodes in contemporary electrochemical methods and from expensive starting materials. A direct and cost‐efficient electrochemical synthesis of periodate from iodide, which is less costly and relies on a readily available starting material, is reported. The oxidation is conducted at boron‐doped diamond anodes, which are durable, metal‐free, and nontoxic. The avoidance of lead dioxide ultimately lowers the cost of purification and quality assurance. The electrolytic process was optimized by statistical methods and was scaled up in an electrolysis flow cell that enhanced the space–time yields by a cyclization protocol. An LC‐PDA analytical protocol was established enabling simple quantification of iodide, iodate, and periodate simultaneously with remarkable precision.     

Regenerable‐Catalyst‐Aided,Opened to Air and Sunlight‐Driven “CuAAC&ATRP” Concurrent Reaction for Sequence‐Controlled Copolymer

An ideal stimuli‐responsive controlled/living radical polymerization should have the ability to manipulate the reaction through spatiotemporal “on/off” controls, achieving the polymerization under fully open conditions and allowing for precise control over macromolecular architecture with defined molecular weights and monomer sequence. In this contribution, the photo (sunlight)‐induced electron transfer atom transfer radical‐polymerization (PET‐ATRP) can be realized to be reversibly activated and deactivated under fully open conditions utilizing one‐component copper(II) thioxanthone carboxylate as multifunctional photocatalyst and oxygen scavenger. The polymerization behaviors are investigated, presenting controlled features with first‐order kinetics and linear relationships between molecular weights and monomer conversions. More importantly, “CuAAC&ATRP” concurrent reaction combining PET‐ATRP, photodriven deoxygenation, and photoactivated CuAAC click reaction is successfully employed to synthesize the sequence‐defined multiblock functional copolymers, in which the iterative monomer additions can be easily manipulated under fully open conditions.     

A Suite of “Minimalist” Photo‐Crosslinkers for Live‐Cell Imaging and Chemical Proteomics: Case Study with BRD4 Inhibitors

Affinity‐based probes (Af BPs) provide a powerful tool for large‐scale chemoproteomic studies of drug–target interactions. The development of high‐quality probes capable of recapitulating genuine drug–target engagement, however, could be challenging. “Minimalist” photo‐crosslinkers, which contain an alkyl diazirine group and a chemically tractable tag, could alleviate such challenges, but few are currently available. Herein, we have developed new alkyl diazirine‐containing photo‐crosslinkers with different bioorthogonal tags. They were subsequently used to create a suite of Af BPs based on GW841819X (a small molecule inhibitor of BRD4). Through in vitro and in situ studies under conditions that emulated native drug–target interactions, we have obtained better insights into how a tag might affect the probe's performance. Finally, SILAC‐based chemoproteomic studies have led to the discovery of a novel off‐target, APEX1. Further studies showed GW841819X binds to APEX1 and caused up‐regulation of endogenous DNMT1 expression under normoxia conditions.     

ROMP based photoinitiator‐coinitiator systems with improved migration stability

Nowadays, migration stability is one of the key features for photoinitiators used in radiation curable formulations, especially when the material is in contact with food or the human body. Herein, the synthesis and characterization of statistical copolymers with covalently bound eosin and/or ethyl dimethylamino benzoate units by ring opening metathesis polymerization is presented. The prepared compounds were tested as macroinitiators for the photopolymerization of acrylates aiming at an initiator/coinitiator system which combines good polymerization activity with improved migration stability. An acrylate modified eosin derivative which is incorporated into the polymer network during the photopolymerization reaction and, therefore, less likely to leak from the polymer compound was used as reference. Photoinitiating activities of low and high molecular weight initiators and coinitiators were investigated by photo‐DSC. Moreover, leakage studies and viability tests with osteoblast‐like cells were performed to proof the suitability of this concept. The use of polymeric eosin in combination with a low molecular weight coinitiator was found to be a good compromise when aiming at a photoinitiating system with sound performance and improved migration stability. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3648–3661, 2008     

Time‐delayed photo‐induced depolymerization of poly(phthalaldehyde) self‐immolative polymer via in situ formation of weak conjugate acid

Poly(phthalaldehyde) (PPHA) can be used as a structural material in transient devices and photo‐catalytically depolymerized at the end of device life by the use of a photo‐acid generator (PAG). However, device degradation requires the presence of a radiation source at the end of device mission. It has been found that the onset of PPHA depolymerization after PAG photo‐exposure can be delayed by incorporation of a particular weak bases in the PPHA/PAG mixture. This method of delayed PPHA depolymerization allows for PAG activation prior to or during device deployment when the device is under full user control. The basicity of specific lactams and amides was found to slow the PPHA depolymerization, giving the transient device a longer but finite mission lifetime. The weak base reacts with the photo‐generated strong acid to form a weak conjugate acid, which reacts more slowly with PPHA to extend the onset of PPHA depolymerization. The addition of a molar excess of specific lactams or amides, with respect to PAG, maintains PPHA stability and mechanical properties for more than 80 minutes after photo‐exposure at room temperature. The amide or lactam mediated acid activation of PPHA follows first‐order kinetics. The time delay of PPHA depolymerization can allow for prelaunch photo‐exposure and eliminates the need for postmission photo‐exposure where reliable light‐sources may not be available.     

High transmission 3D printed flex‐PCB‐based ion funnel

In this study a novel fabrication method for a radio frequency (RF) ion funnel is presented. RF ion funnels are important devices for focusing ion clouds at low vacuum conditions for mass spectrometry or deposition‐related applications. Typically, ion funnels are constructed of stainless steel plate ring electrodes with a decreasing diameter where RF and direct current potentials are applied to the electrodes to focus the ion cloud. The presented novel design is based on a flexible circuit board that serves both as the signal distribution circuit and as the electrodes of the ion funnel. The flexible circuit board is rolled into a 3D printed scaffold to create a funnel shape with ring electrodes formed by the copper electrodes of the flexible circuit board. The design is characterized in direct comparison with a conventional steel‐plate electrode design. The discussed results show that the new funnel has similar performance to the conventionally designed funnel despite much lower manufacturing costs. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and properties of UV curable polyvinylsilazane as a precursor for micro‐structuring

Photosensitive acrylated polyvinylsilazanes were prepared by reacting a diacrylate containing compound, 1,1‐bis (acryloyloxyethyl) ethyl isocyanate (BAEI), with polyvinylsilazane (PVSZ) and utilized as an inorganic photoresist for generating SiCN‐based ceramic microstructures. The acrylate‐modified polymers (m‐PVSZ) were characterized by ¹H‐NMR, ¹³C‐NMR and FT‐IR methods to determine the chemical reaction mechanism. Differential photo‐calorimeter and FT‐IR analysis were employed to examine its photosensitive properties. Line patterns were fabricated by a UV nano‐imprinting method; multi‐layered octagon structures were fabricated by a two‐photon absorption stereolithography process. The results indicate that m‐PVSZ is quite a novel inorganic photoresist for the fabrication of micro ceramic structures. Copyright © 2015 John Wiley & Sons, Ltd.     

Injectable poloxamer/graphene oxide hydrogels with well‐controlled mechanical and rheological properties

Although significant progress has been made in the design and application of injectable hydrogels for biomedical applications, concurrent control of rheological and mechanical properties of injectable hydrogels has remained as an open challenge to the researchers. In this work, we introduce and put into practice a photo‐curable poloxamer (also known as Pluronic)/graphene oxide (Plu/GO) injectable hydrogel with well‐controlled rheological and mechanical properties. Acrylate group was anchored to hydrogel structure to endow photo‐crosslinking ability through decelerating degradation rate of poloxamer hydrogels after injection. It was found that the modified Plu remains stable in biological media for a long‐term period without significant weight loss. Rheological properties of hydrogels were also carried out as essential prerequisite for an ideal injectability via frequency sweep, flow curve, recovery, and yield stress before and after modification, signifying shear‐thinning behavior of Plu/GO hydrogels with high recoverability. The viscosity of shear‐thinning‐like hydrogels dropped at higher shear stress, which facilitated injection process. Moreover, mechanical behavior of Plu was optimized by manipulating the content of Plu, degree of modification with reactive precursor, curing, and particularly incorporation of GO without deteriorating effects on rheological behavior of Plu.     

Photo‐alignment material with azobenzene‐functionalized polymer linked in film

Application of a new azo‐polymer as a photo‐alignment material for liquid crystals (LCs) was demonstrated. 4‐(Vinyloxyethyloxy)azobenzene (VAZO), which has thermally reactive vinyl ether groups, reacted with the ? OH groups of poly(4‐hydroxystyrene) (PHS) during the baking process. The azo‐attached polymer (PHS‐VAZO) film showed anisotropic spectra after exposure to 365‐nm linear polarized light (LPL) unlike the VAZO‐doped poly(methylmethacrylate) (PMMA) film. The anisotropy of the film was small at high concentration of the azo‐chromophore because of thermal randomization of the polarized state. In the evaluation of photo‐alignment of the LC, the LC hybrid cell using the PHS‐VAZO film achieved high LC alignment. The azo‐attached polymer using the thermal reaction of vinyl ethers is useful for a photo‐alignment material. Copyright © 2002 John Wiley & Sons, Ltd.