SUPERABSORBENCY AND VOLUME PHASE TRANSITION IN CROSSLINKED POLY[[3-(METHACRYLOYLAMINO)PROPYL]-TRIMETHYLAMMONIUM CHLORIDE] HYDROGELS†

Hydrogels of poly[[3-(methacrylolylamino) propyl]tri-methyl-ammon-ium chloride] (PMAPTAC) were synthesized by polymerizing an aqueous solution of [3-(methacryloyl-amino)propyl]-trimethylammonium chloride using N,N′-mehtylenebis(acrylamide) (Bis) as crosslinker. The swelling behavior of the hydrogel was monitored as a function of temperature, pH, and solvent composition. The hydrogel exhibits ampholytic behavior. Solvent induced volume phase transition (VPT) is observed in systems such as acetone-water and ethanol-water. The swelling kinetics conform to second order kinetics.

     

Free‐volume change during the volume phase transition of polyacrylamide gel studied by positron annihilation: Solvent‐composition dependence

Changes in the free‐volume parameters of polyacrylamide (PAAm) gels during the volume phase transition (VPT) were studied with the positron annihilation lifetime technique. The VPT was induced through the variation of the solvent composition in a mixture of acetone and water. The PAAm gels containing 0 and 4 mol % carboxyl groups in their polymer chains were adapted to compare the effect of the presence of ionic groups on the microscopic environment. The change of the free‐volume property is discussed on a nanoscopic scale, with attention paid to the interactions between the polymer chains and the solvent molecules. It is proven that the variations of the free‐volume parameters correlate significantly with the VPT phenomenon. The results of the free volume for both gels are well‐explained when an interaction parameter, ε_g, is assumed. The interpretation suggests that the state of the interactions among the components (the polymer chain, acetone, and water molecules) plays an important role in the change of the free volume of PAAm gels during the VPT. An increase of the dispersion of the free‐volume size near the VPT point was observed for the ionized PAAm gel. The broadened size distribution of the free volume of the ionized PAAm gel around the VPT point lay between those of pure water and the corresponding mixed solvent, suggesting that a local minimum of the average free‐volume size at the VPT point is caused by the increase of a specific interaction, hydrogen bonding. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 922–933, 2000     

Visual detection of lead(II) using a label-free DNA-based sensor and its immobilization within a monolithic hydrogel

Lead is highly toxic and its detection has attracted a lot of research interests. In recent years, DNA has been used for Pb(2+) recognition and many fluorescent sensors with low to sub-nM detection limits have been reported. These figures of merit were typically measured using a spectrophotometer that can detect nM DNA with a high signal-to-noise ratio. For visual detection, however, μM DNA or dye was required, making it difficult to detect low nM targets. We recently achieved a visual sensitivity of 10 nM Hg(2+) by immobilizing a DNA probe in a hydrogel. This was made possible because the gel was able to actively adsorb Hg(2+). In this work, we aim to test whether this method can be extended to the detection of Pb(2+). First, a new Pb(2+) sensor was designed based on a guanine-rich DNA and DNA binding dyes such as thiazole orange and SYBR Green I. The free DNA showed a detection limit of 8 nM Pb(2+) using 40 nM DNA. For visual detection in solution with 1 μM of the DNA probe, however, ～300 nM Pb(2+) was required. After immobilization in a monolithic polyacrylamide hydrogel, even 20 nM Pb(2+) could be visually detected with a sample volume of 50 mL. Therefore, sensitive detection without signal amplification was achieved. Finally, we demonstrated simultaneous detection of both Hg(2+) and Pb(2+) in the same water sample with shape encoded hydrogel sensors.     

Stimuli-responsive properties of N-isopropylacrylamide-based ultrathin hydrogel films prepared by photo-cross-linking

To develop stimuli-responsive ultrathin polymer films on a solid substrate, a novel photo-cross-linkable polymer with both temperature- and pH-responsive properties was prepared. The photoreactive 4-aminobenzophenone (BP) was introduced onto the side groups of poly(N-isopropylaclylamide-co-2-carboxyisopropylaclylamide) [poly(NIPAAm-co-CIPAAm)]. This copolymer was designed for highly random sequences of comonomers. After the formation of spin-coated polymer films on a solid substrate, UV-light irradiation started the cross-linking reaction. The spin-coating processes and stability of the polymer films were quantitatively monitored by a quartz crystal microbalance (QCM), and the thickness was estimated using an atomic force microscope (AFM). These measurements confirmed the formation of a very plain polymer film, and the film thickness was precisely controlled by the concentration of the polymer solution used for spin coating. Moreover, the obtained films showed a high stability due to the cross-liking reaction and UV irradiation. Cyclic voltammetry using potassium ferricyanide revealed that the ions could permeate the photo-cross-linked ultrathin polymer films. The permeability of the ultrathin hydrogel films was dramatically changed by varying the pH and temperature of the aqueous media. These observations suggest that the preparation of isopropylacrylamide-based stimuli-responsive ultrathin hydrogel films is possible.     

Inverse opal pH sensors with various protic monomers copolymerized with polyhydroxyethylmethacrylate hydrogel

pH sensitive inverse opal sensors were synthesized using various vinyl monomers containing acidic or basic substituents. Acrylic acid (AA), vinylphosphonic acid (VPA), vinylimidazole (VI), and dimethylaminoethylmethacrylic acid (DMAEMA) were respectively copolymerized with hydroxyethylmethacrylate (HEMA), the building block monomer of the hydrogel via UV-initiated photopolymerization. Opal templating and subsequent template removal enabled the fabrication of four inverse opal (IO) hydrogel colorimetric sensors, which responded to pH in different fashions. pH-dependent swelling of the IO hydrogel induced the red-shift of the diffracted color. The sensors containing AA or VPA, the proton donating monomers showed the color shifts from green to red with pH increase due to the increased concentration of carboxylate anions bound to the hydrogel. Diprotic VPA sensor exhibited two-step increases of diffracted wavelengths at its pK_a1 and pK_a2 respectively. The sensors containing proton acceptors, VI and DMAEMA showed the pH-dependent color changes in an opposite way to the AA sensor and the VPA sensor since their ionizations take place by lowering pH due to the protonation at the amino groups. The shapes of pH response curves of VI and DMAEMA sensors were similar but pK_bs were different from each other. Optical diffraction responses of four sensors were compared with the calculated concentration ratios of the ionized species to the total monomer with pH variation, and a deswelling effect in the vicinities of pK_as of phosphate buffer on the swelling response could be explained by shrinkage of PHEMA hydrogel under high ionic environment. In addition, copolymerization of AA, VPA and HEMA was carried out which resulted in a pH sensor exhibiting a wider range of pH for color change.     

The Research on Intelligent Controlled DDS of Polymer Carrier

The intelligent controlled drug delivery systems (DDS) are a series of the preparations including microcapsules or nanocapsules composed of intelligent polymers and medication. The properties of preparations can change with the external stimuli, such as pH value, temperature,chemical substance, light, electricity and magnetism etc. According to this properties, the DDS can be intelligently controlled. This paper has reviemed research on syntheses and applications of intelligent controlled DDS of polymer carriers.Drug delivery system with pH stimuliThe volume of polymer hydrogel can change with the pH value of external environment. The sensitive polymer hydrogels to pH are often as carriers. The polymer hydrogel carrying medicine is especially suitable for taking orally. In order to protect medicine from losing activation, we enwrapped medicine into polymer hydrogel with acidic group. In the acidic environment of stomach,the volume of polymer hydrogel contracts because of the hydrogen bond. The medicine in the polymer hydrogel cannot disperse out. When it goes to the intestine of basic environment, the hydrogen bond will be broken, and the medicine can release.Drug delivery system with temperatureTemperature sensitive polymer hydrogel can change its volume with changing of environmental temperature. This kind of polymer hydrogel can be also used as a carrier of medicine. At a low temperature, the polymer chains form hydrogen bond with water to swell to let medicine disperse out from the hydrogel. On the other hand, the hydrogen bond will be broken and polymer chain will lose water to contract with temperature's increasing. And the medicine will not disperse out. For example,the poly(N-isopropylacrylamide)(PNIPAAm) is the hydrogel that is swelled at lower temperature and contracted at higher temperature. PNIPAAm has the lower critical solution temperature(LCST).We can adjust its LCST to control PNIPAAm hydrogel's swelling or contraction to let medicine release or not.Drug delivery system with other stimuliThe polymer carrier drug delivery system can be intelligently controlled with the stimuli of pH value and temperature. In addition, there are still some other stimuli for DDS. For example, DDS with light; DDS with electricity(or electric field); DDS with magnetism(magnetic field); DDS with chemical substance; etc. The characteristic of intelligent polymer carrier is based on P.J.Flory's gel-swelling theory. Intelligent polymer carrier DDS will be widely used in biological and medical fields.     

In-situ AFM studies of the phase-transition behavior of single thermoresponsive hydrogel particles

The volume phase transition (VPT) behavior of individual thermally responsive poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm-co-AAc) hydrogel microparticles was studied by in-situ dynamic mode atomic force microscopy (AFM) and force spectroscopy during heating and cooling cycles. Hydrogel samples were prepared by electrostatic immobilization of microparticles to amine-modified gold surfaces. The AFM studies of particle deswelling were performed by varying the force applied on the particles during imaging as a function of the geometry and material of the AFM probe. Aluminum-coated silicon cantilevers were found to influence substantially the behavior of the particles during the VPT, leading to a significant shape change. Low force impact magnetic excitation of the AFM probe (MAC mode) during dynamic mode measurements resulted in an undisturbed deswelling behavior enabling observation of the expected volume changes of the particles without significant tip-sample interaction. Hence, MAC-mode AFM was determined to be the most suitable technique for in-situ AFM studies on volume and shape changes at single hydrogel particles during VPT. Elasticity measurements performed at single particles at temperatures below and above the VPT revealed a 15-fold increase in the Young's modulus after passing the VPT, indicating the transition from a soft, swollen network to a stiffer, deswollen state.     

PVA-PAMPS-PAA三元互穿网络型水凝胶的合成及其性能研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酸(AA)以及聚乙烯醇(PVA)为原料,制备了PVA-PAMPS-PAA三元互穿网络型(T-IPN)水凝胶.红外分析表明,PVA与PAA以及PAMPS之间形成了较强的氢键,使得PVA分子上的C—O伸缩震动吸收峰移向了低波数处.X射线衍射以及电镜分析表明,当PVA用量较低时,PVA能均匀的穿插于凝胶网络中,形成完善的互穿网络结构,当PVA用量过高时,部分的PVA结晶而使得凝胶出现相分离.研究了该三元互穿网络型水凝胶的溶胀性能,结果表明,该水凝胶的平衡溶胀比在200至340之间,并且随着AA以及AMPS用量的增加,凝胶的溶胀速率以及平衡溶胀比均升高.该三元互穿网络型水凝胶在酸性溶液中和在碱性溶液中表现出截然不同的消溶胀性能;并且随着溶液pH的升高,凝胶在pH=9.0附近出现体积突变,表现出pH敏感性.通过研究T-IPN水凝胶的抗压缩性能发现,利用线型高分子、柔性高分子网络以及刚性高分子网络制备的三元互穿网络型水凝胶能在高溶胀比下保持较高的强度.溶胀比为180的T-IPN水凝胶,其最大抗压缩强度可达12.1 MPa.进一步研究发现,凝胶的组成以及溶胀比均对凝胶的抗压缩强度和压缩应变均存在较大的影响.     

应用于生物发酵在线监测的聚合物pH传感膜

微型生物反应器的成功操作依赖于对培养液pH值的监测和控制,聚合物pH荧光探针可以制成传感膜安装在微型反应器上,具有高通量筛选、非入侵性、容易集成等特征。甲基丙烯酸羟乙酯和N-(2-甲基丙烯酰乙酯基)-4-(N-甲基哌嗪基)-1,8-萘酰亚胺(NI)共聚形成的聚合物,具有良好亲水性、成膜性和生物相容性,并在pH=6~8之间具有良好的响应性能和稳定性。为了进一步提高膜的响应速率,将含有金刚烷的单体引入聚合物中,结果显示随着侧链金刚烷基团的含量增加,共聚物膜的pH响应时间变长;而将强亲水性的聚乙二醇引入共聚合物中,发现共聚物膜的pH响应速率得到了提高。将此pH传感膜应用于酵母发酵液中进行测试,具有良好的pH值在线监测性能。     

A Novel Colorimetric and Fluorescent pH Sensor Derived from Iminocoumarin and Thiophene‐Carboxaldehyde

A novel colorimetric and fluorescent pH sensor derived from iminocoumarin and thiophene‐carboxaldehyde was designed and synthesized. The structures of the dye and related compounds were characterized by IR, ¹H NMR, ¹³C NMR, and mass spectra. Color change from green to yellow of the new sensor solution in ethanol–water with the decrease in the pH value from 7 to 2 was observed by the naked eye. Under acidic conditions, the intensity of the maximum fluorescence emission peak of the sensor increased gradually with the decrease in the acidity of the solution (the increase in the pH value from 2 to 7) and attained to the maximum value at about pH 6. Under basic conditions, the fluorescence intensity of the emission peak of the sensor did not exhibit a distinct change at pH ≤ 11.85, and the fluorescence was quenched at pH 13.36, concomitant with the green color of the solution turning pale. The sensor can be used as a fluorescent pH probe in the presence of common metal cations and anions without interference.     

温度及pH敏感聚(丙烯酸)/聚(N-异丙基丙烯酰胺)互穿聚合物网络水凝胶的合成及性能研究

合成聚（丙烯酸）／聚（Ｎ 异丙基丙烯酰胺）互穿聚合物网络（ＰＡＡｃ／ＰＮＩＰＡＩＰＮ）水凝胶，具有温度及ｐＨ双重敏感特性．这种水凝胶在弱碱性条件下的溶胀率远大于酸性条件下的溶胀率．在酸性条件下，随着温度上升，凝胶的溶胀率也随之逐渐上升；而在弱碱性条件下，温度低于聚（Ｎ 异丙基丙烯酰胺）（ＰＮＩＰＡ）的较低临界溶解温度（ＬＣＳＴ）时，溶胀率也随着温度的上升而上升，当温度达到ＬＣＳＴ时，凝胶的溶胀率突然急剧下降，并随着温度的逐渐上升而下降．     

Electrochemical and surface characterization of pH sensor based on bisulfate-doped poly(pyrrole)

Pyrrole was electrochemically polymerized on glassy carbon support in NaHSO₄ solutions under different conditions (method applied, concentration of monomer, concentration of the main solution, thickness of the film). These variables were used to study the preparation effect on the resulting properties, in particular on the potentiometric response of the PPy-HSO₄ electrodes. The electrodes were characterized by cyclic voltammetry, as well as by STM and AES techniques. Utilities of the polymer application as a sensor were studied by direct potentiometric measurements. The results obtained show that poly(pyrrole) doped with bisulfate ions can serve as pH sensor, with the slope of E/pH curves approaching the theoretical value.     

活性炭复合改善聚丙烯酸凝胶耐盐性及其溶胀机理

在活性炭(Ac)存在的情况下通过自由基溶液聚合,以过硫酸铵为引发剂,N,N′-亚甲基双丙烯酰胺为交联剂,制备了活性炭复合聚丙烯酸凝胶(PAA/AC)。 考察了凝胶在蒸馏水、生理盐水和不同pH值缓冲溶液中的平衡溶胀比以及溶胀动力学,结果表明,活性炭能有效提高凝胶的平衡溶胀比,在实验设计的pH值范围内复合凝胶具有比PAA凝胶更高的平衡溶胀比,蒸馏水和生理盐水中PAA/AC凝胶的平衡溶胀比分别可达到303和60 g/g,约为PAA凝胶的2.4倍。 讨论了凝胶的溶胀机理,结果表明,活性炭成分的介入破坏了聚合物链段之间的聚集态结构,减弱了聚合物链段之间的相互作用,提高了凝胶的溶胀能力。 示差扫描量热仪测定复合前后凝胶的玻璃化转变温度,扫描电子显微镜观察了复合前后凝胶的断面网络结构,结果进一步表明活性炭复合后聚合物链段之间的作用力减弱。     

Prussian Blue Modified Submicron Structured Gold Electrodes for Amperometric Hydrogen Peroxide Sensing

In this work, we present a simple and effective approach for fabricating sub‐micron structured gold (SM−Au) electrodes by chemically etching the magnetron co‐sputtered gold film in KI solution for certain time. Such electrodes with a large surface area to volume ratio were used as the matrix for electrochemical deposition of Prussian blue (PB) to develop an electrochemical hydrogen peroxide sensor. Experimental characterization using scanning electron microscope and atomic force microscope shows that the thickness of PB layer on SM−Au electrode is around 140 nm, and is composited with cubic PB nanocrystals. The electrochemical performance of the designed sensor, studied using cyclic voltammograms and chronoamperometry methods, suggests that the sensor based on SM−Au/PB electrode presents the direct electron transfer of PB particle towards SM−Au film, and exhibits fast response, wide linearity, low detection limit and high stability. Under the optimized conditions, the sensitivity of the developed sensor for the detection of H₂O₂ reaches the value of 512 mA cm⁻² M⁻¹ with a linear range from 1 μM to 4.5 mM.     

A Zn2+-specific turn-on fluorescent probe for ratiometric sensing of pyrophosphate in both water and blood serum

A novel fluorescent sensor composed of a naphthalene functionalized tetraazamacrocycle ligand 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-3-methyl naphthalene (1) and Zn(2+) has been designed and prepared, which can be utilized for selective and ratiometric sensing of pyrophosphate (PPi) over other phosphate-containing anions in aqueous solution at physiological pH. Notably, the water soluble 1 itself also exhibits a selective enhanced fluorescent response to Zn(2+), and the complex 1-Zn(2+) thus formed eventually fulfils the synergic Zn(2+) coordination-altered strategy with PPi. Furthermore, the ratiometric sensing of 1-Zn(2+) towards PPi performed well even in blood serum milieu. Finally, the sensor 1-Zn(2+) was successfully employed to monitor a real-time assay of inorganic pyrophosphatase (PPase) by means of ratiometric fluorescent measurements for the first time.     

Sensitive Amperometric Sensing of Hydrogen Peroxide Using Ag Nanowire Array Electrode

The amperometric sensor based on a silver nanowire (80 nm in diameter Ag NW) array electrode was fabricated and characterized with scanning electron microscope (SEM). The electrode showed good electrocatalytic activity for reduction of hydrogen peroxide. The effects of the applied polarization potential, pH, time interval between successive injections of analyte, injection volume and H₂O₂ concentration in a single injection on the electrochemical performance of the sensor were studied. It was found that the optimized operating conditions for the proposed sensor are: the potential of ?200 mV, pH between 7.4 and 9.0, 60 s time interval, 10 µL injection volume, and 500 µM H₂O₂ in single injection. The proposed Ag NW array sensor is free of interference from ascorbic acid, uric acid and glucose.     

Periodicity-controlled two-dimensional crystalline colloidal arrays

We developed a convenient and fast approach to preparing close-packed two-dimensional (2-D) particle arrays on mercury surfaces. Addition of cosolvents, such as alcohols, to aqueous colloidal particle suspensions induces spreading and self-assembly of the particles into 2-D arrays on top of the mercury surface. We can fabricate large-area close-packed 2-D arrays (>70 cm(2)) within 30 s. We attached these 2-D arrays to functional hydrogel films such that the 2-D array spacings were altered by the hydrogel volume response to the environment. We directly observed the hydrogel volume induced 2-D array spacing changes by using confocal laser scanning microscopy to monitor the spacings of fluorescent polystyrene particle 2-D arrays in response to changes in pH, solvent composition, temperature, etc.     

Application of sensitive hydrogels in chemical and pH sensors

In the present work, pH-sensitive poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) blends as well as hydrogels based on poly(N-isopropylacrylamide) (PNIPAAm), which are sensitive to organic solvent concentration in aqueous solutions, were used in silicon micromachined sensors. A sensitivity of approximately 15 mV/pH was obtained for a pH sensor with a 50 μm thick PVA/PAA hydrogel layer in a pH range above the acid exponent of acrylic acid (pK_a=4.7). The output voltage versus pH-value characteristics and the long-term signal stability of hydrogel-based sensors were investigated and the measurement conditions necessary for high signal reproducibility were determined. The influence of the preparation conditions of the hydrogel films on the sensitivity and response time of the chemical and pH sensors is discussed.     

Application of nanostructure ZnLI2 complex in construction of optical pH sensor

This is for the first time that application of complex nanostructure is reported as pH indicator in PVC matrix. This new optical pH sensor was constructed based on incorporation of ZnLI₂ complex nanostructure in PVC matrix. The synthesized nanostructure ZnLI₂ complex was characterized by SEM and XRD technique. The membrane solution was speared on the glass plate to provide thin film and the membrane surface morphology was investigated via field emission scanning microscope (FE‐SEM) technique. Central composite design (CCD) combined with desirability function (DF) was applied to find the best experimental composition of membrane providing the highest absorbance. These conditions were found in correspondence with 3 mg of pH indicator, 3 mg of ionic additive and 1.5 mg/mg of DBP/PVC weight ratio. Under optimum conditions, the proposed pH sensor has two linear working ranges of 4 ‐ 8 at 393 nm (R² = 0.9897) and 5 ‐ 8 (R² = 0.9982) at 570 nm with response time of 4 min. The pK_a of proposed pH optical sensor was calculated through three methods that found to be 5.63. The present optical sensor shows stability after 2 months without any significant divergence in response properties (less than 5% RSD). Furthermore, current pH optode was exhibited good repeatability (RSD = 1.14%) as well as reproducibility (RSD = 4.06%). No significant variation was observed on sensor response with increasing the ionic strength in the range of 0.0–0.5 M of sodium chloride. All above features indicated that the proposed sensor can be successfully used for detection of pH in solutions with different ionic strength.     

An ultrasensitive method of real time pH monitoring with complementary metal oxide semiconductor image sensor

CMOS sensors are becoming a powerful tool in the biological and chemical field. In this work, we introduce a new approach on quantifying various pH solutions with a CMOS image sensor. The CMOS image sensor based pH measurement produces high-accuracy analysis, making it a truly portable and user friendly system. pH indicator blended hydrogel matrix was fabricated as a thin film to the accurate color development. A distinct color change of red, green and blue (RGB) develops in the hydrogel film by applying various pH solutions (pH 1–14). The semi-quantitative pH evolution was acquired by visual read out. Further, CMOS image sensor absorbs the RGB color intensity of the film and hue value converted into digital numbers with the aid of an analog-to-digital converter (ADC) to determine the pH ranges of solutions. Chromaticity diagram and Euclidean distance represent the RGB color space and differentiation of pH ranges, respectively. This technique is applicable to sense the various toxic chemicals and chemical vapors by situ sensing. Ultimately, the entire approach can be integrated into smartphone and operable with the user friendly manner.