Colorimetric and fluorimetric pH sensing using polydiacetylene embedded within PVC-PCL nanofibers

The applicability of model polydiacetylenes (PDAs) in hydrogen ions sensitive optodes was tested. Nanofibers mats were electrospun using a mixture of polyvinyl chloride (PVC) and polycaprolactone (PCL) together with 10, 12-tricosadiynoic acid (TCDA) or 10,12-pentacosadiynoic acid (PCDA). After the polymerization the mats were applied in colorimetric and fluorimetric pH sensors. The PDAs were formed by photopolymerization with a UV lamp (254 nm), resulting in a change of mats color from white to dark blue. The morphology of both fiber mats is similar (SEM images), and the average diameters of fibers were estimated as equal to 228±73 and 248±61 nm for TCDA and PCDA, respectively. As the pH increases, the color of the fiber mat changes from blue to red and the process can be followed visually. The result obtained by computer image analysis showed a sigmoidal increase in the intensity of red and a decrease in the intensity of blue color with increasing pH. A similar sigmoidal response is observed for the dependence of the emission intensity on the pH. Changes in the recorded signal occur in the pH range from 7 to 8.5 or from 8 to 9.5 for mats with TCDA and PCDA, respectively. Both readout modes can be successfully used for pH sensing with proposed nanofibrous mats in the range of pH close to the physiological pH range.     

Effect of amphiphilic molecules upon chromatic transitions of polydiacetylene vesicles in aqueous solutions

Effect of amphiphilic molecules upon the chromatic transitions of polymerized 10,12-pentacosadiynoic acid (PCDA) vesicles in aqueous solutions was reported. The colorimetric response of polymerized PCDA vesicles for 1-pentanol is higher than that for ethanol due to more hydrophobic property of 1-pentanol. The colorimetric response of polymerized PCDA vesicles for sodium dodecyl sulfate (SDS) and Triton X-100 is lower than that for cetyltrimethylammonium bromide (CTAB). The strong ability of CTAB to induce chromatic transition of the vesicles is related to the positively charged headgroups of CTAB, which favors approach of CTAB to the negatively charged carboxylate groups at the vesicle surface. The insertion of alkyl chain of CTAB into the hydrophobic domain perturbs the conformation of the conjugated polymer backbone and induces color change of polydiacetylene vesicles. For a series of alkylamine hydrochloric salts, the longer the alkyl chain, the stronger the ability of alkylamine to induce chromatic transition of polydiacetylene vesicles.     

Effect of alkyl chain length on chemical sensing of polydiacetylene and polydiacetylene/ZnO nanocomposites

Polydiacetylenes (PDAs) and PDA/ZnO nanocomposites based on the monomers 10,12-pentacosadiynoic acid (PCDA), 10,12-tricosadiynoic acid (TCDA), and 10,12-docosadiynedioic acid (DCDA) monomers have been investigated for chromatic chemical sensing of a number of organic liquids. Chromatic sensitivity is associated with the interaction of the organic liquid with the PDA side chain to give rise to the strain-induced blue to red colorimetric transition. Attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy demonstrated that in the PDA/ZnO nanocomposites, the PDA side chains form chelates with ZnO. The chromatic properties of PDAs and PDA/ZnO composites in organic liquids, to certain extent, depend on the side-chain length and the number of carboxylic head groups. Pure PDAs and PDA/ZnO nanocomposites in different organic liquids studied by Raman spectroscopy show that the chromatic selectivity of PDAs for certain organic liquids with respect to the blue to red phase transition is closely related to the side-chain structure of the PDAs. Moreover, the interactions are stronger with those PDAs where the blue to red transition is irreversible. Density functional theory (DFT) simulations show that the chromatic sensitivity of the PDAs toward a particular organic correlates with the C–C bond torsion angle of the PDA backbone.     

Colorimetric and Fluorometric Detection of Neomycin Based on Conjugated Polydiacetylene Supramolecules

Utilizing the colorimetric and fluorogenic changes, a system based on polydiacetylenes (PDAs) is developed for the detection of neomycin. The PDA supramolecules polymerized from the mixed liposome composed of N‐(3‐hydroxyphenyl)pentacosa‐10,12‐diynamide (PCDA‐AP) and pentacosa‐10,12‐diynoic acid (PCDA) at an optimized ratio of 1:9 display a unique colorimetric change (blue to red) and fluorescent enhancement in the presence of neomycin. The detection limit for neomycin is estimated to be 2.55 × 10⁻⁷ M by the fluorogenic method. The optical changes induced by neomycin can be attributed to the disruption of the hydrogen bonding between phenol and carboxylic acid from PCDA‐AP and PCDA.

     

聚联乙炔囊泡负载的Bola型两亲分子识别三聚氰胺过程中Chaotrope促进型显色机制及热力学

用聚联乙炔囊泡为载体,将bola型两亲分子1,12-二乳清酸十二胺盐(DDO)对三聚氰胺的分子识别作用用肉眼可见的颜色变化显示出来.通过比较不同碳链长度的聚联乙炔囊泡对分子识别过程的反映,发现二十三烷基-2.4-二炔酸(TCDA)囊泡的显色灵敏度较高.研究表明,TCDA肉眼可见的颜色变化来自于DDO与三聚氰胺多重氢键的形成以及溶液环境中水结构的变化.为了更好地理解显色机理,用差示扫描量热(DSC)仪详细研究了分子识别过程中聚联乙炔囊泡的相变行为及热力学参数.结果表明:TCDA囊泡和带有识别分子的DDO/TCDA囊泡在三聚氰胺存在下,相变温度Tm均向高温方向移动,并且,随三聚氰胺浓度的增加,Tm值逐渐增大直至囊泡瓦解;但是Tm值的变化没有与囊泡变色必然关联,仅仅DDO/TCDA囊泡具有变色现象,而且,只有当三聚氰胺的浓度超过分子识别氢键形成所需理论量时,肉眼才能可见明显的由蓝到红的颜色变化.为了理解溶液中过量的三聚氰胺对囊泡变色的作用,选用蔗糖和尿素作为典型的水结构促进剂和水结构破坏剂(chaotrope),详细研究了它们对聚联乙炔囊泡反映分子识别过程中相变温度的影响及显色规律.结果表明,过量的三聚氰胺在溶液中起到类似尿素水结构破坏剂的作用.这种作用和分子识别过程中多重氢键的形成对聚联乙炔囊泡的变色缺一不可.本研究首次揭示了由水结构破坏剂参与的聚联乙炔囊泡变色机理,有助于理解共轭聚合物热相变过程中的Hofmeister效应.     

热致可逆变色的聚二炔／稀土离子纳米复合物

将Dy^＋或Sm^＋掺杂到具有层状结构的10,12-二十五碳二炔酸（PCDA）纳米粒子中,得到二炔酸／稀土离子（PCDA-RE）纳米复合物．随后在稍微高于二炔酸熔点的温度下对PCDA—RE纳米复合物进行退火处理,退火后的PCDA—RE纳米复合物发生拓扑聚合反应得到聚二炔酸／稀土离子（PDA-RE）纳米复合物．虽然纯聚二炔酸的热致变色过程是不可逆的,但是PDA—Sm纳米复合物和PDA-Dy纳米复合物分别具有不完全和完全热致可逆变色的性能．研究表明,PDA-RE纳米复合物的层间距为5,4nm,比纯聚二炔酸的层间距（4．7nm）要大．对于PDA—RE纳米复合物,稀土离子和聚二炔酸之间的强相互作用是纳米复合物实现大部分或完全可逆变色的原因．同时退火处理对实现聚二炔酸可逆变色非常重要,因为退火处理消除了材料结构中的所有缺陷,最终促使材料具有热致可逆变色性能．     

Assembly of polydiacetylene vesicles on solid substrates

A method to create assembly of polydiacetylene vesicles on solid substrates in a novel fashion is described. The formation of the assembly is based on electrostatic layer-by-layer deposition using negatively charged 10,12-pentacosadiynoic acid (PCDA) vesicles and polyelectrolyte polyethylenimine, or positively charged PCDA-2(')-aminoethylamide (PCDANH2) vesicles. This is an efficient method for preparing the chromatic sensor films of polydiacetylene vesicles after ultraviolet light irradiation. The strategy would be useful in the development of polydiacetylene-based chemosensors and biosensors.     

以物理力将糖脂引入聚联乙炴基质脂的变色囊泡

囊泡具有与生物膜结构类似的封闭双分子层结构,具有模拟生物膜结构的突出优点,因此受到人们的极大重视．因为它具有胶体粒子的大小尺寸,其表面膜的性质易于控制,具有较大的输送客最以及生物相容性,因此,囊泡在药物的传输、基因治疗、癌症的化学治疗、分子识别、分子光学器件的组装、超细颗粒的制备、太阳能转化及反应性能的控制等领域都具有十分重要的意义．然而,在分子识别及药物输送过程中,由丁蟹池的稳定性差而严重影响其应用．聚合表面活性剂囊泡的出现较好地解决了其稳定性差的问题．在众多的可聚合的表面活性剂单体中,具有联…     

Chromatic immunoassay based on polydiacetylene vesicles

A new approach of chromatic immunoassay based on polydiacetylene vesicles is described. Antibodies were covalently coupled with mixed vesicles of 10,12-tricosadiynoic acid (TCDA) and dimyristoylphosphatidycholine (DMPC). The vesicle-antibody conjugates were irradiated with UV light to yield a blue-colored polydiacetylene. After antigen injection, specific immunoreactions took place at the vesicle surface alter polydiacetylene conformation and lead to a color change from blue to red. The chromatic immunoassay described here is simple, rapid, sensitive; the color change was readily discernible by naked eye when the concentration of antigen is 1 ng/mL. Incorporation of DMPC in the mixed vesicles increases the sensitivity of the chromatic immunoassay.     

Microbead-assisted PDA sensor for the detection of genetically modified organisms

A simple and sensitive approach for the detection of marker protein, phosphinothricin acetyltransferase, from genetically modified crops was developed based on the colorimetric transition of polydiacetylene (PDA) vesicles in combination with silica microbeads. PDAs have attracted a great deal of interests as a transducing material due to their special features that allow colorimetric response to sensory signals, as well as their inherent simplicity. However, most PDA-based biosensors require additional analytical equipment such as a fluorescence microscope or UV–Vis spectrometer. In this study, we report a new approach to increase the degree of color transition by coupling antibody-conjugated PDA vesicles with silica microbeads in an effort to monitor the results with the unaided eye or simple RGB analysis. By immobilizing PDA vesicles on silica microbeads, we were able to overcome the disadvantages of colloidal PDA-based sensors and increase the degree of colorimetric changes in response to target molecules to a concentration as low as 20 nM. The additional stresses were given to PDA vesicles by antigen–antibody bridging of PDA vesicles coupled with microbeads, resulting in enhanced blue–red color transition. All the results showed that PDA vesicles in conjunction with silica microbeads will be a promising transducing material for the detection of target proteins in diagnostic and biosensing applications.     

Copper-catalyzed azide-alkyne cycloaddition in the synthesis of polydiacetylene: "click glycoliposome" as biosensors for the specific detection of lectins

Supramolecular self-assembly of conjugated diacetylenic amphiphile-tethered ligands photopolymerize to afford polydiacetylene (PDA) functional liposomes. Upon specific interaction with a variety of biological analytes in aqueous solution, PDA exhibits rapid colorimetric transitions. The PDA nanoassemblies, which are excellent membrane mimics, include an ene-yne polymeric reporter responsible for the chromatic transitions and the molecular recognition elements that are responsible for selective and specific binding to the biological target. A bottleneck in the fabrication of these colorimetric biosensors is the preparation of the diacetylenic monomer embedded with the recognition element of choice. In the present work, we make use of copper-catalyzed azide-alkyne cycloaddition (CuAAC) as key step in the preparation of sugar-coated liposome biosensors. The regioselective click ligation of the triacetylenic N-(2-propynyl)pentacosa-10,12-diynamide (NPPCDAM) with a variety of mannose- and lactose-tethered azides afforded chemo- and regioselectively the corresponding 1,2,3-triazole. The obtained diacetylenic monomers were incorporated efficiently into vesicles to afford functional mannose- and lactose-coated glycoliposomes. The obtained PDA-based click glycoliposomes have been characterized by using transmission electronic microscopy (TEM), dynamic light scattering (DLS), and UV/Vis spectroscopy. The efficiency of the reported approach was demonstrated by the rapid optimization of the hydrophilic spacer between the lipidic matrix and the mannose head group for the colorimetric detection of Concavalin A.     

Preparation of optical active polydiacetylene through gelating and the control of supramolecular chirality

Achiral diacetylene 10,12-pentacosadinoic acid (PCDA) and a chiral low-molecular-weight organogelator could form co-gel in organic solvent and it could be polymerized in the presence of Zn(II) ion or in the corresponding xerogel under UV-irradiation. Optically active polydiacetylene (PDA) were subsequently obtained. Supramolecular chirality of PDA could be controlled by the chirality of gelators. Left-handed and right-handed helical fibers were obtained by using Land D-gelators in xerogels respectively, and...     

Design of polydiacetylene-phospholipid supramolecules for enhanced stability and sensitivity

We present polydiacetylene (PDA) liposome assemblies with various phospholipids that have different headgroup charges and phase transition temperatures (T(m)). 10,12-Pentacosadiynoic acid (PCDA)-epoxy was used as a base PDA monomer and the insertion of highly charged phospholipids resulted in notable changes in the size of liposome and reduction of the aggregation of PDA liposome. Among the various phospholipids, the phospholipid with a moderate T(m) demonstrated enhanced stability and sensitivity, as measured by the size and zeta potential over storage time, thermochoromic response, and transmission electron microscopy images. By combining these results, we were able to detect immunologically an antibody of bovine viral diarrhea virus over a wide dynamic range of 0.001 to 100 μg/mL.     

Electronic absorption spectroscopy probed side-chain movement in chromic transitions of polydiacetylene vesicles

Thermochromism, solvatochromism, and alkalinochromism of a poly-10,12-pentacosadiynoic acid (poly(PCDA)) vesicle solution are studied by electronic absorption spectroscopy. The spectroscopic profiles reveal different sequences of side-chain movement during the chromic transitions. The gradual hypsochromic shift and reversibility of the purple solution at low temperature in the thermochromic transition indicates that the transition starts with reversible conformational alteration of methylene side chains leading to metastable purple vesicles. Further heating to 80 degrees C or higher eventually causes the hydrogen bonds at the carboxylic head groups to break and turns the vesicle solution to red. The irreversibility of the red vesicles indicates that it is the most thermodynamically stable form. In the ethanolochromism and alkalinochromism, the processes are however induced at the vesicle-media interface, directly bringing about the hydrogen bond breaking. The purple solutions observed in the ethanolochromism and alkalinochromism cannot reverse back to the blue one. The absorption spectra clearly demonstrate that they are mixtures of the blue and red vesicles.     

Aqueous sols of oligo(ethylene glycol) surface decorated polydiacetylene vesicles for colorimetric detection of Pb 2+

A series of ethylene glycol (EG), triethylene glycol (3EG) and pentaethylene glycol (5EG) esters of 10,12-pentacosadiynoic acid (PCDA) are synthesized. The glycol ester lipids can be hydrated and well dispersed in water but they cannot form polydiacetylenes upon UV irradiation. They however can be mixed with PCDA up to 30 mol% and polymerized to form blue sols. The mixed polydiacetylene sols show blue to red thermochromic transition with two-stepped transition temperatures. The first transition temperature decreases with the increase of the glycol ester content as well as the length of their chains indicating greater fluidity of the self-assembled structure due to less collaborative hydrogen bonding among the lipid head groups. These mixed polydiacetylene sol prepared from 30 mol% of the penta(ethylene glycol) ester show linear colorimetric response selectively to Pb²⁺ in the range of 5-30 μM.     

Self-suspended Pure Polydiacetylene Nanoparticles with Selective Response to Lysine and Arginine

We demonstrate a very convenient access to self-suspended pure poly(10,12-pentacosadiynoic acid) (PDA) nanoparticles (NPs) simply by adding the ethanol solution of diacetylene monomer to water, followed by UV irradiation. The as-obtained PDA NPs are of high purity because no any initiator, catalyst or stabilizer was used during the whole process. The stabilizer-free PDA NPs are stable in the aqueous suspension. Due to the high purity and stability, the PDA NPs can respond sensitively and selectively to lysine and arginine among 18 kinds of water soluble natural amino acids; without the competitive interaction from the stabilizer, the sensitivity was enhanced.     

糖脂功能化聚二乙炔Langmuir-Schaefer薄膜与大肠杆菌的分子识别及动力学过程研究

在气液界面上研究了α-D-甘露糖苷-十六烷(MC₁₆)与10,12-二十五碳双炔酸混合单分子膜行为,二者具有较好的互溶性.在疏水的玻璃衬底上用Langmuir-Schaefer(LS)薄膜技术制备单层MC₁₆/PDA薄膜,研究了这种仿生薄膜与大肠杆菌jm109的相互作用.大肠杆菌jm109对MC₁₆修饰的聚二乙炔LS薄膜的吸附,使薄膜颜色由蓝色变为红色,用紫外-可见吸收光谱可进行定量检测.动力学研究显示比色响应值随时间的增加而增加,3min内即有显著变化,15min后趋于饱和,20min后CR值达到28%,进一步探讨了分子识别的动力学过程.     

Polydiacetylene‐Based Electrospun Fibers for Detection of HCl Gas

Polydiacetylenes (PDAs), a family of conjugated polymers, are very intriguing materials in several aspects. Especially, the stimulus‐induced apparent blue‐to‐red transition of the PDAs has led to the development of a variety of PDA‐based chemosensors. In the current work, we synthesized PDA monomers bearing trimethyl amine (PCDA‐DMEDA) and incorporated them with Poly(ethylene oxide) (PEO) into electrospun fibers. For the first time, we successfully demonstrated that PDA‐based electrospun fibers can be used for the naked‐eye detection of HCl gas by simple color change (blue to red).     

Deliberately designed processes to physically tether the carboxyl groups of poly(pentacosadiynoic acid) to a poly(vinyl alcohol) glassy matrix to make poly(pentacosadiynoic acid) thermochromically reversible in the matrix

In this article, we demonstrate that by tethering carboxyl groups of poly(10,12-pentacosadiynoic acid) (PDA) to a poly(vinyl alcohol) (PVA) matrix, PDA, which is irreversible in its pure form, becomes reversible in the thermochromism. The tethering is realized by simple but deliberately designed processes: (1) Disperse the commercially available monomer 10,12-pentacosadiynoic acid (DA) nanocrystals in a PVA aqueous solution by the "NCCM" method invented in our laboratory. (2) Anneal and dry the mixture solution at a temperature higher than the melting point of pure DA crystal. (3) Polymerize the as-annealed DA/PVA blend films by UV irradiation. After the polymerization, PDA/PVA films with completely reversible thermochromism are obtained. The reversible PDA/PVA films can be easily dissolved in water, leading to water-dispersible nanoaggregates with the reversibility. Blends of PDA with other water-soluble polymers such as poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA) and poly(allyamine) (PAM), were prepared respectively, by the same processes and under the same conditions. It is found that all these nanocomposites are irreversible or partially reversible in the thermochromism; either the relatively low glassy transition temperature of the polymer matrix (in the case of PEO) or the partial ionization nature of the polymer (in the cases of PAA and PAM) is responsible for the irreversibility or the partial reversibility.     

A colorimetric and fluorescent chemosensor for detection of Hg2+ using counterion exchange of cationic polydiacetylene

In this study, a colorimetric and fluorescent chemosensor for mercury ions (Hg²⁺) was developed. Cationic polydiacetylene (PDA) vesicles with a quaternary ammonium cation and iodide as a counterion show a blue-to-red color transition; the color change is accompanied by a fluorescence enhancement in selective response to Hg²⁺ ions because of a perturbation of the ene–yne conjugated backbone induced by counterion exchange. It allows for selective detection of Hg²⁺ with the naked eye and the sensor is used to determine Hg²⁺ concentrations in tap water samples.