Solvent colorimetric paper-based polydiacetylene sensors from diacetylene lipids

A well known unique property of polydiacetylenes (PDAs) is the colorimetric response to external stimuli making it one of the most studied conjugated polymers for sensing applications. Here we report the synthesis of a novel series of diacetylene acids from the condensation of pentacosa-10,12-diynylamine (PCDAmine) and dicarboxylic acid or its anhydrides. One of these diacetylene lipids, 4-(pentacosa-10,12-diynylamino)-4-oxobutanoic acid (PCDAS), is used in combination with pentacosa-10,12-diynoic acid (PCDA) for dropcasting on pieces of filter paper which are consequently irradiated by UV light to generate a paper based sensor array for solvent detection and identification. Upon the exposure to various types of organic solvents, the blue colored sensors colorimetrically respond to give different shades of colors between blue to red. The color patterns of the sensor array are recorded as RedGreenBlue (RGB) values and statistically analyzed by principal component analysis (PCA). The PCA score plot reveals that the array is capable of identifying eleven common organic solvents.     

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).     

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.     

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.     

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.     

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.

     

Polydiacetylene/silica nanocomposites with tunable mesostructure and thermochromatism from diacetylenic assembling molecules

Conjugated polydiacetylene (PDA)/silica nanocomposites with tunable mesostructures and reversible thermochromatism were synthesized through self-directed assembly of diacetylenic silanes. In contrast to the previous studies, where the PDA side chains interacted weakly through noncovalent interactions, the side chains in the present nanocomposites are covalently connected to the inorganic silica frameworks, providing control over the molecular alignment, stability, and electronic properties. Furthermore, tuning the molecular architecture (e.g., the shape and side-chain length) allows control over the mesostructure (e.g., cubic and lamellar) and chromatic response of the nanocomposites (from irreversible to partially reversible and then to completely reversible). As a result of the covalent interactions, the nanocomposites also demonstrate higher reversible chromatic transition temperatures. This work not only provides responsive robust chromatic materials toward practically reusable PDA sensors but also is of great fundamental value for the design of supramolecular assembly and the understanding of the chromatic mechanism of PDA.     

Effect of metal cations on polydiacetylene Langmuir films

Polydiacetylene (PDA) Langmuir films (LFs) are a unique class of materials that couple a highly aligned conjugated backbone with tailorable pendant side groups and terminal functionalities. The films exhibit chromatic transitions from monomer to blue polymer and finally to a red phase that can be activated optically, thermally, chemically, and mechanically. The properties of PDA LFs are strongly affected by the presence of metal cations in the aqueous subphase of the film due to their interaction with the carboxylic head groups of the polymer. In the present study the influence of divalent cadmium, barium, copper, and lead cations on the structural, morphological, and optical properties of PDA LFs was investigated by means of surface pressure-molecular area (π-A) isotherms, atomic force microscopy, optical absorbance, and Raman spectroscopy. The threshold concentrations for the influence of metal cations on the film structure, stability, and phase transformation were determined by π-A analyses. It was found that each of the investigated cations has a unique influence on the properties of PDA LFs. Cadmium cations induce moderate phase transition kinetics with reduced domain size and fragmented morphology. Barium cations contribute to stabilization of the PDA blue phase and enhanced linear strand morphology. On the other hand, copper cations enhance rapid formation of the PDA red phase and cause fragmented morphology of the film, while the presence of lead cations results in severe perturbation of the film with only a small area of the film able to be effectively polymerized. The influence of the metal cations is correlated with the solubility product (K(sp)), association strength, and ionic-covalent bond nature between the metal cations and the PDA carboxylic head groups.     

Enhanced affinochromism of polydiacetylene monolayer in response to bacteria by incorporating CdS nano-crystallites

By incorporating bio-specific receptors, such as p-10,12-pentacosadiyne-1-N-(3,6,9-trioxaundecylamide)-alpha-D-mannopyranoside (MPDA), into 10,12-pentacosadiyonic acid (PDA) monolayer, the MPDA/PDA monolayer underwent affinochromatic transition in response to the bacteria binding to the receptor. Here, we described a new method to study the membrane/macromolececular interaction between Escherichia coli (E. coli) and mannose and its relative affinochromism by modifying MPDA/PDA with CdS nano-crystallites (MPDA/PDA-CdS). CdS not only triggered the strong tropism of the bacteria but also reduced the rigidity of the MPDA/PDA backbone, resulting in the enhanced affinochromism. This discovery might be of significance in basic biophysical studies of membrane/macromolececular and designing novel biosensor.     

Roles of head group architecture and side chain length on colorimetric response of polydiacetylene vesicles to temperature, ethanol and pH

In this contribution, we report the relationship between molecular structures of polydiacetylene (PDA) vesicles, fabricated by using three monomers, 10,12-tricosadiynoic acid (TCDA), 10,12-pentacosadiynoic acid (PCDA) and N-(2-aminoethyl)pentacosa-10,12-diynamide (AEPCDA), and their color-transition behaviors. The modification of side chain length and head group of the PDA vesicles strongly affects the colorimetric response to temperature, ethanol and pH. A shorter side chain of poly(TCDA) yields weaker inter- and intra-chain dispersion interactions in the bilayers compared to the system of poly(PCDA), which in turn results in a faster color transition upon exposure to all stimuli. A change of head group in poly(AEPCDA) slightly reduces the transition temperature. Interestingly, the colorimetric response of poly(AEPCDA) vesicles to the addition of ethanol is found to occur in a two-step fashion while the response of poly(PCDA) vesicles takes place in a one-step process. The amount of ethanol required for inducing complete color-transition of poly(AEPCDA) vesicles is also much higher, about 87% v/v. The increase of pH to ~9 and ~10 causes a color-transition of poly(TCDA) and poly(PCDA) vesicles, respectively. The poly(AEPCDA) vesicles, on the other hand, change color upon decreasing pH to ~0. The colorimetric response also occurs in a multi-step fashion. These discrepancies are attributed to the architecture of surface layers of poly(AEPCDA), constituting amine and amide groups separated by ethyl linkers.     

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...     

Micro‐Patterning of Polydiacetylene Supramolecules using Micromolding in Capillaries (MIMIC)

Micrometer‐sized polydiacetylene (PDA) vesicle patterns on titanium substrates have been successfully fabricated by using a micromolding in capillaries (MIMIC) technique. The shape and width of the PDA patterns are well matched with polydimethylsiloxane (PDMS) molds used in the MIMIC process. However, the thicknesses of the patterned films are less than the depths of the PDMS molds, which may be a consequence of the poor water wettability of the PDMS and/or low concentrations of the PDA solutions. Heat‐treatment of the solid substrate, immobilized with blue‐phase PDAs, induces a blue‐to‐red‐phase transition and results in the formation of patterned fluorescence images.

     

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.     

Polydiacetylene‐Tb3+ Nanosheets of Which Both the Color and the Fluorescence Can Be Reversibly Switched between Two Colors

Polydiacetylenes (PDAs), an organic layered compound, show a series of intriguing properties, such as thermochromism and fluorescence emission in the red‐phase. However, their irreversible color change, and weak and single‐color fluorescence emitted only from the red‐phase PDAs, have limited their applications. Herein, we report double‐reversible PDA‐Tb³⁺ nanosheets of which both the color and the fluorescence can be reversibly switched between two colors. PDA‐Tb³⁺ nanosheets have the nearly defect‐free intercalated structure in which a layer of Tb³⁺ ions was intercalated in between each two PDA bilayers to tether almost all of the carboxyl groups at the end of the side chains of the PDA. When the PDA is in the blue phase, the PDA‐Tb³⁺ nanosheets emit the green fluorescence of Tb³⁺ ions. When the PDA is in the red phase, the Tb³⁺ fluorescence disappears while the intrinsic red fluorescence of PDA is effectively enhanced through the fluorescence resonance energy transfer (FRET) process; the PDA‐Tb³⁺ nanosheets emit stronger red fluorescence compared with the PDA in red phase. Moreover, the tethering of almost all of the carboxyl groups at the end of the side chains of the PDA endows the nanosheets with the double reversibility in both the color and fluorescence transitions.     

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.     

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.     

Enantioselective recognition between polydiacetylene nucleolipid monolayers and complementary oligonucleotides

A two-dimensional bio/synthetic hybrid system at the air-solution interface made of a polymerized diacetylene Langmuir film with nucleobase modified headgroups is presented. The polymerized film presents a crystalline array of nucleobases, capable of specific binding of complementary mononucleoside or oligonucleotide sequences. Mixed monolayers of the linear polyconjugated polydiacetylene (PDA) films derivatized with cytosine (10,12-pentacosadiyne-cytidyl, PDC) monomers and alcohol-terminated diacetylene lipid (10,12-pentacosadiynol, PDOH) at a 3:1 ratio (PDC 75%) were compressed and polymerized at the air-water interface with circular polarized light (CPL) or nonpolarized UV light. Here we report a grazing incidence X-ray diffraction (GIXD) investigation of PDC films polymerized to different chirality and hybridized with complementary ssDNA strands. We have demonstrated enantioselective interactions on synthetic structured interfaces produced by Langmuir surface compression followed by polymerization with circular polarized UV light (CPL). The left- and right-CPL polymerized light exhibit the same well-defined crystalline structure. The observed difference between left- and right-CPL polymerized PDC 75% Langmuir films compressed over the complementary mononucleotide guanosine or hybridized with fully complementary ssG(12)T(5) oligonucleotide in the subphase suggests that they are indeed enantiomeric structures, capable of enantioselective binding of their natural ligand, guanosine, solely as a result of surface induced asymmetry in "left" but not in "right" form. This observation may also be related to the intriguing question of chiral selection during the early period of "Origin of Life". We show that achiral compounds, as a result of irradiation with circular polarized light, can organize in chiral surface structures capable of amplification of biopolymer binding of particular handedness.     

Blue-to-red chromatic sensor composed of gold nanoparticles conjugated with thermoresponsive copolymer for Thiol sensing

We describe the first determination of thiol compounds with gold nanocomposites composed of gold nanoparticles and thermoresponsive copolymers having polyamino groups. The gold nanocomposites, which are used as a chromatic sensor, reveal chromatic change from blue to red with thermal stimuli, heating followed by cooling the solution. The blue-to-red chromatic change results from disassembly of the gold nanocomposites, which arises from shrinkage of the thermoresponsive copolymers bound to the gold nanoparticle surfaces due to the phase transition induced by thermal stimuli. The disassembly is inhibited by addition of thiol compounds through displacement of the adhered thermoresponsive copolymers. The detached copolymers no longer influence morphological change of the gold nanocomposites. Corresponding with increase of concentration of the thiol compounds, a solution of the gold nanocomposites after the thermal stimuli shows chromatic change, which was quantified with the a* value in L*a*b* chromatic coordinates. A linear relationship between the a* value and concentration of cysteine, examined as a bio-important thiol, is obtained below 7x10(-6) mol dm(-3), estimating a detection limit defined as 3sigma of the blank to be 2.8x10(-7) mol dm(-3). The chromatic sensor of the gold nanocomposites is applied to the determination of cysteine in commercial supplements containing ascorbic acid, which seriously interferes with redox-based determination of cysteine. Analytical results obtained with the chromatic sensor are identical to those obtained with HPLC.     

Biosensors and chemosensors based on the optical responses of polydiacetylenes

Polydiacetylenes (PDAs), a family of conjugated polymers, have very unique electrical and optical properties. Upon environmental stimulation, such as by viruses, proteins, DNAs, metal ions, organic molecules etc., the blue PDAs can undergo a colorimetric transition from blue to red, which is accompanied by a fluorescence enhancement. Since the first report on polymerized diacetylene molecules as sensors of influenza virus, the development of efficient sensory systems based on PDAs continues to be of great interest. This tutorial review highlights the recent advances in bio- and chemo-sensors derived from polydiacetylenes.     

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．