Impact of doping on the mechanical properties of conjugated polymers.

Conjugated polymers exhibit a unique portfolio of electrical and electrochemical behavior, which - paired with the mechanical properties that are typical for macromolecules - make them intriguing candidates for a wide range of application areas from wearable electronics to bioelectronics. However, the degree of oxidation or reduction of the polymer can strongly impact the mechanical response and thus must be considered when designing flexible or stretchable devices. This tutorial review first explores how the chain architecture, processing as well as the resulting nano- and microstructure impact the rheological and mechanical properties. In addition, different methods for the mechanical characterization of thin films and bulk materials such as fibers are summarized. Then, the review discusses how chemical and electrochemical doping alter the mechanical properties in terms of stiffness and ductility. Finally, the mechanical response of (doped) conjugated polymers is discussed in the context of (1) organic photovoltaics, representing thin-film devices with a relatively low charge-carrier density, (2) organic thermoelectrics, where chemical doping is used to realize thin films or bulk materials with a high doping level, and (3) organic electrochemical transistors, where electrochemical doping allows high charge-carrier densities to be reached, albeit accompanied by significant swelling. In the future, chemical and electrochemical doping may not only allow modulation and optimization of the electrical and electrochemical behavior of conjugated polymers, but also facilitate the design of materials with a tunable mechanical response.

Fine wettability control created by a photochemical combination method for inkjet printing on self-assembled monolayers.

Wettability tuning for organic solvents is demonstrated with the "combination method", a reversal of the conventional "cleavage method". Several advantages are inherent to this method: for example, the syntheses are simple, various surface-active groups can be used, and the reaction proceeds with a low-energy light source. The image shows the result after UV irradiation through a patterning mask.

What kind of "soft materials" can we design from molecular gels?

Since their discovery, over the years, molecular gels have been constantly drawing the attention of chemists from various scientific fields. Their structural softness together with the orderliness at the molecular level provides such molecules immense potential for the amplification of their properties. Using this chemistry, one can easily realize a macroscopic outcome from a molecular level modulation. This phenomenon is governed by the principle of supramolecular interactions that introduce a unique "reversibility" to the system. The new generation of gel chemistry is now tending more towards the development of new attractive functions to create smart materials for achieving outstanding response or unprecedented selectivity over a process. However, for the successful implementation of this mission, it is really essential to correlate gel functions with their structures. This focus review is an attempt to find such a correlation, which can motivate and stimulate this existing field towards precisely designing molecular gels for the desired functions.

Transcription of chirality in the organogel systems dictates the enantiodifferentiating photodimerization of substituted anthracene.

An organogelator (G) that contains 2-anthracenecarboxylic acid (2Ac) attached covalently to a gelator counterpart that consists of 3,4,5-tris(n-dodecan-1-yloxy)benzoic acid by means of a chiral amino alcohol linkage has been synthesized. G acts as an efficient gelator of organic solvents, including mixed solvents and chiral solvents. Photodimers isolated after the photoreaction of the gel samples display different degrees of stereoselectivity. In the gel state, the formation of head-to-head (h-h) photodimers is always favored over head-to-tail (h-t) photodimers. Enantiomeric excess (ee) values of the major h-h photodimers reached as high as -56% in the case of the gels with enantiomeric glycidyl methyl ethers. Here, the solvent chirality is outweighed by the intrinsic chirality of the gelator molecule. The packing of the chromophore in the gel state has been characterized by the absorption and the emission behaviors and their variations during the course of gel-to-sol phase transition. Whereas for the hexane gel, emission intensity increases with an increase in temperature, other systems show a decrease in emission intensity. Redshift of the lambda(max) in the gel spectra indicates the J-aggregate arrangement of the chromophores. Chiral transcription in the gel state has been investigated by CD spectroscopy, which shows a decrease in CD intensity during the gel-to-sol phase transition. The X-ray diffraction study clearly differentiates among the gels in terms of the order of molecular arrangements. The gel systems are categorized as strong, moderately strong, and weak, that originate from the cooperative or individual participations of intermolecular hydrogen-bonding and pi-pi interactions, fine-tuned by the solvent polarity and the gelation temperature. A simple model based on the experimental findings and the molecular preorientation as evidenced by the stereochemistry of the photodimers has been proposed.

Control of polythiophene redox potentials based on supramolecular complexation with helical schizophyllan.

A novel method to control polythiophene redox potentials based on supramolecular complexation with the native polysaccharide, schizophyllan (SPG) is reported, which can importantly improve air stability for easy handling and processing.

Studies on a new class of organogelator containing 2-anthracenecarboxylic acid: influence of gelator and solvent on stereochemistry of the photodimers.

A new class of binary organogelator (G1, G2 and G3) based on 2-anthracenecarboxylic acid (2Ac), attached noncovalently with the gelator counterpart containing a 3,4,5-tris(n-dodecyloxy)benzoylamide backbone has been developed. Among the three gelators, two (G2 and G3) are chiral containing D-alanine or L-2-phenylglycine moieties, respectively. They can act as efficient gelators of organic solvents with varying polarity depending upon the gelator systems. Gelator G1 even gelates chiral solvents. The photoirradiation of the gel samples produces photocyclodimers having different degrees of stereoselectivity for different systems. Gels with G1 and G2 produce head-to-head (h-h) photodimers as major products, whereas the stereoselectivity is reversed for the gels with G3 producing head-to-tail (h-t) photodimers as major products. Among those, G2/cyclohexane gel shows the highest degree of stereoselectivity, producing only h-h photodimers with some significant amount of chiral induction. Other chiral systems exhibit low to moderate chiral inductions. The gelator G1 can differentiate between the racemic and enantiomerically pure varieties of a solvent by exhibiting different gel melting temperatures (T(gel)). For different gel systems, T(gel) increases in all the cases as a consequence of photoreaction, except for the G2/cyclohexane gel, where a prominent gel-to-sol phase transition can be observed during the photoreaction. Hydrogen-bonding and pi-pi stacking interactions play the principal roles in constructing the gel structure. The morphologies of the gel systems vary between one-dimensional fibrils and a fibrillar network structure. In addition, the influences of the gelator and solvent polarity on the rate of photoreactions, photoproduct distributions as well as gel structures are investigated.

On the helical motif of the complexes created by association of helix-forming schizophyllan (SPG) and helix-forming polythiophene derivatives.

pi-Conjugated polymers can finely tune their electrical and optical properties in response to their conformational changes. We believe that a deeper understanding of their higher-order structures will stimulate further development of their applications. We had revealed that one helix-forming natural polysaccharide (SPG) and one polythiophene derivative (PT-1) formed a stable one-dimensional complex and in the polythiophene main chain a helical conformation was induced through the dynamic conformational changes. The objective of our present research is to obtain a better mechanistic understanding on the interaction between SPG and polythiophenes. Here we have used particular left- and right-handed helix-forming polythiophene derivatives (D- and L-POWTs, respectively) and studied their influence on the helical motif of the complexes. We observed that SPG interacts with both D- and L-POWTs through their dynamic conformational changes and both D- and L-POWTs form the right-handed co-helical complexes with SPG according to the inherent helical motif of SPG. In addition, it was confirmed that 1) the complexes do not coagulate in aqueous solution, and 2) the exchange in the helical motif can occur only when the polymers experience the denature-renature process. We believe, therefore, that the mechanism of the helical induction of the SPG/POWT complexes is very unique, being different from conventional equilibrium reactions.

Quantum dots arrangement and energy transfer control via charge-transfer complex achieved on poly(phenylene ethynylene)/schizophyllan nanowires.

Assemblies of organic and inorganic compounds in the nanoscale region have contributed to the development of novel functional materials toward future applications, including sensors and opto-electronics. We succeed in fabricating hybrid nanowires composed of a conjugated polymer and semiconductor quantum dots (QDs) by a supramolecular assembly technique. The 1-D fashion of the nanowire structure is obtained by the polymer wrapping of cationic poly(phenylene ethynylene) (PPE) with helix-forming polysaccharide schizophyllan (SPG). The electrostatic interaction between cationic PPE and anionic QDs affords the nanowires decorated with QDs. Upon addition of an acceptor molecule, tetranitrofluorenone (TNF), the charge-transfer (CT) complex between PPE and TNF is formed, resulting in energy transfer from the QDs to PPE arising from the induced spectral overlap. Furthermore, the employment of the conjugated polymer allows highly sensitive quenching of the QD's emission by raising the transmission efficiency to the CT complexed electron deficient sites along the polymer backbone.

An organogel system can control the stereochemical course of anthracene photodimerization.

A novel photoresponsive organogel with a binary gelator containing 2-anthracenecarboxylic acid shows a high degree of stereochemical control, resulting in head-to-head photocyclodimers exclusively together with significant enantiomeric excess induced by the chiral counterpart of the gelator.

Creation of polynucleotide-assisted molecular assemblies in organic solvents: general strategy toward the creation of artificial DNA-like nanoarchitectures.

The influence of added polynucleotide on the gelation ability of nucleobase-appended organogelators was investigated. Uracil-appended cholesterol gelator formed a stable organogel in polar organic solvents such as n-butanol. It was found that the addition of the complementary polyadenylic acid (poly(A)) not only stabilizes the gel but also creates the helical structure in the original gel phase. Thymidine and thymine-appended gelators can form stable gel in apolar solvents, such as benzene, where poly(A)-lipid complex can act as a complementary template for the gelator molecules to create the fibrous composites. Based on these findings, we can conclude that self-assembling modes and gelation properties of nucleobase-appended organogelators are controllable by the addition of their complementary polynucleotide in organic solvents. We believe, therefore, that the present system can open the new paths to accelerate development of well-controlled one-dimensional molecular assembly systems, which would be indispensable for the creation of novel nanomaterials based on organic compounds.

Controlled stability of the triple-stranded helical structure of a beta-1,3-glucan with a chromophoric aromatic moiety at a peripheral position.

We synthesized a semiartificial beta-1,3-glucan, curdlan with dialkylaniline groups (CUR-DA), that bears chromophoric aromatic groups at its peripheral positions. Spectroscopic studies as well as microscopic observations indicate that CUR-DA adopts a triple-stranded helical structure in water- or methanol-rich solutions of dimethyl sulfoxide (DMSO). This triple-stranded helical structure exhibits high thermal stability and resistance to base, attributes that are similar to those of the triple-stranded helical structure of native beta-1,3-glucans such as schizophyllan. Moreover, we found that the stability of the triple-stranded helical structure can be easily modulated by solvent composition and metal-ion (Zn2+) binding. As beta-1,3-glucan polysaccharides are known to serve as "polymeric" hosts, including certain DNA molecules, carbon nanotubes, and conjugated polymers, and complexation occurs only with the single-stranded structure, this information is very useful for the creation of these attractive polymeric composites, the controlled release of DNA, and so on.

Beta-1,3-glucan polysaccharide (schizophyllan) acting as a one-dimensional host for creating supramolecular dye assemblies.

We have demonstrated that one-dimensional supramolecular dye assemblies with a uniform diameter can be created by utilizing schizophyllan (SPG) as a one-dimensional host. In the supramolecular nanofibers, the dye molecules are assembled into the different aggregation modes depending on the preparation procedures. The findings establish that SPG is useful for creating the supramolecular nanofibers, where temporal superstructures can be stabilized by the SPG-specific helical higher-order structure. [structure: see text].

'Click chemistry' on polysaccharides: a convenient, general, and monitorable approach to develop (1-->3)-beta-D-glucans with various functional appendages.

(1-->3)-beta-D-Glucans having various functional appendages (lactoside, ferrocene, pyrene, and porphyrin) can be prepared in an convenient, quantitative, and regioselective manner through regioselective bromination-azidation of curdlan to afford 6-azido-6-deoxycurdlan followed by chemoselective [3+2]-cycloadditions with various functional modules bearing a terminal alkyne group. The ability to monitor reaction conversions is an additional advantage of this synthetic approach over the conventional direct modifications on polysaccharides; the reaction can be readily monitored based on the intensity of azido peaks in the in situ attenuated total reflection infrared spectra.

Oligosilane-nanofibers can be prepared through fabrication of permethyldecasilane within a helical superstructure of schizophyllan.

[chemical structure: see text]. Schizophyllan can interact with permethyldecasilane to produce the corresponding decasilane-nanofiber, in which the decasilane adopts helical conformations in a tubular hollow created by the helical superstructure of schizophyllan.

Poly(diacetylene)-nanofibers can be fabricated through photo-irradiation using natural polysaccharide schizophyllan as a one-dimensional mold.

Schizophyllan interacts with various 1,4-diphenylbutadiyne derivatives to induce their chirally-twisted packing. A series of referential experiments using other polysaccharides (amylose, pullulan, dextran, etc.) and a carbohydrate-appended detergent (dodecyl-beta-d-glucopyranoside) indicates that these 1,4-diphenylbutadiyne derivatives are accommodated within a tubular cavity constructed by a helical superstructure of schizophyllan. In these 1,4-diphenylbutadiyne derivatives, 1,4-bis(p-propionamidophenyl)butadiyne can be easily polymerized through UV-irradiation, in which schizophyllan acts as a one-dimensional mold to produce the corresponding poly(diacetylene)s with fibrous morphologies. Detailed investigations on this unique approach to prepare the nanofibers revealed that it includes two individual processes, that is, 1) UV-mediated polymerization of encapsulated 1,4-bis(p-propionamidophenyl)butadiyne to produce immature nanofibers and 2) their reorganization through hydrophobic interfiber interactions into ordered nanofibers. The other 1,4-diphenylbutadiyne derivatives could not be polymerized through UV-irradiation, indicating that the p-propionamido-functionalities play substantial roles for a suitable packing of the monomer for the polymerization. The other 1,4-diphenylbutadiyne derivatives, however, can be also polymerized through gamma-ray irradiation in the presence of schizophyllan to give the corresponding poly(diacetylene)-nanofibers, emphasizing the wide applicability of the schizophyllan-based strategy for polymerization of various 1,4-diphenylbutadiyne derivatives.

Schizophyllan-folate conjugate as a new non-cytotoxic and cancer-targeted antisense carrier.

Schizophyllan having folate-appendages was synthesized from native schizophyllan through NaIO(4)-oxidation and the subsequent reductive amination in aqueous ammonia followed by amido-coupling with folic acid. The resulting folate-appended schizophyllan can form stable complex with poly(dA), show specific affinity toward folate binding protein, and mediate effective antisense activity in cancer cells.