Intense Chiral Optical Phenomena in Racemic Polymers by Cocrystallization With Chiral Guest Molecules: A Brief Overview

This review is devoted to the chiral optical behavior of films of racemic polymers whose chirality is induced by cocrystallization with nonracemic (also temporary) guest molecules. We provide examples of macromolecular amplification of chirality, produced by molecular and supramolecular mechanisms, on industrially relevant polymers like poly(2,6‐dimethyl‐1,4‐phenylene)oxide (PPO) and syndiotactic polystyrene (s‐PS). Chirality 28:29–38, 2016. © 2015 Wiley Periodicals, Inc.     

Quirks of dye nomenclature. 6. Malachite green

Malachite green was discovered independently by two researchers in Germany in the 19^th century and found immediate employment as a dye and a pigment. Subsequently, other uses, such as staining biological specimens, emerged. A much later application was the control of fungal and protozoan infections in fish, for which the dye remains popular, although illegal in many countries owing to a variety of toxicity problems. In solution, malachite green can exist as five different species depending on the pH. The location of the positive charge of the colored cation on a carbon atom or a nitrogen atom is still debated. The original names of this dye, and their origins, are briefly surveyed.     

Single‐Ion Conducting Electrolyte Based on Electrospun Nanofibers for High‐Performance Lithium Batteries

Herein, a novel electrospun single‐ion conducting polymer electrolyte (SIPE) composed of nanoscale mixed poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) and lithium poly(4,4′‐diaminodiphenylsulfone, bis(4‐carbonyl benzene sulfonyl)imide) (LiPSI) is reported, which simultaneously overcomes the drawbacks of the polyolefin‐based separator (low porosity and poor electrolyte wettability and thermal dimensional stability) and the LiPF₆ salt (poor thermal stability and moisture sensitivity). The electrospun nanofiber membrane (es‐PVPSI) has high porosity and appropriate mechanical strength. The fully aromatic polyamide backbone enables high thermal dimensional stability of es‐PVPSI membrane even at 300 °C, while the high polarity and high porosity ensures fast electrolyte wetting. Impregnation of the membrane with the ethylene carbonate (EC)/dimethyl carbonate (DMC) (v:v = 1:1) solvent mixture yields a SIPE offering wide electrochemical stability, good ionic conductivity, and high lithium‐ion transference number. Based on the above‐mentioned merits, Li/LiFePO₄ cells using such a SIPE exhibit excellent rate capacity and outstanding electrochemical stability for 1000 cycles at least, indicating that such an electrolyte can replace the conventional liquid electrolyte–polyolefin combination in lithium ion batteries (LIBs). In addition, the long‐term stripping–plating cycling test coupled with scanning electron microscope (SEM) images of lithium foil clearly confirms that the es‐PVPSI membrane is capable of suppressing lithium dendrite growth, which is fundamental for its use in high‐energy Li metal batteries.     

Steric Engineering of Alkylthiolation Side Chains to Finely Tune Miscibility in Nonfullerene Polymer Solar Cells

Morphology and miscibility control are still a great challenge in polymer solar cells. Despite physical tools being applied, chemical strategies are still limited and complex. To finely tune blend miscibility to obtain optimized morphology, chemical steric engineering is proposed to systemically investigate its effects on optical and electronic properties, especially on a balance between crystallinity and miscibility. By changing the alkylthiol side chain orientation different steric effects are realized in three different polymers. Surprisingly, the photovoltaic device of the polymer PTBB‐m with middle steric structure affords a better power conversion efficiency, over 12%, compared to those of the polymers PTBB‐o and PTBB‐p with large or small steric structures, which could be attributed to a more balanced blend miscibility without sacrificing charge‐carrier transport. Space charge‐limited current, atomic force microscopy, grazing incidence wide angle X‐ray scattering, and resonant soft X‐ray scattering measurements show that the steric engineering of alkylthiol side chains can have significant impacts on polymer aggregation properties, blend miscibility, and photovoltaic performances. More important, the control of miscibility via the simple chemical approach has preliminarily proved its great potential and will pave a new avenue for optimizing the blend morphology.     

An Ultra‐Mechanosensitive Visco‐Poroelastic Polymer Ion Pump for Continuous Self‐Powering Kinematic Triboelectric Nanogenerators

A mechanosensitive, visco‐poroelastic polymer ion pump that can rapidly establish a dense electrical double layer via mechanical pressure, thereby significantly enhancing output performance of an ionic triboelectric nanogenerator (iTENG), is described. A working mechanism of an iTENG using a highly mechanosensitive, visco‐poroelastic ion pump is suggested and the optimal characteristics of the polymer ion pump are reported by investigating optical, mechanical, electrical, and electrochemical properties. Surprisingly, the pressure sensitivity of the iTENG reaches 23.3 V kPa^?1, which is tens of times the record value. To achieve controlled high‐frequency pulses from an iTENG, kinematic systems using a gear train and a cam are integrated with a single grounded iTENG, which produces a maximum of 600 V and 22 mA (≈2.2 W cm^?2) at an input frequency of 1.67 Hz; after power transforming, those values are converted to 1.42 V and 225 mA. A capacitor of 1 mF can be fully charged to 2 V in only 60 s, making it possible to continuously operate a wireless‐communicating self‐powered humidity sensor. Also, due to the high transparency and deformability of the polymer ion pump, a self‐powered transparent tactile sensor is successfully assembled using a 5 × 5 iTENG array.     

Room Temperature Processed Highly Efficient Large‐Area Polymer Solar Cells Achieved with Molecular Engineering of Copolymers

The room temperature (RT) processability of the photoactive layers in polymer solar cells (PSCs) from halogen‐free solvent along with their highly reproducible power conversion efficiencies (PCEs) and intrinsic thickness tolerance are extremely desirable for the large‐area roll‐to‐roll (R2R) production. However, most of the photoactive materials in PSCs require elevated processing temperatures due to their strong aggregation, which are unfavorable for the industrial R2R manufacturing of PSCs. These limiting factors for the commercialization of PSCs are alleviated by synthesizing random terpolymers with components of (2‐decyltetradecyl)thiophen‐2‐yl)naphtho[1,2‐c:5,6‐c′]bis[1,2,5]thiadiazole and bithiophene substituted with methyl thiophene‐3‐carboxylate (MTC). In contrast to the temperature‐dependent PNTz4T polymer, the resulting random terpolymers (PNTz4T‐MTC) show better solubility, slightly reduced crystallinity and aggregation, and weaker intermolecular interaction, thus enabling PNTz4T‐MTC to be processed at RT from a halogen‐free solvent. Particularly, the PNTz4T‐5MTC‐based photoactive layer exhibits an excellent PCE of 9.66%, which is among the highest reported PCEs for RT and ecofriendly halogen‐free solvent processed fullerene‐based PSCs, and a thickness tolerance with a PCE exceeding 8% from 100 to 520 nm. Finally, large‐area modules fabricated with the PNTz4T and PNTz4T‐5MTC polymer have shown 4.29% and 6.61% PCE respectively, with an area as high as 54.45 cm² in air.     

Bringing Conducting Polymers to High Order: Toward Conductivities beyond 105 S cm−1 and Thermoelectric Power Factors of 2 mW m−1 K−2

Here, an effective design strategy of polymer thermoelectric materials based on structural control in doped polymer semiconductors is presented. The strategy is illustrated for two archetypical polythiophenes, e.g., poly(2,5‐bis(3‐dodecyl‐2‐thienyl)thieno[3,2‐b]thiophene) (C₁₂‐PBTTT) and regioregular poly(3‐hexylthiophene) (P3HT). FeCl₃ doping of aligned films results in charge conductivities up to 2 × 10⁵ S cm^?1 and metallic‐like thermopowers similar to iodine‐doped polyacetylene. The films are almost optically transparent and show strongly polarized near‐infrared polaronic bands (dichroic ratio >10). The comparative study of structure–property correlations in P3HT and C₁₂‐PBTTT identifies three conditions to obtain conductivities beyond 10⁵ S cm^?1: i) achieve high in‐plane orientation of conjugated polymers with high persistence length; ii) ensure uniform chain oxidation of the polymer backbones by regular intercalation of dopant molecules in the polymer structure without disrupting alignment of π‐stacked layers; and iii) maintain a percolating nanomorphology along the chain direction. The highly anisotropic conducting polymer films are ideal model systems to investigate the correlations between thermopower S and charge conductivity σ. A scaling law S ∝ σ^?1/4 prevails along the chain direction, but a different S ∝ ?ln(σ) relation is observed perpendicular to the chains, suggesting different charge transport mechanisms. The simultaneous increase of charge conductivity and thermopower along the chain direction results in a substantial improvement of thermoelectric power factors up to 2 mW m^?1 K^?2 in C₁₂‐PBTTT.     

A molecularly imprinted polymer based chemiluminescence array sensor for one‐step determination of phenothiazines and benzodiazepines in pig urine

The residues of phenothiazines and benzodiazepines in foods of animal origin are dangerous to consumers. For inspection of their abuses, this study for the first time reported on the use of a chemiluminescence array sensor for the simultaneous determination of four phenothiazines and five benzodiazepines in pig urine. Two molecularly imprinted polymers were coated in different wells of a conventional 96‐well microtiter plate as the recognition reagents. After sample loading, the absorbed analytes were initiated directly by using an imidazole enhanced bis(2,4,6‐trichlorophenyl)oxalate–hydrogen peroxide system to emit light. The assay process consisted of only one sample‐loading step prior to data acquisition, so one test was finished within 10 min. The limits of detection for the nine drugs in the pig urine were in a range of 0.1 to 0.6 pg/mL, and the recoveries from the fortified blank urine samples were in a range of 80.3 to 95%. Furthermore, the sensor could be reused six times. Therefore, this sensor could be used as a simple, rapid, sensitive and reusable tool for routine screening for residues of phenothiazines and benzodiazepines in pig urine.     

Artificial cationic peptides that increase nuclease resistance of siRNA without disturbing RNAi activity

Properties of cationic peptides bearing amino or guanidino groups with various side chain lengths that bind to double stranded RNAs (dsRNAs) were investigated. Peptides with shorter side chain lengths effectively bound to dsRNAs (12mers) increasing their thermal stability. NMR measurements suggested that the cationic peptide binds to the inner side of the major groove of dsRNA. These peptides also increased the thermal stability of siRNA and effectively protected from RNase A digestion. On the other hand, both peptides containing amino groups and guanidine groups did not disturb RNAi activity.     

Cationic micelle: A promising nanocarrier for gene delivery with high transfection efficiency

Micelles have demonstrated an excellent ability to deliver several different types of therapeutic agents, including chemotherapy drugs, proteins, small‐interfering RNA and DNA, into tumor cells. Cationic micelles, comprising self‐assemblies of amphiphilic cationic polymers, have exhibited tremendous promise with respect to the delivery of therapy genes and gene transfection. To date, research in the field has focused on achieving an enhanced stability of the micellar assembly, prolonged circulation times and controlled release of the gene. This review focuses on the micelles as a nanosized carrier system for gene delivery, the system‐related modifications for cytoplasm release, stability and biocompatibility, and clinic trials. In accordance with the development of synthetic chemistry and self‐assembly technology, the structures and functionalities of micelles can be precisely controlled, and hence the synthetic micelles not only efficiently condense DNA, but also facilitate DNA endocytosis, endosomal escape, DNA uptake and nuclear transport, resulting in a comparable gene transfection of virus.