Electroactive Ionic Polymer of Intrinsic Microporosity for High-Performance Capacitive Energy Storage.

Here, we report an ionic polymer of intrinsic microporosity (PIM) as a high-functioning supercapacitor electrode without the need for conductive additives or binders. The performance of this material is directly related to its large accessible surface area. By comparing electrochemical performance between a porous viologen PIM and a non-porous viologen polymer, we reveal that the high energy and power density are both due to the ability of ions to rapidly access the ionic PIM. In 0.1 M H2SO4 electrolyte, a pseudocapacitve energy of 315 F g-1 is observed, whereas in 0.1 M Na2SO4, a capacitive energy density of 250 F g-1 is obtained. In both cases, this capacity is retained over 10,000 charge-discharge cycles, without the need for stabilizing binders or conductive additives even at moderate loadings (5 mg cm-2). This desirable performance is maintained in a prototype symmetric two-electrode capacitor device, which had >99% Coloumbic efficiency and a <10 mF capacity drop over 2000 cycles. These results demonstrate that ionic PIMs function well as standalone supercapacitor electrodes and suggest ionic PIMs may perform well in other electrochemical devices such as sensors, ion-separation membranes, or displays. This article is protected by copyright. All rights reserved.

π-Conjugated Nanohoops: A new generation of curved materials for organic electronics.

Nanohoops, cyclic association of π-conjugated systems to form a hoop-shaped molecule, have been widely developed in the last 15 years. Beyond the synthetic challenge, the strong interest towards these molecules arise from their radially-oriented π-orbitals, which provide singular properties to these fascinating structures. Thanks to their particular cylindrical arrangement, this new generation of curved molecules have been already used in many applications such as  host-guest complexation, biosensing, bioimaging, solid-state emission and catalysis. However, their potential in organic electronics has only started to be explored. From the first incorporation as an emitter in fluorescent Organic Light Emitting Diode (OLED), to the recent first incorporation as host in Phosphorescent OLED or as charge transporter in Organic Field-Effect Transistor (OFET) and in Organic Photovoltaics (OPV), this field has shown important breakthroughs in recent years. These finding have revealed that curved materials can play a key role in the future and can even be more efficient than their linear counterparts. This can have important repercussions for the future of electronics. Time is now come to overview the different nanohoops used to date in electronic devices in order to stimulate the future molecular designs of functional materials based on these macrocycles.

Intrinsically thermally conductive polymers.

Here, we describe the design features that lead to intrinsically thermally conductive polymers. Though polymers are conventionally assumed to be thermal insulators (<0.3 W m-1 K-1), significant efforts by the thermal transport community have shown that polymers can be intrinsically thermally conductive (>1.0 W m-1 K-1). However, these findings have not yet driven comprehensive synthetic efforts to expose how different macromolecular features impact thermal conductivity. Preliminary theoretical and experimental investigations have revealed that high k polymers can be realized by enhancing the alignment, crystallinity, and intermolecular interactions. While a holistic mechanistic framework does not yet exist for thermal transport in polymeric materials, contemporary literature suggests that phonon-like heat carriers may be operative in macromolecules that meet the abovementioned criteria. In this review, we offer a perspective on how high thermal conductivity polymers can be systematically engineered from this understanding. Reports for several classes of macromolecules, including linear polymers, network polymers, liquid-crystalline polymers, and two-dimensional polymers substantiate the design principles we propose. Throughout this work, we offer opportunities for continued fundamental and technological development of polymers with high thermal conductivity.

Ultrafast symmetry-breaking charge separation in Perylenemonoimide-embedded multichromophores: impact of regioisomerism.

Symmetry-breaking charge separation (SB-CS) has recently evolved as an emerging concept offering its potential to the latest generation of organic photovoltaics. However there are several concerns that need to be addressed to reach the state-of-the-art in SB-CS chemistry, for instance, the desirable molecular geometry, interchromophoric distance and extent of electronic coupling. To shed light on those features, it is reported herein, that ortho-functionalized perylene monoimide (PMI) constituted regioisomeric dimer and trimer derivatives with varied molecular twisting and electronic conjugation have been synthesized. In steady-state photophysical studies, all the dimers and trimer derivatives exhibit a larger bathochromic shift in the emission spectra and a significant reduction of fluorescence quantum yield in polar DMF. Among the series of multichromophores, ortho- and self-coupled dimers display the strikingly different optical feature of SB-CS with a very fast charge separation rate (τCS = 80.2 ps) upon photoexcitation in DMF, which is unveiled by femtosecond transient absorption (fs-TA) studies. The SB-CS for two dimers is well-supported by the formation of PMI˙+ and PMI˙- bands in the fs-TA spectra. Further analysis of fs-TA data revealed that, among the other multichromophores the trimer also exhibits a clear charge separation, whereas SB-CS signatures are less prominent, but can not be completely disregarded, for the meta- and para-dimers. Additionally, the charge separation dynamics of those above-mentioned PMI derivatives are devoid of a kinetically favorable excimer or triplet formation. The evidence of a profound charge transfer phenomenon in the ortho-dimer is characterized by density functional theory (DFT) calculations on excited state electronic structures. The excitonic communications in the excited state electronic arrangements unravel the key role of dihedral twisting in SB-CS. The thermodynamic feasibility of CS (ΔGCS) and activation barrier (ΔG≠) of the derivatives in DMF are established from the Rehm-Weller equation and Marcus's theory, respectively. This work is an in-depth study of the effect of mutual orientation of PMIs and regioisomerism in determining sustainable guidelines for using SB-CS.

Ultrasensitive colorimetric detection of fluoride and arsenate in water and mammalian cells using recyclable metal oxacalixarene probe: a lateral flow assay.

Globally 3 billion people are consuming water with moderately high concentrations of fluoride and arsenic. The development of a simple point of care (PoC) device or home device for the detection of fluoride/arsenic ensures safety before consuming water. Till date, lateral flow assay (LFA) based PoC devices can detect nucleic acids, viruses and diseases. An aluminium complex of rhodamine B functionalized oxacalix[4]arene (L) was designed to execute the LFA-based PoC device. Initially, Al3+ and Fe3+ ions were involved in complexation with the rhodamine B functionalized oxacalix[4]arene (L), resulting C1 (L-Al3+) and C2 (L-Fe3+) complexes respectively. The receptor L, as well as the probes (C1, C2), were characterized thoroughly using mass spectroscopy, FTIR, NMR, and EA. C1 and C2 were further utilized as recyclable probes for the detection of aqueous fluoride (21 ppb) and arsenate (1.92 ppb) respectively. The computational calculation indicates that upon complexation, the spirolactam ring opening at the rhodamine B site leads to optoelectronic changes. The consistency of LFA-based portable sensing device has been tested with water samples, synthetic fluoride standards and dental care products like toothpaste and mouthwash with concentrations ≥ 3 ppm. Moreover, fixed cell imaging experiments were performed to ascertain the in-vitro sensing phenomena.

Red to NIR-emissive anthracene-conjugated PMI dyes with dual functions: singlet-oxygen response and lipid-droplet imaging.

The rich chemistry of solution-processable red and near-infrared (NIR) organic emitters has emerged as an attractive and progressive research field because of their particular applications in organic optoelectronics and bioimaging. Also, one can see that the research area of perylene monoimide-based red and NIR-emissive fluorophores is underexplored, which prompted us to design and synthesize three anthracene-conjugated PMI dyes exhibiting strong emission in the red and NIR window in solution. Three PMI-based fluorophores were synthesized via conjoining anthracene and donor moieties (-Ph, -N,N-PhNMe2) with a PMI core via an acetylene linkage at the peri-position, which helped to attain extensive electronic conjugation, which was reflected in red and NIR-emission in solution. The key molecular features to be highlighted here are: all three dyes are strongly emissive in solution, as unveiled by the excellent absolute fluorescence QYs; and they possess tuneable emission properties, guided by the donor strength and a profound Stokes shift (100-200 nm). The three fluorescent dyes demonstrated appreciable singlet-oxygen (1O2) sensitivity when photoirradiated with methylene blue (MB) in solution, showing a substantial blue-shift in emission in a ratiometric manner. Further, the treatment of dye-MB solution with α-tocopherol (1O2 scavenger) validated the presence of 1O2 as the only oxidizing species generated by MB in solution. Computational investigations gave insight into the twisting of donor moieties in their ground-state optimized geometries, the modulation of the FMO energy gap, and the thermodynamic feasibility of the 1O2 reaction. Finally, via taking advantage of the red and NIR-emission, we successfully utilized one of the fluorophores as a lipid-droplet marker for bioimaging in HepG2 cells.

Interplay of Anion-π+ and π+ -π+ Interactions in Novel Pyrido[2,1-a]isoquinolinium-Based AIEgens - Substituent- and Counterion-Dependent Fluorescence Modulation and Applications in Live Cell Mitochondrial Imaging.

Recently, the concept of anion-π+ interactions has witnessed unique applications in the field of AIEgen development. In this contribution, we disclose a consolidated study of a library of N-doped ionic AIEgens accessed through silver-mediated cyclization of pyridino-alkynes. A thorough photophysical, computational and crystallographic study has been conducted to rationalize the observed substituent- and counterion-dependent fluorescence properties of these luminogens. We further elucidate the prominent role of anion-π+ interactions, π+ -π+ interactions and other non-covalent interactions, in inhibiting the undesired ACQ effect. Finally, we have also demonstrated the application of selected AIEgens for imaging of mitochondria in live cells.

Aggregation Induced Emission Switching Based Ultrasensitive Ratiometric Detection of Biogenic Diamines Using a Perylenediimide-Based Smart Fluoroprobe.

In recent years, the widely explored phenomenon "aggregation-induced emission (AIE)" has played a crucial role in the development of luminescent materials for light-emitting applications. In the same direction, the contribution of its sister concept "AIE switching" has been impressive. In comparison, the application of this concept in the field of biosensing or bioimaging is still in its infancy. Therefore, to shed light into the sensing of bioanalytes, we have developed a new perylenediimide (PDI)-based small fluorescent probe, benzoannulated PDI (Bp(Im)2MA), that selectively detects diamines and biogenic amines (BAs) in solution via an "AIE-switching" phenomenon. The synthesized probe containing the bay-annulated anhydride moiety exhibits strong cyan emission in solution. In the mechanism, we have shown that the terminal free amine group of BAs readily reacts with a highly reactive anhydride moiety, which opens the cyclic anhydride moiety. In the open conformation, the free amine group along with a carboxylate group modulates the polarity of the system strikingly. Because of this induced polarity, the monomer of Bp(Im)2MA-BAs conjugate aggregated in solution, thereby exhibiting a significant change in emission property in solution. This method may also be called a very simple and straightforward "naked eye" detection of BAs in solution, with a nanomolar detection limit. A detailed spectroscopic and microscopic investigation demonstrated the existence of the aggregated state. As the reporter dye also emits strongly in the solid state (yellowish orange), it therefore instantly made vapor-phase detection of BAs feasible. Finally, this vapor-phase detection of BAs by the probe was applied very effectively in the determination of spoilage of raw fish.

ortho-Oxygenative 1,2-Difunctionalization of Diarylalkynes under Merged Gold/Organophotoredox Relay Catalysis.

Reported herein is an ortho-oxygenative 1,2-difunctionalization of diarylalkynes under merged gold/organophotoredox catalysis to access highly functionalized 2-(2-hydroxyaryl)-2-alkoxy-1-arylethan-1-ones. Detailed mechanistic studies suggested a relay process, initiating with gold-catalyzed hydroalkoxylation of alkynes, to generate enol-ether followed by a key formal [4+2]-cycloaddition reaction. The successful application of the present methodology was also shown for the synthesis of benzofurans.

Synthesis of highly-soluble push-pull perylenemonoimide derivatives by regioselective peri-functionalization for switchable memory applications.

A regioselective synthetic protocol is developed via tetrabromination of perylenemonoimide (PMI) which leads to a series of PMI derivatives. The push-pull characteristics of these derivatives are established by spectroscopic and theoretical investigations. Finally, the semiconducting properties of the PMI dyes are utilized for the development of a switchable memory device.

Diagnostic evaluation and surgical outcome of idiopathic isolated, acquired inferior oblique palsy: a rare presentation.

Isolated inferior oblique muscle palsy is the least common of all extra-ocular muscle palsies and very few reports are available in the literature. It can present a formidable therapeutic challenge to the ophthalmologist, as treatment options need to be titrated on an individual basis. A patient of 60 years old of idiopathic right inferior oblique palsy who underwent an adjustable superior rectus recession in his left eye, with a satisfactory surgical outcome and symptomatic resolution of diplopia is reported.

Myocardial infarction increases progressive visual field defects in well treated early primary open angle glaucoma--a prospective case control study.

The purpose of the study was to evaluate the progression of glaucomatous field damage in patients with stable primary open angle glaucoma after an attack of myocardial infarction. In this case control study, 62 open angle glaucoma patients were selected and regularly followed up. Among 62 patients, 9 had an attack of myocardial infarction. The intra-ocular pressure and visual field progression of both the groups (myocardial infarction versus no myocardial infarction) were analysed. Three (33.3%) out of 9 patients who had suffered from myocardial infarction showed progressive visual field loss whereas only 9 (16.9%) out of 53 patients who did not suffer from myocardial infarction, showed progressive field changes. Both the groups had stable target intra-ocular pressure between 14 and 16 mm Hg. Myocardial infarction may adversely influence the progression of primary open angle glaucoma which is suspected to result from ischaemia induced neuronal loss and only control of intraocular pressure is not the only solution. We have to look for other drugs that prevents ischaemia induced neuronal damage.

Solitary fibrous tumour of the orbit: an unusual presentation.

Solitary fibrous tumour is a rare tumour that usually arises from the pleura and very uncommonly from the orbit. This unusual unilateral orbital mass can be differentiated from the more common haemangiopericytoma by the use of histopathological and immunohistochemical studies. The tumour is strongly Immunoreactive for CD34, which supports its diagnosis.

Inadvertent intracorneal injection of local anesthetic during lid surgery.

PURPOSE: To report a case of inadvertent intracorneal injection of anesthetic agents during lid anesthesia and corneal penetration without full-thickness perforation. METHOD: Case report. RESULTS: Corneal edema with acute loss of vision was noted. The patient was treated with topical, antibiotic, cycloplegic, hyperosmotic agent and lubricant. While the edema slowly subsided, a loss in endothelial cell count was noted. CONCLUSIONS: The effects of intracorneal injection of lignocaine, bupivacaine, and its preservatives have not previously been reported in the literature. A lower postinjection endothelial cell count and associated clinical features in our case indicate that endothelial toxicity occurred. This potential complication should be kept in mind with necessary precautions taken during injection of the eyelid, particularly in cases with preexisting lid laxity.

Tissue adhesive in ophthalmology.

Tissue adhesive in ophthalmology is commonly used for corneal wound and restricted for superficial closure. Only synthetic adhesive available is butyl-2-cyanoacrylate. However, if it gets between the wound margins it inhibits healing by forming impervious barrier.