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ABSTRACTA series of porous organic polymers based on a singlet oxygen generating oxoporphyinogen (‘OxP’) has been successfully prepared from a pseudotetrahedral OxP-tetraamine precursor (OxP(4-NH2Bn)4) by its reaction with tetracarboxylic acid dianhydrides under suitable conditions. Of the compounds studied, those containing naphthalene (OxP-N) and perylene (OxP-P) spacers, respectively, have large surface areas (~530 m2 g−1). On the other hand, the derivative with a simple benzene spacer (OxP-B) exhibits the best 1O2 generating capability. Although the starting OxP-tetraamine precursor is a poor 1O2 generator, its incorporation into OxP POPs leads to a significant enhancement of 1O2 productivity, which is largely due to the transformation of NH2 groups to electron-withdrawing diimides. Overall 1O2 production efficacy of OxP-POPs under irradiation by visible light is significantly improved over the common reference material PCN-222. All the materials OxP-B, OxP-N and OxP-P promote oxidation of thioanisole involving conversion of ambient triplet state oxygen to singlet oxygen under visible light irradiation and its reaction with the sulfide. Although the reaction rate of the oxidation promoted by OxP POPs is generally lower than for conventional materials (such as PCN-222) or previously studied OxP derivatives, undesired overoxidation of the substrate to methyl phenyl sulfone is suppressed. For organic sulfides, selectivity of oxidation is especially important for detoxification of mustard gas (bis(2-chloroethyl)sulfide) or similarly toxic compounds since controlled oxidation leads to the low toxicity bis(2-chloroethyl)sulfoxide while overoxidation leads to intoxification (since bis(2-chloroethyl)sulfone presents greater toxicity to humans than the sulfide substrate). Therefore, OxP POPs capable of promoting selective oxidation of sulfides to sulfoxides have excellent potential to be used as mild and selective detoxification agents.

Abstract Methods to encode digital data items as strands of synthetic DNA followed by selective data retrieval have been demonstrated. However, these initially bio‐oriented processes remain slow and not optimized. DNA field‐effect transistor (DNA‐FET) is studied here as a possible random‐access memory (RAM) device for simple, selective and rapid ssDNA fragment retrieval used as data pool identifier. The DNA‐FET is based on a co‐planar Au‐gated fully organic transistor appended with short single‐stranded DNA (ssDNA) probes bearing a blocking molecule to prevent partial hybridization and achieve near perfect selectivity for short length ssDNA (up to 45 nt). Examination of transconductance of the novel active layer incorporating a DNA nanopore architecture reveals enhanced binding site accessibility. This, in turn, facilitates discriminatory hybridization, particularly in the physical retrieval of short‐length ssDNA from a competitive, concentrated ssDNA background pool consisting of nine different sequences, with at least one nucleotide difference. The DNA‐FET exhibits rapid operation (9 min) in the millivolt range, low detection limit (sub‐femtomolar), high selectivity and reusability. Considering the straightforward concept, near error‐free identification capacity and hypothetically outstanding scalability, the DNA‐FET described here has potential as a foundation for further exploration of advanced RAM technology in the DNA data storage process.

Pyrazinacenes are linearly fused heteroaromatic rings, with N atoms replacing all apical CH moieties. Component rings may exist in a reduced state, having NH groups instead of N, causing cross-conjugation. These compounds have interesting optical and electronic properties, including strong fluorescence in the near-infrared region and photocatalytic properties, leading to diverse possible applications in bio-imaging and organic synthesis, as well as obvious molecular electronic uses. In this study, we investigated the behavior of seven-ring pyrazinacene 2,3,11,12-tetraphenyl-7,16-dihydro-1,4,5,6,7,8,9,12,13,14,15,16,17,18-tetradecaazaheptacene (Ph4H2N14HEPT), with an emphasis on protic processes, including oxidation, tautomerism, deprotonation, and protonation, and the species resulting from those processes. We used computational methods to optimize the structures of the different species and generate/compare molecular orbital structures. The aromaticity of the species generated by the different processes was assessed using the nucleus-independent chemical shifts, and trends in the values were associated with the different transformations of the pyrazinacene core. The computational data were compared with experimental data obtained from synthetic samples of the molecule tBu8Ph4H2N14HEPT.

Electro-catalytic activity of Pt in the oxygen reduction reaction (ORR) depends strongly on its morphology. For an understanding of how morphology affects the catalytic properties of Pt, the investigation of Pt materials having well-defined morphologies is required. However, the challenges remain in rational and facile synthesis of Pt particles with tuneable well-defined morphology. A promising approach for the controlled synthesis of Pt particles is ‘self-assembly of building blocks’. Here, we report a unique synthesis method to control Pt morphology by using a self-assembly route, where nanoflower, nanowire, nanosheet and nanotube morphologies of Pt particles have been produced in a controlled manner. In the growth mechanism, Pt nanoparticles (5–11 nm) are rapidly prepared by using NaBH4 as a reductant, followed by their agglomeration promoted by adding 1,2-ethylenediamine. The morphology of the resulting Pt particles can be easily controlled by tuning hydrophobic/hydrophilic interactions by the addition of isopropanol and H2O. Of the Pt particles prepared using this method, Pt nanotubes show the highest ORR catalytic activity in an acid electrolyte with an onset potential of 1.02 V vs. RHE.

In 1907, Lapicque proposed that an electric field passes through the neuronal membrane and transmits a signal. Subsequently, a “snake curve” or spike was used to depict the means by which a linear flat current undergoes a sudden Gaussian or Laplacian peak. This concept has been the accepted scenario for more than 115 years even appearing in textbooks on the subject. It was not noted that the membrane spike should have a cylindrical shape. A nerve spike having a dot shape on membrane surface cannot propagate through a cylindrical surface since it would dissipate instantaneously. A nerve spike should have the appearance of a ring, encompassing the diameter of a cylindrical axon or dendron. However, this subtle change has remarkable implications. Maintaining a circular form of an electric field is not easy, especially at the surface of an organic object. Here, we suggest that neuroscience could redefine itself if we accept that a nerve spike is not a localized 3D Gaussian or Laplacian wave packet, rather it is a 3D ring encompassing the diameter of a neural branch.

Abstract Nuclear magnetic resonance (NMR) lineshape analysis is a powerful tool for the study of chemical kinetics. Here we provide techniques for analysis of the relationship between experimentally observed spin kinetics (transitions between different environments $$A,B,\dots$$ A , B , ⋯ ) and corresponding chemical kinetics (transitions between distinct chemical species; e.g., free host and complexed host molecule). The advantages of using analytical solutions for two-, three- or generally N-state exchange lineshapes (without J-coupling) over the widely used numerical calculation for NMR spectral fitting are presented. Several aspects of exchange kinetics including the generalization of coalescence conditions in two-state exchange, the possibility of multiple processes between two states, and differences between equilibrium and steady-state modes are discussed. ‘Reduced equivalent schemes’ are introduced for spin kinetics containing fast-exchanging states, effectively reducing the number of exchanging states. The theoretical results have been used to analyze a host–guest system containing an oxoporphyrinogen complexed with camphorsulfonic acid and several other literature examples, including isomerization, protein kinetics, or enzymatic reactions. The theoretical treatment and experimental examples present an expansion of the systematic approach to rigorous analyses of systems with rich chemical kinetics through NMR lineshape analysis.

In this work the authors report how human mesenchymal stem cells rapidly adapt to dynamic microenvironment through lipid raft in membrane microdomains that direct neurogenesis.

High-surface-area porous carbon materials with high porosity and well-defined pore structures are the preferred advanced supercapacitors electrode materials. Here, we report the electrochemical supercapacitive performance of novel high-porosity activated carbon materials prepared from biowaste Terminalia chebula (Harro) seed stones involving zinc chloride (ZnCl2) activation. Activation is achieved by mixing ZnCl2 with Harro seed powder (1:1 w/w) followed by carbonization at 400–700 °C under a nitrogen gas atmosphere. The amorphous carbon materials obtained exhibit excellent performance as electrical double-layer capacitor electrodes in aqueous electrolyte (1 M sulfuric acid) due to high specific surface areas (as high as 1382.6 m2 g−1) based on well-developed micropore and mesopore structures, and partial graphitic structure containing oxygenated surface functional groups. An electrode prepared using material having the optimal surface textural properties achieved a large specific capacitance of 328.6 F g−1 at 1 A g−1 in a three-electrode cell setup. The electrode achieved a good capacitance retention of 44.7% at a high 50 A g−1 current density and outstanding cycling performance of 98.2% even following 10,000 successive charge/discharge cycles. Electrochemical data indicate the significant potential of Terminalia chebula seed-derived porous carbons as high-performance electrode materials for high-energy-storage supercapacitor applications.

Acenes are a promising class of organic materials with distinctive electronic and optical properties. Here decaazapentacene and octaazatetracenes are prepared and their self-assembly behaviour at different oxidation states is analysed.

Abstract Ultrathin 2D nanoporous materials offer enhanced sensitivity and high spatial resolution in sensing applications making them important for the selective discrimination of guest molecules. Here bottom‐up fabrication is reported of a novel molecularly‐thin nitrogen‐doped 2D fullerphene. Thermal annealing at 700 °C of a bottom‐up assembled fullerene C60‐ethylenediamine (EDA) thin film results in formation of a nitrogen‐doped ultrathin carbon film, fullerphene, which exhibits a hierarchically micro/mesoporous structure at its surfaces. N‐doping of fullerphene is dominated by pyrrolic and quaternary nitrogen atoms, which allow selective and repetitive adsorption and desorption of low‐molecular‐weight carboxylic acid vapors through noncovalent interactions. The large surface area (655.2 m2 g–1) and pore volume (0.659 cc g–1) offered by the hierarchical micro/mesoporous architecture leads to superior sensitivity of fullerphene to formic acid over acetic acid in the vapor phase demonstrating that novel 2D fullerphene provides an attractive platform for the discrimination of carboxylic acids at the single‐carbon‐atom level.

The energy storage performances of supercapacitors are expected to be enhanced by the use of nanostructured hierarchically micro/mesoporous hollow carbon materials based on their ultra-high specific surface areas and rapid diffusion of electrolyte ions through the interconnected channels of their mesoporous structures. In this work, we report the electrochemical supercapacitance properties of hollow carbon spheres prepared by high-temperature carbonization of self-assembled fullerene-ethylenediamine hollow spheres (FE-HS). FE-HS, having an average external diameter of 290 nm, an internal diameter of 65 nm, and a wall thickness of 225 nm, were prepared by using the dynamic liquid-liquid interfacial precipitation (DLLIP) method at ambient conditions of temperature and pressure. High temperature carbonization (at 700, 900, and 1100 °C) of the FE-HS yielded nanoporous (micro/mesoporous) hollow carbon spheres with large surface areas (612 to 1616 m2 g−1) and large pore volumes (0.925 to 1.346 cm3 g−1) dependent on the temperature applied. The sample obtained by carbonization of FE-HS at 900 °C (FE-HS_900) displayed optimum surface area and exhibited remarkable electrochemical electrical double-layer capacitance properties in aq. 1 M sulfuric acid due to its well-developed porosity, interconnected pore structure, and large surface area. For a three-electrode cell setup, a specific capacitance of 293 F g−1 at a 1 A g−1 current density, which is approximately 4 times greater than the specific capacitance of the starting material, FE-HS. The symmetric supercapacitor cell was assembled using FE-HS_900 and attained 164 F g−1 at 1 A g−1 with sustained 50% capacitance at 10 A g−1 accompanied by 96% cycle life and 98% coulombic efficiency after 10,000 consecutive charge/discharge cycles. The results demonstrate the excellent potential of these fullerene assemblies in the fabrication of nanoporous carbon materials with the extensive surface areas required for high-performance energy storage supercapacitor applications.

Photons that acquire orbital angular momentum move in a helical path and are observed as a light ring. During helical motion, if a force is applied perpendicular to the direction of motion, an additional radial angular momentum is introduced, and alternate dark spots appear on the light ring. Here, a third, centrifugal angular momentum has been added by twisting the helical path further according to the three-step hierarchical assembly of helical organic nanowires. Attaining a third angular momentum is the theoretical limit for a photon. The additional angular momentum converts the dimensionless photon to a hollow spherical photon condensate with interactive dark regions. A stream of these photon condensates can interfere like a wave or disintegrate like matter, similar to the behavior of electrons.

The development of science and technology of advanced materials using nanoscale units can be conducted by a novel concept involving combination of nanotechnology methodology with various research disciplines, especially supramolecular chemistry. The novel concept is called ‘nanoarchitectonics’ where self-assembly processes are crucial in many cases involving a wide range of component materials. This review of self-assembly processes re-examines recent progress in materials nanoarchitectonics. It is composed of three main sections: (1) the first short section describes typical examples of self-assembly research to outline the matters discussed in this review; (2) the second section summarizes self-assemblies at interfaces from general viewpoints; and (3) the final section is focused on self-assembly processes at interfaces. The examples presented demonstrate the strikingly wide range of possibilities and future potential of self-assembly processes and their important contribution to materials nanoarchitectonics. The research examples described in this review cover variously structured objects including molecular machines, molecular receptors, molecular pliers, molecular rotors, nanoparticles, nanosheets, nanotubes, nanowires, nanoflakes, nanocubes, nanodisks, nanoring, block copolymers, hyperbranched polymers, supramolecular polymers, supramolecular gels, liquid crystals, Langmuir monolayers, Langmuir–Blodgett films, self-assembled monolayers, thin films, layer-by-layer structures, breath figure motif structures, two-dimensional molecular patterns, fullerene crystals, metal–organic frameworks, coordination polymers, coordination capsules, porous carbon spheres, mesoporous materials, polynuclear catalysts, DNA origamis, transmembrane channels, peptide conjugates, and vesicles, as well as functional materials for sensing, surface-enhanced Raman spectroscopy, photovoltaics, charge transport, excitation energy transfer, light-harvesting, photocatalysts, field effect transistors, logic gates, organic semiconductors, thin-film-based devices, drug delivery, cell culture, supramolecular differentiation, molecular recognition, molecular tuning, and hand-operating (hand-operated) nanotechnology.

Molecules that can switch between multiple stable states in response to stimuli are promising for many applications, but are challenging to construct. Here, the authors design a resorcinarene switching manifold with multiple oxidation states and coupled charge-transfer states, which can access up to five distinct switch-states with unique optical outputs.

Pure graphene in the form of few-layer graphene (FLG) – 1 to 6 layers – is biocompatible and non-cytotoxic. This makes FLG an ideal material to incorporate into dental polymers to increase their strength and durability. It is well known that graphene has high mechanical strength and has been shown to enhance the mechanical, physical and chemical properties of biomaterials. However, for commercial applicability, methods to produce larger than lab-scale quantities of graphene are required. Here, we present a simple method to make large quantities of FLG starting with commercially available multi-layer graphene (MLG). This FLG material was then used to fabricate graphene dental-polymer composites. The resultant graphene-modified composites show that low concentrations of graphene (ca. 0.2 wt %) lead to enhanced performance improvement in physio-mechanical properties – the mean compressive strength increased by 27% and the mean compressive modulus increased by 22%. Herein we report a new, cheap and simple method to make large quantities of few-layer graphene which was then incorporated into a common dental polymer to fabricate graphene-composites which shows very promising mechanical properties.

Chiral molecules possess enantiomers that have non-superimposable chemical structures but exhibit identical nuclear magnetic resonance (NMR) spectra. This feature prevents the use of NMR spectroscopic methods for the determination of enantiomeric excesses (ee) of chiral molecules, using simple mixtures of their enantiomers. Recently, however, it was reported that the addition of a symmetrical prochiral molecule (a reporter or host) into a solution of chiral analyte can lead to estimation of ee through interactions involving rapid exchange of the chiral analyte (guest) in the formed host–guest complex. This is due to the ee-dependent splitting of NMR resonances of the prochiral host molecule based on averaging the chemical shift non-equivalency caused by the presence of a chiral guest. The mechanism is not dependent on diastereomer formation, and 1:1 host–guest complexes can also show ee-dependent NMR peak splitting. Prochiral molecules capable of ee sensing using the NMR technique are now referred to as so-called prochiral solvating agents (pro-CSAs). pro-CSAs represent a family of reagents distinct from the commonly used NMR chiral derivatizing reagents (where chiral auxiliaries are used to derivatize enantiomers to diastereomers) or chiral solvating agents (where chiral auxiliaries interact in an asymmetric manner with analyte enantiomers). pro-CSA methods are unique since neither pro-CSA nor NMR contains chiral factors, making the technique neutral with respect to chirality. Here, we review our recent work on this matter involving several different nominally achiral receptor molecules whose unique guest binding properties and solution characteristics (especially with regard to NMR spectroscopy) allow for the estimation of ee in the corresponding chiral guests.

Carbon nanotubes (CNTs) have atomically smooth surfaces and tend not to form covalent bonds with composite matrix materials. Thus, it is the magnitude of the CNT/fiber interfacial strength that limits the amount of nanomechanical interlocking when using conventional CNTs to improve the structural behavior of composite materials through reinforcement. This arises from two well-known, long standing problems in this research field: (a) inhomogeneous dispersion of the filler, which can lead to aggregation and (b) insufficient reinforcement arising from bonding interactions between the filler and the matrix. These dispersion and reinforcement issues could be addressed by using branched multiwalled carbon nanotubes (b-MWCNTs) as it is known that branched fibers can greatly enhance interfacial bonding and dispersability. Therefore, the use of b-MWCNTs would lead to improved mechanical performance and, in the case of conductive composites, improved electrical performance if the CNT filler was better dispersed and connected. This will provide major benefits to the existing commercial application of CNT-reinforced composites in electrostatic discharge materials (ESD): There would be also potential usage for energy conversion, e.g., in supercapacitors, solar cells and Li-ion batteries. However, the limited availability of b-MWCNTs has, to date, restricted their use in such technological applications. Herein, we report an inexpensive and simple method to fabricate large amounts of branched-MWCNTs, which opens the door to a multitude of possible applications.

We have investigated the textural properties, electrochemical supercapacitances and vapor sensing performances of bamboo-derived nanoporous carbon materials (NCM). Bamboo, an abundant natural biomaterial, was chemically activated with phosphoric acid at 400 °C and the effect of impregnation ratio of phosphoric acid on the textural properties and electrochemical performances was systematically investigated. Fourier transform-infrared (FTIR) spectroscopy confirmed the presence of various oxygen-containing surface functional groups (i.e. carboxyl, carboxylate, carbonyl and phenolic groups) in NCM. The prepared NCM are amorphous in nature and contain hierarchical micropores and mesopores. Surface areas and pore volumes were found in the range 218–1431 m2 g−1 and 0.26–1.26 cm3 g−1, respectively, and could be controlled by adjusting the impregnation ratio of phosphoric acid and bamboo cane powder. NCM exhibited electrical double-layer supercapacitor behavior giving a high specific capacitance of c.256 F g−1 at a scan rate of 5 mV s−1 together with high cyclic stability with capacitance retention of about 92.6% after 1000 cycles. Furthermore, NCM exhibited excellent vapor sensing performance with high sensitivity for non-aromatic chemicals such as acetic acid. The system would be useful to discriminate C1 and C2 alcohol (methanol and ethanol).

Nanoporous activated carbon materials derived from agro-wastes could be suitable low-cost electrode materials for high-rate performance electrochemical supercapacitors. Here we report high surface area nanoporous carbon materials derived from Lapsi seed agro-waste prepared by zinc chloride (ZnCl2) activation at 700 °C. Powder X-ray diffraction (pXRD) and Raman scattering confirmed the amorphous structure of the resulting carboniferous materials, which also incorporate oxygen-containing functional groups as confirmed by Fourier transform infrared (FTIR) spectroscopy. Scanning and transmission electron microscopy (SEM and TEM) analyses revealed the granular, nanoporous structures of the materials. High-resolution TEM (HR-TEM) confirmed a graphitic carbon structure containing interconnected mesopores. Surface areas and pore volumes of the materials were found, respectively, in the ranges from 931 to 2272 m2 g−1 and 0.998 to 2.845 cm3 g−1, and are thus superior to commercially available activated carbons. High surface areas, large pore volumes and interconnected mesopore structures of these Lapsi seed-derived nanoporous carbon materials lead to their excellent electrochemical supercapacitance performance in aqueous electrolyte (1 M H2SO4) with a maximum specific capacitance of 284 F g−1 at a current density of 1 A g−1. Furthermore, the electrodes showed high-rate capability sustaining 67.7% capacity retention even at high current density of 20 A g−1 with excellent cycle stability achieving 99% capacitance retention even after 10,000 charge–discharge cycles demonstrating the potential of Lapsi seed derived nanoporous carbons as suitable electrode materials in high-performance supercapacitor devices.

Self-assembly has been recognised as a ubiquitous aspect of modern chemistry. Our understanding and applications of self-assembly are substantially based on what has been learned from biochemical systems. In this review, we describe various aspects of self-assembly commencing with an account of the soft structures that are available by assembly of surfactant amphiphiles, which are important scientific and industrial materials. Variation of molecular design using rules defined by surfactant self-assembly permits synthesis of functional nanostructures in solution and at surfaces while increasing the strength of intermolecular interactions through π-π stacking, metal cation coordination and/or hydrogen bonding leads to formation of highly complex bespoke nanostructured materials exemplified by DNA assemblies. We describe the origins of self-assembly involving aggregation of lipid amphiphiles and how this subject has been expanded to include other highly advanced chemical systems.

Several dynamic processes, including tautomerism and macrocyclic inversion, in 1H-NMR prochiral solvating agents (pro-CSAs) are investigated. Various features of pro-CSA, including modes of interaction for complex formation, stoichiometry, binding strength and temperature effects were compared for three representative pro-CSA molecules. Structural effects of conjugated tetrapyrrole pro-CSA on the mechanism of enantiomeric excess determination are also discussed. Detailed analysis of species (complexes) and dynamic processes occurring in solution and their 1H-NMR spectral manifestations at various temperatures is presented.

Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized.

In this short review, we have selected three main subjects: (i) mesoporous materials, (ii) sensing applications, and (iii) the concept of nanoarchitectonics, as examples of recent hot topics in nanomaterials research. Mesoporous materials satisfy the conditions necessary not only for a wide range of applications but also for ease of production, by a variety of simple processes, which yield bulk quantities of materials without loss of their well-defined nanometric structural features. Sensing applications are of general importance because many events arise from interaction with external stimuli. In addition to these important features, nanoarchitectonics is a concept aimed at production of novel functionality of whole units according to concerted interactions within nanostructures. For the combined subject of mesoporous sensor nanoarchitectonics, we present recent examples of research in the corresponding fields categorized according to mechanism of detection including optical, electrical, and piezoelectric sensing.

Coronary sinus reducer (CSR) implantation is an emerging treatment option for patients with refractory angina. This condition represents a major global cardiovascular healthcare challenge, with patients experiencing chronic anginal symptoms that significantly impair their quality of life and for whom few effective treatments exist. The clinical burden of refractory angina is only set to grow because of improved survival from coronary artery disease, increased life expectancy and the presence of residual angina after percutaneous or surgical coronary revascularisation. Therefore, new, effective, evidence-based therapies are urgently needed. In this review, we highlight the unmet clinical needs of patients with refractory angina, discuss the development of the CSR device and review the preclinical and clinical evidence base underlying CSR implantation. In addition, we discuss the current role of CSR implantation in contemporary interventional practice, highlighting knowledge gaps and discussing areas of on-going research.