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$\gamma$-Graphyne is the most symmetric sp2/sp1 allotrope of carbon, which can be viewed as graphene uniformly expanded through insertion of two-carbon acetylenic units between all the aromatic rings. To date, synthesis of bulk $\gamma$-graphyne has remained a challenge. We here report the synthesis of multilayer $\gamma$-graphyne through crystallization-assisted irreversible cross-coupling polymerization. Comprehensive characterization of this new carbon phase is described, including synchrotron X-ray diffraction, electron diffraction, lateral force microscopy, Raman and infrared spectroscopy, and cyclic voltammetry. Experiments indicate that $\gamma$-graphyne is a 0.48 eV bandgap semiconductor, with a hexagonal a-axis spacing of 6.88 {\AA} and an interlayer spacing of 3.48 {\AA}, which is consistent with theoretical predictions. The observed crystal structure has an aperiodic sheet stacking. The material is thermally stable up to 240 $^\circ$C but undergoes a transformation at higher temperatures. While conventional 2D polymerizations and reticular chemistry rely on error correction through reversibility, we demonstrate that a periodic covalent lattice can be synthesized under purely kinetic control. The reported methodology is scalable and inspires extension to other allotropes of the graphyne family., Comment: Additional supporting information files are available at https://pubs.acs.org/doi/10.1021/jacs.2c06583

The prebiotic origin of catalyst-controlled peptide synthesis is fundamental to understanding the emergence of life. Building on our recent discovery that thiols catalyze the ligation of amino acids, amides, and peptides with amidonitriles in neutral water, we demonstrate the outcome of ligation depends on pH and that high p

RSC Advances 13(15), 10097-10109 (2023). doi:10.1039/D3RA01210G, Published by RSC Publishing, London

Stretching a coiled carbon nanotube (CNT) yarn can provide large, reversible electrochemical capacitance changes, which convert mechanical energy to electricity. Here, it is shown that the performance of these "twistron" harvesters can be increased by optimizing the alignment of precursor CNT forests, plastically stretching the precursor twisted yarn, applying much higher tensile loads during precoiling twist than for coiling, using electrothermal pulse annealing under tension, and incorporating reduced graphene oxide nanoplates. The peak output power for a 1 and a 30 Hz sinusoidal deformation are 0.73 and 3.19 kW kg

Herein we report a fundamental discovery on the use of tris(dialkylamino)phosphine reagents for peptide and protein modification. We discovered that C-terminal thiophosphonium species, which are uniquely stable, could be selectively and rapidly generated from their disulfide counterparts. In sharp and direct contrast, internal thiophosphonium species rapidly degrade to dehydroalanine. We demonstrate this remarkable chemoselectivity on a bis-cysteine model peptide, and the formation of a stable C-terminal-thiophosphonium adduct on an antibody fragment, as well as characterise the species in various small molecule/peptide studies.

The palladium‐catalysed sp3 C−H arylation of a selection of saturated amine scaffolds was investigated using substituted picolinamide directing groups. On the bornylamine scaffold, highly selective monoarylation takes place using unsubstituted picolinamide or 3‐methylpicolinamide, whereas a double C−H arylation occurs with other substituents present, becoming a significant product with 3‐trifluoromethylpicolinamide. DFT calculations were used to help rationalise the effect of directing groups on the C−H palladation steps which were found experimentally to be irreversible. The substituted picolinamide directing groups were also examined on acyclic amine scaffolds and in many cases increased yields and selectivity could be obtained using methylpicolinamides. For a selection of other amine scaffolds, the yield of C−H arylation could be improved significantly using 3‐methylpicolinamide as the directing group and/or 3‐methylpentan‐3‐ol as the solvent.

Creation of innovative products and technological breakthrough – phrases most often used in relation to objects located in the nanoscale area. Carbon nanomaterials (CNMs) of various morphologies and structures, which include nanotubes, graphene, nanoporous carbon, are one of the most studied materials of the nanotechnology industry at present. This is due primarily to the fact that their physico-mechanical and physico-chemical characteristics have a direct effect on the final product. At the same time, for a number of applications, the best performance is achieved at the highest possible values of specific surface parameters and porosity. Methods and an experimental technology for producing micro- and mesoporous carbon material have been developed. Depending on the feedstock and technological synthesis modes, a nanoporous carbon material is obtained with a predominance of micro- or mesopores, with a BET specific surface area in the range of 2000–4000 m2/g. The technology includes carbonization of the starting materials and subsequent chemical activation. The obtained activated carbon material can be used as sorbents for gaseous media, both in purification systems and as gas batteries for safe storage and transportation systems, as well as for solving a number of environmental problems.

Three-dimensional models of the body parts were developed using the basic 3D modeling operations (rotation, extrusion, threading, etc.) of the T-FLEX CAD 3D CAD system, which made it possible to significantly simplify the work with assembly 3D models representing a complex structure consisting of a large number of parts. During the trial operation, the advantages of using the T-FLEX CAD 3D CAD system have been proven when working with complex 3D models. The advantages of using the program in the machine-building cluster are shown.

A new synthesis of poly(methyl methacrylate) vinylterminated macromonomer is performed using the disproportionation between propagating methyl methacrylate radical and nitroxide TEMPO. The ability of the macromonomer to polymerize and copolymerize with styrene and poly(ethylene glycol) methacrylate was confirmed by GPC and isothermal calorimetry.

The monocyclic 1,4-benzoquinone, HU-331, the direct oxidation product of cannabidiol, inhibits the catalytic activity of topoisomerase II but without inducing DNA strand breaks or generating free radicals, and unlike many fused-ring quinones exhibits minimal cardiotoxicity. Thus, monocyclic quinones have potential as anti-cancer agents, and investigation of the structural origins of their biological activity is warranted. New syntheses of cannabidiol and (±)-HU-331 are here reported. Integrated synthetic protocols afforded a wide range of polysubstituted resorcinol derivatives; many of the corresponding novel 2-hydroxy-1,4-benzoquinone derivatives are potent inhibitors of the catalytic activity of topoisomerase II, some more so than HU-331, whose monoterpene unit replaced by a 3-cycloalkyl unit conferred increased anti-proliferative properties in cell lines with IC50 values extending below 1 mM, and greater stability in solution than HU-331. The principal pharmacophore of quinones related to HU-331 was identified. Selected monocyclic quinones show potential for the development of new anticancer agents.

A comparison of chlorido-gallium functionalized alkoxides as precursors for aerosol-assisted chemical vapor deposition (AACVD) was carried out. Variable-temperature (VT)-NMR studies were used to probe the fluxional behavior of these alkoxides in solution, and hence their utility as precursors. The synthesis involved the initial isolation of the dimer [GaCl(NMe2)2]2 via a salt metathesis route from GaCl3 and 2 equiv of LiNMe2. This dimer was then reacted with 4 equiv of HOCH2CH2CH2NEt2, resulting in the formation of Ga[μ-(OCH2CH2CH2NEt2)2GaCl2]3 (1). Mass spectrometry and VT-NMR confirmed the oligomeric structure of 1. Tuning of the ligand properties, namely, the chain length and substituents on N, resulted in formation of the monomers [GaCl(OR)2] (R = CH2CH2NEt2, (2); CH2CH2CH2NMe2, (3)). VT-NMR studies, supported by density functional theory calculations, confirmed that the ligands in both 2 and 3 possess a hemilabile coordination to the gallium center, owing to either a shorter carbon backbone (2) or less steric hindrance (3). Both 2 and 3 were selected for use as precursors for AACVD: deposition at 450 °C gave thin films of amorphous Ga2O3, which were subsequently annealed at 1000 °C to afford crystalline Ga2O3 material. The films were fully characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, UV–visible spectroscopy, and energy dispersive X-ray analysis., A comparison of chlorido-gallium functionalized alkoxides for use as precursors toward gallium oxide (Ga2O3) via aerosol-assisted chemical vapor deposition was carried out. Variable-temperature NMR studies were used to probe the fluxionality of these alkoxides in solution, combined with computational modeling of their dynamic behavior and hence their utility as precursors. Thin films of gallium oxide were deposited, and full characterization of the films was carried out.

Ene-reductases (ERs) of the Old Yellow Enzyme family catalyse asymmetric reduction of activated alkenes providing chiral products. They have become an important method in the synthetic chemists' toolbox offering a sustainable alternative to metal-catalysed asymmetric reduction. Development of new biocatalytic alkene reduction routes, however needs easy access to novel biocatalysts. A sequence-based functional metagenomic approach was used to identify novel ERs from a drain metagenome. From the ten putative ER enzymes initially identified, eight exhibited activities towards widely accepted mono-cyclic substrates with several of the ERs giving high reaction yields and stereoselectivities. Two highly performing enzymes that displayed excellent co-solvent tolerance were used for the stereoselective reduction of sterically challenging bicyclic enones where the reactions proceeded in high yields, which is unprecedented to date with wild-type ERs. On a preparative enzymatic scale, reductions of Hajos-Parish, Wieland-Miescher derivatives and a tricyclic ketone proceeded with good to excellent yields.

We present the state-of-the-art performance of air-coupled thermophones made of thin, freestanding films of randomly oriented single-walled carbon nanotubes (SWCNTs). The work demonstrates both experimentally and theoretically that extremely low heat capacity per unit area of SWCNT films allows centimeter-sized thermophones to achieve record sound pressures (normalized to the input power and geometry) in the frequency range of 1–100 kHz. Our SWCNT films have an aerogel structure. We systematically investigated their thermoacoustic performance as a function of the film thickness and purity. On the theoretical side, we obtained an analytic formula for the sound pressure in the ultrasound region and confirmed it by experiments and numerical simulations.

Purpose The incidence of paediatric fractures is known to peak during the summer as a consequence of unsupervised physical activity. A more sedentary lifestyle is a potential cause for changes in paediatric seasonal fracture frequency and severity. The aim of this study was to evaluate the current seasonal variations of paediatric fractures in order to determine resource allocation in hospitals, community clinics and prevention programs. Methods A single institutional review of historical data of all patients aged 0 to 16 years that were diagnosed with fractures between April 2014 and July 2017 in the emergency department of a level 3 orthopaedic trauma centre was conducted. In all, 3484 fractures were reviewed, of which 2991 were included. We stratified fractures according to patients’ variants and the hour, day and month with respect to holidays, weekends and weather. Results While the fracture rate on school days was 6.62 per day, the fracture rate during the summer vacation was 4.45 (p < 0.01). Hot weather was correlated with low fracture rates. The peak hours of admission were 12:00 to 13:00 and 18:00 to 22:00, with more moderate differences during non-school periods. Conclusion The local seasonal variation of paediatric fractures has a bimodal distribution, with similar nadirs during both summer and winter. These rates might reflect a shift to a more sedentary lifestyle during the summer vacation. The presented data can assist in improving the value of injury prevention measures and medical resources allocation. Level of evidence II

Here we discuss effect of spin-polarization on plasmon excitation in deep ultra-violet spectral range for Co nanoparticles with a single-domain magnetic structure. Structural, magnetic, and optical characterizations of Co nanoparticles shine a light on a mechanism of the magneto-plasmonic response.

The palladium-catalysed sp3 C-H arylation of a selection of saturated amine scaffolds was investigated using substituted picolinamide directing groups. On the bornylamine scaffold, highly selective monoarylation takes place using unsubstituted picolinamide or 3-methylpicolinamide, whereas a double C-H arylation occurs with other substituents present, becoming a significant product with 3-trifluoromethylpicolinamide. DFT calculations were used to help rationalise the effect of directing groups on the C-H palladation steps which were found experimentally to be irreversible. The substituted picolinamide directing groups were also examined on acyclic amine scaffolds and in many cases increased yields and selectivity could be obtained using methylpicolinamides. For a selection of other amine scaffolds, the yield of C-H arylation could be improved significantly using 3-methylpicolinamide as the directing group and/or 3-methylpentan-3-ol as the solvent

Correction for ‘Use of pyridazinediones as extracellular cleavable linkers through reversible cysteine conjugation’ by Calise Bahou et al., Chem. Commun., 2019, 55, 14829–14832, https://doi.org/10.1039/C9CC08362F.

Because of its electrically conducting properties combined with excellent thermal stability and transparency throughout the visible spectrum, tin oxide (SnO2) is extremely attractive as a transparent conducting material for applications in low-emission window coatings and solar cells, as well as in lithium-ion batteries and gas sensors. It is also an important catalyst and catalyst support for oxidation reactions. Here, we describe a novel nonaqueous sol–gel synthesis approach to produce tin oxide nanoparticles (NPs) with a low NP size dispersion. The success of this method lies in the nonhydrolytic pathway that involves the reaction between tin chloride and an oxygen donor, 1-hexanol, without the need for a surfactant or subsequent thermal treatment. This one-pot procedure is carried out at relatively low temperatures in the 160–260 °C range, compatible with coating processes on flexible plastic supports. The NP size distribution, shape, and dislocation density were studied by powder X-ray powder diffraction analyzed using the method of whole powder pattern modeling, as well as high-resolution transmission electron microscopy. The SnO2 NPs were determined to have particle sizes between 3.4 and 7.7 nm. The reaction products were characterized using liquid-state 13C and 1H nuclear magnetic resonance (NMR) that confirmed the formation of dihexyl ether and 1-chlorohexane. The NPs were studied by a combination of 13C, 1H, and 119Sn solid-state NMR as well as Fourier transform infrared (FTIR) and Raman spectroscopy. The 13C SSNMR, FTIR, and Raman data showed the presence of organic species derived from the 1-hexanol reactant remaining within the samples. The optical absorption, studied using UV–visible spectroscopy, indicated that the band gap (Eg) shifted systematically to lower energy with decreasing NP sizes. This unusual result could be due to mechanical strains present within the smallest NPs perhaps associated with the organic ligands decorating the NP surface. As the size increased, we observed a correlation with an increased density of screw dislocations present within the NPs that could indicate relaxation of the stress. We suggest that this could provide a useful method for band gap control within SnO2 NPs in the absence of chemical dopants.

A range of novel β-nitroacetamides with an alkenyl- or alkynyl tether were synthesized using the deprotonative or conjugate addition nitro-Mannich reaction. They were subjected to radical denitration-cyclisation with a 10 equivalent excess of tributyltin hydride, catalytic AIBN in refluxing benzene to explore the structural and electronic requirements for efficient cyclisation. Cyclisations of the β-nitroacetamides were successful in most cases, undergoing 5-exo-trig cyclisation to give the desired cyclopentyl or indanyl structures. Radical 1,4-translocation of a phenyl group was observed in several cases. Diastereoselectivity was low, with 2 or 3 of 4 possible diastereoisomers observed in most cases. Further purification by crystallisation allowed the isolation of some as single diastereoisomers. It was found that higher yields were obtained by increasing the substitution or reducing the degrees of freedom of the tether between the nitro group and the radical acceptor.

Four new conjugated microporous polymers (CMPs) were synthesized by a Buchwald-Hartwig (BH) cross-coupling reaction of tri-and tetrafunctionalized precursors to yield materials with tunable surface area and pore size distribution. This approach yielded LPCMP1-4, CMPs with significantly higher Brunauer-Emmett-Teller (BET) surface areas (more than 5 times higher) than other related BH-based CMPs. These CMPs possess not only high BET specific surface areas and high chemical and thermal stabilities, but also exhibit outstanding swellability. To the best of our knowledge, swellable behavior was studied in great detail for CMPs for the first time, with the greatest degree of swelling for methanol reaching 16.5 and 16.3 mL g -1 for LPCMP1 and LPCMP3, respectively. Owing to their excellent swellability, we further studied the adsorption capacity of these CMPs for different toxic organic vapors (including toluene and methanol). LPCMP1 and LPCMP3 adsorbed 124 and 117 mg g -1 toluene, respectively, at saturated vapor pressure. For methanol, the adsorption capacities of LPCMP1 and LPCMP3 were up to 250 and 215 mg g -1, respectively, which are the highest recorded values when compared with published data for CMPs, HCPs, MOFs, and porous carbons. These materials are promising candidates for the removal and elimination of hazardous organic vapors and chemical warfare agents. Moreover, all the polymers show high sensitivity to nitroaromatic explosives. LPCMP2 and LPCMP4 exhibit high selectivity for TNT and may be suitable as new candidates to selectively detect TNT for security or environmental applications.

In this paper we outline how dihalohydration reactions of propargylic alcohols can be used to access a wide variety of useful halogenated building blocks. A novel procedure for dibromohydration of alkynes has been developed, and a selection of dichloro and dibromo diols and cyclic ethers were synthesized. The dihalohydration of homo‐propargylic alcohols provides a useful route to 3‐halofurans, which were shown to readily undergo cycloaddition reactions under mild conditions. Finally, a novel ring‐expansion of propargylic alcohols containing a cyclopropylalkyne provides access to halogenated alkenylcyclobutanes.

The relative strength of noncovalent interactions between a thioether sulfur atom and various π systems in designed top pan molecular balances was determined by NMR spectroscopy. Compared to its oxygen counterpart, the sulfur atom displays a remarkable ability to interact with almost equal facility over the entire range of π systems studied, with the simple alkene emerging as the most powerful partner. With the exception of the O⋅⋅⋅heteroarene interaction, all noncovalent interactions of sulfur with π systems are favoured over oxygen.

The combustion of mercury(II) thiocyanate to form "Pharaoh's serpents" is a spectacular reaction first described nearly two centuries ago. The large volume of distinctive yellow branches that grow from a tiny quantity of flaming reactants makes this an enchanting demonstration, often used to depict the magic of chemistry. In recent years several videos of this bizarre process have "gone viral" online. Formally, the reaction should yield a carbon nitride with the ideal formula C 3 N 4 along with HgS. However, since early characterization attempts there has been little further study of the materials produced. Herein we apply modern characterization techniques to reinvestigate the nature of the carbon nitride and its intimate relationship to the HgS produced. The HgS phase forms nanoparticles that decorate the surfaces of a C 3 N 4 foam matrix. Both of these compounds are important wide-gap semiconductors and we propose that the "Pharaoh's serpents reaction" could be used to produce a potentially important heterojunction nanocomposite materials that could be useful optoelectronic and photocatalytic applications.

Herein we report a retro-Michael deconjugation pathway of thiol-pyridazinedione linked protein bioconjugates to provide a novel cleavable linker technology. We demonstrate that the novel pyridazinedione linker does not suffer from off-target modification with blood thiols (e.g., glutathione, human serum albumin (HSA)), which is in sharp contrast to an analogous maleimide linker.

Twisting is cool Rubber bands that are stretched and held in an extended shape for a while will extract heat from their surroundings as they are allowed to relax, owing to a reversal of stress-induced crystallization, which is an exothermic process. Wang et al. examine the potential for solid-state cooling of twisted fibers, along with configurations such as supercoiling, for materials including natural rubber, polyethylene, and nickel-titanium fibers. The cooling is related to the change in entropy of the material as it is mechanically deformed. Science , this issue p. 216

Herein, various molecular balances used for comparing the strengths of intramolecular noncovalent interactions are reviewed. Our overview indicates that considerable quantitative insight into the strength of noncovalent interactions can be gained through the careful design of molecular balances. Many exciting opportunities certainly exist for the design of further new balances to quantify and dissect the relative strengths of noncovalent interactions as a function of solvation and the importance of the many factors that contribute to overall molecular recognition. However, even simple model molecules can show a multiplicity of intramolecular noncovalent interactions acting in a combined fashion. It is therefore essential to undertake a detailed computational analysis to identify all possible noncovalent interactions present in a selected molecular balance prior to a quantitative experimental assessment of the strength of a particular noncovalent interaction. It is also argued that the words "torsion" and "molecular balance" seem to have become inextricably linked and, in consequence, even top pan and seesaw balances have been mistakenly referred to in these terms.

Here it is experimentally shown that Co nanoparticles with a single-domain crystal structure support a plasmon resonance at approximately 280 nm with better quality than gold nanoparticle resonance in the visible. Magnetic nature of the nanoparticles suggests a new type of these plasmons. The exchange interaction of electrons splits the energy bands between spin-up electrons and spin-down electrons. It makes it possible for coexistence of two independent channels of conductivity as well as two independent plasmons in the same nanoparticle with very different electron relaxation. Indeed, the density of empty states in a partially populated d-band is high, resulting in a large relaxation rate of the spin-down conduction electrons and consequently in low quality of the plasmon resonance. In contrast, the majority electrons with a completely filled d-band do not provide final states for the scattering processes of the conduction spin-up electrons, therefore supporting a high quality plasmon resonance. The scattering without spin flip is required to keep these two plasmons independent.

Crystalline layered carbon nitrides can be inter-converted by simple ion exchange process allowing their properties to be tuned., The development of processes to tune the properties of materials is essential for the progression of next-generation technologies for catalysis, optoelectronics and sustainability including energy harvesting and conversion. Layered carbon nitrides have also been identified as of significant interest within these fields of application. However, most carbon nitride materials studied to date have poor crystallinity and therefore their properties cannot be readily controlled or easily related to their molecular level or nanoscale structures. Here we report a process for forming a range of crystalline layered carbon nitrides with polytriazine imide (PTI) structures that can be interconverted by simple ion exchange processes, permitting the tunability of their optoelectronic and chemical properties. Notable outcomes of our work are (a) the creation of a crystalline, guest-ion-free PTI compound that (b) can be re-intercalated with ions or molecules using “soft chemistry” approaches. This includes the intercalation of HCl, demonstrating a new ambient pressure route to the layered PTI·xHCl material that was previously only available by a high-pressure-high-temperature route (c). Our work also shows (d) that the intercalant-free (IF-) PTI material spontaneously absorbs up to 10 weight% H2O from the ambient atmosphere and that this process is reversible, leading to potential applications for membranes and water capture in dry environments.

Carbon nanotube sheets exhibiting extremely low heat capacity have enabled the development of thermoacoustic projectors (TAPs) for a wide range of frequencies (1- 106 Hz). The sound pressure level of carbon nanotube (CNT) based TAPs is proportional to the frequency, resulting in a reduced performance at low frequencies. Hence, there is a need to determine the governing parameters of TAPs that can be used to increase performance at low frequencies. A comprehensive, validated model is presented, involving structure-fluid-acoustic interactions, which sheds light on the physical behavior of CNT-based TAPs. The theoretical and numerical model incorporates all the controlling steps, from input electrical power to vibroacoustic wave generation in an outer fluid media. Using this model, the impact of the governing parameters on TAP performance has been studied.

As one of the first semi-synthetic plastics produced industrially, cellulose acetate (CA)-based artefacts represent valued items in museum collections and archives which, however, present stability issues. High temperature and relative humidity conditions have long been known to promote changes in CA properties, for instance, due to the deacetylation of CA polymer chains and the loss of plasticiser from the polymer matrix. However, there is a need for improved methods for the quantification of plasticiser loss and CA deacetylation. In this context, this contribution presents a new approach for enabling the investigation of plasticiser loss and deacetylation degradation processes in historic plasticised CA-based artefacts which is based on high-resolution proton nuclear magnetic resonance spectroscopy (1H NMR). The proposed methods allow for simple and fast quantification of diethyl phthalate contents and average degree of substitution (DS), while requiring no need for extractive separation between the plasticiser and the CA polymer matrix prior to analysis. Both methods are demonstrated by their application towards a series of reference samples, historic artefacts and artificially aged plasticised CA materials. Our analysis indicates that plasticiser content and DS can be accurately quantified by using high-resolution 1H NMR and both methods have been compared to analyses performed using infrared spectroscopy.

Lightweight artificial muscle fibers that can match the large tensile stroke of natural muscles have been elusive. In particular, low stroke, limited cycle life, and inefficient energy conversion have combined with high cost and hysteretic performance to restrict practical use. In recent years, a new class of artificial muscles, based on highly twisted fibers, has emerged that can deliver more than 2,000 J/kg of specific work during muscle contraction, compared with just 40 J/kg for natural muscle. Thermally actuated muscles made from ordinary polymer fibers can deliver long-life, hysteresis-free tensile strokes of more than 30% and torsional actuation capable of spinning a paddle at speeds of more than 100,000 rpm. In this perspective, we explore the mechanisms and potential applications of present twisted fiber muscles and the future opportunities and challenges for developing twisted muscles having improved cycle rates, efficiencies, and functionality. We also demonstrate artificial muscle sewing threads and textiles and coiled structures that exhibit nearly unlimited actuation strokes. In addition to robotics and prosthetics, future applications include smart textiles that change breathability in response to temperature and moisture and window shutters that automatically open and close to conserve energy.

The use of biomass-sourced chemical feedstocks creates a conflict over land use between food and fuel/chemical production. Such conflict could be reduced by making use of the annual 1.3 Pg food waste resource. Oleic acid is available from seed oils such as pumpkin, grape, avocado and mango. Its esterification with diols 1,3-propanediol, resorcinol and orcinol was used to form diesters and the naturally occurring norspermidine was used to prepare a diamide, all under ambient conditions. These compounds were then epoxidized and polymerized. When esterification was followed by epoxidation and subsequent curing at elevated temperature with p-phenylenediamine or diethylenetriamine, hard insoluble resins were formed. When the sequence was changed such that the epoxidized oleic acid was first reacted with cis-1,2-cyclohexanedicarboxylic anhydride and then esterified with orcinol and resorcinol, insoluble crosslinked polymers were also obtained. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3159–3170

The fabrication and characterization of highly flexible textiles are reported. These textiles can harvest thermal energy from temperature gradients in the desirable through-thickness direction. The tiger yarns containing n- and p-type segments are woven to provide textiles containing n-p junctions. A high power output of up to 8.6 W m(-2) is obtained for a temperature difference of 200 °C.

Transparent conductive indium-tin oxide (ITO) thin films, electrochemically intercalated with alkali (Li+, Na+, K+, Rb+, Cs+), alkali earth (Mg+2, Ca+2), or complex NH $_{4}^{+}$ ions, show tunable superconducting transitions with dome-shaped behavior of T c versus electron density around the maximum at ∼ 5 K. On field cooling, the transition into the superconducting state is accompanied by a paramagnetic response, i.e., an increase of magnetization, rather than the usual diamagnetic Meissner response. We provide an extensive study of this so-called paramagnetic Meissner effect (PME), using DC SQUID, transport measurements and a variety of sample sizes and growth conditions. We show that the PME in electrochemically doped ITO films results from a higher T c at the sample edges than at the center of disk-shaped samples, causing flux to be expelled towards the center of the disk, following the flux-compression theory of Koshelev and Larkin. Changing to the opposite spatial T c profile largely removes the paramagnetic response. The paramagnetic magnetization is strongly influenced by sample geometry and flux pinning conditions. The reduction of pinning defects by thermal annealing removes the paramagnetic response. An alternation of the external magnetic field restores the usual Meissner diamagnetism.

Based on detailed analysis of newly acquired NMR data, we show that the previously revised structure of tagetitoxin is incorrect. A new structure of tagetitoxin is proposed which is consistent with the NMR and MS data.

The article analyzes the changes in the phenomenon of terrorism at the beginning of the XXI century, draws conclusions about the influence of religious fundamentalism on the growth of terrorist activity and the mutual influence of the activities of terrorist organizations and the global geopolitical situation.

We report a new dry-state technique for non-contact patterning of nanostructured conducting materials, and demonstrate its use for carbon nanotube forests and freestanding sheets of carbon nanotubes, graphene, graphene sponge, and MXene. This method uses self-generated electron-emission pulses (~20 ns) in air. On a substrate - tip separation scale of 10 to 20 nm, the few molecules of gas at atmospheric pressure enables electron-emission-based interaction between a sharp tungsten tip and elements of nanostructured materials. Using the advantages of field enhancement at sharp ends of nanostructured materials, the discharge voltage is reduced to 25 - 30 V, depending upon the materials density. This method causes largely non-oxidative sequential decomposition of nanostructure elements neighboring the tungsten tip. The main decomposition mechanism is thermal dissociation facilitated by Joule heating and electrostatic removal of debris. The non-contact-based patterning of nanomaterials can be as fast as 10 cm/s. The resulting precisely patterned structures (< 200 nm) are largely free of foreign contaminants, thermal impact and sub-surface structural changes.

The combination of smooth, continuous sound spectra produced by a sound source having no vibrating parts, a nanoscale thickness of a flexible active layer and the feasibility of creating large, conformal projectors provoke interest in thermoacoustic phenomena. However, at low frequencies, the sound pressure level (SPL) and the sound generation efficiency of an open carbon nanotube sheet (CNTS) is low. In addition, the nanoscale thickness of fragile heating elements, their high sensitivity to the environment and the high surface temperatures practical for thermoacoustic sound generation necessitate protective encapsulation of a freestanding CNTS in inert gases. Encapsulation provides the desired increase of sound pressure towards low frequencies. However, the protective enclosure restricts heat dissipation from the resistively heated CNTS and the interior of the encapsulated device. Here, the heat dissipation issue is addressed by short pulse excitations of the CNTS. An overall increase of energy conversion efficiency by more than four orders (from 10-5 to 0.1) and the SPL of 120 dB re 20 μPa @ 1 m in air and 170 dB re 1 μPa @ 1 m in water were demonstrated. The short pulse excitation provides a stable linear increase of output sound pressure with substantially increased input power density (>2.5 W cm-2). We provide an extensive experimental study of pulse excitations in different thermodynamic regimes for freestanding CNTSs with varying thermal inertias (single-walled and multiwalled with varying diameters and numbers of superimposed sheet layers) in vacuum and in air. The acoustical and geometrical parameters providing further enhancement of energy conversion efficiency are discussed.

We here show that infiltrated bridging agents can convert inexpensively fabricated graphene platelet sheets into high-performance materials, thereby avoiding the need for a polymer matrix. Two types of bridging agents were investigated for interconnecting graphene sheets, which attach to sheets by either π–π bonding or covalent bonding. When applied alone, the π–π bonding agent is most effective. However, successive application of the optimized ratio of π–π bonding and covalent bonding agents provides graphene sheets with the highest strength, toughness, fatigue resistance, electrical conductivity, electromagnetic interference shielding efficiency, and resistance to ultrasonic dissolution. Raman spectroscopy measurements of stress transfer to graphene platelets allow us to decipher the mechanisms of property improvement. In addition, the degree of orientation of graphene platelets increases with increasing effectiveness of the bonding agents, and the interlayer spacing increases. Compared with other materials that are strong in all directions within a sheet, the realized tensile strength (945 MPa) of the resin-free graphene platelet sheets was higher than for carbon nanotube or graphene platelet composites, and comparable to that of commercially available carbon fiber composites. The toughness of these composites, containing the combination of π–π bonding and covalent bonding, was much higher than for these other materials having high strengths for all in-plane directions, thereby opening the path to materials design of layered nanocomposites using multiple types of quantitatively engineered chemical bonds between nanoscale building blocks.