From Ion‐Like Ethylzinc Aluminates to [EtZn(arene)2]+[Al(ORF)4]− Salts

Attempts to prepare previously unknown simple and very Lewis acidic [RZn]⁺[Al(OR^F)₄]^? salts from ZnR₂, AlR₃, and HO?R^F delivered the ion‐like RZn(Al(OR^F)₄) (R=Me, Et; R^F=C(CF₃)₃) with a coordinated counterion, but never the ionic compound. Increasing the steric bulk in RZn⁺ to R=CH₂CMe₃, CH₂SiMe₃, or Cp*, thus attempting to induce ionization, failed and led only to reaction mixtures including anion decomposition. However, ionization of the ion‐like EtZn(Al(OR^F)₄) compound with arenes yielded the [EtZn(arene)₂]⁺[Al(OR^F)₄]^? salts with arene=toluene, mesitylene, or o‐difluorobenzene (o‐DFB)/toluene. In contrast to the ion‐like EtZn(η³‐C₆H₆)(CHB₁₁Cl₁₁), which co‐crystallizes with one benzene molecule, the less coordinating nature of the [Al(OR^F)₄]^? anion allowed the ionization and preparation of the purely organometallic [EtZn(arene)₂]⁺ cation. These stable materials have further applications as, for example, initiators of isobutene polymerization. DFT calculations to compare the Lewis acidities of the zinc cations to those of a large number of organometallic cations were performed on the basis of fluoride ion affinity. The complexation energetics of EtZn⁺ with arenes and THF was assessed and related to the experiments.     

Construction of a Graphene/Au‐Nanoparticles/Cucurbit[7]uril‐Based Sensor for Pb2+ Sensing

The development of highly sensitive and selective methods for the detection of lead ion (Pb²⁺) is of great scientific importance. In this work, we develop a new surface‐enhanced Raman scattering (SERS)‐based sensor for the selective trace measurement of Pb²⁺. The SERS‐based sensor is assembled from gold nanoparticles (AuNPs) and graphene using cucurbit[7]uril (CB[7]) as a precise molecular glue and a local SERS reporter. Upon the addition of Pb²⁺, CB[7] forms stronger complexes with Pb²⁺ and desorbs from AuNPs, resulting in a sensitive “turn‐off” of SERS signals. This SERS‐based assay shows a limit of detection (LOD) of 0.3 nm and a linear detection range from 1 nm to 0.3 μm for Pb²⁺. The feasibility of the assay is further demonstrated by probing Pb²⁺ in real water samples. This SERS‐based analytical method is highly sensitive and selective, and therefore holds promising applications in environmental analysis.     

Orientation and conformation of two [6]carbohelicenes in stretched polystyrene and a thermoresponsive polyaspartate

Two functionalized [6]carbohelicenes, one of which was also available in its two enantiomeric pure forms, were oriented in stretched polystyrene in CDCl₃, and in a recently introduced chiral thermoresponsive lyotropic polyaspartate (poly(benzyl)_0.5(phenethyl)_0.5-L-aspartate) in C₂D₂Cl₄. From the resulting ¹H,¹³C residual dipolar couplings, the helical pitch of a methylated [6]carbohelicene was determined and found to be in agreement with theoretical predictions and existing crystal structures (d(C2,C2′) ≈ 4.3 Å). For a second [6]carbohelicene with para-methoxyphenyl substituents, a clear conformational preference of the substituents was observed. The orientational properties of the two helicene enantiomers in the chiral polyaspartate are very similar, but both drastically change around 306 K. We suggest this behavior is due to an unusual phase transition in the liquid crystal.     

Effective permittivity of liquid crystal nanodispersions and composites with different pore structure

The volume filling fraction dependence of the effective permittivity of the nematic liquid crystal 4-n-pentyl-4’-cyanobiphenyl embedded in different porous membranes and dispersed with aerosil nanoparticles was determined using broadband dielectric spectroscopy in the frequency range from 10⁶ to 10⁹ Hz. The experimental data were analyzed and compared with some existing theories based on the effective medium approximation and their modifications. The obtained effective permittivities as a function of the volume filling fraction lie between the lower limits of the Wiener and Hashin–Shtrikman bounds. The observed shift of the experimental points reflects the changes in the structure of the investigated composites.     

Brodie's or Hummers’ Method: Oxidation Conditions Determine the Structure of Graphene Oxide

Synthesis and studies of graphite oxide started more than 150 years ago and turned into a boom by the measurements of the outstanding physical properties of graphene. A series of preparation protocols emanated trying to optimize the synthesis of graphene oxide in order to obtain a less defective material, as source for graphene. However, over-oxidation of the carbon framework hampered establishing structure-property relationships. Here, the fact that two different synthetic methods for graphene oxide preparation lead to very similar types of graphene oxide with a preserved graphene lattice is demonstrated. Either sodium chlorate in nitric acid (similar to Brodie's method) or potassium permanganate in sulfuric acid (similar to Hummers’ method) treatment are possible; however, reaction conditions must be controlled. With a preserved carbon lattice analytical differences between the samples relate to the altered on-plane functionality. Consequently, terming preparation protocols “according to Brodie's/Hummers’ method” is not sufficient.     

Synthesis and crosslinking reaction of a novel polymer containing benzoxazine and phenyleneethynylene moieties in the main chain

A novel polymer, poly( 1 ) containing benzoxazine and phenyleneethynylene moieties in the main chain with number‐average molecular weights ranging from 1400 to 9800 was obtained quantitatively by the Sonogashira–Hagihara coupling polymerization of the corresponding iodophenyl‐ and ethynylphenyl‐substituted monomer 1 . Poly( 1 ) was heated at 200 °C under N₂ for 2 h to obtain the cured polymer, poly( 1 )′ via the ring‐opening polymerization of the benzoxazine moieties. The structures of the polymer before and after curing were confirmed by ¹H‐NMR, IR, and UV–vis absorption and reflectance spectroscopies. Poly( 1 )′ was thermally more stable than monomer 1 and poly( 1 ). A specimen was prepared from a mixture of poly( 1 ) and phenol‐diaminodiphenylmethane type benzoxazine 2 by heating at 200 °C for 2 h under N₂. The poly( 1 )/ 2 resin was thermally stable than bisphenol‐A type benzoxazine resin 3 . Poly( 1 ) exhibited XRD peaks corresponding to the d‐spacings of 1.26–0.98 and 0.40 nm, assignable to the repeating monomer unit and alignment of polymer molecules, respectively. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2581–2589     

Nano-bio interface study between Fe content TiO2 nanoparticles and adenosine triphosphate biomolecules

The advent of nano-biotechnology has inspired the interface interaction study between engineered nanoparticles (NPs) and biomolecules. The interaction between Fe content titanium dioxide (TiO₂) NPs and adenosine triphosphate (ATP) biomolecules has been envisioned. The effect of Fe content in TiO₂ matrix was studied using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The increase in Fe content caused a decrease in particle size with change in morphology from spherical to one-dimensional rod structure. The Fe incorporation in the TiO₂ matrix reduced the transition temperature from anatase to rutile (A-R) phase along with formation of haematite phase of iron oxide at 400°C. The interaction of Fe content TiO₂ NPs with ATP molecule has been studied using spectroscopic method of Raman scattering and infrared vibration spectrum along with TEM. Fe content in TiO₂ has enhanced the interaction efficiency of the NPs with ATP biomolecules. Raman spectroscopy confirms that the NPs interact strongly with nitrogen (N₇) site in the adenine ring of ATP biomolecule. Engineering of Fe content TiO₂ NP could successfully tune the coordination between metal oxide NPs with biomolecules, which could help in designing devices for biomedical applications.     

Efficient Detection of Phthalate Esters in Human Saliva via Fluorescence Spectroscopy

The detection of phthalates in human biologic fluids remains an important research objective because it provides an important measure of an individual’s exposure to this class of compounds, which have known deleterious health effects. Moreover, the ability to accomplish such detection in fluids that are easy to collect, such as saliva and urine, provides additional practical advantages. Reported herein is the application of cyclodextrin-promoted fluorescence energy transfer and fluorescence modulation to accomplish precisely such detection: the development of sensitive and selective florescence-based detection methods for phthalates in saliva, an easily collectable human biologic fluid. Such saliva-based detection methods occur with high levels of selectivity (100% differentiation) and sensitivity (limits of detection as low as 0.089?µM), and provide significant potential in the development of practical phthalate detection devices.     

Distorted Phthalocyanines by Click Chemistry: Photoacoustic,Photothermal, and Surface-Enhanced Resonance Raman Studies

Distortion of nominally planar phthalocyanine macrocycles affects the excited state dynamics in that most of the excited-state energy decays through internal conversion. A click-type annulation reaction on a perfluorophthalocyanine platform appending a seven-membered ring to the β-positions on one or more of the isoindoles distorts the macrocycle and modulates solubility. The distorted derivative enables photoacoustic imaging, photothermal effects, and strong surface-enhanced resonance Raman signals.     

Weak Pnictogen Bond with Bismuth: Experimental Evidence Based on Bi−P Through-Space Coupling

To study pnictogen bonding involving bismuth, flexible accordion-like molecular complexes of the composition [P(C₆H₄-o-CH₂SCH₃)₃BiX₃], (X=Cl, Br, I) have been synthesised and characterised. The strength of the weak and mainly electrostatic interaction between the Bi and P centres strongly depends on the character of the halogen substituent on bismuth, which is confirmed by single-crystal X-ray diffraction analyses, DFT and ab initio computations. Significantly, ²⁰⁹Bi–³¹P through-space coupling (J=2560 Hz) is observed in solid-state ³¹P NMR spectra, which is so far unprecedented in the literature, delivering direct information on the magnitude of this pnictogen interaction.