Solvent-Free Synthesis of Core-Functionalised Naphthalene Diimides by Using a Vibratory Ball Mill: Suzuki,Sonogashira and Buchwald–Hartwig Reactions

Solvent-free synthesis by using a vibratory ball mill (VBM) offers the chance to access new chemical reactivity, whilst reducing solvent waste and minimising reaction times. Herein, we report the core functionalisation of N,N’-bis(2-ethylhexyl)-2,6-dibromo-1,4,5,8-naphthalenetetracarboxylic acid (Br₂-NDI) by using Suzuki, Sonogashira and Buchwald–Hartwig coupling reactions. The products of these reactions are important building blocks in many areas of organic electronics including organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaic cells (OPVCs). The reactions proceed in as little as 1 h, use commercially available palladium sources (frequently Pd(OAc)₂) and are tolerant to air and atmospheric moisture. Furthermore, the real-world potential of this green VBM protocol is demonstrated by the double Suzuki coupling of a monobromo(NDI) residue to a bis(thiophene) pinacol ester. The resulting dimeric NDI species has been demonstrated to behave as an electron acceptor in functioning OPVCs.     

Magnetic resonance imaging of microstructure transition in stainless steel

Magnetic resonance images are prone to artifacts caused by metallic objects. Such artifacts may not only hamper image interpretation, but also have been shown to provide information about the magnetic properties of the substances involved. In this work, we aim to explore the potential of MRI to detect, localize and characterize changes in magnetic properties that may occur when certain alloys have been exposed to a thermomechanical stress. For this purpose, stainless steel 304 L wires were drawn to induce a change from paramagnetic austenitic into ferromagnetic martensitic microstructure. The changes in magnetic behavior were quantified by analyzing the geometric distortion in spin echo and the geometric distortion and intravoxel dephasing in gradient echo images at 0.5, 1.5 and 3 T. The results of both imaging strategies were in agreement and in accordance with independent measurements with a vibrating sample magnetometer. Drawing wire to 2% of its cross-sectional area was found to increase the volume fraction of the ferromagnetic martensite from 0.3% to 80% and to enhance the magnetization up to two or three orders of magnitude. The results demonstrate the potential of MRI to locate and quantify stress-induced changes in the magnetic properties of alloys in a completely noninvasive and nondestructive way.     

An unconventional method for measuring the Tc L3‐edge of technetium compounds

Tc L₃‐edge XANES spectra have been collected on powder samples of SrTcO₃ (octahedral Tc⁴⁺) and NH₄TcO₄ (tetrahedral Tc⁷⁺) immobilized in an epoxy resin. Features in the Tc L₃‐edge XANES spectra are compared with the pre‐edge feature of the Tc K‐edge as well as other 4d transition metal L₃‐edges. Evidence of crystal field splitting is obvious in the Tc L₃‐edge, which is sensitive to the coordination number and oxidation state of the Tc cation. The Tc L₃ absorption edge energy difference between SrTcO₃ (Tc⁴⁺) and NH₄TcO₄ (Tc⁷⁺) shows that the energy shift at the Tc L₃‐edge is an effective tool for studying changes in the oxidation states of technetium compounds. The Tc L₃‐edge spectra are compared with those obtained from Mo and Ru oxide standards with various oxidation states and coordination environments. Most importantly, fitting the Tc L₃‐edge to component peaks can provide direct evidence of crystal field splitting that cannot be obtained from the Tc K‐edge.     

Epidemic contact tracing with smartphone sensors

ABSTRACT

Contact tracing is widely considered as an effective procedure in the fight against epidemic diseases. However, one of the challenges for technology based contact tracing is the high number of false positives, questioning its trust-worthiness and efficiency amongst the wider population for mass adoption. To this end, this paper proposes a novel, yet practical smartphone-based contact tracing approach, employing WiFi and acoustic sound for relative distance estimate, in addition to the air pressure and the magnetic field for ambient environment matching. We present a model combining six smartphone sensors, prioritising some of them when certain conditions are met. We empirically verified our approach in various realistic environments to demonstrate an achievement of up to 95% fewer false positives, and 62% more accurate than Bluetooth-only system. To the best of our knowledge, this paper was one of the first work to propose a combination of smartphone sensors for contact tracing.     

Strong Bragg gratings photoinduced by 633-nm illumination in evaporated As2Se3 thin films

Bragg gratings are used in several photonic devices to reflect, and thus to isolate, specific wavelengths of light. Gratings can be photoinduced in chalcogenide glasses by illumination of bandgap light in an interference pattern. We used holographic interferometry to create Bragg gratings in amorphous As2Se3 thin films with a period of 0.56 microm by illumination with 633-nm light. The quality of the gratings was tested in real time, and refractive-index modulations as high as 0.037 were measured. These gratings were found to be stable over a period of several months if they were kept in the dark.     

Investigation of free base, Mg, Sn, and Zn substituted porphyrin LB films as gas sensors for organic analytes

The visible absorption spectra of various substituted porphyrin compounds both in chloroform solution and as Langmuir-Blodgett (LB) solid-state films have been investigated. The porphyrin compounds examined were the Zn, Sn, Mg, and free base derivatives of 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphine (EHO). Changes in the absorption spectra of these materials induced by their exposure to various organic compounds are reported with a view toward determining whether this is a useful approach toward an optical gas sensor.     

SPECTRAL PERTURBATIONS OF THE AEQUOREA GREEN-FLUORESCENT PROTEIN

Abstract— In the jellyfish Aequorea, the green-fluorescent protein (GFP) functions as the in vivo bio-luminescence emitter via energy transfer from the photoprotein aequorin. Accumulated evidence has indicated that the Aequorea GFP is a relatively inflexible protein. Present evidence, however, indicates that the chromophore environment is readily accessible to a variety of external perturbants. Native Aequorea GFP has an absorbance maximum at 395 nm and a shoulder at 470 nm. In low ionic strength buffer at neutral pH and room temperature the 395/470 nm absorbance ratio is about 2.0. We show that this ratio is highly variable depending upon temperature, ionic strength, protein concentration, and pH. A maximum ratio of 6.5 (at a protein concentration of 18.6 mg/m/) and minimum of 0.42 (at a pH of 12.2) have been measured. In the latter case, the resulting absorption and excitation spectra resemble those of Renilla GFP in spectral shape (but not wavelength maximum). In all cases as the perturbant is varied the resulting spectra pass through a sharp isosbestic point, suggesting a relatively simple two-state mechanism. These spectral perturbations are fully reversible. On the basis of these results, we suggest that the chromophore binding site is conformationally flexible. pH-Dependent changes in the near-UV and visible circular dichroism spectra plus spectrophotometric titration of tyrosine residues lend additional support to this hypothesis.     

Rheo-attenuated total reflectance infrared spectroscopy: a new tool to study biopolymers

Whilst rheology is the reference technique to study the mechanical properties of unspun silk, we know little of the structure and the dynamics that generate them. By coupling infrared spectroscopy and shearing forces to study silk fibroin conversion, we are introducing a novel tool to address this gap in our knowledge. Here the silk conversion process has been studied dynamically using polarized attenuated total reflectance Fourier transform infrared spectroscopy whilst applying shear, thus revealing silk protein conformation and molecular orientation in situ. Our results show that the silk conversion process starts with a pre-alignment of the proteins followed by a rapid growth of the β-sheet formation and then a subsequent deceleration of the growth. We propose that this tool will provide further insight into not only silk but any biopolymer solution, opening a new window into biological materials.     

Generation and reactivity of N,N-dimethylaminobenzotriazolylcarbene a new nucleophilic carbene

N,N-Dimethylaminobenzotriazolylcarbene ( 5 ) reacted with phenyl isocyanate in a [1+2+2] cycloaddition and then with nucleophiles to generate various hydantoins 10 in a one-pot procedure. It was also found that this novel carbene reacted with trans-dibenzoylethylene ( 11 ) in a [1+4] cycloaddition, generating 2-dimethylamino-3-benzoyl-5-phenylfuran ( 13 ) and 2-phenyl-3-[benzotriazol-1-yl]-4-benzoylfuran ( 14 ) whose structures were confirmed by ¹H-¹³C long range correlations as well as the structure of furan 14 being confirmed by X-ray crystallography.