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Practical applications like very thin stress-strain sensors require high strength, stretchability, and conductivity, simultaneously. One of the approaches is improving the toughness of the stress-strain sensing materials. Polymeric materials with movable cross-links in which the polymer chain penetrates the cavity of cyclodextrin (CD) demonstrate enhanced strength and stretchability, simultaneously. We designed two approaches that utilize elastomer nanocomposites with movable cross-links and carbon filler (ketjenblack, KB). One approach is mixing SC (a single movable cross-network material), a linear polymer (poly(ethyl acrylate), PEA), and KB to obtain their composite. The electrical resistance increases proportionally with tensile strain, leading to the application of this composite as a stress-strain sensor. The responses of this material are stable for over 100 loading and unloading cycles. The other approach is a composite made with KB and a movable cross-network elastomer for knitting dissimilar polymers (KP), where movable cross-links connect the CD-modified polystyrene (PSCD) and PEA. The obtained composite acts as a highly sensitive stress-strain sensor that exhibits an exponential increase in resistance with increasing tensile strain due to the polymer dethreading from the CD rings. The designed preparations of highly repeatable or highly responsive stress-strain sensors with good mechanical properties can help broaden their application in electrical devices., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Short-lived radioactive metals are important tracers in clinical diagnosis. Radioactive metals for clinical use are produced from suitable target metals in cyclotrons. The trace amount of radioactive metal produced is contained in a relatively large amount of target metal. A rapid and effective method is required to isolate the radioactive metal. In the present study, selective complex formation followed by cation-exchange adsorption was performed in a continuous flow-based system. Ethylenediamine -N , N , N ', N '-tetraacetic acid (EDTA) was selected as the ligand after simulation of the separation of radioactive Ga from the target (Zn). Selectively, the Ga-EDTA complex passed through the cation trap, while Zn 2+ was trapped. This separation principle is opposite to that of typical solid-phase extraction, which captures the target ion. The proposed separation was performed in a flow-based system with a parallel, open-channel ion trap. The performance was optimized by altering the channel dimensions, channel-filling mesh, and flow rate. Finally, the target radioactive metal, Ga, was selectively and effectively (>99%) separated from a mixture of 50 fg Ga/L and 100 mg Zn/L. The concentration of Zn remaining in the Ga solution was 2.3 μg/L. The complexed Ga was converted to free Ga 3+ by a simple UV irradiation method. The proposed method effectively and rapidly separates trace amounts of radioactive metals contained in larger amounts of target metals using a simple flow system that can be operated on site.

Heterostructures of two-dimensional (2D) atomic crystals provide fascinating molecular-scale design elements for emergent physical phenomena and functional materials, as integrating distinct monolayers into vertical heterostructures can afford coupling between disparate properties. However, the available examples have been limited to either van der Waals (vdW) or electrostatic (ES) heterostructures that are solely composed of noncharged and charged monolayers, respectively. Here, we propose a "vdW-ES heterostructure" chemical design in which charge-neutral and charged monolayer-building blocks with highly disparate chemical and physical properties are conjugated vertically through asymmetrically charged interfaces. We demonstrate vdW-ES heteroassembly of semiconducting MoS 2 and dielectric Ca 2 Nb 3 O 10 - (CNO) monolayers using an amphipathic molecular starch, resulting in the emergence of trion luminescence observed at the lowest energy among MoS 2 -related materials, probably due to interfacial confinement effects given by vdW-ES dual interactions. In addition, interface engineering leads to tailored exciton of the vdW/ES heterostructures owing to the pronounced dielectric proximity effects, bringing an intriguing interlayer chemistry to modify 2D materials. Furthermore, the current approach was successfully extended to create a graphene/CNO heterostructure, which verifies the versatility of the preparative method.

Graphite-related materials play an important role in various kinds of devices and catalysts. Controlling the properties of such materials is of great significance to widen the potential applications and improve the performance of such applications as field emission devices and catalyst for fuel cells. In particular, the work function strongly affects the performance, and thus development of methods to tune the work function widely is urgently required. Here, we achieved wide-range control of the work function of graphite by nitrogen and hydrogen plasma treatments. The time of hydrogen plasma treatment and the amount of nitrogen atoms doped beforehand could control the work function of graphite from 2.9 to 5.0 eV. The formation of a surface dipole layer and the nitrogen-derived electron donation contributed to such lowering of the work function, which is advantageous for applications in various fields., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

The runt-related transcription factor (RUNX) family has been associated with cancer development. The binding of RUNX family members to specific DNA sequences is hypothesized to promote the expression of downstream genes and cause cancer proliferation. On the basis of this proposed mechanism of cancer growth, we developed conjugate 1, which inhibits the binding of RUNX to its target DNA. Conjugate 1 is a DNA-alkylating pyrrole-imidazole (PI) polyamide conjugate containing chlorambucil as an anticancer agent. Conjugate 1 was reported to have a marked anticancer effect in mouse models of acute myeloid leukemia. Although the effectiveness of 1 has been demonstrated in vivo, the detailed mechanism by which it alkylates DNA is unknown. Here, we chemically elucidated the molecular characteristics of conjugate 1 to confirm its potential as a RUNX-inhibiting drug. We also generated an alternative conjugate 2, which targets the same DNA sequence, by replacing one pyrrole with β-alanine. Comparison of the characteristics of conjugates 1 and 2 suggested that reaction selectivity and binding affinity to the RUNX-binding sequence were improved by the introduction of β-alanine. These findings indicate the possibility of DNA-alkylating PI polyamides as candidates for cancer chemotherapeutics.

The G-quadruplex (G4) is one type of higher-order structure of nucleic acids and is thought to play important roles in various biological events such as regulation of transcription and inhibition of DNA replication. Pyrrole-imidazole polyamides (PIPs) are programmable small molecules that can sequence-specifically bind with high affinity to the minor groove of double-stranded DNA (dsDNA). Herein, we designed head-to-head hairpin PIP dimers and their target dsDNA in a model G4-forming sequence. Using an electrophoresis mobility shift assay and transcription arrest assay, we found that PIP dimers could induce the structural change to G4 DNA from dsDNA through the recognition by one PIP dimer molecule of two duplex-binding sites flanking both ends of the G4-forming sequence. This induction ability was dependent on linker length. This is the first study to induce G4 formation using PIPs, which are known to be dsDNA binders. The results reported here suggest that selective G4 induction in native sequences may be achieved with PIP dimers by applying the same design strategy.

We proposed a novel but facile method for growing organic semiconductor single-crystals via solvent vapor annealing (SVA) under electric field. In the conventional SVA growth process, nuclei of crystals appeared anywhere on the substrate and their crystallographic axes were randomly distributed. We applied electric field during the SVA growth of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) on the SiO2/Si substrate on which a pair of electrodes had been deposited beforehand. Real-time observation of the SVA process revealed that rodlike single crystals grew with their long axes parallel to the electric field and bridged the prepatterned electrodes. As a result, C8-BTBT crystals automatically formed a field effect transistor (FET) structure and the mobility reached 1.9 cm(2)/(V s). Electric-field-assisted SVA proved a promising method for constructing high-mobility single-crystal FETs at the desired position by a low-cost solution process.

We have investigated the motion of growing pentacene single crystals in solution under various electric fields. The pentacene single crystals in 1,2,4-trichlorobenzene responded to the electric field as if they were positively charged. By optimizing the strength and frequency of an alternating electric field, the pentacene crystals automatically bridged the electrodes on SiO2. The pentacene crystal with a large aspect ratio tended to direct the [1̅10] orientation parallel to the conduction direction, which will be suitable from a viewpoint of anisotropy in mobility. The present result shows a possibility of controlling the position and orientation of organic single crystals by the use of an electric field, which leads to high throughput and low cost industrial manufacturing of the single crystal array from solution.

The phase transition behavior of the 5-aminotetrazole (5-ATZ) crystal was studied in the range of room temperature to the melting point by the differential scanning calorimetry and powder X-ray diffraction techniques to investigate the dehydration phenomenon and to obtain the physical state of the high temperature phase. We found that 5-ATZ has one monohydrate crystal phase and three anhydrous crystal phases (I, II, and III) up to its melting point. The dehydration reaction of the monohydrate crystal occurred at about 50 °C. The dehydration enthalpy was 12.2 kcal/mol. The required activation energy was calculated using the Kissinger method, yielding the value of 27.1 kcal/mol. The phase transitions accompanying the sublimation from phase I to phase II and from phase II to phase III were observed during the prolonged heating at 175 °C. The dehydration phenomenon was also examined through quantum chemical calculations, and the calculated energy to eliminate a water molecule from the monohydrate crystal by the density functional theory at the M06/cc-pVTZ level basically agreed with the experimentally determined dehydration enthalpy.

Farnesyl diphosphate synthases have been shown to possess seven highly conserved regions (I-VII) in their amino acid sequences [Koyama et al. (1993) J. Biochem. (Tokyo) 113, 355-363]. Site-directed mutants of farnesyl diphosphate synthase from Bacillus stearothermophilus were made to evaluate the roles of the conserved aspartic acids in region VI and lysines in regions I, V, and VI. The aspartate at position 224 was changed to alanine or glutamate (mutants designated as D224A and D224E, respectively); aspartates at positions 225 and 228 were changed to isoleucine and alanine (D225I, D228A); lysine at position 238 was changed to either alanine or arginine (K238A, K238R). The lysines at positions 47 and 183 were changed to isoleucine and alanine (K471, K183A), respectively. Kinetic analyses of the wild-type and mutant enzymes indicated that the mutagenesis of Asp-224 and Asp-225 resulted in a decrease of Kcat values of approximately 10(4)- to 10(5)-fold compared to the wild type. On the other hand, D228A showed a Kcat value approximately one-tenth of that of the wild type, and the k(m) value for isopentenyl diphosphate increased approximately 10-fold. Both K471 and K183A showed k(m) values for isopentenyl diphosphate 20-fold larger and kcat values 70-fold smaller than the wild type. These results suggest that the two conserved lysines in regions I and V contribute to the binding of isopentenyl diphosphate and that the first and the second aspartates in region VI are involved in catalytic function. Aspartate-228 is also important for the binding of isopentenyl diphosphate rather than for catalytic reaction.

p-(Chloromercuri)benzoic acid inhibited the catalytic activity of Bacillus stearothermophilus farnesyl diphosphate synthase (FPP synthase), which contains only two cysteine residues at positions 73 and 289. In order to explore the role of the cysteine residues, either or both of them were replaced with phenylalanine or serine. Five mutant enzymes, C73F, C73S, C289F, C289S, and C73S-C289S, were overproduced in Escherichia coli and purified to homogeneity. All of them were active as farnesyl diphosphate synthase, showing specific activities comparable to that of the wild-type enzyme. These results indicate that neither of the cysteines is essential for catalytic function. The C73F mutant, however, was very sensitive to heat treatment, while C73S was as highly stable as the wild type. The Km value of C289F for isopentenyl diphosphate is 10 times that of the wild type. The wild-type enzyme was converted into an oxidized form which was separable from the native enzyme on ion-exchange chromatography, and this conversion was accelerated by cupric ions. Similar conversion has previously been reported by several researchers, who found the occurrence of two forms of pig liver FPP synthase and who attributed this phenomenon to the oxidoreduction of sulfhydryl and disulfide groups. However, even the C73S-C289S mutant, which has no cysteine residues, was also converted into an oxidized form as in the case of the wild-type enzyme. These results provide evidence that residues other than cysteine are involved in the conversion of this enzyme into the oxidized form.