Superconductivity in the α-Form Layer Structured Metal Nitride Halide

Layered metal nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I) have two polymorphs, including α- and β-forms, which have the FeOCl and SmSI structures, respectively. These compounds are band insulators and become metals and show superconductivity after electron doping by intercalating alkali metals between the layers. The superconductivity of β-form had been extensively characterized from decades ago, but it is not easy to consistently interpret all experimental results using conventional phonon-mediated Bardeen–Cooper–Schriefer mechanisms. The titanium compound TiNCl crystallizes only in the α-form structure. TiNCl also exhibits superconductivity as high as ~16 K after electron doping by intercalating metals and/or organic basis. It is important to compare the superconductivity of different M–N networks. However, α-form compounds are vulnerable to moisture, unlike β-form ones. The intercalation compounds are even more sensitive to humid air. Thus, there are few experimental studies on the superconducting mechanism of α-form, although it has been discussed for exotic Cooper-pairing mechanisms. This short review gathers the recent progress in experimental studies of TiNCl

Soft x-ray irradiation induced metallization of layered TiNCl

We have performed soft x-ray spectroscopy in order to study the photoirradiation time dependence of the valence band structure and chemical states of layered transition metal nitride chloride TiNCl. Under the soft x-ray irradiation, the intensities of the states near the Fermi level (EF) and the Ti3+ component increased, while the Cl 2p intensity decreased. Ti 2p–3d resonance photoemission spectroscopy confirmed a distinctive Fermi edge with Ti 3d character. These results indicate the photo-induced metallization originates from deintercalation due to Cl desorption, and thus provide a new carrier doping method that controls the conducting properties of TiNCl

Change in the electronic structure of the bismuth chalcogenide superconductor CsBi4-xPbxTe6 by dissociation of the bismuth dimers

CsBi4−x Pb x Te6 is synthesized and the superconductivity associated with the structural transition from Pb substitution is studied. Photoemission spectroscopy measurements are performed in order to elucidate the relationship between the electronic structure and the occurrence of the superconductivity. When Bi is substituted with Pb, an electron doping-like change in the electronic structure is directly observed which is contrary to the naive expectation of hole doping. This observation is consistent with band structure calculations and appears to be a unique characteristic of CsBi4−x Pb x Te6 because of the dissociation of Bi dimers upon Pb substitution. These results indicate that it may be possible to control the electron and hole doping via manipulating the Bi dimers through Pb substitution

Synthetic Route of Layered Titanium Nitride Chloride TiNCl Using Sodium Amide

A synthetic route in a closed system for layered titanium nitride chloride TiNCl has been developed using sodium amide NaNH2 as a nitrogen source. A highly crystalline sample is obtained by an appropriate thermal decomposition of aminated titanium chloride. The obtained TiNCl was also characterized using electronic resistivity measurement and photoemission spectroscopy. TiNCl showed hopping conduction compatible with an in-gap state revealed by photoelectron spectroscopy. However, it appeared highly electron-doped, albeit without showing superconductivity. Comparison with the spectrum of superconducting sodium-doped samples suggests the presence of the microstructure required to exhibit superconductivity

Soft x-ray irradiation induced metallization of layered TiNCl

We have performed soft x-ray spectroscopy in order to study the photoirradiation time dependence of the valence band structure and chemical states of layered transition metal nitride chloride TiNCl. Under the soft x-ray irradiation, the intensities of the states near the Fermi level (EF) and the Ti3+ component increased, while the Cl 2p intensity decreased. Ti 2p–3d resonance photoemission spectroscopy confirmed a distinctive Fermi edge with Ti 3d character. These results indicate the photo-induced metallization originates from deintercalation due to Cl desorption, and thus provide a new carrier doping method that controls the conducting properties of TiNCl

Microarray-Based Transcriptional Profiling of Renieramycin M and Jorunnamycin C, Isolated from Thai Marine Organisms

Renieramycin M and jorunnamycin C, two isoquinolinequinone compounds differing only at the C-22 ester side chain, were evaluated for their cytotoxic effects on human colon (HCT116) and breast (MDA-MB-435) cancer cell lines. These two compounds displayed potent cancer cell growth inhibition, their IC50 values reaching nanomolar order. To examine their effects on transcription, we carried out oligonucleotide microarray analysis with focus on the similarities and differences between the two compounds in terms of transcriptional profiles. We found that the down-regulation of PTPRK (protein tyrosine phosphatase receptor type K) can be considered as a biomarker responsive to the cytotoxic effects of this class of antitumor marine natural products

Chemistry of Renieramycins. Part 14: Total Synthesis of Renieramycin I and Practical Synthesis of Cribrostatin 4 (Renieramycin H)

The first total synthesis of (±)-renieramycin I, which was isolated from the Indian bright blue sponge Haliclona cribricutis, is described. The key step is the selenium oxide oxidation of pentacyclic bis-p-quinone derivative (3) stereo- and regioselectively. We also report a large-scale synthesis of cribrostatin 4 (renieramycin H) via the C3-C4 double bond formation in an early stage based on the Avendaño’s protocol, from readily available 1-acetyl-3-(3-methyl-2,4,5-trimethylphenyl)methyl-piperazine-2,5-dione (8) in 18 steps (8.3% overall yield). The synthesis provides unambiguous evidence supporting the original structure of renieramycin I