Acylation of heteroaromatic amines . Perbenzoylation of diaminopyridazines

Some diaminopyridazines such as 4,7-diaminoimidazo[4,5-d]pyridazine, 1-methyl-4,7-diaminoimidazo[4,5-d]pyridazine, 5,8-diaminopyrazino[2,3-d]pyridazine, 2,3-dimethyl-5,8-diaminopyrazino[2,3-d]pyridazine and 1,4-diaminophthalazine, all of which were prepared by the reaction of hydrazine with the respective vic-dicyanide as starting material, were reacted with benzoyl chloride in the presence of triethylamine, giving novel perbenzoylated derivatives in good yield. A dibenzoylation mechanism of the amino group has been proposed.     

Imaging mass spectrometry distinguished the cancer and stromal regions of oral squamous cell carcinoma by visualizing phosphatidylcholine (16:0/16:1) and phosphatidylcholine (18:1/20:4)

Most oral cancers are oral squamous cell carcinoma (OSCC). The anatomical features of OSCC have been histochemically evaluated with hematoxylin and eosin. However, the border between the cancer and stromal regions is unclear and large portions of the cancer and stromal regions are resected in surgery. To reduce the resected area and maintain oral function, a new method of diagnosis is needed. In this study, we tried to clearly distinguish the border on the basis of biomolecule distributions visualized by imaging mass spectrometry (IMS). In the IMS dataset, eleven signals were significantly different in intensity (p?<?0.01) between the cancer and stromal regions. Two signals at m/z 770.5 and m/z 846.6 were distributed in each region, and a clear border was revealed. Tandem mass spectrometric (MS/MS) analysis identified these signals as phosphatidylcholine (PC) (16:0/16:1) at m/z 770.5 in the cancer region and PC (18:1/20:4) at m/z 846.6 in the stromal region. Moreover, the distribution of PC species containing arachidonic acid in the stromal region suggests that lymphocytes accumulated in response to the inflammation caused by cancer invasion. In conclusion, the cancer and stromal regions of OSCCs were clearly distinguished by use of these PC species and IMS analysis, and this molecular identification can provide important information to elucidate the mechanism of cancer invasion.     

O1s and Mn2p NEXAFS on single-layered La1-xSr1+xMnO4: crystal field effect versus orbital coupling mechanism

O1s and Mn2p near-edge X-ray absorption spectroscopy on La_1-xSr_1+xMnO₄ (0 ≤x ≤0.5) single crystals shows that Sr doping does not only provide holes to the system but also induces a continuous transfer of electrons from out-of-plane d_3z2-r2 to in-plane d_3x2-r2/d_3y2-r2 orbitals. Furthermore, a non-vanishing electron occupation of in-plane d_x2-y2 and out-of-plane d_3z2-r2 orbitals is observed up to relatively high doping contents. These findings demonstrate that the energy difference between all these orbital types has to be very small and manifest that the orbital degree of freedom is determined not just by crystal field effects but also by orbital coupling. Moreover, the doping-dependent transfer of spectral weight observed in the current data identifies La_1-xSr_1+xMnO₄ as a charge-transfer insulator.     

Surface-modified lead–zirconium-titanate system for solution-processed ferroelectric-gate thin-film transistors

We propose the use of a La₂O₃ (LO) film as the capping layer for improvement of a semiconductor/insulator interface in a solution-processed indium–tin–oxide (ITO) ferroelectric-gate thin-film transistor (FGT) device. It is demonstrated that the LO layer acts as a good barrier film not only for preventing the interdiffusion between the ITO semiconductor and lead–zirconium-titanate (PZT) insulator layers, but also for stabilizing the PZT surface structure. The fabricated FGT device exhibited high I _on/I _off, large M _w, high μ _FE and improved retention time of about 10⁹, 3.5 V, 7.94 cm²?V^?1?s^?1 and 1 day, respectively, which are comparable to or better than those obtained with FGTs fabricated by means of conventional vacuum processes. We also point out that the key origin of the interface improvement is likely due to the incorporation of La into the PZT system, forming a La surface-modified PZT system which is more stable than the pure PZT in terms of Pb volatility and formation of oxygen vacancies.     

Viscoelastic properties of bis(phenyl)fluorene‐based cardo polymers with different chemical structure

Viscoelastic properties of urethane and ester conjugation cardo polymers that contain fluorene group, 9,9‐bis(4‐(2‐hydroxyethoxy)phenyl)fluorene (BPEF), were investigated. As for the urethane‐type cardo polymers containing BPEF in the main chain, it had a high glass‐transition temperature (T_g), which was observed as the α dispersion on viscoelastic measurement, and its temperature depended on the chemical structure of the spacing unit, such as toluene diisocyanate (TDI), 4,4′‐methylene diphenyl diisocyanate (MDI), methylene dicycloexyl diisocyanate (CMDI), and hexamethylene diisocyanate (HDI). Moreover, the T_g of urethane‐type cardo copolymers with various cardo contents increased with an increase of cardo content. Owing to the increase of T_g of cardo polymers, another molecular motion can be measured at the temperature between the α and β dispersion that was assigned to the molecular motion of urethane conjugation unit around 200 K, and it was referred to as the α_sub dispersion. The peak temperature of the α_sub dispersion was influenced by the chemical structure of the spacing unit, but it did not change for the cardo polymer containing the same spacing unit. Consequently, it was deduced that the α_sub dispersion was originated in the subsegmental molecular motions of the cardo polymers. Ester‐type cardo polymer had higher T_g in comparison with noncardo polymer that consisted of dimethyl groups (BPEP) instead of BPEF as well. The α_sub dispersion was also measured at the temperature between the α and β dispersion, which was assigned to the molecular motion of ester conjugation unit, around 220 K. For ester cardo polymer, the γ dispersion was measured in a low‐temperature region around 140 K, and it was due to a small unit motion in the ester‐type cardo polymers, such as ethoxyl unit, ? C₂H₄O? . Moreover, the intensity of the γ dispersion of noncardo polymer was higher than that of cardo polymer, which means the molecular motion was much restricted by the cardo structure of BPEF. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2259–2268, 2005     

Amorphous metal-hydrogen alloys prepared by mechano-chemical reaction

The mechano-chemical formation of crystalline and amorphous hydrides is described. Niobium transformed into β-Nb hydride by milling with liquid normal-heptane. Chromium and manganese were transformed into amorphous hydrides. The hydrocarbon served as the source of hydrogen atoms through a dehydrogenation reaction.     

Upper bound for the decay rate of the joint queue-length distribution in a two-node Markovian queueing system

This paper studies the geometric decay property of the joint queue-length distribution {p(n ₁,n ₂)} of a two-node Markovian queueing system in the steady state. For arbitrarily given positive integers c ₁,c ₂,d ₁ and d ₂, an upper bound of the decay rate is derived in the sense