Chromogenic crown ether reagents for spectrophotometric determinations of sodium and potassium

Crown ethers carrying a phenolic group, 2-hydroxyphenoxymethyl-15-crown-5 and -18-crown-6, were synthesized. Introduction of nitro groups in the 3- and 5-positions of the aromatic nucleus or introduction of a 4-nitrophenylazo group in the 5-position gives a series of chromogenic reagents suitable for the extraction spectrophotometry of sodium and potassium. Sodium in human blood serum was successfully determined by using the (2-hydroxy-3,5-dinitrophenyl)oxymethyl-15-crown-5 reagent. The molar absorptivity of the sodium complex is 14 000 l mol^-1 cm^-1 at 423 nm.     

New vesicle formation upon oleate addition to preformed vesicles

The size distribution of new vesicles formed after addition of oleate in different forms to preformed egg yolk phosphatidylcholine (EggPC) vesicles was studied by gel exclusion chromatography. The addition of oleate to preformed vesicles resulted in the formation of new small vesicles. Fission of preformed vesicles incorporated by oleate and partial solubilization of the vesicles by addition of oleate in micellar form were involved in the process of the new small vesicle formation.     

Tunable design strategy for fluorescence probes based on 4-substituted BODIPY chromophore: improvement of highly sensitive fluorescence probe for nitric oxide

4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) is a well-known fluorophore, with a high molar extinction coefficient and high fluorescence quantum efficiency (Phi(fl)). Furthermore, its structure can be modified to change its excitation and emission wavelengths. However, little work has been done on the structural modification of fluorines at the B-4 position with other functional groups. We synthesized 4-methoxy-substituted BODIPY derivatives in satisfactory yields, and found that they exhibited improved solubility in aqueous solution. Moreover, their oxidation and reduction potentials were greatly decreased without any change in their absorbance and fluorescence properties. These features of 4-substituted BODIPYs may be useful for developing novel fluorescence probes based on the intramolecular photoinduced electron transfer (PeT) mechanism, because it is possible to optimize the PeT process precisely by modulating the electrochemical properties of the fluorophore. The value of this approach is exemplified by its application to the development of a highly sensitive and pH-independent fluorescence probe for nitric oxide.     

Beta-NMR measurement of 58Cu in Si

The β-NMR study of short-lived nucleus ⁵⁸Cu (I ^π ?=?1^?+?, T _1/2?=?3.2 s) in Si has been performed. Spin polarization of ⁵⁸Cu induced by the charge exchange reaction of ⁵⁸Ni was observed in Si at 15 K. The ⁵⁸Cu magnetic moment $|\upmu[^{58}\mbox{Cu}]| = (0.46 \pm 0.03)\upmu_{\rm N}$ deduced from the β-NMR spectrum is consistent with the previous results on the laser spectroscopy. The present result shows that the ⁵⁸Cu nucleus is promising as a new nuclear probe for the microscopic study of Cu impurities in Si.     

Precise nuclear moments of extremely proton-rich nuclus 23 Al

Electric quadrupole coupling constant eqQ/h of the extremely proton-rich ²³Al (I ^π ?=?5/2^?+?, T _1/2?=?0.47 s) nucleus implanted into an Al₂O₃ single crystal has been measured for the first time, using the β-ray detecting nuclear quadrupole resonance method (β-NQR) in a high magnetic field. As a preliminary result, the quadrupole coupling constant was determined as |eqQ/h(²³Al) |?=?2.66±0.77 MHz. Using the quadrupole coupling constant of ²⁷Al in Al₂O₃ as a reference, the Q moment of the ground state of ²³Al was extracted as |Q(²³Al)|?~?160 mb, which is well explained by the shell model calculation in the sd-shell model space with the USD interaction.     

Mechanochromism,Twisted/Folded Structure Determination,and Derivatization of (N‐Phenylfluorenylidene)acridane

(N‐Phenylfluorenylidene)acridane (Ph‐FA) compounds with electron‐withdrawing and ‐donating substituents (H, MeO, Ph, NO₂, Br, F) at the para position of the phenyl group were successfully synthesized by Barton–Kellogg reactions of N‐aryl thioacridones and diazofluorene. By using the substituent on the nitrogen atom to alter the electronic properties, both the folded and twisted conformers of p‐NO₂‐C₆H₄‐FA could be crystallographically characterized, which enabled the charge transfer from the electron‐donating acridane moiety to the electron‐accepting fluorenylidene moiety to be understood. Ground‐state mechanochromism, thermochromism, vapochromism, and proton‐induced chromism were demonstrated between the folded and twisted conformations of the conformers. Protonation and chemical oxidation of Ph‐FA gave two stable acridinium compounds, namely, the fluorenylacridinium and acridinium radical cations. The present study will contribute to the development of functional dyes and organic semiconductors.     

Recoil effects in high-energy photoemission beyond single-site approximation

Recoil effects of photoelectrons excited by high-energy X-rays are studied beyond the simplest approximation where elastic scatterings of photoelectrons are completely neglected (single-site approximation). At first we have shown that the simple free atom energy shift is accurately obtained within the harmonic and the single-site approximations. Beyond the single-site approximation, this simple formula does not work, but still simple classically acceptable formula can be used to explain the recoil energy shift. Illustrative numerical calculations show that the energy shifts caused by the photoelectron diffraction amounts to 5–8 meV for graphite-like carbon and about 100 meV for LiI₆${\text{LiI}}_6$ cluster at _?k=5${?}_k=5$–7 keV, and show oscillations as functions of the photoelectron energy. Furthermore we discuss the recoil effects in photoemission from extended levels by use of the tight-binding approach. Our approach naturally provides not only Debye–Waller factors but also the recoil factors. In addition to the phonon excitation, we also study the recoil effects associated with plasmon losses where intrinsic and extrinsic processes can interfere each other. Only the latter can contribute to the recoil energy shift.     

Prospective trial of a navigator setting under left hepatic lobe on magnetic resonance cholangiopancreatography using a free-breathing prospective acquisition correction technique

PURPOSE: To prospectively compare the image acquisition time and image quality obtained by navigator setting under the left hepatic lobe vs. on the right diaphragm on magnetic resonance cholangiopancreatography (MRCP) using a free-breathing navigator-triggered prospective acquisition correction technique (PACE). MATERIALS AND METHODS: Fifty consecutive patients prospectively underwent three-dimensional T2-weighted turbo spin-echo MRCP using PACE with the navigator randomly set either under the left hepatic lobe or on top of the right diaphragm. Image acquisition time and subjective image quality were compared on a five-point scale using Student's t-test and Mann-Whitney's U test, respectively. RESULTS: There was no significant difference for mean acquisition time (6.1+/-1.6 vs. 6.3+/-1.2 min, P=.689) between the left hepatic lobe group and right diaphragm group. Mean subjective image quality was significantly worse in the left hepatic lobe group than in the right diaphragm group (4.1 vs. 4.7, P=.044). CONCLUSION: Setting the navigator under the left hepatic lobe for MRCP using PACE causes the data processing to be more difficult. As well, under current circumstances, it does not contribute to reducing acquisition time or improving the image quality.