Development of Ion-Conductive and Vapoluminescent Porous Coordination Polymers Composed of Ruthenium(II) Metalloligand.

We synthesized two new porous coordination polymers (PCPs) {Ln7(OH)5[Ru(dcbpy)3]4·4nH2O} (Ln7-Ru4; Ln = Ce, Nd) composed of the luminescent ruthenium(II) metalloligand [Ru(4,4'-dcbpy)3]4- ([4Ru]; 4,4'-dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) and lanthanide ions Ln3+ (Ln = Ce, Nd). These two PCPs Ln7-Ru4 are isomorphous with the previously reported PCP La7-Ru4, and the lattice constants (a, c, and unit cell volume V) changed systematically according to the lanthanide contraction. All three Ln7-Ru4 compounds have OH- anion containing porous structures and a large number of hydrate water molecules within the pores, resulting in moderate ion conductivities (10-6-10-7 S cm-1) at 90% relative humidity (RH) and 298 K. In contrast, the structural transformation of Ln7-Ru4 associated with water-vapor adsorption/desorption strongly depends on the lanthanide ion; the Ln7-Ru4 compounds with larger Ln3+ ions recover the original porous structure at lower relative humidities (RH). A similar trend was observed for the ion conduction activation energy, suggesting that the bridging Ln3+ ion plays an important role in the formation of the ion-conductive pathways. La7-Ru4 and Ce7-Ru4 exhibit vapochromic luminescence associated with water vapor adsorption/desorption, arising from the 3MLCT emission of [4Ru]. This vapochromic behavior is also affected by the replacement of the Ln3+ ion; the vapochromic shift of Ce7-Ru4 was observed at RH values (near 100% RH) higher than that of La7-Ru4. 3MLCT emissions of the [4Ru] metalloligand in Nd7-Ru4 were barely observable in the visible region, but sharp emission bands characteristic of 4f-4f transitions of the Nd3+ ion were observed in the near-infrared (NIR) region (arising from the 1MLCT transition of [4Ru]), suggesting the transfer of energy from the [4Ru] 3MLCT excited state to the 4f-4f transition state of the Nd3+ ions.

Visualization of Ion Conductivity: Vapochromic Luminescence of an Ion-Conductive Ruthenium(II) Metalloligand-Based Porous Coordination Polymer.

We synthesized a new porous coordination polymer {La1.75(OH)1.25[Ru(dcbpy)3]· 16H2O} (La7-[4Ru]4; H2dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) composed of a luminescent ruthenium(II) metalloligand [Ru(4,4'-dcbpy)3](4-) and La(3+) cations. X-ray analysis for La7-[4Ru]4 revealed that the La(3+) cations and [4Ru] metalloligands are crystallized in a molar ratio of 7:4 with OH(-) counteranions and a void fraction of ∼ 25.5%. Interestingly, La7-[4Ru]4 shows a reversible structural transition triggered by water ad/desorption, which affects not only the triplet metal-to-ligand charge-transfer ((3)MLCT) emission energy but also the ion conductivity in the solid state. This correlation suggests that La7-[4Ru]4 is an interesting material that enables visualization of the ion conductivity via the (3)MLCT emission energy.

Flexible coordination polymers composed of luminescent ruthenium(II) metalloligands: importance of the position of the coordination site in metalloligands.

Coordination polymerization reactions between ruthenium(II) metalloligands [Ru(n,n'-dcbpy)](4-) ([nRu]; n = 4, 5; n,n'-dcbpy = n,n'-dicarboxy-2,2'-bipyridine) and several divalent metal salts in basic aqueous solutions afforded porous luminescent complexes formulated as [Mg(H2O)6]{[Mg(H2O)3][4Ru]·4H2O} (Mg2[4Ru]·13H2O), [Mg2(H2O)9][5Ru]·10H2O (Mg2[5Ru]·19H2O), {[Sr4(H2O)9][4Ru]2·9H2O} (Sr2[4Ru]·9H2O)2, {[Sr2(H2O)8][5Ru]·6H2O} (Sr2[5Ru]·14H2O), and {[Cd2(H2O)2][5Ru]·10H2O} (Cd2[5Ru]·12H2O). Single-crystal X-ray structural analyses revealed that the divalent metal ions were commonly coordinated by the carboxyl groups of the [nRu] metalloligand, forming porous frameworks with a void fraction varying from 11.4% Mg2[4Ru]·13H2O to 43.9% Cd2[5Ru]·12H2O. M2[4Ru]·nH2O showed a reversible structural transition accompanied by water and methanol vapor adsorption/desorption, while the porous structures of M2[5Ru]·nH2O were irreversibly collapsed by the removal of crystal water. The triplet metal-to-ligand charge-transfer emission energies of M2[4Ru]·nH2O were lower than those of [4Ru] in aqueous solution, whereas those of M2[5Ru]·nH2O were close to those of [5Ru] in aqueous solution. These results suggested that the position of the coordination site in the metalloligand played an important role not only on the structure of the porous framework but also on the structural flexibility involving the guest adsorption/desorption properties.

Up-regulation of blood arachidonate (20:4) levels in patients with chronic obstructive pulmonary disease.

CONTEXT AND OBJECTIVE: Plasma arachidonate (20:4) levels in patients with chronic obstructive pulmonary disease (COPD) were investigated. METHODS: Plasma was extracted and free fatty acids (FFAs) were separated using column chromatography and measured by fluorescence. Plasma 20:4 levels and its percentage relative to total FFA levels (%20:4) were measured in COPD (n = 18) and control (n = 20) subjects. RESULTS AND CONCLUSIONS: FFA levels were lower in COPD compared with normals. However, there was a significant increase in %20:4 levels in COPD patients (GOLD stage I/II 0.9 ± 0.4%; GOLD stage III/IV 1.1 ± 0.1%) compared with control subjects (0.6 ± 0.1, p < 0.05). %20:4 is a potential biomarker for COPD.

Cross-cultural validation of the Japanese version of the lung cancer subscale on the functional assessment of cancer therapy-lung.

BACKGROUND: The Functional Assessment of Cancer Therapy-Lung (FACT-L) questionnaire, which consists of a core questionnaire (the General Measure of FACT [FACT-G]) and a 9-item Additional Concerns comprised of a 7-item Lung Cancer Subscale (LCS), was developed in an English-speaking culture. The validation of the Japanese FACT-G was reported previously, and this report describes the cross-cultural validation of the LCS. METHODS: The Japanese version of the LCS was developed through an iterative forward-backward translation sequence used throughout the FACT Multilingual Translation Project. In evaluating psychometric performance, its construct validity was investigated with Cronbach's alpha coefficient and factor analysis. Clinical validities of a known-groups comparison and longitudinal validity were also investigated. RESULTS: The FACT-L was administered twice to 180 patients with lung cancer within 2 weeks. The Japanese LCS had borderline values for Cronbachs alpha coefficients (0.62-0.67). Factor analysis indicated that the LCS had the three dimensions of respiratory symptoms, appetite plus body weight, and clear thinking. For clinical validity, a known-groups comparison showed that the LCS could differentiate patients according to truth disclosure, as Japanese doctors sometimes do not fully inform terminally ill patients. However, responsiveness was not proved when performance status was used as an anchor, probably owing to the short interval between the administration of the two measures. CONCLUSION: The Japanese version of the LCS asked questions about multiple symptoms of patients with lung cancer, as did the original English LCS. The longitudinal clinical validity of the Japanese version should be investigated in future clinical trials.

Increased oxidative stress in patients with chronic obstructive pulmonary disease (COPD) as measured by redox status of plasma coenzyme Q10.

STUDY OBJECTIVES: The percentage of oxidized coenzyme Q10 in total coenzyme Q10 (%CoQ-10) has been shown to indicate the degree of systemic oxidative stress. Chronic obstructive pulmonary disease (COPD) is regarded as a systemic disease that is linked to oxidative stress in its pathogenesis. In this study, the plasma %CoQ-10 levels in COPD patients were determined and assessed. In addition, the effect of oxygen supplementation on plasma %CoQ-10 was also evaluated. MATERIAL AND METHODS: Thirteen COPD patients who had not received oxygen supplementation (COPD-Pt), five COPD patients who had received oxygen supplementation (COPD + O2) and 20 age-matched control subjects (CONTROL) were enrolled. We have also enrolled 83 young healthy non/slight smokers (smoking index <20 pack-year) and 24 young healthy smokers (smoking index > or = 20 pack-year) in order to assess the effect of smoking history on %CoQ-10 level. Their plasma was collected and plasma %CoQ-10 levels were determined and compared. RESULTS AND CONCLUSION: The plasma %CoQ-10 of COPD-Pt was 6.3 +/- 2.3, significantly higher than that of CONTROL, 4.7 +/- 1.6 (p < 0.05), indicating an increased oxidative stress in the patients. In contrast, no significant difference in %CoQ-10 was observed between young healthy non/slight smokers (%CoQ-10 = 3.2 +/- 0.9) and young healthy smokers (%CoQ-10 = 3.7 +/- 1.3). Our observation of five COPD patients who received an oxygen supplementation revealed that their %CoQ-10 values (4.0 +/- 1.5) were significantly lower than those in COPD-Pt subjects (p < 0.05), suggesting that oxygen supplementation ameliorates the oxidative stress. In contrast, our study showed that no significant difference was observed among the three groups in plasma levels of Vitamin C or E. In conclusion, plasma %CoQ-10 levels are increased in COPD patients and oxygen supplementation attenuates this increasing effect by COPD. This implies that %CoQ-10 might be used practically to assess the COPD patients systemically.

[Alveolar hemorrhage as a possible adverse drug reaction by gefitinib (ZD1839, Iressa)].

We experienced a case in which severe alveolar hemorrhage occurred in the course of gefitinib therapy. A 56-year-old man with non-small cell lung cancer had been treated with CDDP + CPT-11, CDDP + GEM + VNR, CDDP + TXT. After the chemotherapy with these regimens was found to be ineffective, daily oral gefitinib was started. Four weeks later, the patient complained of cough, bloody sputum and dyspnea. Chest X-ray and CT showed bilateral infiltrations with air bronchogram. Fiberoptic bronchoscopy revealed alveolar hemorrhage with an increase of lymphocytes in the BALF. After the cessation of gefitinib therapy and the administration of steroid, he gradually recovered.