A photoinduced charge transfer (PCT)-based 1,3-alternate calix[4]crown fluoroionophore containing two cation recognition sites, a crown ether ring and two facing pyreneamide groups, is synthesized. Upon addition of K+, Pb2+, or Cu2+, wavelength changes are observed in both the fluorescence and absorption spectra, but with different binding modes. With K+, fluorescence emissions of the ligand scarcely change, while addition of Pb2+ or Cu2+ produces a remarkable change in both the excimer and monomer emissions. The observed data indicate that the metal cation is encapsulated in the crown-5 ring for K+ and by the two facing amide groups in the latter case, which is verified by a metal ion exchange experiment. The wavelength shifts in both fluorescence and absorption spectra upon addition of Cu2+ show that, in contrast to Pb2+, Cu2+ interacts with the nitrogen atoms of the amide groups, resulting in a PCT mechanism.

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New fluorogenic or/and chromogenic calix[4]arenes 1-3 with two facing amide groups linked to fluorescent pyrene units are synthesized. Orientations of the pyrene units are remote from each other in 1 and face-to-face pi-stacked in 2, which produces different photophysical properties. In the excited state, the two pyrene units of 2 form a strong intramolecular excimer displaying an emission at 472 nm with a relatively weak monomer emission at 395 nm. In contrast, 1 exhibits only a monomer emission at 398 nm because intramolecular hydrogen bonding between the phenolic OH oxygens and the amide hydrogens prevents pi-stacking of the two pyrene groups. Fluorescence changes upon addition of various metal ions show that 1 has a remarkably high selectivity for In(3+) over the other metal ions tested. Compound 1 forms 2:1 (metal:ligand), as well as 1:1 complexes, with In(3+), with fluorescence varying uniquely with the complex stoichiometry. Compound 3, which possess two pyrene units and two chromogenic azo groups, shows almost the same binding behavior toward metal ions as does 1, together with additional bathochromic shifts of the absorption maximum. Compared with 1, compound 3 emits a considerably weaker fluorescence, which is attributed to electron transfer from the pyrene units to the nitro groups of the phenylazo moieties.

The objectives of this study were to identify ultrasonographic (US) abnormalities and to compare physical examination with US findings, especially of rotator cuff abnormalities in patients with shoulder pain. A total of 120 patients with shoulder pain were prospectively studied. The physical examination of shoulders was performed as follows: (1) the area of tenderness; (2) the range of passive and active motion for abduction, forward flexion, external rotation, and internal rotation; (3) Neer and Hawkins's tests for shoulder impingement; and (4) maneuvers for determining the location of the tendon lesions. Transverse and longitudinal planes from the long head of the biceps, supraspinatus, infraspinatus, and subscapularis tendons, the subacromial-subdeltoid bursa, and the glenohumeral and acromioclavicular joints were included for US examination. The range of motion most affected by shoulder pain was abduction, followed by external rotation and forward flexion. The most frequent US finding was effusion in the long head of the biceps tendon. Among the rotator cuff tendons, supraspinatus was the most frequently involved. Physical examination had low sensitivity and specificity for the detection of tendon tear. US examination leads to an anatomical diagnosis of shoulder pain in many patients. Whether the US examination of the painful shoulder improves its treatment should be investigated.

The objectives of this study were: 1) to identify the ultrasonographic (US) abnormalities and 2) to compare the findings of physical examination with US findings in rheumatoid arthritis (RA) patients with shoulder pain. We studied 30 RA patients. Physical examination was performed systemically as follows: 1) area of tenderness; 2) range of passive and active shoulder motion; 3) impingement tests; 4) maneuvers for determining the location of the tendon lesions. US investigations included the biceps, the supraspinatus, infraspinatus, and subscapularis tendons; the subacromial-subdeltoid bursa; and the glenohumeral and acromioclavicular joints. Thirty RA patients with 35 painful and 25 non-painful shoulders were examined. The range of motion affected the most by shoulder pain was abduction. The most frequent US finding of shoulder joint was effusion in the long head of the biceps tendon. Among the rotator cuff tendons, subscapularis was the most frequently involved. Tendon tear was also common among non-painful shoulders. Physical examination used for the diagnosis of shoulder pain had low sensitivity and specificity for detecting abnormalities in the rheumatoid shoulder joint. In conclusion, US abnormalities showed frequent tendon tears in our RA patients. Physical examination had low sensitivity and specificity for detecting rotator cuff tear in the rheumatoid shoulder joint.

[Reaction: see text]. Fluorogenic calix[4]arenes (1 and 2) bearing a pendent ethyleneamine on their triazacrown rings, respectively, were synthesized in the cone conformation. Compared with 4, free 1 and 2 display a relatively weak emission, reflecting that a PET process from the pendent amine group (-CH2CH2NH2) to the fluorogenic pyrenes is mainly operated. Addition of various metal ions or anions to the solution of 1 or 2 reduces the PET because the pendent alkylamine takes part in the complexation, causing their fluorescence spectra to be changed. When Pb2+, a quenching metal ion, is added to 1 or 2, their pyrene monomer emission is enhanced with their excimer emission quenched, which is due to conformational changes of the facing carbonyl groups as well as to the participation of the ethyleneamine into the three-dimensional Pb2+ ion encapsulation. In contrast, upon addition of alkali metal ions to the 1 and 2, both monomer and excimer emissions are observed to increase, which is attributable to the CHEF effect and the retained conformations. For anion sensing, both 1 and 2 show a high selectivity for F- ions over other anions tested. When the F- ion is bound to 1 or 2 by hydrogen bonding between the amide NH of the triazacrown ring and F-, both their monomer and excimer emissions are weakened due to PET from the bound F- to the pyrene units.

Background:Since its reemergence in 1993, a number of cases of Plasmodium vivax malaria have been reported in Korea. We analyzed the cases of malaria patients living in Chuncheon and its neighboring communities, to characterize its clinical manifestations and laboratory findings, and to identify any differences between our clinical findings and those of previous studies.Methods:We reviewed the clinical records of cases that were confirmed as malaria by peripheral blood smear at Chuncheon Sacred Heart Hospital from July 1998 to September 2001.Results:Forty-four cases were included in the study. All patients were infected with Plasmodium vivax, and presented with high fever; however, tertian fever developed in only 15 patients (35.7%). A number of cases showed various symptoms, which included headache, abdominal pain, nausea and vomiting. Of the 44 cases identified, 41 (93.2%) developed malaria between June and September.Thrombocytopenia was a prominent finding in 75% of the cases at diagnosis, but resolved during or after therapy. Other laboratory abnormalities such as, anemia, elevated transamines, coagulopathies, and elevated lactose dehydrogenase (LDH) were also noted. Cerebrospinal fluid (CSF), studies were performed in five cases, one of which showed pleocytosis in the CSF.Conclusion:We noted only 15 patients (35.7%) with tertian fever; the other patients showed variable fever patterns. Thrombocytopenia was the most prominent laboratory finding. Therefore, we suggest that malaria should be included in the differential diagnosis of febrile diseases with an onset between June to and September, regardless of the pattern of the fever.

1,3-Alternate calix[4]arene-based fluorescent chemosensors bearing two-photon absorbing chromophores have been synthesized, and their sensing behaviors toward metal ions were investigated via absorption band shifts as well as one- and two-photon fluorescence changes. Free ligands absorb the light at 461 nm and weakly emit their fluorescence at 600 nm when excited by UV-vis radiation at 461 nm, but no two-photon excited fluorescence is emitted by excitation at 780 nm. Addition of an Al(3+) or Pb(2+) ion to a solution of the ligand causes a blue-shifted absorption and enhanced fluorescence due to a declined resonance energy transfer (RET) upon excitation by one- and two-photon processes. Addition of a Pb(2+) ion to a solution of 1.K(+) results in a higher fluorescence intensity than the original 1.Pb(2+) complex regardless of one- or two-photon excitation, due to the allosteric effect induced by the complexation of K(+) with a crown loop.