Since we discovered pillar
n
arenes in 2008, many chemists have developed a strong interest in pillar
n
arene chemistry because of the many advantages associated with these materials, including their ...facile and high yielding synthesis, versatile functionality, planar chirality and unique host-guest properties. In this feature article, we discuss recent advances in the field of supramolecular chemistry based on the use of pillar
n
arenes as substrates for copper(
i
)-catalysed alkyne-azide cycloaddition (CuAAC) "click" chemistry. The CuAAC reaction provides facile access to 1,4-disubstituted triazoles by a reaction between alkyne and azido substrates in the presence of a Cu(
i
) catalyst. Pillar
n
arenes bearing alkyne or azido groups can therefore be used as substrates for this reaction. Herein, we discuss not only the synthesis of pillar
n
arenes bearing alkyne or azido groups but also the application of these functionalised systems to the CuAAC reaction to construct supramolecular assemblies. We also discuss the rational molecular design and synthesis of guest compounds using the CuAAC reaction because linear alkanes sandwiched between 1,2,3-triazole moieties are good guests for cyclic pentamer pillar5arenes.
We discuss the functionalization of pillar
n
arenes using copper(
i
)-catalysed alkyne-azide cycloaddition (CuAAC) "click" chemistry.
The widely accepted threshold of <65 μm for coronary plaque fibrous cap thickness was derived from postmortem studies of ruptured plaques and may not be appropriate for in vivo rupture-prone plaques. ...We investigated the relationship between fibrous cap thickness and plaque rupture using optical coherence tomography (OCT).
We studied 266 lesions (103 from patients with acute coronary syndrome and 163 from patients with stable angina) before percutaneous coronary intervention using OCT. Ruptured and non-ruptured lipid-rich plaques were identified and the thinnest and most representative fibrous cap thickness were determined. Cap thickness was reliably measured in 71 ruptured and 111 non-ruptured plaques. From the ruptured plaques, the median thinnest cap thickness was 54 μm (50-60). The median most representative cap thickness was 116 μm (103-136). For non-ruptured plaques, the median thinnest cap thickness was 80 μm (67-104) and 182 μm (156-216) for most representative cap thickness. In 95% of ruptured plaques, the thinnest cap thickness and most representative cap thickness were <80 and <188 μm, respectively. The best cut-offs for predicting rupture were <67 μm (OR: 16.1, CI: 7.5-34.4, P < 0.001) for the thinnest cap thickness and <151 μm (OR: 35.6, CI: 15.0-84.3, P < 0.001) for most representative cap thickness. These two measures were modestly correlated (r(2) = 0.39) and both independently associated with rupture.
In vivo critical cap thicknesses were <80 μm for the thinnest and <188 μm for most representative fibrous cap thickness. Prospective imaging studies are required to establish the significance of these values.
Aims Transradial coronary intervention (TRI) introduces a trauma to the radial artery (RA), possibly influencing quality as a bypass conduit if subsequently used. We sought to determine the acute and ...chronic effects of TRI on the RA by optical coherence tomography (OCT). Methods and results Immediately after TRI completion, 73 RAs in 69 patients were examined. The sheath was pulled back 2 cm distal to the puncture site, and OCT imaging was performed. The acute injuries and intimal thickening were compared between first-TRI RAs and repeat-TRI RAs. Intimal tears were observed in 49 RAs (67.1%) and were more frequent in the distal than in the proximal RA (P = 0.001). Medial dissections were not uncommon (26 RAs, 35.6%). The frequency of acute injury was significantly higher in repeat-TRI RAs (P < 0.001). Intima/medial area, the maximum intimal thickness/medial thickness ratio, and per cent narrowing were all significantly greater in repeat-TRI RAs in the distal and proximal RA. Multivariate analysis revealed that a repeated TRI procedure was the only independent predictor of intimal thickening. Conclusion Optical coherence tomography clearly demonstrated significant acute injuries and chronic intimal thickening of RA after TRI. Further study should evaluate the impact of these effects when TRI RAs are subsequently used as conduits, on long-term graft patency and on clinical outcomes after bypass surgery.
A host–guest conjugate consisting of a pillar5arene and an ethylene moiety containing a triazole group at one end and a perfluorooctyl group at the other end was synthesized. The host–guest conjugate ...displayed unusual real-time scale solid-state self-inclusion complexation behaviour. The host–guest conjugate formed a de-threaded supramolecular structure only in solution, even at high concentrations. However, heating the solid-state host–guest conjugate led to the formation of a self-inclusion complex structure at a real-time scale; at 100 °C, it took ca. 20 h to form the self-inclusion complex at the equilibrium state at a conversion of 85%. The self-inclusion complex converted to the de-threaded form at a real-time scale when it was stored in solvents with small molecules, which worked as competitive guests.
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IJS, KILJ, NUK, UL, UM, UPUK
The objective is to assess electrocardiographic characteristics predicting the precise location of ventricular arrhythmia (VA) origin within the right ventricle (RV) close to the His bundle (HB) ...region.
Twenty-five patients (14 men, age 65 ± 14 years) underwent successful catheter ablation of para-Hisian VA. Ventricular arrhythmias were considered to arise in the vicinity of the HB region based on the criteria that mapping exhibited the earliest RV activation before QRS onset in the HB region. Surface 12-lead electrocardiogram during the para-Hisian VAs was analysed. Of the 25 patients, 8 originated from the RV antero-septum just above the HB region, and 17 arose from the RV mid-septum just below the HB region. There was no significant difference in precedence of the local ventricular electrogram of the HB region from the onset of surface QRS during VAs. Surface electrocardiographic findings were characterized according to R-wave amplitude in lead I (0.43 ± 0.18 vs. 0.67 ± 0.19 mV, P = 0.005), mean R-wave amplitude in inferior leads (1.12 ± 0.32 vs. 0.71 ± 0.24 mV, P = 0.002), R-wave amplitude ratio of leads III/II (0.77 ± 0.10 vs. 0.50 ± 0.23, P = 0.005), incidence of S-wave in lead III 1/8 (13%) vs. 16/17 (94%), P < 0.001, and QS morphology in lead V1 3/8 (38%) vs. 17/17 (100%), P = 0.001.
Despite their adjacent locations, para-Hisian VAs could be classified into two subgroups with distinctive electrocardiographic characteristics according to origin either above or below the HB region. The present findings can be helpful for planning catheter ablation of para-Hisian VAs, and can reduce the risk of inadvertent atrioventricular block.
Decolorization of an organic dye by discharge in high conductive water using a pulsed power generator and a discharge reactor was investigated. The discharge reactor consisted of a glass tube and a ...tungsten wire inserted into the glass tube, which was immersed in the water. Room air was injected into the glass tube to generate bubbles in the water. High voltage pulses were generated by an inductive-energy storage system using semiconductor opening switch (SOS) and by a magnetic pulse compression circuit. Fast recovery diodes were used as SOS diode in the inductive-energy storage system. The pulse width was changed in range from 10 to 1200 ns. The high voltage was applied to the tungsten wire. Indigo carmine was employed as a specimen to evaluate decolorization efficiency. Potassium nitrate was used to adjust the solution conductivity. The dye solution was successfully decolorized at 7 mS/cm conductivity. Energy efficiency for decolorization increased from 0.680 to 55.6 mg/Wh with decreasing the pulse width from 1200 to 10 ns owing to the reduction of ohmic loss.
Hyperinsulinemia has been implicated in the development of diabetic nephropathy. In the present study we compared the renoprotective effects of the thiazolidinedione, pioglitazone (PGZ), to that of ...insulin in a hypertensive, obese, type II diabetic rat model. PGZ aggravated obesity and gave less glycemic control than insulin. However, renoprotection was markedly better with PZG compared to insulin as shown by lower proteinuria, improved renal function, and less histological evidence of diabetic glomerular and tubulointerstitial lesions. PZG and insulin both reduced renal accumulation of pentosidine and oxidative stress to a similar extent. In contrast, PGZ but not insulin suppressed enhanced transforming growth factor-β (TGF-β) expression. We further confirmed in cultured rat proximal tubular cells that insulin enhanced TGF-β mRNA expression and protein production. Our results identify hyperinsulinemia and the attendant increase of TGF-β expression as potential therapeutic targets in diabetes independent of glycemic control. This confirms prior clinical evidence that PZG provides renoprotection in obese, diabetic patients with nephropathy.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
For food industry production processes and other uses, a mold that produces high levels of feruloyl esterase was obtained from laboratory mold collections and other sources. It was Aspergillus ...awamori G-2 that produces high levels of feruloyl esterase. The feruloyl esterase was purified using ion-exchange chromatography, size-exclusion chromatography, and HPLC chromatography. The enzyme was identified as a monomer protein using size-exclusion chromatography. Its optimum temperature and pH were, respectively, 40 °C and pH 5. Its activity was stable at pH 3 to 5. The enzyme was combined with xylan and starch, but it was absorbed by cellulose. The km of the feruloyl esterase was 0.0019% (0.01 mM). The enzyme showed stable activity at pH 3 and 50 °C, making this enzyme useful for food production.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Vitamin K is considered to be involved in the pathological mechanisms of coronary artery calcification (CAC). Correlation between CAC and plasma vitamin K levels was studied. A total of 103 patients, ...with at least one coronary risk factor, were studied. CAC was measured using 64-slice multislice computed tomography (MSCT) and divided into three groups: none (CAC score = 0; n 25), mild to moderate (0 < CAC score < 400; n 52) and severe (CAC score > 400; n 26). Phylloquinone (PK) and menaquinone (MK)-4 and MK-7 were measured by HPLC-tandem MS. Mean age of patients was 64 (sd 13) years, of which 57 % were male. Median CAC score was 57·2. Median levels of PK, MK-4 and MK-7 were 1·33, 0 and 6·99 ng/ml, showing that MK-7 was the dominant vitamin K in this population. MK-7 showed a significant inverse correlation with uncarboxylated osteocalcin (ucOC, P = 0·014), protein induced by vitamin K absence of antagonist-2 (PIVKA-2, P = 0·013), intact parathyroid hormone (P = 0·007) and bone-specific alkaline phosphatase (P = 0·018). CAC showed an inverse correlation with total circulating uncarboxylated matrix Gla protein (t-ucMGP, P = 0·018) and Hb (P = 0·05), and a positive correlation with age (P < 0·001), creatinine, collagen type 1 cross-linked N-terminal telopeptide (NTX, P = 0·03), pulse wave velocity (P < 0·001) and osteoprotegerin (P < 0·001). However, CAC did not have a significant correlation with plasma levels of PK, MK-4 or MK-7. In conclusion, plasma MK-7, MK-4 or PK level did not show significant correlation with CAC despite the association between plasma vitamin K levels and vitamin K-dependent proteins such as ucOC or PIVKA-2.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
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