Chiral molecules play indispensable roles in advanced materials and technologies. Nevertheless, no conventional, yet reliable logical strategies are available for designing chiral molecules of desired chiroptical properties. Here, we propose a general protocol for rationally aligning multiple chiral units to boost the chiroptical responses, using hexahelicene as a prototype. In this proof-of-concept study, we align two hexahelicenes in various orientations and examine by theoretical calculations to predict the best chiroptical performance for X-shaped and S-shaped double hexahelicenes. We synthesize and optically resolve both double hexahelicenes and show that they exhibit more than a twofold increase in intensity of circular dichroism and circularly polarized luminescence, experimentally validating the protocol. The enhanced chiroptical responses are theoretically assignable to the electric and magnetic transition dipole moments of component hexahelicenes aligned in the correct symmetry. A guiding principle for designing advanced molecular and supramolecular chiral materials is further discussed.
Under environmental stress, microbes are known to alter their translation patterns using sequence-specific endoribonucleases that we call RNA interferases. However, there has been limited insight regarding which RNAs are specifically cleaved by these RNA interferases, hence their physiological functions remain unknown. In the current study, we developed a novel method to effectively identify cleavage specificities with massive parallel sequencing. This approach uses artificially designed RNAs composed of diverse sequences, which do not form extensive secondary structures, and it correctly identified the cleavage sequence of a well-characterized Escherichia coli RNA interferase, MazF, as ACA. In addition, we also determined that an uncharacterized MazF homologue isolated from Pseudomonas putida specifically recognizes the unique triplet, UAC. Using a real-time fluorescence resonance energy transfer assay, the UAC triplet was further proved to be essential for cleavage in P. putida MazF. These results highlight an effective method to determine cleavage specificity of RNA interferases.
This study demonstrated prospectively the feasibility of short-term low-volume hydration.
ABSTRACT. Pulsed tissue Doppler imaging (pulsed TDI) has been demonstrated to be useful for the estimation of left ventricular (LV) systolic and diastolic functions in various human cardiac diseases. The objectives of this study were to investigate the relationship between pulsed TDI and LV function by using cardiac catheterization in healthy dogs and to evaluate the clinical usefulness of pulsed TDI in dogs with spontaneous mitral regurgitation (MR). The peak early diastolic velocity (E'), peak atrial systolic velocity (A'), and peak systolic velocity (S') were detectable in the velocity profiles of the mitral annulus in all the dogs. In the healthy dogs, S' and E' were correlated with LV peak +dP/dt and -dP/dt, respectively. E' was lower in dogs with MR than in dogs without cardiac diseases. E/E' in the MR dogs with decompensated heart failure was significantly increased in comparison with those with compensated heart failure. The sensitivity and specificity of the E/E' cutoff value of 13.0 for identifying decompensated heart failure were 80% and 83%, respectively. In addition, E/E' was significantly correlated with the ratio of left atrial to aortic diameter. These findings suggest that canine pulsed TDI can be applied clinically for estimation of cardiac function and detection of cardiac decompensation and left atrial volume overload in dogs with MR. KEY WORDS: canine, cardiac function, echocardiography, mitral regurgitation, pulsed tissue Doppler.J. Vet. Med. Sci. 67(12): 1207-1215, 2005 Doppler echocardiography is a predominant noninvasive modality that provides a large variety of useful information on cardiac conditions in human and small animal patients. Pulsed tissue Doppler imaging (pulsed TDI) derived from Doppler echocardiography can quantify the velocity of myocardial wall and/or valve annulus motions [30,31,40]. In humans, pulsed TDI of the mitral annulus and myocardial wall has been demonstrated to reflect the systolic and diastolic left ventricular (LV) function in normal subjects [30,45] and patients with dilated cardiomyopathy (DCM) [22,46], hypertrophic cardiomyopathy (HCM) [36,39,46], restrictive cardiomyopathy (RCM) [14,16,35], constrictive pericarditis [14,16,35], ischemic heart diseases [4,31,43,46], heart failure [1,24], mitral regurgitation (MR) [2,3,17], atrial fibrillation [29], arterial hypertension [13,46], and cardiac amyloidosis [20].Analysis of pulsed TDI revealed that the peak early diastolic velocity (E'), peak atrial systolic velocity (A'), and peak systolic velocity (S') are typically derived from the velocity profiles of myocardial or valve annulus motions (Fig. 1) [30]. Several studies have revealed that E' and A' are correlated with LV diastolic function [1,13,16,20,24,26,31,36,39,40,45], and S' is correlated with LV systolic function [17,20,22,29,30,43,46]. E' was almost independent of preload and showed no pseudonormal pattern in contrast to the peak early diastolic velocity of LV inflow (E) [5,24]. In addition, a ratio of E to E' (E/E') showed good correlation with pulmo...
The synthesis of the triphosphates of 4′-thiouridine and 4′-thiocytidine, 4′-thioUTP (7; thioUTP) and 4′-thioCTP (8; thioCTP), and their utility for SELEX (systematic evolution of ligands by exponential enrichment) is described. The new nucleoside triphosphate (NTP) analogs 7 and 8 were prepared from appropriately protected 4′-thiouridine and -cytidine derivatives using the one-pot method reported by J. Ludwig and F. Eckstein [(1989) J. Org. Chem., 54, 631–635]. Because SELEX requires both in vitro transcription and reverse transcription, we examined the ability of 7 and 8 for SELEX by focusing on the two steps. Incorporation of 7 and 8 by T7 RNA polymerase to give 4′-thioRNA (thioRNA) proceeded well and was superior to those of the two sets of frequently used modified NTP analogs for SELEX (2′-NH2dUTP and 2′-NH2dCTP; 2′-FdUTP and 2′-FdCTP), when an adequate leader sequence of DNA template was selected. We revealed that a leader sequence of about +15 of DNA template is important for the effective incorporation of modified NTP analogs by T7 RNA polymerase. In addition, reverse transcription of the resulting thioRNA into the complementary DNA in the presence of 2′-deoxynucleoside triphosphates (dNTPs) also proceeded smoothly and precisely. The stability of the thioRNA toward RNase A was 50 times greater than that of the corresponding natural RNA. With these successful results in hand, we attempted the selection of thioRNA aptamers to human α-thrombin using thioUTP and thioCTP, and found a thioRNA aptamer with high binding affinity (Kd = 4.7 nM).
Pentahelicene (PH) exhibits the largest absorption ( g) and luminescence ( g) dissymmetry factors among the helicene family but is configurationally and (photo)chemically labile, encumbering its application to chiroptical materials. To bypass the pitfalls, three PH units are merged in a single molecule to build D-symmetric triple pentahelicene, hexabenzotriphenylene (HBT), which attains indeed the configurational and (photo)chemical robustness through equilibrium with a C-symmetric conformer that interrupts the racemization and photocyclization. UV-vis, circular dichroism (CD), and circularly polarized luminescence (CPL) spectral examinations reveal the significantly larger g and g values for HBT than for any of configurationally robust single [ n]helicene ( n ≥ 6) and C-symmetric triple pentahelicene, trinaphthotriphenylene (TNT). Theoretical calculations precisely reproduce the main features of the experimental CD and CPL spectra of PH, HBT, and TNT, and the relevant electric and magnetic transition moments and their mutual angles well rationalize the relative CD and CPL intensities of all the single and triple pentahelicenes.
ABSTRACT. Increase in circulating vascular endothelial growth factor (VEGF) is suggested as a prognostic indicator in human patients with malignant tumors. The purpose of this study was to evaluate the clinical significance of circulating VEGF in dogs with mammary gland tumors (MGT). Both plasma and serum VEGF were significantly higher in dogs with MGT when compared with those in the healthy dogs. In dogs with MGT, the plasma and serum VEGF of the malignant group increased significantly compared with those of the benign group. Additionally, there was a significant difference between the plasma and serum VEGF in the groups with postoperative metastasis and no metastasis. Circulating VEGF is expected to be clinically available for the determination of prognosis in canine MGT. KEY WORDS: canine, mammary gland tumor, vascular endothelial growth factor.
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