Fourier transform microwave spectroscopy of the 13C- and 18O-substituted tropolone. Proton tunneling effect for the isotopic species with the asymmetric potential wells.

Fourier-transform microwave spectroscopy has been applied for the 13C/18O-substituted tropolone to observe tunneling-rotation transitions as well as pure rotational transitions. The tunneling-rotation transitions were observed between the 13C-4 and -6 forms as well as between 13C-3 and -7, between 13C-1 and -2, and between 18O-8 and -9 (we denote these tunneling pairs as 13C-46, etc., below) although they have an asymmetric tunneling potential due to the difference in the zero point energy (ZPE). From the observed tunneling splittings ΔEij (0.9800-1.6824 cm-1), the differences in ZPE Δij for the 13C-46, -37, -12, and 18O-89 species are derived to be -0.1104, 0.5652, -1.3682, and 1.3897 cm-1 to agree well with the DFT calculation. The state mixing ratio of the tunneling states decreases drastically from (44%:56%) to (8.7%:91.3%) for 13C-46 and 18O-89 with an increase in the asymmetry Δij of the tunneling potential function. The observed tunneling-rotation interaction constants Fij decrease from 16.001 to 9.224 cm-1 as the differences in ZPE Δij increase, while the diagonal tunneling-rotation interaction constants Fu increase from 1.767 to 13.70 cm-1, explained well by the mixing ratio of the tunneling states.

Online Multi-Contact Motion Replanning for Humanoid Robots with Semantic 3D Voxel Mapping: ExOctomap.

This study introduces a rapid motion-replanning technique driven by a semantic 3D voxel mapping system, essential for humanoid robots to autonomously navigate unknown territories through online environmental sensing. Addressing the challenges posed by the conventional approach based on polygon mesh or primitive extraction for mapping, we adopt semantic voxel mapping, utilizing our innovative Extended-Octomap (ExOctomap). This structure archives environmental normal vectors, outcomes of Euclidean Cluster Extraction, and principal component analysis within an Octree structure, facilitating an O(log N) efficiency in semantic accessibility from a position query x∈R3. This strategy reduces the 6D contact pose search to simple 3D grid sampling. Moreover, voxel representation enables the search of collision-free trajectories online. Through experimental validation based on simulations and real robotic experiments, we demonstrate that our framework can efficiently adapt multi-contact motions across diverse environments, achieving near real-time planning speeds that range from 13.8 ms to 115.7 ms per contact.

Hedgehog Signal Inhibitor GANT61 Inhibits the Malignant Behavior of Undifferentiated Hepatocellular Carcinoma Cells by Targeting Non-Canonical GLI Signaling.

The Hedgehog (HH)-GLI pathway plays an important role in cell dedifferentiation and is therefore pivotally involved in the malignant transformation of cancer cells. GANT61, a selective inhibitor of GLI1 and GLI2, was reported as a promising treatment for cancer in various tissues; however, the biological impact of GANT61 in hepatocellular carcinoma (HCC), especially in undifferentiated HCC cells, remains unclear. In this study, we investigated the antitumor effect of GANT61 using two undifferentiated hepatoma cell lines: HLE and HLF. Quantitative PCR and RT-PCR analyses revealed that these cells express GLI transcripts, showing mesenchymal phenotypes characterized by the loss of epithelial and hepatic markers and specific expression of epithelial-mesenchymal transition (EMT)-related genes. GANT61 significantly reduced the proliferation and cell viability after drug treatment using 5-FU and Mitomycin C. We showed that GLI transcript levels were down-regulated by the MEK inhibitor U0126 and the Raf inhibitor sorafenib, suggesting that non-canonical signaling including the Ras-Raf-MEK-ERK pathway is involved. Sphere formation and migration were significantly decreased by GANT61 treatment, and it is suggested that the underlying molecular mechanisms are the down-regulation of stemness-related genes (Oct4, Bmi1, CD44, and ALDH) and the EMT-related gene Snail1. The data presented here showed that direct inhibition of GLI might be beneficial for the treatment of dedifferentiated HCC.

Millimeter-wave spectroscopy of HDC=CH.

Rotational transitions of the mono(ß)-deuterated vinyl radical, HDC=CH, produced in a supersonic jet expansion by the ArF excimer laser photolysis, were observed by millimeter-wave spectroscopy. The b-type rotational transitions together with the weak a-type transitions were observed only for the lower component of the tunneling doublet, and no tunneling-rotation transitions connecting the lower and upper components were observed, suggesting that state mixing between the two components is negligibly small. The derived molecular constants such as the A rotational constant, Fermi contact interaction constants, and magnetic dipolar interaction constants indicate that the carrier of the observed spectrum is the trans-form of HDC=CH isomers, where the α-proton is located on the opposite side of the ß-deuteron. The present conclusion of the trans-form of HDC=CH was also supported by the ab initio calculation in the CCSD(T)/cc-pVTZ level since the trans-form is calculated to be located by 30.04 cm-1 lower than the cis-form due to the difference in the zero point energy. As a result, the tunneling components in the ground state of HDC=CH behave as two different isomers localized at the trans- and cis-wells of the asymmetric double minimum potential. Observed hyperfine constants for HDC=CH were compared with those for H2C=CH to be consistent with each other.

High-resolution Fourier transform emission spectroscopy of the A∼2Πi-X∼2Πi band of the OCS+ ion.

High resolution Fourier transform emission spectroscopy of the A∼2Πi-X∼2Πi band of the OCS+ ion was performed in the UV region to observe the ν1 (CO stretch) progression bands (υ1 = 0 → 2-5) for both the Ω=3/2 and 1/2 spin components. Accurate molecular constants including the rotational constants, B0 = 0.194 765(13) and 0.187 106(13) cm-1, and the spin-orbit interaction constants, A0 = -381.0(56) and -126.5(56) cm-1, were determined for the X∼2Π and A∼2Π states, respectively, by the simultaneous analysis of the observed progression bands. The CO bond length (rCO = 1.2810 Å) for the A∼2Π state, derived from the rotational constant B0 and Franck-Condon factors, is longer by 0.1756 Å than that (1.1054 Å) for the X∼2Π state, while the CS bond length for the A∼2Π state is shorter by 0.0905 Å than that for the X∼2Π state. Pure rotational transition frequencies in the ground X∼2Π state are predicted, as well as transition frequencies of the ν1 fundamental band, with the present molecular constants.

Millimeter-wave spectroscopy of the FeCO radical in the ν2 and ν3 vibrationally excited states.

The pure rotational spectra of the FeCO radical in the ν2 (bending) and ν3 (Fe-C stretching) vibrational states of the ground X̃(3)Σ(-) electronic state were observed in the millimeter-wave region. The equilibrium rotational and centrifugal distortion constants were determined to be Be = 4374.631 (58) MHz and De = 1.1666 (20) kHz together with the spin-spin coupling constant λe = 691.89 (37) GHz and spin-rotation coupling constant γe = - 1079.4 (55) MHz with use of the millimeter-wave results and the ν1 IR data. The equilibrium bond length for Fe-C was derived to be 1.725 Å assuming that for C-O to be 1.159 Å. Since the vibronic symmetry of the excited state of bending vibration is (3)Π, the analysis of spectrum in the ν2 state required an effective spin-orbit interaction constant of A2 = 6.0219 (61) GHz together with three parity doubling constants of o2 = 36.168 (10) GHz, p2 = 85.18 (34) MHz, and q2 = 4.7024 (17) MHz. The effective spin-orbit interaction constant A2 is attributed to the vibronic mixing of the (3)Π excited electronic states. The vibronic mixing also cause the parity doubling constants o2 and p2, but the main contribution to q2 is given by the vibrational l-type doubling.

Ortho-para mixing hyperfine interaction in the H2O+ ion and nuclear spin equilibration.

The ortho to para conversion of water ion, H2O(+), due to the interaction between the magnetic moments of the unpaired electron and protons has been theoretically studied to calculate the spontaneous emission lifetime between the ortho- and para-levels. The electron spin-nuclear spin interaction term, Tab(SaΔIb + SbΔIa) mixes ortho (I = 1) and para (I = 0) levels to cause the "forbidden" ortho to para |ΔI| = 1 transition. The mixing term with Tab = 72.0 MHz is 4 orders of magnitude higher for H2O(+) than for its neutral counterpart H2O where the magnetic field interacting with proton spins is by molecular rotation rather than the free electron. The resultant 10(8) increase of ortho to para conversion rate possibly makes the effect of conversion in H2O(+) measurable in laboratories and possibly explains the anomalous ortho to para ratio recently reported by Herschel heterodyne instrument for the far-infrared (HIFI) observation. Results of our calculations show that the ortho ↔ para mixings involving near-degenerate ortho and para levels are high (∼10(-3)), but they tend to occur at high energy levels, ∼300 K. Because of the rapid spontaneous emission, such high levels are not populated in diffuse clouds unless the radiative temperature of the environment is very high. The low-lying 101 (para) and 111 (ortho) levels of H2O(+) are mixed by ∼10(-4) making the spontaneous emission lifetime for the para 101 → ortho 000 transition 520 years and 5200 years depending on the F value of the hyperfine structure. Thus the ortho ↔ para conversion due to the unpaired electron is not likely to seriously affect thermalization of interstellar H2O(+) unless either the radiative temperature is very high or number density of the cloud is very low.

Body Extension by Using Two Mobile Manipulators.

This paper presents a remotely operated robotic system that includes two mobile manipulators to extend the functional capabilities of a human body. Compared with previous tele-operation or robotic body extension systems, using two mobile manipulators helps with enlarging the workspace and allowing manipulation of large or long objects. The system comprises a joystick for controlling the mobile base and robotic gripper, and a motion capture system for controlling the arm poses. They together enable tele-operated dual-arm and large-space manipulation. In the experiments, a human tele-operator controls the two mobile robots to perform tasks such as handover, long object manipulation, and cooperative manipulation. The results demonstrated the effectiveness of the proposed system, resulting in extending the human body to a large space while keeping the benefits of having two limbs.

An Adaptive Imitation Learning Framework for Robotic Complex Contact-Rich Insertion Tasks.

Complex contact-rich insertion is a ubiquitous robotic manipulation skill and usually involves nonlinear and low-clearance insertion trajectories as well as varying force requirements. A hybrid trajectory and force learning framework can be utilized to generate high-quality trajectories by imitation learning and find suitable force control policies efficiently by reinforcement learning. However, with the mentioned approach, many human demonstrations are necessary to learn several tasks even when those tasks require topologically similar trajectories. Therefore, to reduce human repetitive teaching efforts for new tasks, we present an adaptive imitation framework for robot manipulation. The main contribution of this work is the development of a framework that introduces dynamic movement primitives into a hybrid trajectory and force learning framework to learn a specific class of complex contact-rich insertion tasks based on the trajectory profile of a single task instance belonging to the task class. Through experimental evaluations, we validate that the proposed framework is sample efficient, safer, and generalizes better at learning complex contact-rich insertion tasks on both simulation environments and on real hardware.

Millimeter-wave spectroscopy of H(2)C=CD: Tunneling splitting and ortho-para mixing interaction.

The H(2)C=CD isotopic species of vinyl radical produced in a supersonic jet expansion by ultraviolet laser photolysis was studied by millimeter-wave spectroscopy. Due to the tunneling motion of the α deuteron, the ground state is split into two components, 0(+) and 0(-). Tunneling-rotation transitions connecting the lower (0(+)) and upper (0(-)) components of the tunneling doublet were observed in the frequency region of 184-334 GHz, including three R- and two Q-branch transitions. Three and two pure rotational transitions in the K(a)=0 and 1 stacks, respectively, were also observed for each of the 0(+) and 0(-) states in the frequency region of 52-159 GHz. Least-squares analysis of the observed frequencies for the tunneling-rotation and pure rotational transitions with well resolved hyperfine structures yielded a set of precise molecular constants, among which the tunneling splitting in the ground state was determined to be ΔE(0)=1187.234(17) MHz, which is 1/14 that for H(2)C=CH. The potential barrier height derived from the observed tunneling splitting by an analysis of the tunneling dynamics using a one-dimensional model is 1545 cm(-1), consistent with the value 1568 cm(-1) obtained for the normal vinyl. The observed spectrum was found to be perturbed by a hyperfine interaction connecting ortho and para levels. The constant for the interaction, which we call the ortho-para mixing Fermi contact interaction, has been determined to be δa(F) ((ß))=68.06(53) MHz. This is believed to be the first definite detection of such an interaction. By this interaction the ortho and para states of H(2)C=CD are mixed up to about 0.1%. The constant is more than 1000 times larger than spin-rotation interaction constants that cause ortho-para mixing in closed shell molecules and suggests extremely rapid conversion between the ortho and para nuclear spin isomers of H(2)C=CD.

Ortho-para mixing interaction in the vinyl radical detected by millimeter-wave spectroscopy.

Ortho-para mixing interaction due to the coupling of nuclear and electron spins was detected for the first time by millimeter-wave spectroscopy of the deuterated vinyl radical H(2)CCD. The ground state of H(2)CCD is split by the deuteron tunneling into two components 0(+) and 0(-) separated by DeltaE(0)=1186.794(16) MHz. Rotational levels in the 0(+) and 0(-) states, one being an ortho level and the other a para level, are coupled by the interaction expressed by 0(+/-)mid R:H(')mid R:0(-/+)=(deltaa(F)/2)S(I(1)-I(2)), where I(1) and I(2) are spins of the two protons and S is the electron spin. The deltaa(F) constant has been determined to be 68.06(52) MHz. The para to ortho conversion rate constant is predicted to be 1.2x10(5) s(-1) torr(-1).

Developmental outcomes in persistent pulmonary hypertension treated with nitric oxide therapy.

BACKGROUND: The aim of the present study was to assess 3 year auditory and neurodevelopmental outcomes of persistent pulmonary hypertension of the newborn (PPHN) before and after introducing inhaled nitric oxide (i-NO) therapy, and to detect the clinical factors affecting poor outcome. METHODS: A retrospective historical cohort study of 26 survivors with PPHN with oxygenation index (OI) >or=25 (13 infants without i-NO therapy, control group; 13 with i-NO therapy, i-NO group) was performed. Auditory brainstem response (ABR) at 6 and 12 months and neurodevelopmental outcomes at 3 years of age were evaluated. RESULTS: ABR abnormalities at 6 months were observed in one infant in the i-NO group and six in the control group (P = 0.04). At 1 year, one infant in the i-NO group and two of six infants in the control group still had ABR abnormality. In the i-NO group, two children had abnormal neurodevelopmental outcomes, as compared with five children in the control group at 3 year follow up. Two children in the control group and no children in the i-NO group had hearing loss at 3 years of age. Hypocapnea (P = 0.04) and elevated creatine phosphokinase (P = 0.04) were found to be most predictive for neurodevelopmental abnormality. CONCLUSION: Avoidance of excessive hypocapnea via introduction of i-NO therapy might reduce both ABR and neurodevelopmental abnormalities.

Age-related acceleration of endothelial dysfunction and subclinical atherosclerosis in subjects with coronary artery lesions after Kawasaki disease.

The objective of this study was to test the hypothesis that accelerated endothelial dysfunction and the development of premature atherosclerosis are associated with age in subjects with coronary artery lesions after Kawasaki disease (KD). A case-control study was performed at a university hospital that included 35 post-KD subjects across a wide age range (range, 8-42 years) without traditional cardiovascular risk factors and 35 age- and sex-matched healthy control subjects (Cont). Flow-mediated dilatation (FMD) of the brachial artery-induced by reactive hyperemia, intima media thickness (IMT), and elastic modulus (Ep) of the common carotid artery were compared between KD and Cont subjects assessed against age. KD subjects had slightly higher levels of body mass index, lipid profile, and HbA1c than Cont subjects, but the differences were not significant. The mean IMT (p < 0.001), age-adjusted percentage normal IMT (%N IMT; p < 0.0001), and Ep (p < 0.001) were significantly higher in KD than Cont subjects, and the peak FMD% (p < 0.01) was significantly lower in KD than Cont subjects. There were significant correlations between FMD% and age (r = -0.51 p < 0.0001), IMT and age (r = 0.68, p < 0.001), and Ep and age (r = 0.58, p < 0.01) in KD but not Cont subjects. When the difference in FMD% between KD and matched Cont subjects (DeltaFMD%) was plotted against age, no significant relationship was found, although significant correlations between DeltaIMT and age (r = 0.52, p < 0.01) as well as between DeltaEp and age (r = 0.46, p < 0.05) were observed. When we defined values that were +2.0 SD over the mean control values (i.e., %N IMT >or= 120% and/or Ep >or= 50 kPa) as markers of subclinical atherosclerosis, 15 subjects met the criteria. Subjects over the age of 22 years were more likely to have (OR = 16.54, p = 0.0001) subclinical atherosclerosis in this cohort. Our results suggest that endothelial dysfunction and the development of premature atherosclerosis were accelerated in adult post-KD compared to Cont subjects.

Nationwide survey of palivizumab for respiratory syncytial virus prevention in Japanese children with congenital heart disease.

A questionnaire study was performed to determine the current status of palivizumab prophylaxis against respiratory syncytial virus infection in Japanese children with congenital heart disease <2 years of age. Palivizumab prophylaxis decreased the respiratory syncytial virus hospitalization rate by 42.8%.

Millimeter-wave spectroscopy of CoNO produced by UV laser photolysis of Co(CO)3NO.

The rotational spectrum of cobalt mononitrosyl (CoNO) produced by ultraviolet photolysis of Co(CO)(3)NO was observed in the millimeter-wave region. Seven rotational transitions in the ground state ranging from J = 6-5 to 12-11, with hyperfine splittings due to the Co nucleus (I = 7/2), were detected in a supersonic jet environment, while higher-frequency transitions in the range from J = 29-28 to 35-34 were measured in the ground, nu(1), nu(2), nu(3), and 2nu(2) vibrational states using a free-space absorption cell. It was confirmed from the observed spectral pattern that the CoNO molecule has a linear structure with the electronic ground state of (1)Sigma(+) symmetry. The rotational lines in the 2nu(2)(Sigma) and nu(3) states were observed to be perturbed by Fermi resonance. The equilibrium rotational constant B(e) is determined to be 4682.207(15) MHz. The CoN bond length is derived to be 1.5842 A assuming the NO bond length of 1.1823 A. A large nuclear spin-rotation interaction constant, C(I) = 123.8(11) kHz, was determined, suggesting a (1)Pi electronic excited state lying close to the ground state.

Predictive factors for survival for out-born infants born between 23 and 24 weeks of gestation in the post-surfactant era: fourteen years' experience in a single neonatal care unit, 1987-2000.

BACKGROUND: The purpose of the present paper was to identify the predictive factors for survival for out-born infants born between 23 and 24 weeks of gestation. METHODS: Ninety-two infants born between 23 and 24 weeks' gestation who were admitted to a level III neonatal intensive care unit from 1987 to 2000, were retrospectively studied. Survival was defined as discharge from the neonatal intensive care unit. Logistic regression was done to determine which clinical factors were most predictive of survival. The independent variables that were entered into the models were determined by preliminary univariate analysis. RESULTS: Ninety-two infants were enrolled in the present study, 49 of whom survived in the surfactant era. The four variables that were found to be most predictive for survival on logistic regression were systolic blood pressure at 6 h (odds ratio [OR], 1.3; 95% confidence interval [CI]: 1.11-1.44 1 mmHg), ventilatory index < 0.047 (OR, 4.8; 95%CI: 1.07-21.65), initial hemoglobin value (OR, 1.6; 95%CI: 1.09-2.34/1 g/dL), and base excess at 6 h (OR, 2.1; 95%CI: 1.08-1.84/5 mEq/L). CONCLUSIONS: A total of 53.2% of infants delivered between 23 and 24 weeks of gestation survived at discharge after introduction of surfactant replacement therapy. Early cardiopulmonary adaptation and initial hemoglobin value are key factors for survival in infants born at 23-24 weeks of gestation.

Multiple drug-resistant gene 1 in children with steroid-sensitive nephrotic syndrome.

BACKGROUND: A full dose of corticosteroid is required to induce complete remission (CR) in steroid-sensitive nephrotic syndrome (SSNS), unless it is possible to taper and discontinue along with the course after CR. But the mechanism of this change in steroid sensitivity remains unknown. P-glycoprotein (PGP) can eliminate given corticosteroids from cytoplasm, which results in corticosteroid resistance. Therefore, drug delivery was analyzed using real-time polymerase chain reaction (PCR) of multiple drug-resistant gene 1 (MDR1; encoding PGP) mRNA expression. METHODS: Fourteen patients with SSNS (male/female: 14/0; age: 1-23 years; mean 10.4 years) were enrolled in the study. MDR1 mRNA gene expression of peripheral blood nucleated cells (PBNC), before and after CR (19 sets of blood samples), was quantified using real-time PCR. RESULTS: The MDR1 mRNA levels before CR were variable in each patient, but there was an apparent decrease in the MDR1 gene expression of PBNC after CR (P < 0.003). CONCLUSION: PGP may play a role in the tapering of corticosteroids after CR in SSNS.

Effect of hemoglobin on transfusion and neonatal adaptation in extremely low-birthweight infants.

BACKGROUND: The aim of the present paper was to investigate the effect of initial hemoglobin level on red blood cell transfusion and neonatal adaptation in extremely low-birthweight (ELBW) infants. METHODS: Subjects consisted of 54 ELBW infants admitted to level III neonatal intensive care unit between 1995 and 2000, and divided into two groups based on hemoglobin level at birth. High hemoglobin was defined as hemoglobin > or =15.0 g/dL. RESULTS: There were no significant differences in gestational age and birthweight between the high hemoglobin group (n = 28) and low hemoglobin group (n = 26). The high hemoglobin group had decreased probability of requiring red blood cell transfusion (P < 0.05) and number of red blood cell transfusions (P < 0.05). Mortality rate in the low hemoglobin group was significantly higher compared with the high hemoglobin group (P = 0.03). In the high hemoglobin group, blood pressures during the first 24 h were significantly higher (P < 0.05) and the risk of intraventricular hemorrhage was significantly lower (P = 0.04) compared with the low hemoglobin group. The predictive variables, initial hemoglobin level (odds ratio 1.93 [decrease by 1 g/dL]) and intraventricular hemorrhage > or =III (odds ratio 21.76 [positive]) were found to be most predictive for death on logistic regression. CONCLUSION: High hemoglobin level at birth is associated with a significantly reduced requirement for red blood cell transfusion and might contribute to stabilization of blood pressure, and thus reduce mortality and the risk of severe intraventricular hemorrhage.

Relationship between serum adiponectin level and lipid composition in each lipoprotein fraction in adolescent children.

The association of lipid composition in each lipoprotein fraction with adiponectin level in relation to body fatness was investigated. The subjects were 283 children (144 boys and 139 girls) aged 11.6 years (S.D. 1.5). Cholesterol (C) and triglyceride (TG) levels in each lipoprotein fraction were measured by a combination of agarose gel electrophoresis and differential staining. Adiponectin level was not significantly different between girls and boys. In simple regression analyses, an association of adiponectin level with lipoprotein lipid profile was shown only in girls, and not in boys at all. In girls, very low-density lipoprotein (VLDL)-C, low-density lipoprotein (LDL)-C, VLDL-TG and LDL-TG were negatively correlated with adiponectin level, and high-density lipoprotein (HDL)-C and HDL-C/TG ratio were positively correlated. Multiple regression analyses including adiponectin level and body mass index (BMI) as predictors for the lipoprotein lipid profile demonstrated that adiponectin level was a significant independent predictor of VLDL-TG, LDL-C, LDL-TG, HDL-C and HDL-C/TG ratio. In conclusion, adiponectin level correlates with lipoprotein lipid profile independent of body fatness in adolescent girls.

Determination of lipid composition of plasma lipoproteins in children with a rapid agarose gel electrophoresis method.

The agarose gel electrophoresis and differential staining system is an easy and quick method for analyzing the serum lipid composition of each lipoprotein fraction. It has been reported in adults that measured values obtained by this method strongly correlated with those obtained by ultracentrifugation. The aim of this study was to examine the clinical application of this method for children, in comparison with the ultracentrifugation method. The subjects were sixteen hyperlipidemic and twenty-five normolipidemic children, aged from two to eighteen years old. Cholesterol (C) and triglyceride (TG) levels were determined in serum very low density lipoprotein (VLDL), low density lipoprotein (LDL), and high density lipoprotein (HDL) fractions by both methods. Correlation coefficients between the two methods for cholesterol levels were 0.937 (HDL), 0.983 (LDL) and 0.837 (VLDL), and for triglyceride levels were 0.735 (HDL), 0.621 (LDL) and 0.964 (VLDL). We confirmed the clinical application of this method to evaluate the lipoprotein lipid profile in children as well as in adults.