The Rotational Spectrum of 1-cyanocyclopentene and Its Search towards TMC-1

Exercise training increases mitochondrial content in active skeletal muscle. Previous work suggests that mitochondrial-related genes respond favorably to exercise in cold environments. However, the impact of localized tissue cooling is unknown. The purpose of this study was to determine the impact of local muscle cooling during endurance exercise on human skeletal muscle mitochondrial-related gene expression. Twelve subjects (age, 28 ± 6 years) cycled at 65% peak power output. One leg was cooled (C) for 30 min before and during exercise with a thermal wrap while the other leg was wrapped but not cooled, room temperature (RT). Muscle biopsies were taken from each vastus lateralis before and 4 h after exercise for the analysis of gene expression. Muscle temperature was lower in the C (29.2 ± 0.7 °C) than the RT (34.1 ± 0.3 °C) condition after pre-cooling for 30 min before exercise (p < 0.001) and remained lower after exercise in the C (36.9 ± 0.5) than the RT (38.4 ± 0.2, p < 0.001) condition. PGC-1α and NRF1 mRNA expression were lower in the C (p = 0.012 and p = 0.045, respectively) than the RT condition at 4 h after exercise. There were no temperature-related differences in other genes (p > 0.05). These data suggest that local cooling has an inhibitory effect on exercise-induced PGC-1α and NRF1 expression in human skeletal muscle. Those considering using local cooling during exercise should consider other systemic cooling options.Novelty:Local cooling has an inhibitory effect on exercise-induced PGC-1α and NRF1 expression in human skeletal muscle.Local cooling may lead to a less robust exercise stimulus compared with standard conditions.

A classical expression is developed for the partition function of the coupled bending and rotational degrees of freedom of a linear triatomic molecule. The usual rigid-rotator harmonic-oscillator partition function can be derived as an approximation to our result. Analytical approximations to both the bending-rotator and the rigid-rotator partition functions for a molecule with a quadratic—quartic potential are considered and the accuracy of these approximations is assessed by numerical calculations. Values for the thermodynamic functions for C3 are calculated using the best available spectroscopic data. It is shown that for the bending and rotational degrees of freedom, quantum corrections are negligible at temperatures above a few hundred degrees while anharmonicity and vibration—rotation coupling are quite important. For example, at 2400°K, a quartic term in the potential of C3 lowers the calculated value of S° by 2.8 eu, and the vibration—rotation coupling lowers it by another 1.1 eu to a computed value of 81.4 eu. A drastic steepening of the potential gives a lower limit, more or less consistent with the spectroscopic data, of 79.8 eu. The best experimental values for S°2400 are 76 or 77 eu.

The detailed mechanism of propylene carbonate (PC) formation from propylene oxide (PO) and CO2 is investigated using density functional theory (DFT) methods, catalyzed by amine/MeOH binary systems, in propylene oxide under conditions of room temperature and 1 atm. In these systems, amines (MeNH2, Me2NH, Me3N, and pyrrolidine) serve as nucleophiles, while MeOH acts as a hydrogen bond donor (HBD). The catalyzed reaction pathways for PC formation consistently proceed through two transition states, ts1 and ts2, corresponding to the oxide ring-opening and final ring-closing steps, respectively. The ring-closing step was identified as the rate-determining step in all amine/MeOH binary systems. Notably, the three aliphatic amine/MeOH binary systems significantly lower activation barriers for PC formation by approximately 20 kcal mol-1 compared to the uncatalyzed ring-closing pathway under standard conditions. The Me2NH/MeOH binary system demonstrates slightly higher catalytic efficiency than the MeNH2 and Me3N systems. Furthermore, the pyrrolidine/MeOH binary system exhibits comparable catalytic performance to the Me2NH/MeOH system. Since pyrrolidine is liquid under standard conditions, it can act as a homogeneous catalyst when paired with MeOH, enhancing mixing with PO and improving catalytic activity relative to gaseous Me2NH.

We have used continuous-wave cavity ring-down and femto-Fourier transform-cavity-enhanced absorption spectrometers to record the spectrum of the OH-stretching + CH-stretching (ν1 + ν2) combination band in trans-formic acid, with origin close to 6507 cm(-1). They, respectively, allowed resolving and simplifying the rotational structure of the band near its origin under jet-cooled conditions (Trot = 10 K) and highlighting the overview of the band under room temperature conditions. The stronger B-type and weaker A-type subbands close to the band origin could be assigned, as well as the main B-type Q branches. The high-resolution analysis was hindered by numerous, severe perturbations. Rotational constants are reported with, however, limited physical meaning. The ν1 + ν2 transition moment is estimated from relative intensities to be 24° away from the principal b-axis of inertia.

The accurate computation of partition functions in non-rigid molecules

Experiment methods and typical experiment results of acoustics emission (AE) of corona discharge are introduced. Based on numerous experiments, the common characters of AE are summarized: as the increase of test voltage, the count and the intensity of AE event increase, then the AE waves take on regular periodicity and they appear once in every test voltage period. Keep increasing the test voltage, strong AE event and weak AE event become to come forth alternately, and they are respectively symmetrical in positive and negative test period. Combining gas discharge theory and wave theory, above mentioned common characteristic are explored and explained. Dimensional methods in mechanics are introduced to analyze AE of corona discharge and it is discovered that the characteristics of AE waves only depend on initial discharge energy E0 released instantaneously under the condition of room temperature and standard atmospheric pressure when r is much smaller than the gap length. (5 pages)

Ultrahigh-performance fiber-reinforced concrete (UHPFRC) is a new type of concrete with excellent performance and good application prospects. However, expensive heat curing or high-pressure curing was often adopted to ensure the sufficient compressive strength. This study focuses on improving the compressive strength and workability of UHPFRC by changing the composition materials and the mixture ratios under standard curing conditions. The 0-1 mm and 1∼3 mm sintered bauxite was adopted as coarse aggregate. UHPFRC with high compressive strength and good workability was developed by changing the water-binder ratios, by adding ground-granulated blast furnace slag (GGBFS) or fly ash, and by changing the bauxite content of different particle sizes. When the volume ratio of steel fiber was 3%, the recommend water to binder ratio was 0.194 according to this experiment, the dosage of GGBFS-replaced cement is recommended as 20%, the dosage of fly ash instead of silica fume is recommended as 30%. The recommend ratio of 0-1 mm and 1∼3 mm sintered bauxite was 1.51 : 1. Finally, a kind of UHPFRC material with a compressive strength of 152.4 MPa and a slump of 120 mm was developed under the standard curing conditions.

Talaromyces sp. (strain IQ-313) produces duclauxin-type molecules under standard fermentation conditions in rice and oat cereal. Such molecules are of great interest due to their structural complexity and biological activity. Interestingly, application of an OSMAC (One Strain Many Compounds) approach, revealed that the biosynthetic machinery of this fungus can be directed towards the production of other types of molecules, while completely suppressing the biosynthesis of duclauxin (1). To exploit the metabolic potential of Talaromyces sp. (strain IQ-313), it was grown on solid media supplemented with dimethyl sulfoxide (DMSO), an ectopic epigenetic modulator. Metabolomic analysis of the fermentation extract from the strain grown under standard and DMSO-supplemented conditions, using molecular networking, revealed notable differences in the profiles. Chemical investigation of the extract obtained under abiotic stress led to the isolation and characterization of 15 molecules not detected under standard conditions, including nine polyketides, one sesquiterpenoid, two sesterterpenoids, and three meroterpenoids. Among these, talaromophilane (2), an eremophilane sesquiterpenoid, and talaroisochromane (8), an oxoisochromen, have not been previously reported in the literature. The structures of all isolates were established using a combination of spectroscopic and spectrometric data. The absolute configuration of compound 2 was established based on the analysis of NOESY interactions and by comparison of the experimental and theoretical electronic circular dichroism (ECD) curves.

Glycolaldehyde (GA) has been observed toward several different sources, with a broad range of rotational temperatures (8–300 K). At the high end, the temperature is comparable to the energy of the lowest vibrational states of GA, making the vibrational contribution to the partition function significant. Here, we report an analysis of the high-resolution far-infrared spectrum of GA, which features a plethora of well-resolved lines from 170–430 cm−1 (13–5 THz). We focus on the three fundamental vibrational bands in this range, i.e., the symmetric ν 12 bend at 282 cm−1, and the asymmetric ν 17 and ν 18 torsions at 360 and 208 cm−1, respectively. We assigned 23,266 transitions to 13,999 lines within these bands, which, when combined with the previously reported microwave and millimeter-wave spectra, allowed for refinement of the vibrationally excited rotational constants, and accurate determination of their band origins. Additionally, the assignment of a number of lines in several hot bands that are significantly populated at 300 K allowed for determination of their band origins. The rotational constants reported here should be useful in searches of vibrationally excited GA toward warm sources, and the accurately determined band origins allow for refinement of the vibrational partition function, and therefore column density, for a given excitation temperature.

Time-resolved Fourier transform infrared emission spectroscopy is used to measure the nascent rovibrational distribution of low-lying electronically excited NH2(Ã 2A1) produced in the 193.3 nm photolysis of room-temperature and jet-cooled ammonia. Emission is observed predominantly from NH2(Ã) states with rotational motion about the a-axis and without bending excitation, υ2′=0. A bimodal N′=Ka′ rotational state population distribution is observed with up to Ka′=7 in υ2′=0 and with maxima at Ka′=5 and Ka′=1. We suggest that the bimodal rotational distribution may result from the competition between planar and bent geometries during dissociation. Weaker emission from NH2(Ã) with bending excitation, υ2′=1 and 2, is detected; the υ2′=1, N′=Ka′ rotational state population distribution spans from Ka′=0 to the energetic limit of Ka′=4. The vibrational energy partitioning for the formation of NH2(Ã,υ2′=0):NH2(Ã,υ2′=1) is 3:1 and 2:1 in the room-temperature and jet-cooled conditions, respectively. An upper limit of the NH2(Ã,υ2′=2) population is ∼10% of the total NH2(Ã) photofragments. Emission from rotational states with N′&amp;gt;Ka′ (molecules with rotational excitation about the b/c-axes) is also observed. Under jet-cooled conditions the NH2(Ã) b/c-axes rotational temperature of ∼120 K is higher than that expected from the rotationally cold parent species and is attributed to a mapping of the zero-point bending motion in the ν4 H–N–H scissors bending coordinate of the NH3(Ã) predissociative state onto the NH2(Ã,υ2′,N′,Ka′)+H photofragments.

QCD with bosonic quarks at nonzero chemical potential

Laser-induced fluorescence (LIF) excitation spectra of the B-X (2)A(") electronic transition of the CH(2)CHS radical, which is the sulfur analog of the vinoxy (CH(2)CHO) radical, were observed under room temperature and jet-cooled conditions. The LIF excitation spectra show very poor vibronic structures, since the fluorescence quantum yields of the upper vibronic levels are too small to detect fluorescence, except for the vibrationless level in the B state. A dispersed fluorescence spectrum of jet-cooled CH(2)CHS from the vibrationless level of the B state was also observed, and vibrational frequencies in the X state were determined. Precise rotational and spin-rotation constants in the ground vibronic level of the radical were determined from pure rotational spectroscopy using a Fourier-transform microwave (FTMW) spectrometer and a FTMW-millimeter wave double-resonance technique [Y. Sumiyoshi et al., J. Chem. Phys. 123, 054324 (2005)]. The rotationally resolved LIF excitation spectrum for the vibronic origin band of the jet-cooled CH(2)CHS radical was analyzed using the ground state molecular constants determined from pure rotational spectroscopy. Determined molecular constants for the upper and lower electronic states agree well with results of ab initio calculations.

Active acoustic measurements (those requiring the input of acoustic energy) can be broadly classified as either broadband or narrowband. In a broadband technique, the acoustic energy introduced into the system is highly localized in time (i.e., a sharp pulse). When transformed into the frequency domain using Fourier analysis, it becomes clear that this energy is spread over a wide frequency range. In a narrowband technique, the acoustic energy is introduced over a longer time period and occupies a much more localized region in the frequency domain. The limit being a single tone excitation signal. Benefits and drawbacks for each of these methods will be discussed as they are applied to several experimental systems including resonance and pulse-echo measurements.

A SeNSe pincer ligand (L1) and its palladium(II) complex (C1) were synthesized and fully characterized by analytical and spectroscopic methods. Complex C1 displayed excellent catalytic efficiency for the regioselective C-4 arylation of thiophene derivatives, delivering the desired products in yields up to 91% under mild, room-temperature conditions. The method exhibits a broad substrate scope, including heteroarenes relevant to optoelectronic and pharmaceutical applications, and provides high regioselectivity while suppressing homocoupling and other side reactions. Under the standard conditions, unsubstituted thiophenes underwent selective C-3 arylation. A striking regioselectivity switch was observed in the arylation of benzothiophene, favoring C-3 arylation under milder, greener conditions compared to previously reported C-2 selective methods. Mercury-drop and triphenylphosphine poisoning tests confirmed homogeneous catalysis, while radical scavenger experiments excluded radical pathways. Control studies and high-resolution mass spectrometric analysis of reaction intermediates support the proposed catalytic cycle. These findings underscore the impact of ligand design and reaction parameters in directing site-selective C-H activation, establishing the SeNSe-Pd(II) pincer complex as a powerful catalyst for regioselective heteroarene functionalization.

Hysteresis in the relation between water saturation and matric potential is generally regarded as a basic aspect of unsaturated porous media. However, the nature of an upper length scale limit for saturation hysteresis has not been previously addressed. Since hysteresis depends on whether or not capillary rise occurs at the grain scale, this criterion was used to predict required combinations of grain size, surface tension, fluid‐fluid density differences, and acceleration in monodisperse systems. The Haines number (Ha), composed of the aforementioned variables, is proposed as a dimensionless number useful for separating hysteretic (Ha &lt; 15) versus nonhysteretic (Ha &gt; 15) behavior. Vanishing of hysteresis was predicted to occur for grain sizes greater than 10.4 ± 0.5 mm, for water‐air systems under the acceleration of ordinary gravity, based on Miller‐Miller scaling and Haines' original model for hysteresis. Disappearance of hysteresis was tested through measurements of drainage and wetting curves of sands and gravels and occurs between grain sizes of 10 and 14 mm (standard conditions). The influence of surface tension was tested through measurements of moisture retention in 7 mm gravel, without and with a surfactant (sodium dodecylbenzenesulfonate (SDBS)). The ordinary water system (Ha = 7) exhibited hysteresis, while the SDBS system (Ha = 18) did not. The experiments completed in this study indicate that hysteresis in moisture retention relations has an upper limit at Ha = 16 ± 2 and show that hysteresis is not a fundamental feature of unsaturated porous media.