In photodissociation of trans-formic acid (HCOOH) at 193 nm, we have observed two molecular channels of CO + H
O and CO
+ H
by using 1 μs-resolved Fourier-transform infrared emission spectroscopy. ...With the aid of spectral simulation, the CO spectra are rotationally resolved for each vibrational state (v = 1-8). Each of the resulting vibrational and rotational population distributions is characteristic of two Boltzmann profiles with different temperatures, originating from either transition state pathway or OH-roaming to form the same CO + H
O products. The H
O roaming co-product is also spectrally simulated to understand the interplay with the CO product in the internal energy partitioning. Accordingly, this work has evaluated the internal energy disposal for the CO and H
O roaming products; especially the vibrational-state dependence of the roaming signature is reported for the first time. Further, given a 1 μs resolution, the temporal dependence of the CO/CO
product ratio at v ≥ 1 rises from 3 to 10 of study, thereby characterizing the effect of conformational memory and well reconciling with the disputed results reported previously between absorption and emission methods.
Advances in understanding the temperature effect on water dynamics in cellular respiration are important for the modeling of integrated energy processes and metabolic rates. For more than half a ...century, experimental studies have contributed to the understanding of the catalytic role of water in respiration combustion, yet the detailed water dynamics remains elusive. We combine a super-Arrhenius model that links the temperature-dependent exponential growth rate of a population of plant cells to respiration, and an experiment on isotope labeled
O
uptake to H
O transport role and to a rate-limiting step of cellular respiration. We use Phosphofructokinase (PFK-1) as a prototype because this enzyme is known to be a pacemaker (a rate-limiting enzyme) in the glycolysis process of respiration. The characterization shows that PFK-1 water matrix dynamics are crucial for examining how respiration (PFK-1 tetramer complex breathing) rates respond to temperature change through a water and nano-channel network created by the enzyme folding surfaces, at both short and long (evolutionary) timescales. We not only reveal the nano-channel water network of PFK-1 tetramer hydration topography but also clarify how temperature drives the underlying respiration rates by mapping the channels of water diffusion with distinct dynamics in space and time. The results show that the PFK-1 assembly tetramer possesses a sustainable capacity in the regulation of the water network toward metabolic rates. The implications and limitations of the reciprocal-activation-reciprocal-temperature relationship for interpreting PFK-1 tetramer mechanisms are briefly discussed.
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► Arrhenius plots may exhibit deviations from linearity. ► Curvature is accounted by a deformation of exponential function inspired by non-extensive thermodynamics. ► In the limit of ...the deformation parameter
d
→
0, the
deformed-Arrhenius approach coincides with the usual Arrhenius law. ► Various applications illustrate the additional insight gained.
Arrhenius plots, which are used to represent the effects of temperature on the rates of chemical and biophysical processes and on various transport phenomena in materials science, may exhibit deviations from linearity. Account of curvature is provided here by a formula which involves a deformation of the exponential function, of the kind recently encountered in treatments of non-extensivity in statistical mechanics. We present here examples on diverse topics – respiration rates of plants, speed of gliding of bacteria, quantum mechanical tunneling in a chemical reaction – illustrating the variety of possible applications and the additional insight that can be gained.
A photodissociation experiment of (R)-3-bromocamphor was carried out by the hexapole orientation technique by (2 + 1) REMPI detection at about 234 nm. The atomic bromine products in excited state (Br
...2
P
1/2
) and in ground state (Br
2
P
3/2
) were observed by the velocity map imaging. The anisotropy parameters of Br (
2
P
1/2
) and Br (
2
P
3/2
) were obtained as 0.75 ± 0.04 and 0.48 ± 0.03, respectively. In addition, we also successfully controlled (R)-3-bromocamphor, the bulky and asymmetric bio-molecule's, spatial orientation using the electrostatic hexapole. The orientational distribution was derived and its orientation efficiency was estimated as |<cos θ>|=0.35. We carried out a slice imaging experiment with the spatially oriented parent molecules to study the photodissociation dynamics of (R)-3-bromocamphor. The angular analysis of the obtained slice images suggests fast axial recoiling of the bromine atomic fragments and comparable contributions from the multiple upper states involved in A-band excitation, which results in the relatively isotropic angular distributions.
Objective Although lowering the low-density lipoprotein cholesterol (LDL-C) levels using statins can reduce cardiovascular risk, 70% of the cardiovascular risk remains despite treatment with statins. ...Several studies have shown that elevated triglyceride (TG)-rich lipoprotein is the primary therapeutic target for reducing the residual risk. However, conventional treatment with fibrates is frequently associated with adverse drug reactions, especially in patients with chronic kidney disease (CKD), and even with a reduction in TG. Pemafibrate is a novel selective peroxisome proliferator-activated receptor α modulator (SPPARMα) with fewer side effects and greater effectiveness that can overcome these challenges. We aimed to investigate the safety and efficacy of pemafibrate in patients with CKD and herein present a real-world profile of pemafibrate. Methods Between January 2019 and January 2020, 126 consecutive patients with hyperglyceridemia from two institutions (54 patients with CKD; 43%) who received pemafibrate were enrolled in this retrospective observational study. Blood samples were collected before (baseline) and at 24 weeks after commencing pemafibrate therapy. The primary endpoint was a decrease in the serum lipid levels. The secondary endpoints were the incidence of rhabdomyolysis, hepatargy, and an exacerbation of CKD. Results All patients, including 51% of patients who were concurrently taking statins, reported significantly reduced total cholesterol, non-high-density lipoprotein-cholesterol (non-HDL-C), LDL-C, and TG, and increased HDL-C (p<0.05). The subgroup of patients with CKD showed similar results without increased HDL-C. No adverse events were observed in any patients. Conclusion Pemafibrate has a good safety profile and efficacy for treating patients with serum lipid abnormalities, including those with CKD.
•Reiwa First Year East Japan typhoon of 2019 caused great damage in Nagano city.•First report on effect of flood on cardiovascular and cerebrovascular diseases.•Total number of cases did not increase ...significantly compared with previous 2 years.•Cases of heart failure, acute myocardial infarction, unstable angina increased.•Guidelines should be implemented to deal with expected rise in such cases after floods.
The Reiwa First Year East Japan Typhoon of 2019 caused a torrential flood in Japan. In Nagano City, a large area was flooded due to the collapse of the Chikuma River embankment. After large-scale disasters, an increase in cardiovascular and cerebrovascular events has been reported on account of the stressful conditions. However, few reports of disaster-related diseases associated with flood damage have been described. Thus, our aim was to elucidate the effect of floods on the incidences of cardiovascular and cerebrovascular diseases in Nagano City.
The Shinshu Assessment of Flood Disaster Cardiovascular Events (SAVE) trial enrolled 2,426 patients admitted for cardiovascular or cerebrovascular diseases at all five hospitals with an emergency department in Nagano City from October 1 to December 31 in the years 2017, 2018, and 2019. The occurrence of these diseases was calculated in every 2 weeks and the findings of 2019 (year of the flood) were compared with those of 2017 and 2018.
Cardiovascular and cerebrovascular diseases significantly increased during the 2 weeks immediately after the flood disaster (149 in 2019 vs average of 116.5 in the previous 2 years, p < 0.05). Unstable angina cases significantly increased 1.5–2 months after the flood disaster, and cerebral hemorrhage cases significantly increased in the 2 weeks after the flood disaster.
Cardiovascular and cerebrovascular events increased significantly during the 2 weeks immediately after the large-scale flood disaster caused by the Reiwa First Year East Japan typhoon. Because of the increasing frequency of flood disasters, it is necessary to predict the occurrences of cardiovascular and cerebrovascular diseases and to implement guidelines for their appropriate and timely management.
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This account focuses on photodissociation of carbonyl compounds to verify a so‐called roaming route, alternative to those passing through a transition state (TS) invoked in the realm of the kinetics ...of elementary chemical processes. Such a roaming route bypasses the minimum energy path but produces the same molecular products. The photodissociation of the carbonyl compounds of study includes methyl formate (HCOOCH3), formic acid (HCOOH), and aliphatic aldehydes (RCOH, RH, CH3, and large alkyl group). Methyl formate and formic acid were promoted to the excited state, followed by internal conversion via a conical intersection. Then, the energetic precursor dissociated to fragments, which proceeded along either TS or roaming path. As the excitation energy increases, the roaming fraction in methyl formate is significantly interfered with by an open channel of triple fragmentation (H + CO + CH3O), whereas such a channel may not occur in formic acid even at an excitation wavelength of 193 nm. As a distinct roaming type, aliphatic aldehydes are found to possess the structure of the roaming saddle point comprising two moieties weakly bound at a distance. The energy difference between the TS barrier and the roaming saddle point is indicative of the extent for the roaming contribution. The roaming route becomes increasingly dominant when the aliphatic aldehyde is larger. Experimentally, ion imaging was employed to visualize the rotational‐level dependence of the roaming route, while time‐resolved Fourier‐transform infrared emission spectroscopy was applied to determine the vibrational‐state dependence. The roaming signature was verified theoretically by quasi‐classical trajectory calculations. As an alternative, a multi‐center impulsive model was developed to simulate the roaming scalar and vector properties without involving the global energy surface.
In the photodissociation of methyl formate (HCOOCH3), three pathways including transition state, roaming and triple fragmentation (HCOOCH3➔H+CO+OCH3) were found, depending on the excitation wavelength. Comparative plots of the branching ratios for these three channels measured in experiments (left) and obtained in simulations by quasi‐classical trajectory calculations (right). The energy abscissa has taken into account the energy of CO rotational states (J = 10, 14, 19 and 24) from which the jet‐cooled molecule was excited and photolyzed.
Chronic kidney disease is a prognostic factor for cardiovascular disease. Worsening renal function (WRF), specifically, is an important predictor of mortality in patients with acute myocardial ...infarction undergoing primary percutaneous coronary intervention (PCI). We evaluate the prognostic impact of mid-term WRF after PCI on future cardiovascular events. We examined the renal function data of 1086 patients in the first year after PCI using the SHINANO 5-year registry. Patients were divided into two groups, mid-term WRF and non-mid-term WRF, and primary outcomes were major adverse cardiovascular events (MACE) and death. Mid-term WRF was defined as an increase in creatinine (≥ 0.3 mg/dL) in the first year after PCI. Mid-term WRF was found in 101 patients (9.3%), and compared to non-mid-term WRF, it significantly increased the incidence of MACE (
p
< 0.001), and all-cause death (
p
< 0.001), myocardial infarction (
p
= 0.001). Furthermore, mid-term WRF patients had higher incidence of future heart failure (
p
< 0.001) and new-onset atrial fibrillation (
p
= 0.01). Patients with both mid-term WRF and chronic kidney disease had increased MACE compared to patients with either condition alone (
p
< 0.001). Similarly, patients with mid-term WRF and acute kidney injury had increased MACE compared to patients with either condition alone (
p
< 0.001). Multivariate Cox regression analysis revealed mid-term WRF as a strong predictor of MACE (hazard ratio: 2.50, 95% confidence interval 1.57–3.98,
p
< 0.001). Mid-term WRF after PCI negatively affects MACE, as well as future admission due to heart failure and new-onset atrial fibrillation, chronic kidney disease, and acute kidney injury.
Background : The diagnosis of cardiac transthyretin (ATTR) amyloidosis is frequently delayed or missed because of its nonspecific echocardiographic features and the need for histological confirmation ...through biopsy. We evaluated the prevalence of cardiac ATTR amyloidosis diagnosed noninvasively by the combination of the positive cardiac uptake on technetium (99mTc)-labeled pyrophosphate (PYP) scintigraphy and the absence of monoclonal protein among elderly heart failure patients. We also demonstrated the clinical features of cardiac ATTR amyloidosis. Methods : We prospectively enrolled 38 consecutive patients, aged 70 years and older, who were treated for heart failure at our hospital between October 2017 and September 2018 and consented to undergo 99mTc-PYP scintigraphy. Experienced radiologists scored the cardiac uptake from grade 0 to 3, and grades 2 and 3 were defined as positive uptake. The clinical, echocardiographic, and electrocardiographic characteristics were recorded, and monoclonal protein studies were performed. Results : Four patients showed positive cardiac uptake on the 99mTc-PYP scan, and two of them demonstrated grade 2 or 3 uptake and negative monoclonal protein. As one patient with grade 3 uptake and monoclonal protein was proven to have cardiac ATTR amyloidosis histologically, the proportion of cardiac ATTR amyloidosis was 7.9％ (3/38). We compared parameters including clinical, blood test and imaging characteristics between cardiac ATTR amyloidosis patients and others. The electrocardiographic voltage of the R-wave in the precordial leads was lower in cardiac ATTR amyloidosis. Conclusions : This study indicated that cardiac ATTR amyloidosis should not be regarded as a rare cause of heart failure in elderly patients.
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