Search

Ultracold chemical reactions of weakly bound triplet-state alkali-metal dimer molecules have recently attracted much experimental interest. We perform rigorous quantum scattering calculations with a new $ab\, initio$ potential energy surface to explore the chemical reaction of spin-polarized NaLi($a^3\Sigma^+$) and Li($^2$S) to form Li$_2$($a^3\Sigma_u^+$) and Na($^2$S). The reaction is exothermic, and proceeds readily at ultralow temperatures. Significantly, we observe strong sensitivity of the total reaction rate to small variations of the three-body part of the Li$_2$Na interaction at short range, which we attribute to a relatively small number of open Li$_2$($a^3\Sigma_u^+$) product channels populated in the reaction. This provides the first signature of highly non-universal dynamics seen in rigorous quantum reactive scattering calculations of an ultracold exothermic insertion reaction involving a polar alkali-dimer molecule, opening up the possibility of probing microscopic interactions in atom+molecule collision complexes via ultracold reactive scattering experiments., Comment: 26 pages, 5 figures (Supporting information: 12 pages, 5 figures)

Despite intensive studies for decades on synaptic integration in the somatodendritic compartments, its spatio-temporal dynamics remains obscure because of the technical limitation to obtain local potentials at multiple subcellular regions. To address this issue, here we used a genetically-encoded voltage indicator together with local uncaging of glutamate or GABA on cultured hippocampal pyramidal neurons. Fluorescence voltage imaging revealed direction-dependent opposite changes of excitatory postsynaptic potentials (EPSPs) in a dendrite: EPSPs attenuated during propagation toward the soma whereas amplified toward the distal branch end. The direction-dependent local augmentation of EPSPs was mediated by the TTX-resistant Na+ channels and KCC2-dependent deeper dendritic resting potential than in soma, the latter of which was directly unveiled by subcellular patch-clamp recordings from a thin dendrite hundreds um away from the soma. Taken all these results together, our data identifies an asymmetric modulation of excitatory signals in neuronal dendrites, potentially impacting local integration in a branch.

Background: Allergic bronchopulmonary mycosis (ABPM) occurs with fungi, other than Aspergillus fumigatus. However, the clinical characteristics of ABPM caused by non-Aspergillus species are unspecified. Methods: We retrospectively reviewed all patients with ABPM who visited to our hospital between April 2005 and December 2020. The causative fungi and clinical characteristics were analyzed. Patients were divided into the Aspergillus group and the non-Aspergillus group. Results: Fourteen patients and five patients were included in the Aspergillus group and the non-Aspergillus group, respectively. Compared to the Aspergillus group, the non-Aspergillus group had a significantly low serum immunoglobulin E level and low forced vital capacity. In addition, the non-Aspergillus group had a lower rate of the requirement for oral corticosteroid treatment and a low frequency of recurrence. Conclusion: Patients with non-Aspergillus ABPM had lower type 2 inflammation than did patients with allergic bronchopulmonary aspergillosis.

BACKGROUND: Tumor necrosis factor (TNF)-α, a proinflammatory cytokine, is involved in the pathogenesis of rheumatoid arthritis (RA). The omega-3 unsaturated fatty acid-derived metabolites resolvin (Rv) D1, RvE1, and maresin-1 (MaR1) have been reported as anti-inflammatory lipid mediators and are known as specialized pro-resolving mediators (SPMs). In this study, we aimed to investigate the anti-inflammatory effects of SPMs on TNF-α-induced responses in synovial fibroblasts. METHODS: We investigated the effects of SPMs on gene expression and/or production of cyclooxygenase-2 (COX-2), microsomal prostaglandin E synthase-1 (mPGES-1), interleukin (IL)-6, and matrix metalloproteinase (MMP)-3, which are involved in TNF-α-induced synovitis in RA or OA synovial fibroblasts, by quantitative real-time PCR. We also investigated the effects of SPMs on the mitogen-activated protein kinase (MAPK) signaling pathway by western blotting. Anti-inflammatory effects of SPMs were evaluated by applying SPMs to cultured synovial fibroblasts, followed by TNF-α stimulation. RESULTS: The induction of COX-2, mPGES-1, IL-6, and MMP-3 by TNF-α in synovial fibroblasts was not suppressed by omega 3-derived SPMs regardless of their origin such as RA or OA. SPMs had no effect on lipid mediator receptor gene expression induce by TNF-α and did not inhibit the TNF-α-activated MAPK signaling pathway. The production of COX-2 and IL-6 protein was significantly decreased by p38 inhibitor. CONCLUSION: Despite reports on the anti-inflammatory effect of omega 3-derived SPMs, its anti-inflammatory effect on TNF-α-induced responses was not observed in synovial fibroblasts. The reason may be that SPMs have no suppressive effect on p38 activation, which plays an important role in the production of inflammatory cytokines in synovial fibroblasts.

Modification of the halogen constituent in the fluorinated tolane moiety is an effective method for tailoring the functionality of the material.

A novel π-conjugated tricarbocycle with a CF2CF2-containing cyclohexa-1,3-diene skeleton was revealed to show aggregation-induced enhancement emission, which would pave the way for novel solid-state fluorescence materials.

Ph2N-Substituted fluorinated tolanes produced two polymorphisms, which display a distinct photoluminescence behavior; one polymorphism showed green PL and the other exhibited yellow PL.

Precise molecular design of fluorinated tolane-based fluorophores can control both the electron density and molecular aggregated structures.

The calcium monofluoride (CaF) molecule has emerged as a promising candidate for precision measurements, quantum simulation, and ultracold chemistry experiments. Inelastic and reactive collisions of laser cooled CaF molecules in optical tweezers have recently been reported and collisions of cold Li atoms with CaF are of current experimental interest. In this paper, we report ab initio electronic structure and full-dimensional quantum dynamical calculations of the Li + CaF $\to$ LiF + Ca chemical reaction. The electronic structure calculations are performed using the internally contracted multi-reference configuration-interaction method with Davidson correction (MRCI+Q). An analytic fit of the interaction energies is obtained using a many-body expansion method. A coupled-channel quantum reactive scattering approach implemented in hyperspherical coordinates is adopted for the scattering calculations under cold conditions. Results show that the Li + CaF reaction populates several low-lying vibrational levels and many rotational levels of the product LiF molecule and that the reaction is inefficient in the 1-100 mK regime allowing sympathetic cooling of CaF by collisions with cold Li atoms.

Background We describe herein an extremely rare case of intracardiac ectopic thymoma—only two pure cases have been reported to date—associated with myasthenia gravis, an infrequent complication of ectopic thymoma. Case presentation A 71-year-old woman with superior vena cava syndrome was found to have a large mass mainly located in the right atrium. Tumor resection under cardiopulmonary bypass was performed. The pathological diagnosis was type AB ectopic thymoma. The postoperative course was complicated by progressive respiratory failure, and she was diagnosed with myasthenic crisis based on clinical signs and the edrophonium test. The patient recovered and was weaned from prolonged mechanical ventilation after receiving intravenous immunoglobulin, and was subsequently discharged uneventfully. Conclusions This is the first report of myasthenic crisis due to intracardiac ectopic thymoma. Residual thymoma is a risk factor for the development of post-thymectomy myasthenia gravis, and long-term follow-up is required.

In recent experiments using the Stark-induced adiabatic Raman passage technique, Zhou et al. (

In this review, we discuss the use of time-of-flight secondary-ion mass spectrometry (TOF-SIMS) technology for analyzing the viscous glue (is called aggregate glue droplets) of spider orb webs and examine the results obtained. Element distribution images of the aggregate glue droplets were observed by TOF-SIMS. A uniform element distribution is seen for suspended pristine aggregate glue droplets, and a differential spreading of aggregate glue components is seen for attached aggregate glue droplets. We also observed TOF-SIMS images of water in aggregate glue droplets, where water was observed to be consistent with the distribution of oozing salt. We also found that the alkali metal in the aggregate glue droplets showed similar characteristics by feeding cesium carbonate to spiders.

Cisplatin is one of the most popular and traditional platinum-based anti-cancer drugs. Additionally, it is known for its effect on different types of cancers. To clarify the reaction mechanism of anti-cancer drugs in a cell, the visualization of drugs in a single cell is required. In this study, we investigated a secondary ion species obtained from cisplatin, which was bounded to the nucleus in a cell and its intensity. PtCl2- was mainly detected via SIMS during an analysis of pure cisplatin reagent. In contrast, a high-intensity signal for PtCN- was detected from cultured cells that were administered cisplatin. However, this signal was not detected from cisplatin in the reagent state. Chlorine in the cisplatin structure is replaced with water when it is combined with the cell nucleus. Therefore, PtCN- was mainly detected from the intracellular region because the structure was changed by cisplatin binding to the nucleus and which exhibits anti-cancer activity. The results showed that the cisplatin selectively combined with the nucleus. Through TOF-SIMS, we achieved a visual distribution of the cisplatin intracellular nucleus.

Pure organic phosphorescent molecules are attractive alternatives to transition-metal-complex-based phosphores for biomedical and technological applications owing to their abundance and nontoxicity. This article discloses the design, synthesis, and photophysical properties of fluorinated benzil and bisbenzil derivatives as potential pure organic room-temperature phosphorescent molecules. These compounds were separately converted from the corresponding fluorinated bistolanes via PdCl2-catalyzed oxidation by dimethyl sulfoxide, while nonfluorinated bistolane provided the corresponding bisbenzil derivatives exclusively in a similar manner. Intensive investigations of the photophysical properties of the benzil and bisbenzil derivatives in toluene at 25 °C showed both fluorescence with a photoluminescence (PL) band at a maximum wavelength (λPL) of around 400 nm and phosphorescence with a PL band at a λPL of around 560 nm. Interestingly, intersystem crossing effectively caused fluorinated benzils to emit phosphorescence, which may arise from immediate spin-orbit coupling involving the 1(n, π)→3(π, π) transition, unlike the case of fluorinated or nonfluorinated bisbenzil analogues. These findings offer a useful guide for developing novel pure organic room-temperature phosphorescent materials.

Fluorinated tolanes were found to show aggregation-induced emission characteristics and significantly enhanced photoluminescence efficiencies in molecular aggregates when compared with non-fluorinated tolanes. The fluorine atoms play important roles in the formation of tight crystal packing structures to suppress molecular motion in the crystalline state via electrostatic or hydrogen bonding interactions.

In recent experiments using the Stark-induced Adiabatic Raman Passage (SARP) technique, Zhou et al. measured the product's angular distribution for the collisions between He and aligned D2 molecules at cold collision energies. The signatures of the angular distributions were attributed to a l=2 resonance that governs scattering at low energies. A first principles quantum mechanical treatment of this problem is presented here using a highly accurate interaction potential for the He-H2 system. Instead, our results predict a very intense l=1 resonance at low energies, leading to angular distributions that differ from those measured in the experiment. A good agreement with the experiment is achieved only when the l=1 resonance is artificially removed, for example, by excluding the lowest energies present in the experimental velocity distribution. Our analysis revealed that neither the position nor the intensity of the l=1 resonance significantly changes when the interaction potential is modified within its predicted uncertainties. Energy-resolved measurements may help to resolve the discrepancy.

Ion sputtering, whereby atoms on target surfaces are bombarded by energetic ions, is a key process in the film-coating industry. However, its detailed mechanism has not yet been clarified and remains an empirical operation. This article demonstrates that the redeposition of metal on the target surface significantly enhances the sputtering rate. Although the effect differs depending on the metal species, significant enhancement in the sputtering rate occurs in glow-discharge plasma sputtering––a maximum increase of approximately 2.4 times was observed under experimental conditions. The experimental data agree well with the model equation, which superimposes two processes: sputtering by the desorbed redeposited metal and reduction of the enthalpy of sublimation by the adsorbed redeposited metal. The results of this study demonstrate that the metal redeposition effect is a key mechanism missing in the plasma sputtering process and that taking redeposition into account frees us from its empirical use. These findings are expected to address several of the existing questions related to sputtering, enabling the development of a wide variety of applications.

Dual-state emissive (DSE) luminophores, which can luminesce both in solution and in solid states, have recently attracted significant attention because of their broad applications. However, their development is difficult due to the difference in molecular design between solution- and solid-state luminophores. In this study, DSE luminophores based on unsymmetrical hexafluorocyclopentene-linked twisted π-conjugated structures carrying various substituents to tune the electron-density were designed and synthesized in a single-step reaction from heptafluorocyclopentene or perfluoro-1,2-diphenylcyclopentene derivatives. The twisted π-conjugated luminophores exhibited absorption in the UV region at approximately 330 nm, along with several signals in the high-energy region. Upon irradiating the luminophore solution (wavelength 330 nm), light-green to yellow photoluminescence (PL) was observed in the range of 422–471 nm with high PL efficiency. Theoretical calculations revealed that excitation from ground to excited states altered the structural shape of the luminophores from twisted to planar, leading to red-shifted PL and high PL efficiency (ΦPL). The intense blue PL exhibited by the luminophores in the crystalline state was attributed to their twisted molecular structures that suppressed non-radiative deactivation via the effective blocking of π/π stacking interactions.

Background Neuromuscular disorders (NMDs) occur in different forms and are generally diagnosed using muscle biopsy. Among the available anesthetic management options for infants with a suspected NMD are general anesthesia (GA) and regional anesthesia (RA), including spinal anesthesia (SA). Anesthesia selection is often challenging from the point of potential airway risks and anesthetic drug-related complications. Case presentation A 6-month-old male infant repeatedly underwent endotracheal intubation and extubation after birth because of respiratory muscle weakness and copious secretions. He was suspected of having NMD and was scheduled for muscle biopsy. His generalized hypotonia and decreased respiratory function presented a potentially difficult airway and complicated the selection of an appropriate anesthetic method. We selected SA and dexmedetomidine, which are safe for infants. Conclusion We report the successful and effective anesthetic management of SA and dexmedetomidine in an infant with a suspected NMD.

NASICON-type of solid-state electrolyte, Na3Zr2Si2PO12 (NZSP), is one of the potential solid-state electrolytes for all-solid-state Na battery and Na-air battery. However, in solid-state synthesis, high sintering temperature above 1200 °C and long duration are required, which led to loss of volatile materials and formation of impurities at the grain boundaries. This hampers the total ionic conductivity of NZSP to be in the range of 10-4 S cm-1. Herein, we have reduced both the sintering temperature and time of the NZSP electrolyte by sintering the NZSP powders with different amounts of Na2SiO3 additive, which provides the liquid phase for the sintering process. The addition of 5 wt % Na2SiO3 has shown the highest total ionic conductivity of 1.45 mS cm-1 at room temperature. A systematic study of the effect of Na2SiO3 on the microstructure and electrical properties of the NZSP electrolyte is conducted by the structural study with the help of morphological and chemical observations using X-ray diffraction (XRD), scanning electron microscopy, and using focused ion-beam-time of flight-secondary ion mass spectroscopy. The XRD results revealed that cations from Na2SiO3 diffused into the bulk change the stoichiometry of NZSP, leading to an enlarged bottleneck area and hence lowering activation energy in the bulk, which contributes to the increment of the bulk ion conductivity, as indicated by the electrochemical impedance spectroscopy result. In addition, higher density and better microstructure contribute to improved grain boundary conductivity. More importantly, this study has achieved a highly ionic conductive NZSP only by facile addition of Na2SiO3 into the NZSP powder prior to the sintering stage.

Objectives Type II endoleak is a problem after endovascular abdominal aneurysm repair. Preoperative risk factors for Type II endoleak include anatomical factors in the lumbar artery and inferior mesenteric artery; however, preventable postoperative risk factors are unknown. Postimplantation syndrome is associated with lower incidence of Type II endoleak. Therefore, we focused on inflammation, and our aim was to investigate nonsteroidal anti-inflammatory drugs as a postoperative risk factor for Type II endoleak. Methods This was a retrospective study of patients with aortic aneurysm who underwent endovascular aneurism repair at the Department of Cardiovascular Surgery, Beppu Medical Center, Oita, Japan, from January 2011 to August 2018. Clinical characteristics were retrieved from patients’ medical records and included age, sex, body mass index, smoking history, comorbidities, treatment devices, medications, and perioperative information, including postimplantation syndrome. Postimplantation syndrome was defined as body temperature >38.5°C with 12,000/dL white blood cells or >10.0 mg/dL C-reactive protein. The primary outcome was the presence or absence of Type II endoleak assessed on the first postoperative enhanced computed tomography scan. Risk factors for Type II endoleak were assessed. Results and conclusions: Of the eligible 84 patients, 20 (24%) had Type II endoleak identified in the first enhanced computed tomographic scans after endovascular aneurism repair. Nonsteroidal anti-inflammatory drug use (odds ratio (OR): 21.2; 95% confidence interval (95% CI): 1.5–308.4; P = 0.026), cerebrovascular disease (OR: 7.27; 95% CI: 1.06–49.99; P = 0.044), and body mass index 2 (OR: 17.3; 95% CI: 2.1–141.8; P = 0.008) were independent risk factors for Type II endoleak after endovascular aneurism repair. Comparing the rate of Type II endoleak among patients who did not receive nonsteroidal anti-inflammatory drugs within 24 h after endovascular aneurism repair, patients who first used nonsteroidal anti-inflammatory drugs 12–24 h after endovascular aneurism repair, and those who received nonsteroidal anti-inflammatory drugs within 12 h after endovascular aneurism repair, we found a significant difference among the groups (4%, 18%, 45%, respectively; P = 0.001). Nonsteroidal anti-inflammatory drug use within 24 h after endovascular aneurism repair is a risk factor for Type II endoleak. We should know nonsteroidal anti-inflammatory drugs within 24 h after endovascular aneurism repair can be a risk of Type II endoleak.