Search

The structure of the film formed by oleylpropanediamine (OLDA) on the copper (Cu) metal surface in water at 150 °C was investigated by combining quantitative NMR and surface characterization methods. We succeeded in quantifying the amount of film formation by precisely determining all mass balances in the systems examined. 2D IR microscopic mapping showed that the film thickness is uneven in the horizontal direction with a length scale of ~100 μm and hundreds of OLDA layers. This film thickness was also confirmed by AFM. The analysis of the C–H stretching vibrational frequency disclosed that the alkyl chains are highly ordered in the layers close to the Cu surface and are conformationally disordered in the layers distant from the Cu surface in the thicker portion of the film. Combining XPS measurements using argon gas cluster ion beam etching with the ICP-AES analysis, we revealed that the key to multiple layering is the formation of a coordination complex of the unprotonated amino groups of OLDA with Cu that presumably results in polymer chain-like network structures. Contact angle measurements at different OLDA concentrations and treatment times showed that the water repellency of the film originated from the thick layering of OLDA molecules with disordered hydrophobic chains.

Aims Functional decline is associated with worse outcomes in patients with elderly heart failure (HF), but little is known about the prognostic impact of hospital‐acquired disability (HAD) during hospital stay after acute HF. The present study examines the prognostic significance of HAD in the prediction of all‐cause mortality in elderly patients who admitted for acute HF. Methods and results This retrospective study was performed in 1941 elderly patients aged ≥65 years or older from the cardiovascular physiotherapy for acute HF patients in the Tokyo metropolitan area registry and excluded those who died in hospital. HAD was defined as any decline in the Barthel index (BI) before discharge compared with the BI within 1 month before hospital admission. The primary outcome of this study was all‐cause death and HF readmission. A total of 565 (29%) deaths and 789 (41%) HF readmission occurred over a median follow‐up period of 1.7 years. A total of 476 patients (25%) had HAD during hospital stay after acute HF. In multivariable analysis, HAD predicted all‐cause death [hazard ratio (HR): 1.772; 95% confidence interval (CI): 1.450–2.167; P

Infrared (IR) absorption and Raman spectra of methane hydrate (MH) were measured at low temperatures and high pressures to reveal the dynamics and cage occupancy of CH4 molecules and the hydration ...

The public sewage (PS) and night soil mixed with johkasou sludge (JO) have similar chemical compositions; however, the concentrations of organic matter and nitrogen compounds were different. We investigated the microbial community of the rotating biological contactor (RBC) units treating PS and JO, in which the RBC was submerged in the mixed liquor of activated sludge. Here, we observed that the microbial community compositions at the phylum and class levels were similar between the PS-RBC and JO-RBC, whereas the relative abundances of several phyla (Euryarchaeota, Acidobacteria, Chloroflexi, Firmicutes, Patescibacteria, and Betaproteobacteria) significantly differed between them. The microbial community composition of RBC (an attached growth process) was similar to that of the activated sludge (a suspended growth process). The microbial community of activated sludge likely affected that of RBC. The relative abundance of total denitrifying bacteria in the PS-RBC was twice as much as that in JO-RBC, while nitrifying bacterial phylotypes had a similar relative abundance. The predominant denitrifying genera were different between the PS-RBC and JO-RBC, as well as in the cross-sectional layers of the PS-RBC, suggesting the functional diversity of denitrifying bacterial genera inhabiting the RBC.

The present study aimed to report the efficacy and toxicity of our high-dose-rate (HDR) brachytherapy for early stage lip cancer (LC) using customized dental spacers. A retrospective analysis was performed among six patients with early stage LC treated with HDR interstitial brachytherapy between April 2015 and August 2019 using customized dental spacers. The total treatment dose was 49 Gy/7 fractions or 54 Gy/9 fractions. The median follow-up duration for the patients was 13 (range: 2–52) months. All patients completed the entire brachytherapy protocol safely and have experienced no local recurrence thus far. The CTV D100 and D90 values per fraction were median 100 (range: 98.3–100) % prescribed dose (PD) and median 133.4 (range: 129.3–138.9) % PD, respectively. The D2cc and D0.1cc values per fraction for the mandible were median 1.07 (range, 0.79–1.88) Gy and median 1.65 (range: 1.21–2.83) Gy, D2cc and D0.1cc values per fraction for oral cavity were median 1.48 (range, 1.31–1.72) Gy and median 2.73 (range: 1.79–2.88) Gy, respectively. Acute toxicities encountered were mucositis and lip edema limited to the irradiated area; none of them was beyond grade 2 and all were resolved within 1–2 months after treatment. We did not observe any late grade 2 adverse events or worse. This study shows that the adverse effects of HDR brachytherapy for early stage LC can be minimized using a dental spacer. Cooperation with the dentistry department is essential to make spacers that are individually customized for each patient.

This study aimed to evaluate the efficacy and safety of computed tomography-magnetic resonance imaging (CT-MRI)-guided multi-catheter interstitial brachytherapy for patients with bulky (≥4 cm) and high-risk, stage IIB–IVB advanced cervical cancer. Eighteen patients who underwent concurrent chemoradiotherapy with multi-catheter interstitial brachytherapy between September 2014 and August 2020 were enrolled. The prescribed dose of external beam radiotherapy was 45–50.4 Gy, and the brachytherapy high-dose-rate aim was 25–30 Gy per 5 fractions. The endpoints were four-year local and pelvic control rates, four-year disease-free and overall survival rates, and the adverse events rate. The median follow-up period was 48.4 months (9.1–87.5 months). Fifteen patients received concurrent cisplatin therapy (40 mg/m2, q1week). Four (22.2%), seven (38.9%), and seven (38.9%) patients had stage II, III, and IV cervical cancer, respectively. Pelvic and para-aortic lymph node metastases were observed in 11 (61.1%) and 2 (11.1%) patients, respectively. The median pre-treatment volume was 87.5 cm3. The four-year local control, pelvic control, disease-free survival, and overall survival rates were 100%, 100%, 81.6%, and 87.8%, respectively. Three (16.7%) patients experienced grade 3 adverse events, and none experienced grade 4–5 adverse events. CT-MRI-guided multi-catheter interstitial brachytherapy could be a promising treatment strategy for locally advanced cervical cancer.

Background The incidence of penetrating intracranial foreign bodies is rare, and to date, not many relevant studies have been published worldwide. In particular, a nail penetrating intracranially, just near the superior sagittal sinus (SSS), is extremely rare. We treated the case of a large nail that penetrated the middle of the head and strategized its removal. Case Description A 70-year-old man had experienced headache lasting a day. Computed tomography of the brain revealed a nail penetrating the middle of his head; in particular, the tip of the nail had penetrated the right ventricle, causing a slight subarachnoid hemorrhage. Angiography showed that the nail was very close to the SSS and that the venous flow was normal. However, there was a risk of the nail penetrating through the SSS or injuring other arteries, and we removed the nail directly from the intracranial view to stop bleeding from the SSS or other vessels. Fortunately, there was no bleeding, and we washed the hole created by the nail penetration and concluded the surgery. Conclusions Our technique is useful and safe for removing large nails penetrating the head.

Many icy Solar System bodies possess subsurface oceans. On Pluto, Sputnik Planitia’s location near the equator suggests the presence of a subsurface ocean and a locally thinned ice shell. To maintain an ocean, Pluto needs to retain heat inside. On the other hand, to maintain large variations in its thickness, Pluto’s ice shell needs to be cold. Here we show, by thermal evolution and viscous relaxation calculations, that the presence of a thin layer of clathrate hydrates (gas hydrates) at the base of the ice shell can explain both the long-term survival of the ocean and the maintenance of shell thickness contrasts. Clathrate hydrates act as a thermal insulator, preventing the ocean from completely freezing while keeping the ice shell cold and immobile. The most likely clathrate guest gas is methane, derived from precursor bodies and/or cracking of organic materials in the hot rocky core. Nitrogen molecules initially contained and/or produced later in the core would probably not be trapped as clathrate hydrates, instead supplying the nitrogen-rich surface and atmosphere. The formation of a thin clathrate hydrate layer cap to a subsurface ocean may be an important generic mechanism to maintain long-lived subsurface oceans in relatively large but minimally heated icy satellites and Kuiper belt objects. Pluto’s subsurface ocean and thickness variation in its ice shell may be maintained by a layer of methane clathrates forming an insulating cap to the ocean, according to calculations of thermal evolution and viscous relaxation.

While aspiration pneumonia constitutes the majority of pneumonia cases in the elderly, it remains highly underdiagnosed. We experienced a case of recurrent pneumonia and chronic cough that was later diagnosed as aspiration pneumonia and diffuse aspiration bronchiolitis (DAB) due to recurrent hemorrhaging from an intramedullary cavernous malformation. The patient was finally diagnosed when life-threatening respiratory depression caused emergency attention. This is the first report of hemorrhaging from an intramedullary cavernous malformation diagnosed due to aspiration pneumonia and DAB. These findings highlight the importance of considering aspiration in cases with recurrent pneumonia or chronic chough. The underlying cause may be a life-threatening condition.

Tissue diagnosis of brain tumours in eloquent is often done via needle biopsy but this method yields small samples that may not be representative of the whole tumour. The Neuroport® system enables a larger tumour biopsy to be taken via a burr hole. We report our experience on 5 cases October 2017 and June 2018. Brainlab® navigation was used. The diagnosis in all patients was made without worsening of their modified Rankin scale scores.

Trigeminal neuralgia is caused by compression of the trigeminal nerve by arteries or veins in the posterior fossa. A persistent primitive trigeminal artery variant (PPTAv) is an anomalous artery that may cause trigeminal neuralgia. A 65-year-old man presented with left facial pain. Brain magnetic resonance imaging revealed a PPTAv. Constructive interference in steady state showed that both the PPTAv and the superior cerebellar artery (SCA) compressed the trigeminal nerve. Thus, we performed microvascular decompression and the patient’s symptoms improved. PPTAv is a rare anomaly in the posterior fossa that can cause trigeminal neuralgia. Dual compression of the trigeminal nerve by the SCA and PPTAv demonstrates that trigeminal neuralgia may originate from multiple sources. It is therefore important to check preoperative images to adequately treat trigeminal neuralgia.

Chiral quaternary carbon-containing bicyclic compounds possessing carbonyl functionalities were efficiently synthesized through asymmetric intramolecular aldol reactions with organocatalysts. Bicyclo [3.3.0] and [3.4.0] systems were constructed with a diamine catalyst, while bicyclo [4.3.0] and [4.4.0] skeletons were prepared by an acylsulfonamide type catalyst.

Objectives: In the diagnosis of nonconvulsive status epilepticus (NCSE), the use of ongoing ictal electroencephalographic (EEG) findings is the gold standard. However, this is difficult without the availability of continuous EEG monitoring facilities. Given this, a small telemetry EEG amplifier (Headset-EEG; AE-120A EEG Headset™) was introduced for use in simple EEG monitoring facilities. In this study, we examined the diagnostic performance of the Headset-EEG for NCSE in a neuroemergency setting.Methods: We retrospectively selected five patients who were diagnosed with NCSE using Headset-EEG by attending physicians between October 2017 and July 2018. Reevaluation with Headset-EEG was performed, and the findings were compared with the initial diagnosis. Results: In Case 1, Headset-EEG clearly revealed repeated ictal discharges associated with acute subdural hematoma. However, in Cases 2 and 3, the initial EEG diagnosis was incorrectly made because of an EEG interpretation error. In Cases 4 and 5, various artifacts, caused by unstable electrode placement, resulted in an initial diagnosis of ongoing seizure activity. Nevertheless, the initial diagnoses and subsequent treatment of Cases 2–5 did not directly affect the patients' outcomes.Conclusion: The present study indicates that Headset-EEG is a possible tool for use in NCSE screening. However, considerable knowledge of EEG interpretation is needed to establish a correct NCSE diagnosis. When NCSE is suspected per Headset-EEG, a subsequent routine EEG with a full montage of 10–20 EEG electrodes should be performed in collaboration with an epileptologist or electroencephalographer. Keywords: Triphasic waves, Metabolic encephalopathy, Artifact

Tissue diagnosis of brain tumours in eloquent is often done via needle biopsy but this method yields small samples that may not be representative of the whole tumour. The Neuroport

Background: Many known risk factors, including hypertension and hyperlipidemia cause intracerebral hemorrhage (ICH). Recently, microbleeds have been identified as one of the factors leading to ICH. While some patients have been found to have recurrent ICH, risk factors for recurrent ICH are scarcely reported. We conducted an observational study on the risk-factors of recurrent ICH, comparing stroke patients with a single hemorrhagic episode and those with recurrent ICH. Methods: A retrospective analysis of a single-center database was performed to analyze the clinical presentation and characteristics of patients with a single and recurrent ICH. From January 2016 to December 2017, a total of 317 patients were analyzed based on suspected factors including patients’ sex, age, medical history, antiplatelet therapy use, and presence of microbleeds on images. Results: Of the 317 patients, 36 patients (11.4%) developed a second episode of cerebral hemorrhage. Brain magnetic resonance imaging (MRI) of the patients without microbleeds, predicted reduced risk of recurrence. This is the first report strongly associating the presence of microbleeds with the possibility of a recurrent ICH. Other factors under study did not show an apparent association with recurrent ICH probably because of the high statistical significance obtained with the presence of microbleeds. Conclusion: Our findings revealed that the absence of microbleeds on images is a factor that strongly predicts a reduced risk for recurrent ICH and that the detection of microbleeds on MRI performed in patients with a single hemorrhagic episode, is useful in defining further therapeutic management. These findings may benefit physicians treating stroke patients.

We have developed a high-resolution technique based on micro Raman spectroscopy to measure hydrogen isotope diffusion profiles in ice Ih. The calibration curve for quantitative analysis of deuterium in ice Ih was constructed using micro Raman spectroscopy. Diffusion experiments using diffusion couples composed of dense polycrystalline H2O and D2O ice were carried out under a gas confining pressure of 100 MPa (to suppress micro-fracturing and pore formation) at temperatures from 235 K to 245 K and diffusion times from 0.2 to 94 hours. Two-dimensional deuterium profiles across the diffusion couples were determined by Raman imaging. The location of small spots of frost from room air could be detected from the shapes of the Raman bands of OH and OD stretching modes, which change because of the effect of the molar ratio of deuterium on the molecular coupling interaction. We emphasize the validity for screening the impurities utilizing the coupling interaction. Some recrystallization and grain boundary migration occurred in recovered diffusion couples, but analysis of two-dimensional diffusion profiles of regions not affected by grain boundary migration allowed us to measure a volume diffusivity for ice at 100 MPa of ( 2.8 ± 0.4 ) × 10 - 3 exp - 57.0 ± 15.4 kJ / mol RT m 2 / s (R is the gas constant, T is temperature). Based on ambient pressure diffusivity measurements by others, this value indicates a high (negative) activation volume for volume diffusivity of −29.5 cm3/mol or more. We can also constrain the value of grain boundary diffusivity in ice at 100 MPa to be

The volume diffusion coefficient of water in ice VI was determined in the pressure-temperature range of 1.3–1.9 GPa and 300–320 K by in situ isotope tracer diffusion experiments. We determined the activation energy of the volume diffusion to be 61.9 ± 9.5 kJ/mol. The viscosity of polycrystalline ice VI under diffusion creep was estimated from the diffusion coefficients based on the theory of the diffusion creep. From a compilation of viscosity values in the current diffusion creep regime and the viscosity previously determined by plastic deformation experiments of ice VI in a high stress regime (Durham et al. 1996), here we provide the relationships between viscosity, stress, and the average grain size of polycrystalline ice VI. The most plausible deformation mechanism of the layers of ice VI underneath the internal oceans in large icy bodies was inferred from the viscosity-stress-average grain size relationship. We also discuss the critical thickness of the ice VI layer, which determines the onset of thermal convection.

Twenty-two samples of ingredients of recreational drugs before being sold on the drug market obtained from a dubious drug dealer were analyzed by gas chromatography/mass spectrometry, high-resolution mass spectrometry, and nuclear magnetic resonance (NMR) spectroscopy. The present study showed 15 novel designer drugs, which have not been described in scientific literature. They included three NBOMe drugs 25H-NBOMe, 25D-NBOMe, and 25E-NBOMe, three other phenethylamine-type drugs 25I-NBMD, RH34, and escaline, eight cathinone derivatives 5-DBFPV, 3,4-MDPHP, 3,4-dimethyl-NEB, 3,4-dimethyl-α-ethylaminopentiophenone, 3,4-dimethyl-α-PVP, 4F-α-ethylaminopentiophenone, bk-IVP, and bk-IBP, and a phencyclidine derivative MMXE. In addition to the above novel compounds, known compounds such as 25I-NBOMe, ADB-CHIMINACA, 5F-ADB, and butane-1,4-diol were also identified from some samples. The electron ionization mass spectra, high-resolution data of molecular formulae, and NMR spectra presented in this article seem very useful for forensic toxicologists, who are obliged to identify new psychotropic drugs in any dubious products and/or human specimens.

We reported a high-frequency piezoelectric resonator (PZR)-based cascaded fractional-N PLL featuring channel adjusting technique with sub-ppb-order frequency resolution, which can overcome the difficulty using the narrow range GHz PZR. This paper details a design of the proposed cascaded PLL. In order to reduce power consumption of 2nd-PLL, a power-efficient latch for pre-scaler is proposed. 3rd-1st cascaded delta-sigma-modulator can reduce the number of gates. The prototype PLL was fabricated in a 65nm CMOS and achieved 8.484GHz to 8.912GHz output, 180 fs rms-jitter, and −244 dB FOM while consuming 12.7mW.

This paper proposes a cascaded fractional-N phase-locked loop (PLL) based on a high-frequency piezoelectric resonator (PZR). Sub-ppb-order frequency resolution is achieved by a channel adjustment technique. Besides its small form factor, a high- ${Q}$ PZR at gigahertz frequencies realizes a very low phase-noise synthesizer for RF applications. However, three fundamental issues remain to be solved: the narrow tuning range and large process variation of PZR-based oscillators, the low-frequency resolution of a PLL referenced to gigahertz-order frequencies, and the undesirable harmonic oscillation caused by the inductance of the CMOS-PZR bonding wire. To overcome these issues, we propose a channel-adjusting technique (CAT) that adaptively sets the division ratio of two PLLs to maintain constant output frequency of the second PLL while varying the PZR oscillator frequency, hence permitting the narrow tuning range and wide process variation of the PZR oscillator. The first PLL in our PLL architecture determines the output frequency resolution and the second reduces the power consumption of the delta–sigma modulator. We also suppress the harmonic oscillations in the PZR oscillator. The prototype PLL is fabricated in a 65-nm CMOS and achieves an 8.484–8.912-GHz output, 180-fs rms jitter, and −244-dB FOM while consuming 12.7-mW power. We developed a cascaded fractional-N PLL based on a high-frequency PZR with a sub-ppb-order CAT, which overcomes the narrow tuning range problem in gigahertz PZRs. A prototype PLL fabricated in a 65-nm CMOS consumed 12.7 mWand output 8.484–8.912 GHz with 180-fs rms jitter.

Species dissolved in H 2 fluid were investigated in a SiO 2 –H 2 system. Raman and infrared (IR) spectra were measured at high pressure and room temperature after heating experiments were conducted at two pressure and temperature conditions: 2.0 GPa, 1700 K and 3.0 GPa, 1500 K. With the dissolution of quartz, a SiH vibration mode assignable to SiH 4 was detected from Raman spectra of the fluid phase. Furthermore, an OH vibration mode was observed at 3260 cm −1 from the IR spectra at 3.0 GPa. With decreasing pressure, the OH vibration frequencies observed between 3.0 and 2.1 GPa correspond to that of ice VII, and those observed at 1.4 and 1.1 GPa correspond to that of ice VI. These results indicate that the chemical reaction between dissolved SiO 2 components and H 2 fluid caused the formation of H 2 O and SiH 4 , which was contrastive to that observed in SiO 2 –H 2 O fluid. Results imply that a part of H 2 is oxidized to form H 2 O when SiO 2 components of mantle minerals dissolve in H 2 fluid, even in an iron-free system.

The self-diffusion of ice VII in the pressure range of 5.5-17 GPa and temperature range of 400-425 K was studied using micro Raman spectroscopy and a diamond anvil cell. The diffusion was monitored by observing the distribution of isotope tracers: D2O and H2 (18)O. The diffusion coefficient of hydrogen reached a maximum value around 10 GPa. It was two orders of magnitude greater at 10 GPa than at 6 GPa. Hydrogen diffusion was much faster than oxygen diffusion, which indicates that protonic diffusion is the dominant mechanism for the diffusion of hydrogen in ice VII. This mechanism is in remarkable contrast to the self-diffusion in ice Ih that is dominated by an interstitial mechanism for the whole water molecule. An anomaly around 10 GPa in ice VII indicates that the rate-determining process for the proton diffusion changes from the diffusion of ionic defects to the diffusion of rotational defects, which was suggested by proton conductivity measurements and molecular dynamics simulations.

This paper proposes a high-frequency piezoelectric resonator (PZR)-based cascaded fractional-N PLL featuring channel adjusting technique with sub-ppb-order frequency resolution, which can overcome the difficulty using the narrow range GHz PZR. Moreover, undesirable oscillation induced by parasitic inductance of interconnects is suppressed by negative inductance technique. A power-efficient divider contributes to save power of the 2nd-PLL that suppresses output phase noise by the 1 GHz reference. The prototype PLL was fabricated in a 65nm CMOS and achieved 8.484GHz to 8.912GHz output, 180 fs rms-jitter, and −244 dB FOM while consuming 12.7mW.

We developed a micro-Raman and photoluminescence imaging technique for visualizing the internal stress fields in a sapphire crystal. The technique was applied to an Australian sapphire gemstone with a zircon inclusion. Considering piezospectroscopic effects on Raman and photoluminescence spectra, the Raman shifts of sapphire around the zircon inclusion were converted to hydrostatic pressure and deviatoric components of stress tensor. The internal stress was highly concentrated at the tips of the zircon crystal, where the deviatoric stress and the hydrostatic pressure component reached 700 and 470 MPa, respectively. Generation of compressive stress on the crystal surface of zircon can be explained by the difference in thermal expansion coefficients and elastic constants between sapphire and zircon. In general, internal stress fields induced by mineral inclusions reflect the pressure and temperature conditions at which the host sapphire gemstones were crystallized. Thus, the present technique can be utilized to identify the origin of gemstones. Copyright © 2012 John Wiley & Sons, Ltd.

Infrared (IR) absorption spectra of antigorite were measured up to 27 GPa and 320 °C using synchrotron IR radiation to elucidate OH group behavior under high-pressure (HP) and high-temperature (HT) conditions. The absorption bands attributable to the OH stretching modes of outer OH groups (OH outer ) and inner OH groups (OH inner ) show positive pressure dependencies. The shift rate of the OH inner band is almost constant at all pressure ranges. In contrast, that of the OH outer band increases slightly at about 6 GPa. This discontinuous change of the shift rate is consistent with the anomalous behavior of the OH outer upon compression, which was predicted in the previous first-principle calculation study. Specifically, the pressure dependence of the OH outer band shows that the hydrogen ion of an OH outer interacts not only with the nearest basal oxygen ion of the SiO 4 tetrahedron but also with the second nearest two basal oxygen ions upon compression. The latter interaction becomes dominant over the former interaction at about 6 GPa. Pressure-induced amorphization was indicated from IR spectra measured at 300 °C and 25.6 GPa. This P - T condition is out of the thermodynamic stability field of antigorite. A broad absorption band, which is close to the broad band attributable to natural hydrous silicate glass, appeared after amorphization, which suggests that the pressure-induced amorphization of antigorite does not induce dehydration. Hydrogen atoms are retained in amorphized antigorite as OH groups.