Forceless spontaneous delamination of high-aspect ratio fluorohectorite into monolayer nanosheets in chloroform.

One-dimensional dissolution of a layered compound in a nonpolar organic solvent is reported for the first time. A high-aspect ratio fluorohectorite modified with a cationic surfactant (dioctadecyldimethylammonium) showed spontaneous delamination into monolayer nanosheets in chloroform.

Hybridization of layered double hydroxides with functional particles.

Layered double hydroxides (LDHs) are a class of materials with useful properties associated with their anion exchange abilities as well as redox and adsorptive properties for a wide range of applications including adsorbents, catalysts and their supports, electrodes, pigments, ceramic precursors, and drug carriers. In order to satisfy the requirements for each application as well as to find alternative applications, the preparation of LDHs with the desired composition and particle morphology and post-synthetic modification by the host-guest interactions have been examined. In addition, the hybridization of LDHs with various functional particles has been reported to design materials of modified, improved, and multiple functions. In the present article, the preparation, the heterostructure and the application of hybrids containing LDHs as the main component are overviewed.

NiFe Layered Double Hydroxides with Controlled Composition and Morphology for the Efficient Removal of Cr(VI) from Water.

A layered double hydroxide (LDH) composed of Ni2+ and Fe3+ with a Fe3+/(Ni2+ + Fe3+) ratio of 0.05, which is not commonly available, was successfully prepared by coprecipitation from an aqueous solution of glycerol containing nickel nitrate and iron nitrate. Precipitation using NaOH as a precipitating agent at room temperature or 120 °C under hydrothermal conditions gave products with micrometer-sized aggregates of nanometer-sized unshaped particles, while that using urea yielded LDHs with a foam-like porous architecture composed of platy particles with a size of 100-300 nm. The products were examined to remove Cr(VI) from an acidic (pH = 3) aqueous solution of K2Cr2O7 by adsorption and photocatalytic reduction. The foam-like porous NiFe-LDH exhibited the highest adsorbed amount (122 mg g-1) and rate (0.017 g mg-1 min-1) in the dark and the highest rate (0.012 min-1) of photocatalytic Cr(VI) reduction among the NiFe-LDHs prepared in the present study, which can be explained as a positive effect of the foam-like porous architecture. These performances were superior to those of other reported LDHs, showing the importance of the composition and the particle morphology to boost the removal of Cr(VI).

Absence of Anaphylactic Reactions to Injection of Hemoglobin Vesicles (Artificial Red Cells) to Rodents.

The safety and efficacy of hemoglobin vesicles (HbVs) as artificial oxygen carriers encapsulating a purified and concentrated Hb solution in liposomes have been studied extensively. The HbV surface, modified with PEG by incorporating a PEG-conjugated phospholipid, is beneficial for storage and biocompatibility. However, it might be possible that interaction of PEG and the pre-existing anti-PEG antibody in the bloodstream causes acute adverse reaction. This study used two sets of experiments with rats and guinea pigs to ascertain whether the anti-PEG antibody generated by the PEG-modified HbV injection can induce anaphylactic reactions. SD rats received repeated intravenous injection of HbV at a dose rate of 16 or 32 mL/kg three times. Not anti-PEG IgG but anti-PEG IgM was detected. Nevertheless, no anaphylactic reaction occurred. Guinea pigs were used to study the presence of active systemic anaphylaxis further after injections of the PEG-modified liposomes used for HbV. The animals were sensitized by three repeated subcutaneous injections of PEG-modified liposomes (PEG-liposome) along with adjuvant at 1 week intervals. For comparison, unmodified liposomes (liposome) and 10 times excessively PEG-modified liposomes with ionizable lipid (10PEG-DODAP-liposome) were used. Inclusion of PEG modification induced not only anti-PEG IgM but also anti-PEG IgG. Three weeks after the final injection, intravenous injection of both PEG-liposome and liposome (1 mL/kg) induced no anaphylactic reaction. However, the injection of 10PEG-DODAP-liposome showed one lethal anaphylaxis case and one mild anaphylaxis case. Antisera obtained from the animal sensitized as described above were inoculated (0.05 mL) intradermally into fresh guinea pigs. The presence of passive cutaneous anaphylaxis was evaluated after intravenous injections (1 mL/kg) of three liposomes with Evans blue. No dye leakage was detected at any inoculated skin point for PEG-liposome or liposome, but a slight leakage was detected in one inoculated skin point for 10PEG-DODAP-liposome. These results indicate the absence of acute allergic reactions at repeated injections of HbVs despite the anti-PEG antibody induction. Not all the PEG-modified liposomes show anaphylaxis, and it may depend on the amount of PEGylated phospholipid and lipid composition of PEG-modified liposomes.

Nanoarchitectonics of a Smectite with 4,4'-Diammonium-α-truxillic Acid and Its Methyl Ester for the Removal of o-Phenylphenol and Biphenyl from Water.

Adsorbents with hydrophilic and hydrophobic natures were designed by intercalating a bioderived molecule; 4,4'-diammonium-α-truxillic acid (4ATA) and 4,4'-diammonium-α-truxillic acid dimethyl ester (E4ATA), which both are bioderived molecules, into a smectite (purified bentonite) to concentrate o-phenylphenol and biphenyl, respectively, from water. The adsorption isotherm showed high affinity between the 4ATA-smectite hybrid and o-phenylphenol with a high Langmuir constant (0.98 L mg-1). Meanwhile, the E4ATA-smectite hybrid adsorbed biphenyl with a high Langmuir constant (3.61 L mg-1). The adsorption properties of 4ATA- and E4ATA-smectite hybrid were contributed by the chemical characteristics of 4ATA and E4ATA in the interlayer space of the smectite.

Swelling-Induced Chromotropism of Bionanocomposite Hydrogel Beads.

Monodispersed gelatin hydrogel beads containing smectite with adsorbed cyanine dye exhibit chromotropic responses to compression and swelling/deswelling by solvent. Photoluminescence color of the beads changes by swelling in water (blue) and deswelling in ethanol (purple) reversibly. The forces generated by swelling/deswelling are thought to induce the transition between the J-aggregate and the monomer of cyanine dye adsorbed on smectite, giving the photoluminescent color changes.

The Minimal Important Difference of Acoustic Voice Quality Index in the Treatment of Voice Disorders.

OBJECTIVES: The acoustic voice quality index (AVQI) is a reliable tool that objectively assesses dysphonia levels using six acoustic parameters. Despite its high criterion-related concurrent validity, diagnostic accuracy, and minimal detectable change derived from test-retest reliability, the minimal important difference (MID) of the AVQI has not been tested before. This study aimed to estimate the MIDs of AVQI for improvement audibly perceived by clinicians and self-reported improvement by patients. METHODS: A retrospective study was conducted on 110 patients who received treatment for voice disorders. Patients completed AVQI and Voice Handicap Index-10 (VHI-10) questionnaires before and after the therapy. The MIDs of the AVQI were estimated using the anchor of either auditory-perceptual judgment of total dysphonia levels by clinicians or the VHI-10 questionnaire by patients. A distribution-based approach was also used to complement the results. RESULTS: First, using the auditory-perceptual anchor, a decrease of 0.95 in the AVQI was estimated as the MID for clinicians' perception, as a result of the receiver operating curve. Then, using the patient-reported anchor, an improvement of 1.36 in the AVQI was estimated as the MID for patients' voice-related disability. The distribution-based approach also ensured the anchor-based results of both the MIDs. CONCLUSIONS: The AVQI is a reliable and valid tool for evaluating voice quality, and a 0.95 decrease in the AVQI represents a meaningful improvement for clinicians' perception, whereas a 1.36 decrease in the AVQI influences patients' self-reported disability. This study contributes to understanding the minimal change necessary for clinicians to make informed decisions and ensure patient satisfaction. LEVEL OF EVIDENCE: 3 Laryngoscope, 134:2805-2811, 2024.

Validation of Subharmonics Quantification Using Two-Stage Cepstral Analysis.

OBJECTIVES: Hoarseness is primarily perceived as breathiness or roughness. Despite the various tools that quantitatively assess hoarseness, roughness has been difficult to quantify because of its complex acoustic structure, such as subharmonics. The parameter obtained from the two-stage cepstral analysis is promising for evaluating roughness. Thus, this study aimed to improve the accuracy of the parameter using a customized pitch setting and investigate the relationship between roughness and subharmonics. STUDY DESIGN: The design is a retrospective study. METHODS: Two-stage cepstral analysis was used to analyze the voice recordings of 455 participants, speech impaired and normal controls, using the Analysis of Dysphonia in Speech and Voice and Praat software. For validation, the ground truth of subharmonics was visually quantified using a narrowband spectrogram. The reliability and validity of the two-stage cepstral analysis and subharmonics measures on spectrograms were evaluated. RESULTS: The two-stage cepstral analysis showed a very strong correlation (r = 0.963) between the two software programs. Intra- and inter-rater reliability of the subharmonics measures on spectrograms were also good. Two-stage cepstral analysis showed that even with customized pitch settings, the diagnostic systems and correlations for perceptual roughness and subharmonics were weak to moderate. The subharmonics measures on spectrograms showed a strong correlation with roughness and moderate diagnostic accuracy of subharmonics. CONCLUSIONS: The two-stage cepstral analysis showed some improvement in diagnostic accuracy and correlation with customized pitch settings, but it did not sufficiently detect subharmonics or roughness. The analysis using subharmonics measures on spectrograms proved the high correlation between subharmonics and roughness, indicating that developing acoustic analysis parameters that sufficiently detect subharmonics is necessary.

Rehospitalisation rates after long-term follow-up of patients with severe mental illness admitted for more than one year: a systematic review.

AIMS: This study aimed to conduct a systematic review of studies on the outcomes of long-term hospitalisation of individuals with severe mental illness, considering readmission rates as the primary outcome. METHODS: Studies considered were those in which participants were aged between 18 and 64 years with severe mental illness; exposure to psychiatric hospitals or wards was long-term (more than one year); primary outcomes were readmission rates; secondary outcomes were duration of readmission, employment, schooling, and social participation; and the study design was either observational or interventional with a randomised controlled trial (RCT) design. Relevant studies were searched using MEDLINE, PsycINFO, Web of Science, CINAHL, and the Japan Medical Abstract Society. The final search was conducted on 1 February 2022. The risk of bias in non-randomised studies of interventions was used to assess the methodological quality. A descriptive literature review is also conducted. RESULTS: Of the 11,999 studies initially searched, three cohort studies (2,293 participants) met the eligibility criteria. The risk of bias in these studies was rated as critical or serious. The 1-10 years readmission rate for patients with schizophrenia who had been hospitalised for more than one year ranged from 33 to 55%. The average of readmission durations described in the two studies was 70.5 ± 95.6 days per year (in the case of a 7.5-year follow-up) and 306 ± 399 days (in the case of a 3-8-year follow-up). None of the studies reported other outcomes defined in this study. CONCLUSIONS: The readmission rates in the included studies varied. Differences in the follow-up period or the intensity of community services may have contributed to this variability. In countries preparing to implement de-institutionalisation, highly individualised community support should be designed to avoid relocation to residential services under supervision. The length of stay for readmissions was shorter than that for index admissions. The results also imply that discharge to the community contributes to improved clinical outcomes such as improved social functioning. The validity of retaining patients admitted because of the risk of rehospitalisation was considered low. Future research directions have also been discussed.

Novel Floating Adsorbent for Water Treatment: Organically Modified Layered Alkali Silicate by Facile Mechanochemical Reaction.

Adsorption serves as an effective way to collect (remove) contaminants from aqueous solution. In the present study, a novel floating adsorbent was designed through surface modification of a layered alkali silicate (octosilicate) using a silane coupling reagent (chlorodimethyl[3-(2,3,4,5,6-pentafluorophenyl)propyl]silane) to collect metal ions from water. By conducting the grafting by solvent-free mechanochemical reaction at room temperature, the external surface of octosilicate was modified to be hydrophobic while preserving the ion exchange capability in the interlayer space. Characterizations of XRD, IR, SEM, TGA, 29Si MAS NMR, and 19F MAS NMR confirmed the successful grafting at the external surface of octosilicate particles. The modified silicate demonstrated buoyancy at the air-water interface, facilitating the concentration of methylene blue, Ni2+, and Pb2+ from aqueous solutions. The adsorbed amounts of metal ions on the floating adsorbent were greater than those reported for the common nonfloating adsorbents (zeolites, clays, and clay minerals).

Electrochemical and electrical characteristics of ball milled Cs2Ti6O13 modified by the surface-to-bulk migration of hydroxyl groups.

Ball milling of solids under benign conditions leads to surface functionalization without altering the crystal structure and morphology. However, these additional surface functional groups are rarely fixed but instead mobilized across such ball milled solids. This phenomenon, including its effects on electrochemical and electrical properties, has received limited attention. We report herein that dry vibratory ball milling of lepidocrocite-type Cs2Ti6O13 generated hydroxyl groups which subsequently migrated from surfaces to bulk. The increased number of bulk hydroxyl groups is deduced from Raman, IR, and solid state 1H nuclear magnetic resonance spectroscopy, and thermogravimetric analysis. In contrast, the decrease in the relative proportion of surface hydroxyl groups/water and carbon-oxygen species was deduced from X-ray photoelectron spectroscopy. The inaccessible hydroxyl groups in ball milled Cs2Ti6O13 lead to a smaller amount of stored charge and increased charge transfer resistance, according to galvanostatic charge-discharge experiments and electrochemical impedance spectroscopy studies in 1 M Na2SO4. The alternating current electrical properties were also measured, revealing fundamental insights such as the one-dimensional conduction pathway and the relaxation time in microseconds. A model has been proposed for this surface-to-bulk migration of the hydroxyl groups, which competes with surface dangling bonds leading to particle agglomeration.

Controlled Phase Transformation and Crystal Growth of Titanium Dioxide from Anatase/Silica Core/Shell Particles.

Anatase/silica core/shell particles were prepared by the hydrolysis and condensation of tetraethyl orthosilicate on anatase particles with the sizes of 9, 22, and 111 nm, respectively. The thickness of the silica layer was designed from ca. 3 to 14 nm by repeating the coating procedure on anatase with a particle size of 22 nm. By the heat treatment at 1000 °C, though the pristine anatase particles transformed to rutile, anatase remained for the silica-coated particles. Anatase particles (111 nm) transformed to rutile upon heating at 1100 °C, while the transformation was not observed for the smaller particles (9 and 22 nm). With the increase of the silica thickness to 14 nm, anatase did not transform to rutile even after heating at 1150 °C, while resulting in varied compositions of anatase and rutile after heating at 1200 °C. The crystal growth of anatase and rutile was also suppressed for the silica-coated particles compared with that seen for pristine anatase. Thus, the thermal transformation and crystal growth of titania were controlled by the coating with silica, and the effects were shown to affect the coating.

Synthesis of NiFe layered double hydroxides with varied layer charge densities: the templating effect of dioctyl sulfosuccinate.

NiFe layered double hydroxides (LDHs) intercalated with dioctyl sulfosuccinate with varied Fe3+/(Ni2+ + Fe3+) ratios (0.04-0.25) were prepared by constant-pH co-precipitation from an aqueous solution of Ni and Fe perchlorates at room temperature. The interlayer dioctyl sulfosuccinate was exchanged with carbonate by the reaction of the product with an aqueous solution of sodium carbonate. The basal spacing of the NiFe-LDHs containing carbonate varied (0.80-0.90 nm) depending on the Fe3+/(Ni2+ + Fe3+) ratio; larger basal spacing was attained from the LDH with smaller Fe3+/(Ni2+ + Fe3+) due to the weaker attractive force between the LDH layer and the interlayer anion, proving that the Fe3+/(Ni2+ + Fe3+) ratios were associated with the layer charge density of NiFe-LDHs.

A Case of Pharyngeal Stenosis Caused by Behçet's Disease Treated With Transoral Videolaryngoscopic Surgery.

Behçet's disease is a refractory inflammatory disease characterized by recurrent oral aphthous ulcers. Ulcers are commonly seen in the oral cavity and the pharyngeal region. In patients with recurrent pharyngeal ulcers, pharyngeal stenosis may occur and leads to dysphagia. Herein, we report a case of pharyngeal stenosis caused by recurrent ulcers due to incomplete Behçet's disease. Prednisolone, colchicine, and infliximab were administered and resolved the pharyngeal ulcers, however, dysphagia persisted. To improve the swallowing function, a pharyngeal dilation surgery and transoral videolaryngoscopic surgery were performed, which resulted in an enlarged pharyngeal cavity. Oral intake of water was initiated the day after surgery, and after six days, the patient was able to take a normal diet. The pharyngeal stenosis had not recurred for one year after the surgery, and a normal diet continued without any dietary restrictions. Therefore, in a case of a severe oropharyngeal lesion, periodic follow-up and surgical interventions by an otolaryngologist are necessary.

Soap-Free Emulsion Composed of Polymer Solutions and an Aqueous Clay Suspension.

Novel emulsification was found in the system of aqueous suspension of a clay mineral (a synthetic hectorite) and a solution of polyvinyl butyral in 1-butanol without using surface-active agents. Droplets of the oil phase exhibited different sizes depending on the concentration of polyvinyl butyral solution and aqueous clay suspension. Shearing force produced from the high viscosity of the clay suspension was a factor to lead oil droplets to size smaller. The clay mineral was confirmed to be in the water phase, not at the oil and water interface. The emulsion showed useful thermal stability up to 80 °C. The present emulsion was successfully applied as a platform of the photochromic reaction of spiropyran.

Skin Acceleration Levels Estimated by a Neck-surface Accelerometer during Phonation Are Affected by The Mechanical Properties of The Anterior Cervical Skin.

OBJECTIVES: The aim of the present study was to assess whether skin acceleration levels (SAL) estimated by a neck-surface accelerometer (ACC) are affected by the anterior neck skin condition. METHODS: Each of six healthy non-dysphonic participants wore a headset microphone (MIC), had an ACC sensor fitted on the skin over the cervical trachea, and were subsequently asked to gradually increase the vocal loudness during sustained phonation of the vowel /e:/ (crescendo task), while the sound pressure levels on a sound level meter (SPLSLM) and MIC/ACC signals were simultaneously recorded. Root mean squared values were calculated from the MIC and ACC signals as the sound pressure level (SPLMIC) and SAL, respectively, and the relationships between SPLSLM and SAL were compared between neck anteflexion and retroflexion or between outward and inward skin retraction on both sides of the sensor. RESULTS: In the total samples for the successful crescendo performance in a natural head position, the SPLMIC and SPLSLM showed a strong linear correlation (r=0.980), whereas the correlation between the SAL and SPLSLM showed a distorted regression line (r=0.765) with individual differences. In all participants, the anteflexion and inward skin retraction decreased the SAL value at the same SPLSLM value, whereas the retroflexion increased the SAL value at the same SPLSLM value. CONCLUSION: These results demonstrate that the signal intensity of a neck-surface ACC is affected by the condition of the anterior cervical skin, perhaps leading to inter-individual variability in SAL measurements.

The Significant Influence of Hoarseness Levels in Connected Speech on the Voice-Related Disability Evaluated Using Voice Handicap Index-10.

OBJECTIVES: This retrospective study examines the influence of voice quality in connected speech (CS) and sustained vowels (SV) on the voice-related disability in patients' daily living documented by Voice Handicap Index-10 (VHI-10). METHODS: A total of 500 voice recordings of CS and SV samples from 338 patients with voice disturbances were included, along with the patients' age, diagnoses, maximum phonation time, and VHI-10. Dataset-1 comprised of 338 untreated patients, whereas Dataset-2 included 162 patients before and after phonosurgeries. As a preliminary study, the concurrent and diagnostic validities based on auditory-perceptual judgments were examined for cepstral peak prominence (CPP) and CPP smoothed (CPPS) for CS and SV tasks. Next, simple correlations and multivariate regression analyses (MRA) were performed to identify which of the acoustic measures for the CS or SV tasks significantly influenced the total score or improvement of VHI-10. RESULTS: The preliminary study confirmed high correlations with hoarseness levels as well as the excellent diagnostic accuracy of CPP and CPPS for both CS and SV tasks. In Dataset-1, the simple correlations and MRA results showed that cepstral measures in both tasks demonstrated moderate correlations with, and significant contribution to the total score of VHI-10, respectively. However, in Dataset-2, the changes of cepstral measures, as well as the median pitch after phonosurgeries in the CS tasks only, showed significant contributions to the improvement of VHI-10. CONCLUSION: The study demonstrated that the hoarseness levels in both the CS and SV tasks equivalently influenced the VHI-10 scores, and that the post-surgical change of voice quality only in the CS tasks influenced the improvement of voice-related disability in daily living.

The Feasibility of Gastroesophageal Manometry for Continuously Evaluating the Degree of Expiratory Effort During Successful Crescendo Phonation.

OBJECTIVES: This study aimed to assess the feasibility of gastroesophageal manometry for continuously evaluating the degree of expiratory effort by measuring the pressures in the digestive tract during crescendo phonation. METHODS: Each of 18 healthy nondysphonic speakers had a probe with a four-channel gastroesophageal manometer inserted through the nasal cavity to place four pressure sensors in the hypopharynx, cervical-/thoracic esophagus, and stomach, and was asked to gradually increase the vocal loudness during sustained phonation of the vowel /e:/ (vowel-crescendo task), while the sound pressure level and the pressures were simultaneously recorded. RESULTS: 50% of the successful vowel-crescendo task samples with a gradual and adequate sound pressure level increase showed a concomitant gradual increase in both the intra-thoracic-esophageal/intra-gastric pressure values from approximately -5 mmHg /6 mmHg to -10 mmHg/20 mmHg, respectively. The maximum pressure value was the highest in the intra-gastric pressure followed by the intra-thoracic-esophageal and intra-cervical-esophageal pressures in order. However, most of the samples showed less than one of atypical pressure changes, such as fluctuations in the intra-thoracic-esophageal and intra-gastric pressure changes and dispersion in the intra-cervical-esophageal and intra-hypopharyngeal pressure values (perhaps due to the peristaltic motions, and the contact of the sensors to the membranous wall). CONCLUSION: These results show that, during successful crescendo phonation, gastroesophageal manometry reveals a gradual increase in the intra-thoracic and intra-abdominal pressures with increasing the vocal intensity, even though showing some systematic errors, suggesting the usefulness of gastroesophageal manometry for continuously evaluating the degree of expiratory effort without influence by the laryngeal condition.

Photoinduced movement: how photoirradiation induced the movements of matter.

Pioneered by the success on active transport of ions across membranes in 1980 using the regulation of the binding properties of crown ethers with covalently linked photoisomerizable units, extensive studies on the movements by using varied interactions between moving objects and environments have been reported. Photoinduced movements of various objects ranging from molecules, polymers to microscopic particles were discussed from the aspects of the driving for the movements, materials design to achieve the movements and systems design to see and to utilize the movements are summarized in this review.