ABSTRACT
This study investigated whether the brain utilizes morphologically induced tones for semantic processing during online speech perception. An auditory comprehension task was conducted while measuring event-related potentials (ERPs). The study tested whether a discrepancy between contextual expectations and the tonal realizations of the target word would yield an N400 effect, indicative of semantic processing difficulty. An N400 effect was observed, reflecting integration difficulty due to semantic anomalies caused by incongruent tones. Additionally, the ERPs in the congruent conditions were modulated by the cohort entropy of the target word indicating lexical competition. The late negativity observed in this study encompasses both the N400 and preactivation negativity. This overlap underscores the brain's potential for rapidly connecting form and meaning from different sources within the word, relying on statistically based prediction in semantic processing.
Subject(s)
Electroencephalography , Semantics , Speech Perception , Humans , Male , Female , Speech Perception/physiology , Young Adult , Adult , Evoked Potentials/physiology , Acoustic Stimulation/methods , Brain/physiology , Comprehension/physiology , Evoked Potentials, Auditory/physiology , AdolescentABSTRACT
Rising cancer survival rates have led to an increased risk of multiple primary cancers (MPCs). Data on MPCs in South Korea are limited. This study aimed to address incidence and clinical characteristics of MPCs in a single cancer center in Korea during a 20-year period. We retrospectively analyzed 96,174 cancer patients at the Korea Cancer Center Hospital between 2003 and 2022, identifying 2167 patients with metachronous MPCs based on Surveillance, Epidemiology, and End Results SEER criteria. We categorized patients by cancer type (15 major solid cancer groups and 3 major hematologic cancer groups), including pathological diagnosis, assessed latency periods, and relative risks (RRs) for developing MPCs. The overall MPC incidence was 2.3%. Breast cancer (15.7%) was the most common primary cancer, and lung cancer (15.2%) was the most frequent second primary cancer. The median latency period for second primary cancers was 4.1 years. Decreasing latency periods for third and fourth primary cancers were observed (2.1 years and 1.6 years, respectively). Most cancers maintained their dominant pathological type despite notable changes in the prevalence of specific pathologies for certain types of second primaries. Lymphoma showed the highest RR (2.1) for developing MPCs. Significant associations were found between specific primary and subsequent cancers, including breast-ovary, thyroid-breast, stomach-pancreas, colorectal-head and neck, lung-prostate, and lymphoma-myeloid neoplasms. These findings contribute to a better understanding of MPC occurrence. They can inform future research on their etiology and development of improved management strategies.
ABSTRACT
Phototherapeutics has shown promise in treating various diseases without surgical or drug interventions. However, it is challenging to use it in inner-body applications due to the limited light penetration depth through the skin. Therefore, we propose an organic light-emitting diode (OLED) catheter as an effective photobiomodulation (PBM) platform useful for tubular organs such as duodenums. A fully encapsulated highly flexible OLED is mounted over a round columnar structure, producing axially uniform illumination without local hotspots. The biocompatible and airtight OLED catheter can operate in aqueous environments for extended periods, meeting the essential requirements for inner-body medical applications. In a diabetic Goto-Kakizaki (GK) rat model, the red OLED catheter delivering 798 mJ of energy is shown to reduce hyperglycemia and insulin resistance compared to the sham group. Results are further supported by the subdued liver fibrosis, illustrating the immense potential of the OLED-catheter-based internal PBM for the treatment of type 2 diabetes and other diseases yet to be identified.
Subject(s)
Diabetes Mellitus, Type 2 , Hyperglycemia , Animals , Rats , Catheters , Diabetes Mellitus, Type 2/therapy , Duodenum , Hyperglycemia/therapy , PhototherapyABSTRACT
BACKGROUND: Recently, the duodenum has garnered interest for its role in treating metabolic diseases, including type 2 diabetes (T2DM). Multiple sessions of external photobiomodulation (PBM) in previous animal studies suggested it resulted in improved hyperglycemia, glucose intolerance, and insulin resistance with a multifactorial mechanism of action, despite the target organ of PBM not being clearly proven. This study aimed to determine whether a single session of a duodenal light-emitting diode (LED) PBM may impact the T2DM treatment in an animal model. METHODS: Goto-Kakizaki rats as T2DM models were subjected to PBM through duodenal lumen irradiation, sham procedure, or control in 1-week pilot (630 nm, 850 nm, or 630/850 nm) and 4-week follow-up (630 nm or 630/850 nm) studies. Oral glucose tolerance tests; serum glucagon-like peptide 1 (GLP-1), glucose-dependent insulinotropic polypeptide, and insulin levels; liver chemistry and histology; and gut microbiome in the PBM, sham control, and control groups were evaluated. RESULTS: In the 1-week study, duodenal dual-wavelength (D, 630/850 nm) LED PBM showed improved glucose intolerance, alkaline phosphatase and cholesterol levels, and weight gain than other groups. The D-LED PBM group in the 4-week study also showed improved hyperglycemia and liver enzyme levels, with relatively preserved pancreatic islets and increased serum insulin and GLP-1 levels. Five genera (Bacteroides, Escherichia, Parabacteroides, Allobaculum, and Faecalibaculum) were significantly enriched 1 week after the D-LED PBM. Bacteroides acidifaciens significantly increased, while Lachnospiraceae significantly decreased after 1 week. CONCLUSION: A single session of D-LED PBM improved hyperglycemia and hepatic parameters through the change of serum insulin, insulin resistance, insulin expression in the pancreatic ß-cells, and gut microbiome in T2DM animal models.
Subject(s)
Diabetes Mellitus, Type 2 , Gastrointestinal Microbiome , Glucose Intolerance , Hyperglycemia , Insulin Resistance , Animals , Rats , Diabetes Mellitus, Type 2/metabolism , Disease Models, Animal , Duodenum/metabolism , Duodenum/pathology , Glucagon-Like Peptide 1 , Insulin , Liver/metabolismABSTRACT
The objective of this study was to determine whether (5S)-5-(4-benzyloxy-3,5-dimethoxy-phenyl)-5,9-dihydro-8H-furo [3',4':6,7] naphtho [2,3-d] [1,3]dioxol-6-one (JNC-1043), which is a novel chemical derivative of ß-apopicropodophyllin, acts as a novel potential anticancer reagent and radiosensitizer in colorectal cancer (CRC) cells. Firstly, we used MTT assays to assess whether JNC-1043 could inhibit the cell proliferation of HCT116 and DLD-1 cells. The IC50 values of these cell lines were calculated as 114.5 and 157 nM, respectively, at 72 h of treatment. Using doses approximating the IC50 values, we tested whether JNC-1043 had a radiosensitizing effect in the CRC cell lines. Clonogenic assays revealed that the dose-enhancement ratios (DER) of HCT116 and DLD-1 cells were 1.53 and 1.25, respectively. Cell-counting assays showed that the combination of JNC-1043 and γ-ionizing radiation (IR) enhanced cell death. Treatment with JNC-1043 or IR alone induced cell death by 50~60%, whereas the combination of JNC-1043 and IR increased this cell death by more than 20~30%. Annexin V-propidium iodide assays showed that the combination of JNC-1043 and IR increased apoptosis by more 30~40% compared to that induced by JNC-1043 or IR alone. DCFDA- and MitoSOX-based assays revealed that mitochondrial ROS production was enhanced by the combination of JNC-1043 and IR. Finally, we found that suppression of ROS by N-acetylcysteine (NAC) blocked the apoptotic cell death induced by the combination of JNC-1043 and IR. The xenograft model also indicated that the combination of JNC-1043 and IR increased apoptotic cell death in tumor mass. These results collectively suggest that JNC-1043 acts as a radiosensitizer and exerts anticancer effects against CRC cells by promoting apoptosis mediated by mitochondrial ROS.
Subject(s)
Antineoplastic Agents , Colorectal Neoplasms , Radiation-Sensitizing Agents , Humans , Podophyllotoxin/pharmacology , Reactive Oxygen Species/metabolism , Annexin A5 , Acetylcysteine/pharmacology , Propidium/pharmacology , Radiation-Sensitizing Agents/pharmacology , Apoptosis , Antineoplastic Agents/pharmacology , Cell Proliferation , Colorectal Neoplasms/drug therapy , Colorectal Neoplasms/metabolism , Cell Line, TumorABSTRACT
Endoscopic bariatric and metabolic therapies are promising for obesity. We developed a novel gastro-duodenal flow restrictor (G-DFR) device for relative weight loss and lowering of glucose level and evaluated its safety and efficacy in a porcine model. The G-DFR comprised self-expandable gastro-duodenal partially covered polytetrafluoroethylene (PTFE) metal stent distally attached to a PTFE skirt. Eleven juvenile pigs were randomized into the evaluation of migration (n = 3), mid-term efficacy (n = 5), and control (n = 3) groups. Five pigs showed G-DFR migration at 2, 4, 7, and 10 weeks after placement in the migration and mid-term efficacy group. Compared to the control group, the mid-term efficacy group showed up to 55.4% relative weight loss in 12 weeks. Compared to the case group, the control group showed higher mean ghrelin hormone level from 6 to 12 weeks. Glucose level was significantly lower in the efficacy group than in the control group after 6 weeks. Serum alanine transferase levels and histological collagen deposition were lower in the liver of the case group than in the control group. Although it did not demonstrate consistent performance with respect to migration, a well-positioned G-DFR in the pyloroduodenal portion may lead to relative weight loss, lowering of glucose levels, and improved hepatic parameters.
Subject(s)
Obesity , Weight Loss , Animals , Glucose , Pilot Projects , Polytetrafluoroethylene , SwineABSTRACT
Botulinum neurotoxin type A (BoNT/A) causes muscle paralysis by blocking cholinergic signaling at neuromuscular junctions and is widely used to temporarily correct spasticity-related disorders and deformities. The paralytic effects of BoNT/A are time-limited and require repeated injections at regular intervals to achieve long-term therapeutic benefits. Differences in the level and duration of effectivity among various BoNT/A products can be attributed to their unique manufacturing processes, formulation, and noninterchangeable potency units. Herein, we compared the pharmacodynamics of three BoNT/A formulations, i.e., Botox® (onabotulinumtoxinA), Xeomin® (incobotulinumtoxinA), and Coretox®, following repeated intramuscular (IM) injections in mice. Three IM injections of BoNT/A formulations (12 U/kg per dose), 12-weeks apart, were administered at the right gastrocnemius. Local paresis and chemodenervation efficacy were evaluated over 36 weeks using the digit abduction score (DAS) and compound muscle action potential (CMAP), respectively. One week after administration, all three BoNT/A formulations induced peak DAS and maximal reduction of CMAP amplitudes. Among the three BoNT/A formulations, only Coretox® afforded a significant increase in paretic effects and chemodenervation with a prolonged duration of action after repeated injections. These findings suggest that Coretox® may offer a better overall therapeutic performance in clinical settings.
Subject(s)
Botulinum Toxins, Type A , Neuromuscular Agents , Animals , Botulinum Toxins, Type A/toxicity , Injections, Intramuscular , Mice , Muscle Spasticity , Muscle, Skeletal , Neuromuscular Agents/pharmacology , ParesisABSTRACT
ß-apopicropodophyllin (APP), a derivative of podophyllotoxin (PPT), has been identified as a potential anti-cancer drug. This study tested whether APP acts as an anti-cancer drug and can sensitize colorectal cancer (CRC) cells to radiation treatment. APP exerted an anti-cancer effect against the CRC cell lines HCT116, DLD-1, SW480, and COLO320DM, with IC50 values of 7.88 nM, 8.22 nM, 9.84 nM, and 7.757 nM, respectively, for the induction of DNA damage. Clonogenic and cell counting assays indicated that the combined treatment of APP and γ-ionizing radiation (IR) showed greater retardation of cell growth than either treatment alone, suggesting that APP sensitized CRC cells to IR. Annexin V-propidium iodide (PI) assays and immunoblot analysis showed that the combined treatment of APP and IR increased apoptosis in CRC cells compared with either APP or IR alone. Results obtained from the xenograft experiments also indicated that the combination of APP and IR enhanced apoptosis in the in vivo animal model. Apoptosis induction by the combined treatment of APP and IR resulted from reactive oxygen species (ROS). Inhibition of ROS by N-acetylcysteine (NAC) restored cell viability and decreased the induction of apoptosis by APP and IR in CRC cells. Taken together, these results indicate that a combined treatment of APP and IR might promote apoptosis by inducing ROS in CRC cells.
Subject(s)
Antineoplastic Agents/pharmacology , Apoptosis/drug effects , Colorectal Neoplasms/drug therapy , Podophyllin/pharmacology , Radiation-Sensitizing Agents/pharmacology , Reactive Oxygen Species/metabolism , Animals , Cell Line, Tumor , Cell Proliferation/drug effects , Cell Survival/drug effects , Colorectal Neoplasms/metabolism , HCT116 Cells , Humans , Mice , Mice, Inbred BALB C , Mice, Nude , Xenograft Model Antitumor Assays/methodsABSTRACT
Here, we demonstrate that interleukin-1ß (IL-1ß) contributes to the γ-ionizing radiation (IR)-induced increase of migration/invasion in A549 lung cancer cells, and that this occurs via RIP1 upregulation. We initially observed that the protein expression and secreted concentration of IL-1ß were increased upon exposure of A549 cells to IR. We then demonstrated that IR-induced IL-1ß is located downstream of the NF-κB-RIP1 signaling pathway. Treatments with siRNA and specific pharmaceutical inhibitors of RIP1 and NF-κB suppressed the IR-induced increases in the protein expression and secreted concentration of IL-1ß. IL-1Ra, an antagonist of IL-1ß, treatment suppressed the IR-induced epithelial-mesenchymal transition (EMT) and IR-induced invasion/migration in vitro. These results suggest that IL-1ß could regulate IR-induced EMT. We also found that IR could induce the expression of IL-1ß expression in vivo and that of IL-1 receptor (R) I/II in vitro and in vivo. The IR-induced increases in the protein levels of IL-1 RI/II and IL-1ß suggest that an autocrine loop between IL-1ß and IL-1 RI/II might play important roles in IR-induced EMT and migration/invasion. Based on these collective results, we propose that IR concomitantly activates NF-κB and RIP1 to trigger the NF-κB-RIP1-IL-1ß-IL-1RI/II-EMT pathway, ultimately promoting metastasis.
Subject(s)
Interleukin-1beta/metabolism , Lung Neoplasms/metabolism , Lung Neoplasms/radiotherapy , NF-kappa B/metabolism , Nuclear Pore Complex Proteins/metabolism , RNA-Binding Proteins/metabolism , Signal Transduction , A549 Cells , Animals , Cell Movement/radiation effects , Gamma Rays , Humans , Interleukin-1beta/genetics , Lung Neoplasms/genetics , Mice, Inbred BALB C , Neoplasm Invasiveness/genetics , Radiation, Ionizing , Up-Regulation/radiation effectsABSTRACT
Interventional devices including intragastric balloons are widely used to treat obesity. This study aims to develop 3D-printed, patient-specific, and anthropomorphic gastric phantoms with mechanical properties similar to those of human stomach. Using computed tomography gastrography (CTG) images of three patients, gastric phantoms were modelled through shape registration to align the stomach shapes of three different phases. Shape accuracies of the original gastric models versus the 3D-printed phantoms were compared using landmark distances. The mechanical properties (elongation and tensile strength), number of silicone coatings (0, 2, and 8 times), and specimen hardness (50, 60, and 70 Shore A) of three materials (Agilus, Elastic, and Flexa) were evaluated. Registration accuracy was significantly lower between the arterial and portal phases (3.16 ± 0.80 mm) than that between the portal and delayed phases (8.92 ± 0.96 mm). The mean shape accuracy difference was less than 10 mm. The mean elongations and tensile strengths of the Agilus, Elastic, and Flexa were 264%, 145%, and 146% and 1.14, 1.59, and 2.15 MPa, respectively, and their mechanical properties differed significantly (all p < 0.05). Elongation and tensile strength assessments, CTG image registration and 3D printing resulted in highly realistic and patient-specific gastric phantoms with reasonable shape accuracies.
Subject(s)
Phantoms, Imaging , Printing, Three-Dimensional/instrumentation , Stomach/pathology , Gastric Balloon , Hardness , Humans , Models, Biological , Pilot Projects , Radiographic Image Interpretation, Computer-Assisted , Retrospective Studies , Stomach/diagnostic imaging , Tensile Strength , Tomography, X-Ray ComputedABSTRACT
BACKGROUND: The association between long-term exposure to air pollutants, including nitrogen dioxide (NO2), carbon monoxide (CO), sulfur dioxide (SO2), ozone (O3), and particulate matter 10 µm or less in diameter (PM10), and mortality by ischemic heart disease (IHD), cerebrovascular disease (CVD), pneumonia (PN), and chronic lower respiratory disease (CLRD) is unclear. We investigated whether living in an administrative district with heavy air pollution is associated with an increased risk of mortality by the diseases through an ecological study using South Korean administrative data over 19 years. METHODS: A total of 249 Si-Gun-Gus, unit of administrative districts in South Korea were studied. In each district, the daily concentrations of CO, SO2, NO2, O3, and PM10 were averaged over 19 years (2001-2018). Age-adjusted mortality rates by IHD, CVD, PN and CLRD for each district were averaged for the same study period. Multivariate beta-regression analysis was performed to estimate the associations between air pollutant concentrations and mortality rates, after adjusting for confounding factors including altitude, population density, higher education rate, smoking rate, obesity rate, and gross regional domestic product per capita. Associations were also estimated for two subgrouping schema: Capital and non-Capital areas (77:172 districts) and urban and rural areas (168:81 districts). RESULTS: For IHD, higher SO2 concentrations were significantly associated with a higher mortality rate, whereas other air pollutants had null associations. For CVD, SO2 and PM10 concentrations were significantly associated with a higher mortality rate. For PN, O3 concentrations had significant positive associations with a higher mortality rate, while SO2, NO2, and PM10 concentrations had significant negative associations. For CLRD, O3 concentrations were associated with an increased mortality rate, while CO, NO2, and PM10 concentrations had negative associations. In the subgroup analysis, positive associations between SO2 concentrations and IHD mortality were consistently observed in all subgroups, while other pollutant-disease pairs showed null, or mixed associations. CONCLUSION: Long-term exposure to high SO2 concentration was significantly and consistently associated with a high mortality rate nationwide and in Capital and non-Capital areas, and in urban and rural areas. Associations between other air pollutants and disease-related mortalities need to be investigated in further studies.
Subject(s)
Air Pollutants , Air Pollution , Ozone , Air Pollutants/adverse effects , Air Pollutants/analysis , Air Pollution/adverse effects , Air Pollution/analysis , Environmental Exposure/adverse effects , Environmental Exposure/analysis , Humans , Nitrogen Dioxide/adverse effects , Nitrogen Dioxide/analysis , Ozone/analysis , Particulate Matter/adverse effects , Particulate Matter/analysis , Republic of Korea/epidemiology , Sulfur Dioxide/analysisABSTRACT
OBJECTIVES: Foreign patients are more likely to receive inappropriate health service in the emergency room. This study aimed to investigate whether there is health inequality between foreigners and natives who visited emergency rooms with injuries and to examine its causes. METHODS: We analyzed clinical data from the National Emergency Department Information System database associated with patients of all age groups visiting the emergency room from 2013 to 2015. We analyzed data regarding mortality, intensive care unit admission, emergency operation, severity, area, and transfer ratio. RESULTS: A total of 4,464,603 cases of injured patients were included, of whom 67,683 were foreign. Injury cases per 100,000 population per year were 2,960.5 for native patients and 1,659.8 for foreign patients. Foreigners were more likely to have no insurance (3.1% vs. 32.0%, p < 0.001). Serious outcomes (intensive care unit admission, emergency operation, or death) were more frequent among foreigners. In rural areas, the difference between serious outcomes for foreigners compared to natives was greater (3.7% for natives vs. 5.0% for foreigners, p < 0.001). The adjusted odds ratio for serious outcomes for foreign nationals was 1.412 (95% confidence interval [CI], 1.336-1.492), and that for lack of insurance was 1.354 (95% CI, 1.314-1.394). CONCLUSIONS: Injured foreigners might more frequently suffer serious outcomes, and health inequality was greater in rural areas than in urban areas. Foreign nationality itself and lack of insurance could adversely affect medical outcomes.
ABSTRACT
STATEMENT OF PROBLEM: The accuracy of 3D printing technology is essential for clinical applications. However, depending on the 3D printing method, machine, and environment, the accuracy varies even if the same computer-aided design (CAD) model is printed. PURPOSE: The purpose of this in vitro study was to evaluate the differences between the CAD model and the printed parts with a simplified guide designed based on the implant guide and to compare the accuracy among 3 types of 3D printers. MATERIAL AND METHODS: A maxilla and mandible implant guide made of complex anatomic structures is difficult to measure accurately. For accurate measurements, 16 simplified guides were designed based on the maxilla and mandible implant guide. The 16 simplified guides were fabricated by using the following 3 different 3D printer technologies: photopolymer jetting (PolyJet), stereolithography apparatus (SLA), and multijet printing (MJP). Each simplified guide was measured 4 times with digital calipers for 20 linear measurements. The measured simplified guides were compared with the CAD model, and the accuracy of the 3D printers was compared. The mean absolute difference and mean relative difference were calculated, and the Bland-Altman analysis was used to evaluate the limits of agreement between the CAD model and the printed parts. The Wilcoxon signed-rank test was performed to evaluate the significant differences among the 3D printers (α=.05). RESULTS: The mean absolute difference and the mean relative difference between the CAD model and the 3D-printed parts were 0.06 ±0.05 mm (0.46 ±0.51%) for PolyJet, 0.09 ±0.05 mm (0.66 ±0.62%) for SLA, and 0.31 ±0.33 mm (1.11 ±0.70%) for MJP. When the 3D printers were compared, significant differences were found between SLA and MJP (P=.006) and between PolyJet and MJP (P=.001). CONCLUSIONS: When the CAD models and the 3D-printed parts of the simplified implant guides were compared, significant accuracy differences were observed. The PolyJet and SLA 3D printers met the required accuracy for clinical applications in dentistry. The most suitable 3D printer, however, should be selected considering all factors.
Subject(s)
Dental Implants , Computer-Aided Design , Maxilla , Printing, Three-Dimensional , StereolithographyABSTRACT
OBJECTIVES: The purpose of this study was to examine whether a 12-week combined physical exercise training and nutritional intervention improves physical performance and enhances health-related quality of life (HRQOL) among prefrail elderly women living in the community. DESIGN: This was a randomized controlled trial in which participants were recruited and randomly assigned to the exercise and nutrition group (EN, n = 30), exercise only group (E, n = 28), and control group (C, n = 31). SETTING: Group training classes were held at a research center in Itabashi Ward, Tokyo, Japan. PARTICIPANTS: Eighty-nine prefrail women aged 70 years or older. INTERVENTION: The EN group participated in an exercise training and nutritional program (cooking class) once a week, and the E group participated in the exercise training program only. MEASUREMENTS: Outcome measures that included physical performance (handgrip strength, balance, walking speed) and HRQOL (Medical Outcomes Study 36-Item Short Form Health Survey) were obtained at entry, the end of the 12-week intervention, and 6 months after completion of the intervention program. RESULTS: At the end of the 12-week intervention, significant improvements in the physical component summary score and 3 (role physical, bodily pain, role emotional) of the 8 domains of the Medical Outcomes Study 36-Item Short Form Health Survey were observed in the EN group. The E group exhibited a significantly increased handgrip strength at postintervention. The positive effects, however, were not maintained at 6-month follow-up, but were reduced. CONCLUSIONS: The combined physical exercise training and nutritional intervention program has beneficial effects on several domains of HRQOL and handgrip strength in prefrail elderly women living in the community. However, further studies are needed to examine approaches that facilitate maintenance of the improved outcomes by combined exercise training and nutritional intervention.
Subject(s)
Diet , Exercise Therapy/methods , Hand Strength/physiology , Physical Fitness/physiology , Quality of Life , Age Factors , Aged , Aged, 80 and over , Combined Modality Therapy , Double-Blind Method , Female , Frail Elderly/statistics & numerical data , Geriatric Assessment/methods , Humans , Independent Living , Multivariate Analysis , Nutritional Requirements , Risk Factors , Treatment OutcomeABSTRACT
A balloon-catheter optical diffuser for endometrial treatment was evaluated with computational thermal analysis. Various catheter materials and dimensions were implemented to identify the optimal design for the device. Spatial and temporal development of temperature during 30-sec irradiation of 532-nm light demonstrated thermal insulation effects of polyurethane on temperature increase up to 384 K, facilitating the irreversible denaturation. The current model revealed the degree of thermal coagulation 13% thicker than experimental results possibly due to lack of tissue dynamics and light intensity distribution. In combination with photon distribution, the analytical simulation can be a feasible tool to optimize the new optical diffuser for efficient and safe endometrial treatment.
ABSTRACT
Interface layers between reactive and energetic materials in nanolaminates or nanoenergetic materials are believed to play a crucial role in the properties of nanoenergetic systems. Typically, in the case of Metastable Interstitial Composite nanolaminates, the interface layer between the metal and oxide controls the onset reaction temperature, reaction kinetics, and stability at low temperature. So far, the formation of these interfacial layers is not well understood for lack of in situ characterization, leading to a poor control of important properties. We have combined in situ infrared spectroscopy and ex situ X-ray photoelectron spectroscopy, differential scanning calorimetry, and high resolution transmission electron microscopy, in conjunction with first-principles calculations to identify the stable configurations that can occur at the interface and determine the kinetic barriers for their formation. We find that (i) an interface layer formed during physical deposition of aluminum is composed of a mixture of Cu, O, and Al through Al penetration into CuO and constitutes a poor diffusion barrier (i.e., with spurious exothermic reactions at lower temperature), and in contrast, (ii) atomic layer deposition (ALD) of alumina layers using trimethylaluminum (TMA) produces a conformal coating that effectively prevents Al diffusion even for ultrathin layer thicknesses (â¼0.5 nm), resulting in better stability at low temperature and reduced reactivity. Importantly, the initial reaction of TMA with CuO leads to the extraction of oxygen from CuO to form an amorphous interfacial layer that is an important component for superior protection properties of the interface and is responsible for the high system stability. Thus, while Al e-beam evaporation and ALD growth of an alumina layer on CuO both lead to CuO reduction, the mechanism for oxygen removal is different, directly affecting the resistance to Al diffusion. This work reveals that it is the nature of the monolayer interface between CuO and alumina/Al rather than the thickness of the alumina layer that controls the kinetics of Al diffusion, underscoring the importance of the chemical bonding at the interface in these energetic materials.
ABSTRACT
The initial surface chemistry and growth mechanisms of the atomic layer deposition (ALD) of metallic copper on SiO(2) surfaces are investigated using an amidinate precursor (copper(I) di-sec-butylacetamidinate, [Cu((s)Bu-amd)](2)) and molecular hydrogen. Using in situ Fourier transform infrared spectroscopy together with calculations based on density functional theory, we show that the initial surface reaction of [Cu((s)Bu-amd)](2) with hydroxylated SiO(2) takes place by displacement of one of the sec-butylacetamidinate ligands at a surface -OH site, thus forming a Si-O-Cu-((s)Bu-amd) surface species, evident by the stretching vibrations of Si-O-Cu and the chelating -NCN- bonds. Molecular hydrogen exposure during a subsequent pulse dissociates most of the sec-butylacetamidinate ligands bound to surface Cu, which releases free amidine vapor, leaving Cu atoms free to agglomerate on the surface and thus opening more reactive sites for the next [Cu((s)Bu-amd)](2) pulse. Copper agglomeration is evident in the IR absorbance spectra through the partial recovery of the intensity of SiO(2) optical phonon modes upon H(2) reduction, which was lost after the reaction of [Cu((s)Bu-amd)](2) with the initial SiO(2) surface. The thermally activated ligand rearrangement from a bridging to a monodentate structure occurs above 220 degrees C through hydrogenation of the ligand by surface hydroxyl groups after exposure to a [Cu((s)Bu-amd)](2) pulse. As Cu particles grow with further ALD cycles, the activation temperature is lowered to 185 degrees C, and hydrogenation of the ligand takes place after H(2) pulses, catalyzed by Cu particles on the surface. The surface ligand rearranged into a monodentate structure can be removed during subsequent Cu precursor or H(2) pulses. Finally, we postulate that the attachment of dissociated ligands to the SiO(2) surface during the [Cu((s)Bu-amd)](2) pulse can be responsible for carbon contamination at the surface during the initial cycles of growth, where the SiO(2) surface is not yet completely covered by copper metal.
ABSTRACT
Passivation of semiconductor surfaces is conveniently realized by terminating surface dangling bonds with a monovalent atom such as hydrogen using a simple wet chemical process (for example, HF treatment for silicon). However, the real potential of surface chemical passivation lies in the ability to replace surface hydrogen by multivalent atoms to form surfaces with tailored properties. Although some progress has been made to attach organic layers on top of H-terminated surfaces, it has been more challenging to understand and control the incorporation of multivalent atoms, such as oxygen and nitrogen, within the top surface layer of H-terminated surfaces. The difficulty arises partly because such processes are dominated by defect sites. Here, we report mechanistic pathways involved in the nitridation of H-terminated silicon surfaces using ammonia vapour. Surface infrared spectroscopy and first-principles calculations clearly show that the initial interaction is dominated by the details of the surface morphology (defect structure) and that NH and NH(2) are precursors to N insertion into Si-Si bonds. For the dihydride-stepped Si(111) surface, a unique reaction pathway is identified leading to selective silazane step-edge formation at the lowest reaction temperatures.
ABSTRACT
PURPOSE: The present study was conducted to identify the characteristics of non-participants in secondary comprehensive health examinations among community-dwelling elderly. METHODS: The subjects were 728 men and 984 women aged 70 years and over who had participated in comprehensive health examinations in 2002. Multiple logistic regression analysis was performed to assess the characteristics associated with non-participation in comprehensive health examinations after 2 years (in 2004). RESULTS: The rates of participation in follow-up health examinations were 66.3% for men and 67.3% for women. Logistic regression analysis showed that male non-participants had low cognitive function (odds ratio (OR) = 2.19, 95% confidence interval (CI) = 1.07-4.49), low education (OR = 1.58, 95% CI = 1.22-2.22), and suffered from health problems (OR = 1.82, 95% CI = 1.27-2.59), and that female non-participants had low cognitive function (OR = 2.01, 95% CI 1.13-3.59), tended to be smokers (OR = 2.05, 95%, CI = 1.13-3.72), and had no hobby (OR = 0.68, 95% CI = 0.50-0.92). CONCLUSION: Poor cognitive function, health problems, and unfavorable lifestyle factors are related to non-participation in comprehensive health examinations. PROPOSAL: It is necessary to devise various approaches to encourage participation of such individuals.