[Digital transformation for the prevention of delirium in older adults with dementia: Development of simulation intervention using virtual reality and augmented reality programs and its subjective effects].

PURPOSE: We aimed to develop a simulation program for physicians and nurses involved in virtual reality (VR) and augmented reality (AR) treatment and care from the perspective of these professionals and older adults with dementia who developed delirium, and to test the effectiveness of the program. METHODS: effectiveness of the program was analyzed through free-response statements from 67 nurses (84.8%) and 12 doctors (15.2%) who participated in the program between February 16 and April 18, 2023. RESULTS: Regarding the experience of delirium from the perspective of older adults with dementia (personal experience), the following statements were extracted "1. I do not understand where I am, the situation, and the treatment/care that is about to be given"; "2. I want the situation to be explained to me so that I can understand the reasons for my hospitalization and the treatment/care I am receiving"; "3. The eerie environment of the hospital and the high pressure of the staff made me feel anxious and fearful"; "4. Please respect my existence as I endure pain, anxiety, and loneliness"; "5. I feel relieved when doctors and nurses deal with me from my point of view"; and "6. I feel relieved when there is a familiar presence, such as a family member or the name I am calling on a daily basis". CONCLUSION: Specific categories of self-oriented empathy were extracted from the experience of physical restraint at night using VR and the experience of delirium using AR. This suggests the possibility of objective effects on treatment and care in future practice.

Surface defect healing in annealing from nanoporous carbons to nanoporous graphenes.

Nanoporous graphene (NPG) materials have the pronounced electrochemical stability of the seamless graphene structures developed over the 3D space. We revisited the Raman spectra of nanoporous carbons (NPCs) synthesized using θ-/γ-Al2O3 templates and NPGs converted from NPCs by annealing at 1800 °C to identify the type and density of defects. We found that both the NPCs and NPGs mostly consist of single-layered graphene with a few single vacancies and Stone-Wales defects. The density of vacancy defect per hexagon in the graphene sheet is estimated to be 10-2 for NPCs, while the annealing reduced the value to 10-3-10-4 for NPGs. This supports the outstanding chemical and electrochemical stability of the novel porous carbon materials.

The carbon chain growth during the onset of CVD graphene formation on γ-Al2O3 is promoted by unsaturated CH2 ends.

Chemical vapor deposition of methane onto a template of alumina (Al2O3) nanoparticles is a prominent synthetic strategy of graphene meso-sponge, a new class of nano porous carbon materials consisting of single-layer graphene walls. However, the elementary steps controlling the early stages of graphene growth on Al2O3 surfaces are still not well understood. In this study, density functional theory calculations provide insights into the initial stages of graphene growth. We have modelled the mechanism of CH4 dissociation on the (111), (110), (100), and (001) γ-Al2O3 surfaces. Subsequently, we have considered the reaction pathway leading to the formation of a C6 ring. The γ-Al2O3(110) and γ-Al2O3(100) are both active for CH4 dissociation, but the (100) surface has higher catalytic activity towards the carbon growth reaction. The overall mechanism involves the formation of the reactive intermediate CH2* that then can couple to form CnH2n* (n = 2-6) intermediates with unsaturated CH2 ends. The formation of these species, which are not bound to the surface-active sites, promotes the sustained carbon growth in a nearly barrierless process. Also, the short distance between terminal carbon atoms leads to strong interactions, which might lead to the high activity between unsaturated CH2* of the hydrocarbon chain. Analysis of the electron localization and geometries of the carbon chains reveals the formation of C-Al-σ bonds with the chain growing towards the vacuum rather than C-Al-π bonds covering the γ-Al2O3(100) surface. This growth behaviour prevents catalyst poisoning during the initial stage of graphene nucleation.

Substitution effect on the nonradiative decay and trans → cis photoisomerization route: a guideline to develop efficient cinnamate-based sunscreens.

Cinnamate derivatives are very useful as UV protectors in nature and as sunscreen reagents in daily life. They convert harmful UV energy to thermal energy through effective nonradiative decay (NRD) including trans → cis photoisomerization. However, the mechanism is not simple because different photoisomeirzation routes have been observed for different substituted cinnamates. Here, we theoretically examined the substitution effects at the phenyl ring of methylcinnamate (MC), a non-substituted cinnamate, on the electronic structure and the NRD route involving trans → cis isomerization based on time-dependent density functional theory. A systematic reaction pathway search using the single-component artificial force-induced reaction method shows that the very efficient photoisomerization route of MC can be essentially described as "1ππ* (trans) → 1nπ* → T1 (3ππ*) → S0 (trans or cis)". We found that for efficient 1ππ* (trans) → 1nπ* internal conversion (IC), MC should have the substituent at the appropriate position of the phenyl ring to stabilize the highest occupied π orbital. Substitution at the para position of MC slightly lowers the 1ππ* state energy and photoisomerization occurs via a slightly less efficient "1ππ* (trans) → 3nπ* → T1 (3ππ*) → S0 (trans or cis)" pathway. Substitution at the meta or ortho positions of MC significantly lowers the 1ππ* state energy so that the energy barrier of IC (1ππ* → 1nπ*) becomes very high. This substitution leads to a much longer 1ππ* state lifetime than that of MC and para-substituted MC, and a change in the dominant photoisomerization route to "1ππ* (trans) → C[double bond, length as m-dash]C bond twisting on 1ππ* → S0 (trans or cis)". As a whole, the "1ππ* → 1nπ*" IC observed in MC is the most important initial step for the rapid change of UV energy to thermal energy. We also found that the stabilization of the π orbital (i) minimizes the energy gap between 1ππ* and 1nπ* at the 1ππ* minimum and (ii) makes the 0-0 level of 1ππ* higher than 1nπ* as observed in MC. These MC-like relationships between the 1ππ* and 1nπ* energies should be ideal to maximize the "1ππ* → 1nπ*" IC rate constant according to Marcus theory.

Imaging through scattering media based on semi-supervised learning.

We present a method for less-invasive imaging through scattering media. We use an image-to-image translation, which is called a cycle generative adversarial network (CycleGAN), based on semi-supervised learning with an unlabeled dataset. Our method was experimentally demonstrated by reconstructing object images displayed on a spatial light modulator between diffusers. In the demonstration, CycleGAN was trained with captured images and object candidate images that were not used for image capturing through the diffusers and were not paired with the captured images.

Diffractive Imaging of C_{60} Structural Deformations Induced by Intense Femtosecond Midinfrared Laser Fields.

Theoretical studies indicated that C_{60} exposed to linearly polarized intense infrared pulses undergoes periodic cage structural distortions with typical periods around 100 fs (1 fs=10^{-15} s). Here, we use the laser-driven self-imaging electron diffraction technique, previously developed for atoms and small molecules, to measure laser-induced deformation of C_{60} in an intense 3.6 µm laser field. A prolate molecular elongation along the laser polarization axis is determined to be (6.1±1.4)% via both angular- and energy-resolved measurements of electrons that are released, driven back, and diffracted from the molecule within the same laser field. The observed deformation is confirmed by density functional theory simulations of nuclear dynamics on time-dependent adiabatic states and indicates a nonadiabatic excitation of the h_{g}(1) prolate-oblate mode. The results demonstrate the applicability of laser-driven electron diffraction methods for studying macromolecular structural dynamics in four dimensions with atomic time and spatial resolutions.

The direct observation of the doorway 1nπ* state of methylcinnamate and hydrogen-bonding effects on the photochemistry of cinnamate-based sunscreens.

The electronic states and photochemistry including nonradiative decay (NRD) and trans(E) → cis(Z) isomerization of methylcinnamate (MC) and its hydrogen-bonded complex with methanol have been investigated under jet-cooled conditions. S1(1nπ*) and S2(1ππ*) are directly observed in MC. This is the first direct observation of S1(1nπ*) in cinnamate derivatives. Surprisingly, the order of the energies between the nπ* and ππ* states is opposite to substituted cinnamates. TD-DFT and SAC-CI calculations support the observed result and show that the substitution to the benzene ring largely lowers the 1ππ* energy while the effect on 1nπ* is rather small. The S2(ππ*) state lifetime of MC is determined to be equal to or shorter than 10 ps, and the production of the transient T1 state is observed. The T1(ππ*) state is calculated to have a structure in which propenyl C[double bond, length as m-dash]C is twisted by 90°, suggesting the trans → cis isomerization proceeds via T1. The production of the cis isomer is confirmed by low-temperature matrix-isolated FTIR spectroscopy. The effect of H-bonding is examined for the MC-methanol complex. The S2 lifetime of MC-methanol is determined to be 180 ps, indicating that the H-bonding to the C[double bond, length as m-dash]O group largely prohibits the 1ππ* → 1nπ* internal conversion. This lifetime elongation in the methanol complex also describes well a higher fluorescence quantum yield of MC in methanol solution than in cyclohexane, while such a solvent dependence is not observed in para-substituted MC. Determination of the photochemical reaction pathways of MC and MC-methanol will help us to design photofunctional cinnamate derivatives.

Capturing the photo-induced dynamics of nano-molecules by X-ray free electron laser induced Coulomb explosion.

We performed reaction dynamics simulations to demonstrate that the vibrational dynamics of C60 induced by infrared (IR) pulses can be traced by triggering Coulomb explosion with intense femtosecond X-ray free electron laser (XFEL) probe pulses. The time series of the angular anisotropy ß(t) of fast C+ and C2+ fragments of C60 60+ produced by such an XFEL pulse reflects the instantaneous structure of C60 vibrationally excited by IR pulses. The phases and amplitudes of excited vibrational modes and the coupling between excited modes can be successfully extracted from the expansion of ß(t) in terms of vibrational modes. This proof-of-principle simulation clearly demonstrates that various information of the structures and reaction dynamics of large clusters or biomolecules can be retrieved by decomposing the experimentally determined ß(t) into vibrational modes.

Different photoisomerization routes found in the structural isomers of hydroxy methylcinnamate.

An experimental and theoretical study has been carried out to elucidate the nonradiative decay (NRD) and trans(E) → cis(Z) isomerization from the S1 (1ππ*) state of structural isomers of hydroxy methylcinnamate (HMC); ortho-, meta- and para-HMC (o-, m- and p-HMC). A low temperature matrix-isolation Fourier Transform Infrared (FTIR) spectroscopic study revealed that all the HMCs are cis-isomerized upon UV irradiation. A variety of laser spectroscopic methods have been utilized for jet-cooled gas phase molecules to investigate the vibronic structure and lifetimes of the S1 state, and to detect the transient state appearing in the NRD process. In p-HMC, the zero-point level of the S1 state decays as quickly as 9 ps. A transient electronic state reported by Tan et al. (Faraday Discuss. 2013, 163, 321-340) was reinvestigated by nanosecond UV-tunable deep UV pump-probe spectroscopy and was assigned to the T1 state. For m- and o-HMC, the lifetime at the zero-point energy level of S1 is 10 ns and 6 ns, respectively, but it becomes substantially shorter at an excess energy higher than 1000 cm-1 and 600 cm-1, respectively, indicating the onset of NRD. Different from p-HMC, no transient state (T1) was observed in m- nor o-HMC. These experimental results are interpreted with the aid of TDDFT calculations by considering the excited-state reaction pathways and the radiative/nonradiative rate constants. It is concluded that in p-HMC, the trans → cis isomerization proceeds via a [trans-S1 → 1nπ* → T1 → cis-S0] scheme. On the other hand, in o- and m-HMC, the isomerization proceeds via a [trans-S1 → twisting along the C[double bond, length as m-dash]C double bond by 90° on S1 → cis-S0] scheme. The calculated barrier height along the twisting coordinate agrees well with the observed onset of the NRD channel for both o- and m-HMC.

Ultrafast Coulomb explosion of a diiodomethane molecule induced by an X-ray free-electron laser pulse.

Coulomb explosion of diiodomethane CH2I2 molecules irradiated by ultrashort and intense X-ray pulses from SACLA, the Japanese X-ray free electron laser facility, was investigated by multi-ion coincidence measurements and self-consistent charge density-functional-based tight-binding (SCC-DFTB) simulations. The diiodomethane molecule, containing two heavy-atom X-ray absorbing sites, exhibits a rather different charge generation and nuclear motion dynamics compared to iodomethane CH3I with only a single heavy atom, as studied earlier. We focus on charge creation and distribution in CH2I2 in comparison to CH3I. The release of kinetic energy into atomic ion fragments is also studied by comparing SCC-DFTB simulations with the experiment. Compared to earlier simulations, several key enhancements are made, such as the introduction of a bond axis recoil model, where vibrational energy generated during charge creation processes induces only bond stretching or shrinking. We also propose an analytical Coulomb energy partition model to extract the essential mechanism of Coulomb explosion of molecules from the computed and the experimentally measured kinetic energies of fragment atomic ions by partitioning each pair Coulomb interaction energy into two ions of the pair under the constraint of momentum conservation. Effective internuclear distances assigned to individual fragment ions at the critical moment of the Coulomb explosion are then estimated from the average kinetic energies of the ions. We demonstrate, with good agreement between the experiment and the SCC-DFTB simulation, how the more heavily charged iodine fragments and their interplay define the characteristic features of the Coulomb explosion of CH2I2. The present study also confirms earlier findings concerning the magnitude of bond elongation in the ultrashort X-ray pulse duration, showing that structural damage to all but C-H bonds does not develop to a noticeable degree in the pulse length of ∼10 fs.

Breeding of a new potato variety 'Nagasaki Kogane' with high eating quality, high carotenoid content, and resistance to diseases and pests.

'Nagasaki Kogane' is a new potato variety bred from a cross between 'Saikai 35' as a female parent and 'Saikai 33' as a male. 'Saikai 35' is resistant to bacterial wilt, contains the H1 and Rychc genes for resistance to the potato cyst nematode (PCN) and potato virus Y (PVY), respectively, and has high carotenoid content, while 'Saikai 33' has large and high-yielding tubers and is resistant to both bacterial wilt and PCN. The carotenoid content of 'Nagasaki Kogane' is higher than that of 'Dejima', a common double cropping variety. The taste quality of steamed 'Nagasaki Kogane' is comparable to that of 'Inca-no-mezame' tubers, which has high levels of carotenoid, and superior to 'Nishiyutaka', another popular double cropping variety. 'Nagasaki Kogane' is suitable for French fries, because its tuber has high starch content. The marketable yield of 'Nagasaki Kogane' was higher than that of 'Inca-no-mezame' in spring cropping, although it was lower than that of 'Nishiyutaka' in double cropping regions. 'Nagasaki Kogane' tubers are larger on average than 'Inca-no-mezame' tubers in spring cropping. Moreover, the 'Nagasaki Kogane' variety is resistant to PCN and PVY, and exhibits a high level of resistance to bacterial wilt.

Novel regulator PgrR for switch control of peptidoglycan recycling in Escherichia coli.

Peptidoglycan (PG), also designated as murein, forms a skeletal mesh within the periplasm of bacterial membrane. PG is a metabolically stable cell architecture in Escherichia coli, but under as yet ill-defined conditions, a portion of PG is degraded, of which both amino sugar and peptide moieties are either recycled or used as self-generated nutrients for cell growth. At present, the control of PG degradation remains uncharacterized. Using the Genomic SELEX screening system, we identified an uncharacterized transcription factor YcjZ is a repressor of the expression of the initial step enzymes for PG peptide degradation. Under nutrient starvation, the genes encoding the enzymes for PG peptide degradation are derepressed so as to generate amino acids but are tightly repressed at high osmotic conditions so as to maintain the rigid membrane for withstanding the turgor. Taken together, we propose to rename YcjZ as PgrR (regulator of peptide glycan recycling).

Communication: Two-step explosion processes of highly charged fullerene cations C60(q+) (q = 20-60).

To establish the fundamental understanding of the fragmentation dynamics of highly positive charged nano- and bio-materials, we carried out on-the-fly classical trajectory calculations on the fragmentation dynamics of C60(q+) (q = 20-60). We used the UB3LYP/3-21G level of density functional theory and the self-consistent charge density-functional based tight-binding theory. For q ≥ 20, we found that a two-step explosion mechanism governs the fragmentation dynamics: C60(q+) first ejects singly and multiply charged fast atomic cations C(z+) (z ≥ 1) via Coulomb explosions on a timescale of 10 fs to stabilize the remaining core cluster. Thermal evaporations of slow atomic and molecular fragments from the core cluster subsequently occur on a timescale of 100 fs to 1 ps. Increasing the charge q makes the fragments smaller. This two-step mechanism governs the fragmentation dynamics in the most likely case that the initial kinetic energy accumulated upon ionization to C60(q+) by ion impact or X-ray free electron laser is larger than 100 eV.

Toward three-dimensionally ordered nanoporous graphene materials: template synthesis, structure, and applications.

Precise template synthesis will realize three-dimensionally ordered nanoporous graphenes (NPGs) with a spatially controlled seamless graphene structure and fewer edges. These structural features result in superelastic nature, high electrochemical stability, high electrical conductivity, and fast diffusion of gases and ions at the same time. Such innovative 3D graphene materials are conducive to solving energy-related issues for a better future. To further improve the attractive properties of NPGs, we review the template synthesis and its mechanism by chemical vapor deposition of hydrocarbons, analysis of the nanoporous graphene structure, and applications in electrochemical and mechanical devices.

Relationship between the perioperative prognostic nutritional index and postoperative gait function in elderly hip fractures.

Objectives: We investigated the relationship between the perioperative nutritional status and postoperative walking ability in patients with hip fractures. Methods: We included 246 surgically treated elderly patients with hip fractures who were ambulatory before the injury. Patients were divided into two groups: group A, who were able to walk at discharge, and group B, who were unable to walk at discharge. We pair-matched these two groups according to age, preoperative subdivided walking ability, and fracture site to form groups A' and B'. The prognostic nutritional index (PNI; PNI = 10 × serum albumin (g/dL) + 0.005 × blood total lymphocyte count (/mm³)) before surgery and 1 day, 1 week, and 2 weeks after surgery and energy intake 1 and 2 weeks after surgery were compared. Results: After adjustments for age, preoperative subdivided walking ability, and fracture site, there were 51 patients in group A' (mean age 84.6 years) and 51 patients in group B' (mean age 84.7 years). In group A'/group B', PNI was 43.38/42.60 (P = 0.19) before surgery, 33.87/33.31 (P = 0.44) 1 day after surgery, 34.99/32.35 (P = 0.01) 1 week after surgery, and 37.33/35.69 (P = 0.15) 2 weeks after surgery. Energy intake was 1380.8/1203.1 kcal (P = 0.01) 1 week after surgery and 1382.0/1335.6 kcal (P = 0.60) 2 weeks after surgery. Conclusions: PNI and energy intake at 1 week postoperatively were associated with early postoperative nutrition and the recovery of walking ability.

Background factors for intra-operative hypotension during hip fracture repair surgery in the elderly under spinal anesthesia managed by orthopedic surgeons: A retrospective case-control study.

BACKGROUND: Spinal anesthesia is used for femoral trochanteric fracture surgery, but frequently induces hypotension and the causative factors remain unclear. We examined background factors for the use of an intraoperative vasopressor in elderly patients receiving spinal anesthesia for femoral trochanteric fracture surgery. METHODS: We retrospectively analyzed 203 patients >75 years (mean age, 87.9 years) with femoral trochanteric fractures who underwent short nail fixation under orthopedically managed spinal anesthesia at our hospital between April 2020 and July 2023. Patients were divided into two groups: group A (intraoperative vasopressor) and group B (no vasopressor). The following data were compared: age, sex, height, weight, body mass index, antihypertensive medication, years of experience as a primary surgeon, bupivacaine dose, puncture level, anesthesia time, operation time, hemoglobin level and blood urea nitrogen/creatinine ratio on the day of surgery, brain natriuretic peptide level, left ventricular ejection fraction, and percentage of patients operated on the day of transport. RESULTS: There were 65 patients in group A and 138 in group B. The average dose of bupivacaine was 11.7 mg. In a univariate analysis, group A was slightly younger (87.0 vs. 88.3 years), had a higher blood urea nitrogen/creatinine ratio (27.1 vs. 24.5), more frequently received ß-blockers (14.1% vs. 5.8 %) and diuretic medications (21.9% vs. 11.6 %), and had a higher puncture level. A logistic regression analysis identified younger age (p = 0.02) and diuretic medication (p = 0.001) as independent risk factors in group A. Vasopressor use was more frequent at a higher puncture level in group A (57 % for L2/3, 33 % for L3/4, 15 % for L4/5, 0 % for L5/S). CONCLUSIONS: Spinal anesthesia-induced hypotension is attributed to volume deficit or extensive sympathetic blockade and may be prevented by avoiding high puncture levels and increasing preoperative fluid supplementation in patients on diuretics. There is currently no consensus on anesthetic dosages.

[Assessment of fracture risk using quantitative ultrasound (QUS) ].

Previous studies have demonstrated close associations between QUS parameters and osteoporotic status. However, due to the ambiguities in assessing accuracy of QUS and the moderate correlation of DXA and QUS results, currently there is no agreement on how results of QUS devices should be interpreted in order to diagnose osteoporosis. However, I could recommend for clinical application that QUS should be used as the predictor of the risk of osteoporotic fractures. Good portability and low cost of QUS technique might make QUS an attractive technology for assessing risk of fractures in large populations.

Osteogenesis imperfecta with repeated simultaneous bilateral proximal tibial epiphyseal injuries caused by minor trauma: A case report and literature review.

INTRODUCTION: Proximal tibial epiphyseal injuries are rare, accounting for 0.5-3 % of all epiphyseal injuries, of which bilateral cases are extremely rare. Only five cases of bilateral proximal tibial epiphyseal injuries have so far been reported in patients with osteogenesis imperfecta. We herein present a case of repeated bilateral proximal tibial epiphyseal injuries with a diagnosis of osteogenesis imperfecta. We also performed a literature review of 46 cases of bilateral proximal tibial epiphyseal injuries reported since 1955, including 5 of osteogenesis imperfecta. PRESENTATION OF CASE: A 10-year-old boy repeatedly sustained bilateral simultaneous proximal tibial epiphyseal injuries due to minor trauma. Blue sclera was noted and, thus, genetic testing was performed and revealed osteogenesis imperfecta. After the fourth injury, we performed internal fixation with cannulated cancellous screw bilaterally. The patient had a short stature and the marked loss of bone density; therefore, the screw was kept in place until epiphyseal closure and bisphosphonate and human growth hormone were administered to prevent re-fracture and increase bone density and the growth rate. DISCUSSION: The literature review revealed that the mean age of injury was 11.2 years for osteogenesis imperfecta cases and 14.9 years for non-osteogenesis imperfecta cases, with the former being injured at a younger age. CONCLUSION: Osteogenesis imperfecta often causes diaphyseal fractures, which may be attributed to the fragility of the epiphyseal line. Therefore, the possibility of osteogenesis imperfecta needs to be considered when treating patients with epiphyseal injuries at rare sites, particularly younger children.

Neurogenic pulmonary edema caused by right insular cortex infarction.

We report a case of neurogenic pulmonary edema (NPE) caused by middle cerebral artery infarction involving the right insular cortex. Hyperactivity of the insular cortex, which regulates sympathetic function, can cause NPE. The NPE should be considered in the differential diagnosis of dyspneic patients with insular cortex infarction.

Electronic excited state paths of Stone-Wales rearrangement in pyrene: roles of conical intersections.

We investigated the reaction paths of Stone-Wales rearrangement (SWR), i.e., π/2 rotation of two carbon atoms with respect to the midpoint of the bond, in graphene and carbon nanotube quantum chemically. Our particular attention is focused on the roles of electronic excitations and conical intersections (CIs) in the reaction mechanism. We used pyrene as a model system. The reaction paths were determined by constructing potential energy surfaces at the MS-CASPT2//SA-CASSCF level of theory. We found that there are no CIs involved in SWR when both of C-C bond cleavage and formation occur simultaneously (concerted mechanism). In contrast, for the reaction path with stepwise cleavage and formation of C-C bonds, C-C bond breaking and making processes proceed through two CIs. When SWR starts from the ground (S(0)) state, the concerted and stepwise paths have an equivalent reaction barrier ΔE(‡) (9.5-9.6 eV). For the reaction path starting from excited states, only the stepwise mechanism is energetically preferable. This path contains a nonadabatic transition between the S(1) and S(0) states via a CI associated with the first stage of C-C bond cleavage and has ΔE(‡) as large as in the S(0) paths. We confirmed that the main active molecular orbitals and electron configurations for the low-lying electronic states of larger nanocarbons are the same as those in pyrene. This result suggests the importance of the nonadiabatic transitions through CIs in the photochemical reactions in large nanocarbons.