Segment-Based Unsupervised Learning Method in Sensor-Based Human Activity Recognition.

Sensor-based human activity recognition (HAR) is a task to recognize human activities, and HAR has an important role in analyzing human behavior such as in the healthcare field. HAR is typically implemented using traditional machine learning methods. In contrast to traditional machine learning methods, deep learning models can be trained end-to-end with automatic feature extraction from raw sensor data. Therefore, deep learning models can adapt to various situations. However, deep learning models require substantial amounts of training data, and annotating activity labels to construct a training dataset is cost-intensive due to the need for human labor. In this study, we focused on the continuity of activities and propose a segment-based unsupervised deep learning method for HAR using accelerometer sensor data. We define segment data as sensor data measured at one time, and this includes only a single activity. To collect the segment data, we propose a measurement method where the users only need to annotate the starting, changing, and ending points of their activity rather than the activity label. We developed a new segment-based SimCLR, which uses pairs of segment data, and propose a method that combines segment-based SimCLR with SDFD. We investigated the effectiveness of feature representations obtained by training the linear layer with fixed weights obtained by unsupervised learning methods. As a result, we demonstrated that the proposed combined method acquires generalized feature representations. The results of transfer learning on different datasets suggest that the proposed method is robust to the sampling frequency of the sensor data, although it requires more training data than other methods.

Sensor-Based Activity Recognition Using Frequency Band Enhancement Filters and Model Ensembles.

Deep learning methods are widely used in sensor-based activity recognition, contributing to improved recognition accuracy. Accelerometer and gyroscope data are mainly used as input to the models. Accelerometer data are sometimes converted to a frequency spectrum. However, data augmentation based on frequency characteristics has not been thoroughly investigated. This study proposes an activity recognition method that uses ensemble learning and filters that emphasize the frequency that is important for recognizing a certain activity. To realize the proposed method, we experimentally identified the important frequency of various activities by masking some frequency bands in the accelerometer data and comparing the accuracy using the masked data. To demonstrate the effectiveness of the proposed method, we compared its accuracy with and without enhancement filters during training and testing and with and without ensemble learning. The results showed that applying a frequency band enhancement filter during training and testing and ensemble learning achieved the highest recognition accuracy. In order to demonstrate the robustness of the proposed method, we used four different datasets and compared the recognition accuracy between a single model and a model using ensemble learning. As a result, in three of the four datasets, the proposed method showed the highest recognition accuracy, indicating the robustness of the proposed method.

Aromatic Micelles as a New Class of Aqueous Molecular Flasks.

Micelles are a versatile class of molecular assemblies typically composed of aliphatic molecules with hydrophilic groups. Polyaromatic molecules with hydrophilic groups, on the other hand, usually do not assemble into micellar structures in water but rather form columnar, π-stacked architectures. This Minireview article focuses on the recent development of aqueous micellar nanostructures with multiple oligoarylene rods or polyaromatic panels. The new micelles with spherical polyaromatic shells, which we name "aromatic micelles", serve as functional molecular flasks with superior binding abilities for medium to very large molecules in water.

Solubility Switching of Metallophthalocyanines and Their Larger Derivatives upon Encapsulation.

Metallophthalocyanines (MPcs) are very useful pigments but scarcely soluble without appropriate functional groups in common solvents. Herein, we report that bent polyaromatic amphiphiles act as excellent solubilizing reagents for nonfunctionalized MPcs and larger MPc derivatives (e.g., CuPc, perhalogenated CuPcs, Cu-naphthalocyanine, CuPc polymers, and double-decker MPcs) in neutral water upon encapsulation. The resultant MPc nanocomposites display high stability towards heat and pH change. More importantly, the encapsulated MPcs can be released by simple protocols under mild conditions both into a bulk solvent and onto glass or polymer plates.

Local environment inside a novel aromatic micelle investigated by steady-state and femtosecond fluorescence spectroscopy of an encapsulated solvatochromic probe.

The local environment within a recently developed anthracene-shelled micelle (ASM), which is a micelle-like nanocapsule composed of anthracene-embedded amphiphiles, was investigated by steady-state and time-resolved spectroscopy of an encapsulated solvatochromic fluorescent probe molecule, coumarin 153 (C153). The absorption maximum of encapsulated C153 (452 nm) is more red-shifted than that of free C153 in water, indicating a highly polar environment inside the micelle. Despite this, the fluorescence Stokes shift of encapsulated C153 (∼3700 cm-1) is substantially smaller than that of free C153 in water. Femtosecond time-resolved broadband fluorescence measurements further showed that the dynamic Stokes shift is completed within 1 ps, revealing that the reorganization of the micelle interior following photoexcitation of the C153 probe is characterized by a sub-picosecond, limited-amplitude response. The femtosecond fluorescence anisotropy data showed that the orientational diffusion of the host-guest complex is slower (860 ps) than that of the empty micelle (510 ps), suggesting that the micelle structure is flexible enough to expand when the guest molecule is accommodated and that the micelle rotates with the encapsulated guest molecule. This softness of the micelles further allows some of them to simultaneously encapsulate two C153 molecules, as evidenced by the appearance of blue-shifted, H-dimer-like absorption and fluorescence bands. Based on these steady-state and femtosecond time-resolved spectroscopic data, we discuss the electronic state of C153 and micelle structure as well as the host-guest interaction in this novel flexible synthetic nanocapsule.

Engineering Stacks of V-Shaped Polyaromatic Compounds with Alkyl Chains for Enhanced Emission in the Solid State.

A V-shaped bisanthracene derivative with three butyl groups formed two types of emissive solids that display bluish green and blue fluorescence (ΦF =72 and 32 %, respectively), depending on the preparation conditions. The crystal and powder X-ray analyses reveal that the highly emissive solid adopts a head-to-head arrangement with discrete stacks of the anthracene moieties, whereas the moderately emissive solid adopts a head-to-tail arrangement without the stacks. The obtained molecular arrangements are transformed by thermal stimuli accompanying the change in fluorescence. Furthermore, large enhancements of dye emissions (12-45-fold) through highly efficient host-guest energy transfer were achieved in the solid state by adding minute amounts of various fluorescent dyes (e.g. rubrene and Nile red) to the V-shaped compound.

Polyaromatic nanocapsules displaying aggregation-induced enhanced emissions in water.

V-shaped polyaromatic amphiphiles with phenanthrene or naphthalene rings spontaneously and quantitatively formed micelle-like nanocapsules in water at room temperature. In contrast to usual polyaromatic aggregates with weak fluorescent properties, the new capsules providing spherical polyaromatic shells with diameters of ∼2 nm show strong fluorescent emissions due to an aggregation-induced enhanced emission (AIEE) effect and moreover encapsulate a fluorescent coumarin dye to generate highly emissive host-guest composites.

A V-shaped polyaromatic amphiphile: solubilization of various nanocarbons in water and enhanced photostability.

Nanocarbons are synthetic carbon-rich compounds with polyaromatic frameworks that have lately attracted attention as emerging functional materials. However, their extreme hydrophobicity and aggregation peculiarity, besides their shape and size diversities, precluded their study in solution, especially in "green" water. More convenient and general solubilizing methods of nanocarbon frameworks are required by using non-covalent supramolecular interactions. Here we report a protocol for solubilizing a wide range of nanocarbons, that is, fullerenes (C60 , C70 , C84 , and C120 ), polyarenes (tetracene, pentacene, perylene, coronene, and hexabenzocoronene), and carbon nanotubes (single-walled and multi-walled CNTs), in water through manual grinding with V-shaped polyaromatic amphiphiles. The obtained aqueous nanocomposites are composed of nanocarbons encircled by the polyaromatic frameworks of the amphiphiles through multiple aromatic-aromatic interactions. Notably, the encapsulated photosensitive nanocarbons, such as tetracene, pentacene, and fullerene dimer, exhibit unusual stability toward UV/Vis light.

[Pathological diagnosis of renal tumors: up to date].

Renal cell carcinoma (RCC) is composed of heterogenous histological types, with different clinical features and molecular biological characteristics. The "General Rule for Clinical and Pathological Studies on RCC" was revised in 2011, according to the World Health Organization system (WHO) (2004). Although most RCC is clear cell RCC (approximately 70-80% of RCC), papillary and chromophobe RCCs are occasionally encountered (approximately 10 and 5%, respectively). Collecting duct carcinoma is a rare and highly aggressive adenocarcinoma derived from the collecting duct. Additionally, several histological types have been introduced, and "granular RCC" has been omitted as a diagnostic term. For precise diagnosis, careful gross and histological evaluations are required along with immunohistochemical and molecular biological analyses. Additionally, novel histological types have recently been emerging, i.e., 6p21 translocation-associated RCC, dialysis-associated RCC, and tubulocystic carcinoma. Furthermore, mimics of RCC are always considered as differential diagnostic candidates, i.e., metanephric adenoma, epithelioid angiomyolipoma, juxtaglomerular cell tumor, and carcinoid tumor.

Iridium-catalyzed [2 + 2 + 2] cycloaddition of α,ω-diynes with nitriles.

[Ir(cod)Cl](2)/DPPF or BINAP efficiently catalyzed the cycloaddition of α,ω-diynes with nitriles to give pyridines. The reaction can accommodate a very wide range of nitriles. Both aliphatic and aromatic nitriles smoothly reacted with α,ω-diynes to give pyridines. Ten equivalents of unactivated aliphatic nitrile were enough to give the product in high yield. Aliphatic nitriles bearing an acetal or amino moiety could be used for the reaction. The highly regioselective cycloaddition of unsymmetrical diyne bearing two different internal alkyne moieties was achieved. The observed regioselectivity could be reasonably explained by considering the different reactivities of the α-position in iridacyclopentadiene. Regioselective cycloaddition was successfully applied to the synthesis of terpyridine and quinquepyridine. This chemistry was extended to a new and efficient synthesis of oligoheteroarenes. Five aromatic or heteroaromatic rings were connected in a single operation. [Ir(cod)Cl](2)/chiral diphosphine catalyst can be applied to enantioselective synthesis. Kinetic resolution of the racemic secondary benzyl nitrile catalyzed by [Ir(cod)Cl](2)/SEGPHOS gave a central carbon chiral pyridine in 80% ee. The mechanism was analyzed on the basis of the B3LYP level of density functional calculations.

Use of mathematical modeling and its inverse analysis for precise assessment of pesticide dissipation in a paddy environment.

The extrapolability of the lysimeter test as a dissipation simulator in an actual paddy field was evaluated using mathematical models and their inverse analyses for predicting pesticide fate and transport processes in paddy test systems. As a source of experimental data, a four-year comparative experiment in lysimeters and paddy fields was conducted using various paddy pesticides. First, the dissipations for various active ingredients in granule pesticides under submerged applications were statistically compared using simple kinetic modeling. Second, the dissipation pathways, unobserved experimental components, and effect of the experimental setting were evaluated using a higher tier mathematical model with a novel inverse analysis protocol. Finally, owing to experimental constraints, the unobtainable parameters were extracted from the laboratory container test before being transferred to compare the outdoor experimental data under different formulation types.

Inverse modeling of laboratory experiment to assess parameter transferability of pesticide environmental fate into outdoor experiments under paddy test systems.

BACKGROUND: Extraction of environmental fate parameters for pesticides by inverse modeling in laboratory experiments has evolved to become a common practice in higher tier exposure modeling. This study focuses on flooded paddy soil conditions using a simple container test system. Four active ingredients of paddy herbicide were tested. The results were parameterized and transferred to analyze the effect of formulation types on the outdoor experimental data via inverse analyses of two structurally-compatible mathematical models, namely: pesticide concentration in paddy field for laboratory (PCPF-LR) and PCPF for outdoors (PCPF-1Rv1.1 ). RESULTS: After in-laboratory calibration, the PCPF-LR model revealed statistically acceptable or ideal simulations of pesticide concentrations in both the aqueous and soil phases (e.g. Nash-Sutcliffe efficiency > 0.7), in addition to determining the apparent sorption from the laboratory data. The extracted persistence indicators (degradation half-life, DegT50 ) in the aqueous phase were 1.4-38.7 times higher than those of the dissipation (DT50 ) due to the exclusion of partitioning and phase transfer processes (diffusion and sorption). In the outdoor experiment, 72% of the outdoor-calibrated simulations of the PCPF-1Rv1.1 model, showed statistically acceptable representations of the concentrations in paddy water. Furthermore, the DegT50 as 'bulk' degradation in paddy water was statistically insignificant between the formulation types; however, the DT50 demonstrated statistically different results. CONCLUSION: The laboratory/outdoor data interconnections using proposed modeling approach facilitate the data-specific model calibration and analysis. These can be useful in the exposure modeling of paddy pesticide by manipulating the parameter uncertainties associated with the experimental constraints. © 2020 Society of Chemical Industry.

Three host peculiarities of a cycloalkane-based micelle toward large metal-complex guests.

Linear alkanes are essential building blocks for natural and artificial assemblies in water. As compared with typical, linear alkane-based micelles and recent aromatic micelles, we herein develop a cycloalkane-based micelle, consisting of bent amphiphiles with two cyclohexyl frameworks. This uncommon type of micelle, with a spherical core diameter of ~ 2 nm, forms in water in a spontaneous and quantitative manner. The cycloalkane-based, hydrophobic cavity displays peculiar host abilities as follows: (i) highly efficient uptake of sterically demanding Zn(II)-tetraphenylporphyrin and rubrene dyes, (ii) selective uptake of substituted Cu(II)-phthalocyanines and spherical nanocarbons, and (iii) uptake-induced solution-state emission of [Au(I)-dimethylpyrazolate]3 in water. These host functions toward the large metal-complex and other guests studied herein remain unaccomplished by previously reported micelles and supramolecular containers.

[The relationship between human papillomavirus (HPV) infection and penile cancer].

Human papillomavirus (HPV) may be carcinogenic effectors in a variety of human lower genital tract malignancies. We evaluated HPV status with respect to clinical and pathological features and prognosis of penile carcinoma. We searched for HPV infected cells (Koilocytosis) within the primary lesion of cancer tissue from 78 patients with penile squamous cell carcinoma. The following variables were recorded : age, tumor size, clinical stage, lymphatic and venous invasion, histologic and nuclear grade, Broders grade, infiltration status, and lymph node and distant metastasis. Koilocytosis were detected 55.1% (43 of 78) of patients. Tumors with Koilocytosis had better differentiation (p=0.0443) and lower grade (better keratinized) in Broders grading system (p=0.0116) than HPV negative tumors. No difference was found in the 5-year survival rate (p=0.5693). Our data suggest that the presence of Koilocytosis does not influence prognosis in penile cancer.

Inverse analysis to estimate site-specific parameters of a mathematical model for simulating pesticide dissipations in paddy test systems.

BACKGROUND: In Japan, while experimental data for the dissipation behavior of paddy pesticides under a standardized test system are available, the application of a mathematical model is limited. This paper proposes a new model calibration procedure for inversely deriving the model parameters from the experimental data. This procedure is tested in the open software R by running an improved Pesticide Concentration in Paddy Field-1 (PCPF-1) model with R packages to analyze the dissipation of simetryn and molinate in flooded lysimeters and paddy fields. RESULTS: The model fitting was performed by a random minimization routine. Furthermore, the uncertainties of the model parameters envisioned by the global sensitivity analysis were successfully reduced using the Markov chain Monte Carlo technique. The calibrated simulation was validated at each test plot by confirming multiple statistical indices (i.e. Nash-Sutcliffe efficiency 0.88-1.00, percent bias <±5%). The dissipation pathways of two herbicides were quantitatively clarified by the mass balance of calibrated simulations and the effect of the unexpected herbicide runoff was quantified. The case study showed that the adjustment of daily percolation rate in the lysimeter experiment is the key to simulate the actual paddy field condition more accurately, especially in a case where pesticides show higher water solubility and soil mobility. CONCLUSION: The developed procedure can analyze the experimental data with acceptable accuracy and extract the unobservable information quantitatively. Our approach is applicable to the optimization of not only the model but also future experimental design. © 2018 Society of Chemical Industry.

Performance evaluation of lysimeter experiments for simulating pesticide dissipation in paddy fields. Part 1: Submerged application of granular pesticides.

Three-year comprehensive experiments were conducted to compare the dissipation patterns of a total of 16 pesticides, including 3 metabolites, as granular formulations applied in lysimeters and paddy fields with two soil types. Analytical concentrations of the target pesticides in paddy water were analyzed using a granular kinetic model consisting of the following parameters: release rate, decrease rate, and dissolved concentration. Results of parameter grouping analyses of the kinetic models showed that 56% of data reproducibility (entire grouping) was obtained between replicates for the lysimeters. In comparisons between the lysimeters and paddy fields, 48% of decrease rates and 34% of release rates were grouped, although significant differences were observed with a nearly 90% difference for dissolved concentrations. These differences might be attributed to the hydrological components such as water management and meteorological covariates in paddy fields, the daily percolation in lysimeters and the adsorption-desorption kinetics between paddy water and soil.

Performance evaluation of lysimeter experiments for simulating pesticide dissipation in paddy fields. Part 2: Nursery-box application and foliar application.

Comparative experiments investigating the dissipation of four nursery-box-applied pesticides and three foliar-applied pesticides were conducted using lysimeters and in actual paddy fields. In the lysimeter experiments, there were test plots for submerged application for both application types. Analytical concentrations of the pesticides in paddy water were evaluated using appropriate kinetic models. The detection levels of pesticides in the paddy water for the nursery-box and foliar applications were 10-77% and 42-79% of the submerged application, respectively. The times required for 50% dissipation (DT 50s) in case of the nursery-box and foliar applications were 0.8-10.4 days and 0.5-2.7 days, respectively. Although overall dissipations were affected by the physicochemical properties of the pesticide and the experimental design in the test plots, the initial detection levels in the lysimeters, governed by the runoff at transplanting and the deposition at spraying, were comparable with those in the actual paddy fields.

A pH-responsive molecular capsule with an acridine shell: catch and release of large hydrophobic compounds.

Unlike common polyaromatic hydrocarbons, acridine is a characteristic compound bearing both π-stackable large surfaces and a protonable nitrogen atom. Here we report the first synthesis of a supramolecular capsule with multiple acridine panels. In water, the assembly and disassembly of the capsule reversibly occur under neutral and acidic conditions, respectively (≥10 cycles). Notably, the pH-responsive capsule encapsulates a variety of large hydrophobic compounds (up to 1.6 nm in diameter) such as coumarins, metallophthalocyanines and subphthalocyanine in neutral water and subsequently releases them by simple addition of acid.