AuCl-Catalyzed [4+2] Benzannulation between <i>o</i>-Alkynyl(oxo)benzene and Benzyne

The AuCl-catalyzed benzannulation of o-alkynyl(oxo)benzenes with benzenediazonium 2-carboxylate proceeds under mild conditions and a variety of anthracene derivatives, having a ketone group at the 9-position, are produced in good to high yields. The reaction proceeds most probably through the [4+2] cycloaddition between benzyne and benzopyrylium auric ate complex, which would be generated by the gold-induced electrophilic cyclization of o-alkynyl(oxo)benzenes

Controlled Insertion Reaction of Thiirane into Carbamothioate: Novel Synthesis of Well-Defined Polysulfide

The insertion reaction of propylene sulfide (PS) into p-tolylcarbamothioate (PTCT) was examined in the presence of tetrabutylammonium chloride (TBAC) in 1-methyl-2-pyrrolidinone at 60 °C in the feed ratio of PTCT/PS = 1/1−1/40, affording the corresponding polysulfides in satisfactory yields. It was found that the molecular weights (Mn′s) coincided with the feed ratios PS and molecular dispersity ratios (Mw/Mn) were very narrow (Mw/Mn <1.10). i.e., this insertion reaction could be performed under the living system. Furthermore, the insertion living reaction of PS using tricarbamothioate was examined to give the controlled three-arms star-shaped polysulfides

Efficient Method for Synthesis of Angucyclinone Antibiotics via Gold-Catalyzed Intramolecular [4 + 2] Benzannulation: Enantioselective Total Synthesis of (+)-Ochromycinone and (+)-Rubiginone B₂

An efficient synthetic approach to angucyclinone antibiotics, (+)-ochromycinone and (+)-rubiginone B2, is reported. The key step involves the facile formation of 2,3-dihydrophenantren-4(1H)-one skeleton, an important framework of angucyclinone natural products, by using gold-catalyzed intramolecular [4 + 2] benzannulation reaction

AuBr₃- and Cu(OTf)₂-Catalyzed Intramolecular [4 + 2] Cycloaddition of Tethered Alkynyl and Alkenyl Enynones and Enynals: A New Synthetic Method for Functionalized Polycyclic Hydrocarbons

Treatment of tethered alkynyl enynones 8, in which a carbon chain is attached to the carbonyl group, with a catalytic amount of AuBr3 in (ClCH2)2 gave the naphthyl ketones 9 in good to high yields (top-down approach). Analogously, the AuBr3-catalyzed benzannulations of 10, in which a carbon tether is extended from the alkynyl terminus, also proceeded smoothly, and the cyclized naphthyl ketones 11 were obtained in high yields (bottom-up approach). Similarly, when two kinds of tethered alkenyl enynones 12 and 14 were treated with Cu(OTf)2 catalyst, the corresponding dihydronaphthyl ketone products 13 and 15 were obtained in high yields, respectively. The present formal [4 + 2] intramolecular cycloaddition proceeds most probably through the coordination of the triple bond at the ortho position of substrates to Lewis acids, the formation of benzopyrylium ate complex 16 via the nucleophilic addition of the carbonyl oxygen atom, the reverse electron demand type Diels−Alder addition of the tethered alkynes or alkenes to the ate complex, and subsequent bond rearrangement

σ−π Chelation-Controlled Stereoselective Hydrosilylation of Ketones

σ−π Chelation-Controlled Stereoselective Hydrosilylation of Ketone

Example of cadence calculation for a significantly abnormal gait sequence.

(A) Filtered sequential ‘LRdiff’ of gait sequence of our PD patient’s (Pt. 2), whose gait mixed with significant FOG and small steps. The movie is 14 seconds long, the time she took to walk less than 2 m. Many instances of freezing and involuntary oscillations were observed during the gait. The sequential ST-ACF of 11 seconds’ duration (subtracting window length of 3 seconds from the raw movie length) obtained from (A) is shown as (B). (C)–(F) show the ST-ACF at the corresponding tC − tF timings in (A, B). (C)–(F) demonstrate examples in which accurate gait frequency detection is confirmed (D, E) or doubtful (C, F) when applying the same procedure used for the normal gait movies as shown in Fig 3.</p

Table_1_Automated Evaluation of Conventional Clock-Drawing Test Using Deep Neural Network: Potential as a Mass Screening Tool to Detect Individuals With Cognitive Decline.docx

IntroductionThe Clock-Drawing Test (CDT) is a simple cognitive tool to examine multiple domains of cognition including executive function. We aimed to build a CDT-based deep neural network (DNN) model using data from a large cohort of older adults, to automatically detect cognitive decline, and explore its potential as a mass screening tool.MethodsOver 40,000 CDT images were obtained from the National Health and Aging Trends Study (NHATS) database, which collects the annual surveys of nationally representative community-dwelling older adults in the United States. A convolutional neural network was utilized in deep learning architecture to predict the cognitive status of participants based on drawn clock images.ResultsThe trained DNN model achieved balanced accuracy of 90.1 ± 0.6% in identifying those with a decline in executive function compared to those without [positive likelihood ratio (PLH) = 16.3 ± 6.8, negative likelihood ratio (NLH) = 0.14 ± 0.03], and 77.2 ± 2.7 % balanced accuracy for identifying those with probable dementia from those without (PLH = 5.1 ± 0.5, NLH = 0.37 ± 0.07).ConclusionsThis study demonstrated the feasibility of implementing conventional CDT to be automatically evaluated by DNN with a fair performance in a larger scale than ever, suggesting its potential as a mass screening test for ruling-in or ruling-out those with executive dysfunction or with probable dementia.</p

Video data and subjects’ characteristics.

Video data and subjects’ characteristics.</p

Detailed feature extraction process using the OpenPose application.

The detailed process corresponds to the upper line in Fig 1. CASIA Dataset-B contains gait sequences of the same gait recorded from different angles simultaneously: (A) laterally viewed angle; and (B) frontally viewed angle. Flow (A-1) to (A-4) shows the process for laterally viewed movies, while flow (B-1) to (B-4) shows that for frontally viewed movies. After estimating keypoints (A-2, B-2), joint coordinate data of each frame are converted to gait features: leg angle (A-3) and difference in bilateral leg-length ratio (B-3). Then sequential waveform data are obtained (A-4, B-4) to calculate gait cycle frequency in the subsequent steps. Note that 1 cycle in the sequential LRdiff (B-3) corresponds to 2 walked steps (= 1 gait cycle), while 1 cycle in the sequential LRang (A-3) corresponds to 1 walked step (= half of 1 gait cycle), so the raw frequency of sequential LRang in laterally viewed movies is multiplied by 0.5 before being converted to a gait frequency.</p

Data processing flow.

Our proposed method consists of two distinct steps: upper line (A to E), deriving sequential gait feature data from movies via body joint coordinate extraction using OpenPose; lower line, estimating cadence from the sequential data using the short-time autocorrelation function and the subsequent analysis (F to I).</p