Improved U-Net Model to Estimate Cardiac Output Based on Photoplethysmography and Arterial Pressure Waveform.

We aimed to estimate cardiac output (CO) from photoplethysmography (PPG) and the arterial pressure waveform (ART) using a deep learning approach, which is minimally invasive, does not require patient demographic information, and is operator-independent, eliminating the need to artificially extract a feature of the waveform by implementing a traditional formula. We aimed to present an alternative to measuring cardiac output with greater accuracy for a wider range of patients. Using a publicly available dataset, we selected 543 eligible patients and divided them into test and training sets after preprocessing. The data consisted of PPG and ART waveforms containing 2048 points with the corresponding CO. We achieved an improvement based on the U-Net modeling framework and built a two-channel deep learning model to automatically extract the waveform features to estimate the CO in the dataset as the reference, acquired using the EV1000, a commercially available instrument. The model demonstrated strong consistency with the reference values on the test dataset. The mean CO was 5.01 ± 1.60 L/min and 4.98 ± 1.59 L/min for the reference value and the predicted value, respectively. The average bias was -0.04 L/min with a -1.025 and 0.944 L/min 95% limit of agreement (LOA). The bias was 0.79% with a 95% LOA between -20.4% and 18.8% when calculating the percentage of the difference from the reference. The normalized root-mean-squared error (RMSNE) was 10.0%. The Pearson correlation coefficient (r) was 0.951. The percentage error (PE) was 19.5%, being below 30%. These results surpassed the performance of traditional formula-based calculation methods, meeting clinical acceptability standards. We propose a dual-channel, improved U-Net deep learning model for estimating cardiac output, demonstrating excellent and consistent results. This method offers a superior reference method for assessing cardiac output in cases where it is unnecessary to employ specialized cardiac output measurement devices or when patients are not suitable for pulmonary-artery-catheter-based measurements, providing a viable alternative solution.

StomataScorer: a portable and high-throughput leaf stomata trait scorer combined with deep learning and an improved CV model.

To measure stomatal traits automatically and nondestructively, a new method for detecting stomata and extracting stomatal traits was proposed. Two portable microscopes with different resolutions (TipScope with a 40× lens attached to a smartphone and ProScope HR2 with a 400× lens) are used to acquire images of living stomata in maize leaves. FPN model was used to detect stomata in the TipScope images and measure the stomata number and stomatal density. Faster RCNN model was used to detect opening and closing stomata in the ProScope HR2 images, and the number of opening and closing stomata was measured. An improved CV model was used to segment pores of opening stomata, and a total of 6 pore traits were measured. Compared to manual measurements, the square of the correlation coefficient (R2 ) of the 6 pore traits was higher than 0.85, and the mean absolute percentage error (MAPE) of these traits was 0.02%-6.34%. The dynamic stomata changes between wild-type B73 and mutant Zmfab1a were explored under drought and re-watering condition. The results showed that Zmfab1a had a higher resilience than B73 on leaf stomata. In addition, the proposed method was tested to measure the leaf stomatal traits of other nine species. In conclusion, a portable and low-cost stomata phenotyping method that could accurately and dynamically measure the characteristic parameters of living stomata was developed. An open-access and user-friendly web portal was also developed which has the potential to be used in the stomata phenotyping of large populations in the future.

Molecular Details of Protein Condensates Probed by Microsecond Long Atomistic Simulations.

The formation of membraneless organelles in cells commonly occurs via liquid-liquid phase separation (LLPS) and is in many cases driven by multivalent interactions between intrinsically disordered proteins (IDPs). Investigating the nature of these interactions, and their effect on dynamics within the condensed phase, is therefore of critical importance but very challenging for either simulation or experiment. Here, we study these interactions and their dynamics by pairing a novel multiscale simulation strategy with microsecond all-atom MD simulations of a condensed, IDP-rich phase. We simulate two IDPs this way, the low complexity domain of FUS and the N-terminal disordered domain of LAF-1, and find good agreement with experimental information about average density, water content, and residue-residue contacts. We go significantly beyond what is known from experiments by showing that ion partitioning within the condensed phase is largely driven by the charge distribution of the proteins and-in the cases considered-shows little evidence of preferential interactions of the ions with the proteins. Furthermore, we can probe the microscopic diffusive dynamics within the condensed phase, showing that water and ions are in dynamic equilibrium between dense and dilute phases, and their diffusion is reduced in the dense phase. Despite their high concentration in the condensate, the protein molecules also remain mobile, explaining the observed liquid-like properties of this phase. We finally show that IDP self-association is driven by a combination of nonspecific hydrophobic interactions as well as hydrogen bonds, salt bridges, and π-π and cation-π interactions. The simulation approach presented here allows the structural and dynamical properties of biomolecular condensates to be studied in microscopic detail and is generally applicable to single- and multicomponent systems of proteins and nucleic acids involved in LLPS.

Functionalization of Diazo Groups by the Nucleophilic Addition of Two Molecules of a Dimethylsulfonium Ylide to α-Diazo-ß-ketoesters/ketones: Synthesis of Highly Functionalized Hydrazones.

The intrinsic electrophilic feature for the terminal nitrogen of α-diazo-ß-ketoesters/ketones has been elucidated by the intermolecular nucleophilic addition of two molecules of a dimethylsulfonium ylide. This methodology allows for access to highly functionalized hydrazones with a broad scope and good functional group tolerance. The reaction operates under simple and mild conditions without using a catalyst.

Enantioselective carbonyl-ene reactions catalyzed by chiral cationic dirhodium(II,III) carboxamidates.

An enantioselective carbonyl-ene reaction of glyoxylate esters with 1,1-disubstituted alkenes catalyzed by chiral cationic dirhodium(II,III) carboxamidates is described. The paddlewheel dirhodium(II,III) carboxamidates having one open coordination site at each rhodium smoothly catalyze the carbonyl-ene reaction to afford homoallylic alcohol products in good isolated yields with high enantioselectivities.

A survey of enoldiazo nucleophilicity in selective C-C bond forming reactions for the synthesis of natural product-like frameworks.

A survey of in situ, catalytically generated carbocations for coupling with enoldiazoacetate nucleophiles was performed. These couplings facilitate the rapid assembly of complex organodiazo compounds that provide a template for the synthesis of a variety of carbocyclic and heterocyclic ring systems.

Expedient access to substituted 3-amino-2-cyclopentenones by dirhodium-catalyzed [3+2]-annulation of silylated ketene imines and enoldiazoacetates.

In a reaction that proceeds under mild conditions with remarkable functional group tolerance, structurally diverse 3-amino-2-cyclopentenones bearing a quaternary carbon at the 4-position have been synthesized through a formal [3+2]-cycloaddition reaction of silylated ketene imines (SKIs) and enoldiazoaceates by dirhodium catalysis.

Catalytic asymmetric syntheses of quinolizidines by dirhodium-catalyzed dearomatization of isoquinolinium/pyridinium methylides--the role of catalyst and carbene source.

Convenient access to highly enantioenriched substituted quinolizidines has been achieved by chiral dirhodium(II) carboxylate-catalyzed dearomatizing formal [3 + 3]-cycloaddition of isoquinolinium/pyridinium methylides and enol diazoacetates. Coordination of Lewis basic methylides to dirhodium(II) prompts the rearrangement of the enol-carbene that is bound to dirhodium to produce a donor-acceptor cyclopropene. The donor-acceptor cyclopropene is in equilibrium with the dirhodium-bound enol-carbene and undergoes both enantioselective [3 + 3]-cycloaddition from the dirhodium-bound enol-carbene and diastereoselective [3 + 2]-cycloaddition by uncatalyzed reaction of the cyclopropene with isoquinolinium or pyridinium methylides. Increasing the mol % of catalyst loading suppresses the [3 + 2]-cycloaddition pathway.

Dirhodium(II)-catalyzed formal [3+2+1]-annulation of azomethine imines with two molecules of a diazo ketone.

A highly diastereoselective formal [3+2+1]-cycloaddition reaction that produces multi-functionalized bicyclic pyrazolidinone derivatives is achieved in moderate to high yield by Rh2(4S-MPPIM)4-catalyzed reaction of azomethine imines with two molecules of a diazo ketone.

Highly selective catalyst-dependent competitive 1,2-C→C, -O→C, and -N→C migrations from ß-methylene-ß-silyloxy-ß-amido-α-diazoacetates.

Transition-metal catalysts direct 1,2-C→C, -O→C, and -N→C migrations from ß-methylene-ß-silyloxy-ß-amido-α-diazoacetates with high selectivity. The key to achieving this unique display of differential selectivities relies on steric and stereoelectronic control by their catalytically generated metal carbenes.

Enantiomer recognition of amides by dirhodium(II) tetrakis[methyl 2-oxopyrrolidine-5(S)-carboxylate].

Association constants of the chiral dirhodium(II) carboxamidate Rh(2)(5S-MEPY)(4) with Lewis bases including acetonitrile and amides have been determined by UV-vis titration experiments. With chiral lactams and acyclic acetamides in their R- and S-configurations equilibrium constants with chiral dirhodium carboxamidates are measures of chiral differentiation, and equilibrium constant ratios as high as three have been determined. From equilibrium associations with acetamide, N-methylacetamide, and N,N-dimethylacetamide, as well as equilibrium constants for lactams and acyclic amides, higher values occur when both the amide carbonyl oxygen and N-H are bound to Rh(2)(5S-MEPY)(4). This cooperative bonding mode is confirmed by NMR measurements that show a distinctive shift of a N-H absorption, as well as perturbation of the ligands on dirhodium compound, and they suggest N-H association with a ligated oxygen of Rh(2)(5S-MEPY)(4). Measurements were made on the dirhodium(II) compound from which protective axial ligands have been removed to enhance their reliability.