Asymmetric Cycloaddition of -2,2,2-Trifluoroethylisatin Ketimines and Unsymmetrical Dicarbonyl-Activated Alkenes: Construction of 5'-Trifluoromethylated 3,2'-Pyrrolidinyl Spirooxindoles with Three Carbonyl Groups.

The asymmetric cycloaddition between -2,2,2-trifluoroethylisatin ketimines and unsymmetrical dicarbonyl-activated alkenes catalyzed by a bifunctional squaramide has been discovered. The present study demonstrates an efficient approach for the regio-, diastereo-, and enantioselective synthesis of densely functionalized 5'-trifluoromethylated 3,2'-pyrrolidinyl spirooxindoles featuring three different types of carbonyl groups.

Construction of Coordination Spaces with Narrow Pore Windows in Co-Based Metal-Organic Frameworks toward CO/N Separation.

Carbon emission reduction is an important measure to mitigate the greenhouse effect, which has become a hotspot in global climate change research. To contribute to this, here, we fabricated two Co-based metal-organic frameworks (Co-MOFs), namely, {[Co(NTB)(bib)]·(DMA)·(HO)} (DZU-211) and {[Co(NTB)(bmip)]·(DMA)} (DZU-212) (HNTB = 4,4',4″-nitrilotribenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane, bmip = 1,3-bis(2-methyl-1-imidazol-1-yl)propane) to realize efficient CO/N separation by dividing coordination spaces into suitable pores with narrow windows. DZU-211 reveals a 3D open porous framework, while DZU-212 exhibits a 3D double-fold interpenetrated structure.

Integrated analysis of single-cell and bulk RNA-sequencing identifies a signature based on drug response genes to predict prognosis and therapeutic response in ovarian cancer.

Ovarian cancer represents a severe gynecological malignancy with a dire prognosis, underscoring the imperative need for dependable biomarkers that can accurately predict drug response and guide therapeutic choices. In this study, we harnessed online single-cell RNA sequencing (scRNAseq) and bulk RNA sequencing (RNAseq) datasets, applying the Scissor algorithm to identify cells responsive to paclitaxel. From these cells, we derived a gene signature, subsequently used to construct a prognostic model that demonstrated high sensitivity and specificity in predicting patient outcomes.

Squaramide-catalyzed enantioselective Michael addition of nitromethane to 2-enoylazaarenes: synthesis of chiral azaarene-containing γ-nitroketones.

Bifunctional chiral squaramide-catalyzed highly enantioselective Michael addition of nitromethane to diverse 2-enoylazaarenes was successfully performed. This protocol provided a set of chiral azaarene-containing γ-nitroketones with up to 98% yield and 98% ee in a solvent-free catalytic system under mild conditions. Furthermore, gram-scale synthetic utility was also showcased.

Pitfalls in Developing Machine Learning Models for Predicting Cardiovascular Diseases: Challenge and Solutions.

In recent years, there has been explosive development in artificial intelligence (AI), which has been widely applied in the health care field. As a typical AI technology, machine learning models have emerged with great potential in predicting cardiovascular diseases by leveraging large amounts of medical data for training and optimization, which are expected to play a crucial role in reducing the incidence and mortality rates of cardiovascular diseases. Although the field has become a research hot spot, there are still many pitfalls that researchers need to pay close attention to.

DBU-catalyzed diastereoselective 1,3-dipolar [3+2] cycloaddition of trifluoroethyl amine-derived isatin ketimines with chalcones: synthesis of 5'-CF-substituted 3,2'-pyrrolidinyl spirooxindoles.

A diastereoselective 1,3-dipolar cycloaddition reaction between trifluoroethyl amine-derived isatin ketimines and chalcones was successfully achieved in the presence of DBU. A series of 5'-CF-substituted 3,2'-pyrrolidinyl spirooxindoles were efficiently synthesized with high yields and excellent diastereoselectivities (up to 89% yield, and >99 : 1 dr). The anticancer activities of these highly functionalized spiro[pyrrolidin-3,2'-oxindole] derivatives were evaluated.

Dehydroabietane-type bifunctional organocatalysts in asymmetric synthesis: recent progress.

Dehydroabietane-type bifunctional organocatalysts derived from rosane-type diterpenes of dehydroabietic acid (DHAA) and dehydroabietylamine (DA) have been utilized in a wide variety of highly enantioselective reactions. Since one well-documented review exclusively reported on the development of terpene-derived bifunctional thioureas in asymmetric organocatalysis in 2013, fragmentary progress on the dehydroabietane-type bifunctional thioureas and squaramides has been mentioned in other reviews. In this mini-review, we systematically analyze and reorganize the published literature on dehydroabietane-type bifunctional organocatalysts in the recent decade according to the type of catalysts.

Atropisomeric Phosphine Ligands Bearing C-N Axial Chirality: Applications in Enantioselective Suzuki-Miyaura Cross-Coupling Towards the Assembly of Tetra--Substituted Biaryls.

Biaryl phosphines bearing C-C axial chirality are commonly known and have been successfully applied in many asymmetric catalyses. Nevertheless, the development of a chiral ligand having an axially chiral C-N backbone remains elusive due to its undesirable less restricted rotational barrier. In fact, it is highly attractive to overcome this challenge in ligand development as the incorporation of an N-donor component at the chiral axis is more favorable toward the transient metal coordination, and thus, a better outcome of stereocommunication is anticipated to the approaching substrates.

Interpenetrated metal-organic frameworks with enhanced photoluminescence for selective recognition of -xylene from xylene isomers.

Two novel luminescent metal-organic frameworks (MOFs), [Zn(TCA)(BPB)] (DZU-101, where HTCA = 4,4',4''-tricarboxyltriphenylamine and BPB = 1,4-bis(pyrid-4-yl)benzene) and [Zn(TCA)(BPB)DMA] (DZU-102), based on the same ligands and metal ions were synthesized by regulating the amount of water in the solvothermal reaction system. Structural analyses show that the two MOFs have pillar-layered frameworks with Zn clusters connected by the TCA and BPB ligands. Interestingly, DZU-102 possessed a two-fold interpenetrated framework distinct from the individual network of DZU-101.

WVMDA: Predicting miRNA-Disease Association Based on Weighted Voting.

An increasing number of experiments had verified that miRNA expression is related to human diseases. The miRNA expression profile may be an indicator of clinical diagnosis and provides a new direction for the prevention and treatment of complex diseases. In this work, we present a weighted voting-based model for predicting miRNA-disease association (WVMDA).

The Dietary Supplemental Effect of Nitroethanol in Comparison with Monensin on Methane Emission, Growth Performance and Carcass Characteristics in Female Lambs.

This study was conducted to evaluate the dietary supplemental effects of 2-nitroethanol (NEOH) in comparison with monensin on methane (CH) emission, growth performance and carcass characteristics in female lambs. Sixty female, small-tailed Chinese Han lambs (3.5 ± 0.

The Antimethanogenic Nitrocompounds Can be Cleaved into Nitrite by Rumen Microorganisms: A Comparison of Nitroethane, 2-Nitroethanol, and 2-Nitro-1-propanol.

A class of aliphatic short chain nitrocompounds have been reported as being capable of CH reduction both in vitro and in vivo. However, the laboratory evidence associated with the metabolic fate of nitrocompounds in the rumen has not been well documented. The present study was conducted to compare in vitro degradation and metabolism of nitroethane (NE), 2-nitroethanol (NEOH), and 2-nitro-1-propanol (NPOH) incubated with mixed rumen microorganisms of dairy cows.

Nitroethanol in Comparison with Monensin Exhibits Greater Feed Efficiency Through Inhibiting Rumen Methanogenesis More Efficiently and Persistently in Feedlotting Lambs.

This study was conducted to determine the dietary supplemental effects of nitroethanol (NEOH) in comparison with monensin on growth performance and estimated methane (CH) production in feedlotting lambs. Sixty male, small-tailed Chinese Han lambs were arranged at random into three dietary treatment groups: (1) a basal control diet (CTR), (2) the basal diet added with 40 mg/kg monensin (MON), (3) the basal diet added with 277 mg/kg nitroethanol (NEOH). During the 32-day lamb feeding, monensin and nitroethanol were added in period 1 (day 0-16) and then withdrawn in the subsequent period 2 (day 17-32) to determine their withdrawal effects.

Enantioselective synthesis of chiral heterocyclic biaryls via asymmetric Suzuki-Miyaura cross-coupling of 3-bromopyridine derivatives.

A series of chiral heterocyclic biaryls with a pyridyl moiety were prepared in moderate to good yields with up to 92% ee via asymmetric Suzuki-Miyaura coupling. The chiral-bridged biphenyl monophosphine ligand L1 was found to be much more effective in the reaction enantioselection than its counterpart binaphthyl monophosphine ligands.

Synthesis of six-membered spirooxindoles a chiral Brønsted acid-catalyzed asymmetric intramolecular Friedel-Crafts reaction.

By means of the direct condensation of -aminoethylpyrroles and isatins, followed by a chiral phosphoric acid-catalyzed asymmetric intramolecular Friedel-Crafts reaction, a new class of valuable chiral 3',4'-dihydro-2'-spiro[indoline-3,1'-pyrrolo[1,2-]pyrazin]-2-ones bearing a quaternary carbon stereocenter were successfully synthesized in good to excellent yields and with moderate to good enantioselectivities under mild reaction conditions.

The experimental study of shunt-decompression arterialized vein flap.

Background: Arterialized vein flap is a kind of unphysiological flap. Unphysiological reconstruction of blood circulation leads to higher load than that supported by physiological flap and is the culprit of flap swelling, blood stasis, skin blistering, and necrosis after flap grafting. To resolve the multiple disadvantages of traditional flap grafting, by introducing the principles of fluid mechanics, shunt-decompression surgery is prepared to decline the circulation preload and improve the prognosis of arterialized vein flap grafting.

A simultaneous disulfide bond cleavage, N,S-bialkylation/N-protonation and self-assembly reaction: syntheses, structures and properties of two hybrid iodoargentates with thiazolyl-based heterocycles.

Solvothermal reactions of AgI with the vulcanization accelerator 2,2'-dibenzothiazolyl disulfide and hydroiodic acid in alcohols afford two hybrid iodoargentates with one-dimensional structures, namely (Etmbt)[AgI] (1, Hmbt = 2-mercaptobenzothiazole) and {(Hmbt)[AgI]} (2). The syntheses of both 1 and 2 involve unprecedented multiple in situ reactions. Specifically, a simultaneous disulfide bond cleavage, N and S donor atoms bialkylation, and self-assembly reaction lead to 1 that contains a discrete N,S-biethylated cation (Etmbt) and a rare inorganic (AgI) anionic chain, while a simultaneous disulfide bond cleavage, N-protonation and self-assembly reaction affords 2 which features zwitterionic Hmbt molecules coordinating with the opposite side Ag atoms of a neutral inorganic (AgI) chain via forming Ag-S coordination bonds.

[Identification of Official Rhubarb Samples by Using PLS and Terahertz Time-Domain Spectroscopy].

The development of terahertz technology is attracting broad intention in recent years. The quality identification is important for the quality control of Chinese medicine production. In the present work, terahertz time-domain spectroscopy (THz-TDS) combined with partial least squares (PLS) were used for the identification model building and studied based on 41 official and unofficial rhubarb samples.

[The Study on the Far-FTIR and THz Spectra of Azitromycin Drugs with Different Physical Forms].

Far Fourier transform infrared spectroscopy (Far-FTIR) and terahertz time-domain spectroscopy (THz-TDS) were used to measure the fingerprint spectra of Azitromycin suspension, capsule, tablet and dispersible tablet under vacuum and nitrogen conditions, respectively. In the frequency range of 0.2-15 THz, highly resolved spectral features for Azitromycin suspension were measured and some minor differences were observed between domestic and exotic Azitromycin Suspension, such as linewidth broadening and additional peaks.

New Family of Octagonal-Prismatic Lanthanide Coordination Cages Assembled from Unique Ln17 Clusters and Simple Cliplike Dicarboxylate Ligands.

Novel high-nuclearity lanthanide clusters (Ln17) are generated in situ in the coordination-driven self-assembly. A metal-cluster-directed symmetry strategy for building metal coordination cages is successfully applied to a lanthanide system for the first time. A new family of octagonal-prismatic lanthanide coordination cages UJN-Ln, formulated as [Ln(μ3-OH)8][Ln16(μ4-O)(μ4-OH)(μ3-OH)8(H2O)8(μ4-dcd)8][(μ3-dcd)8]·22H2O (Ln = Gd, Tb, Dy, Ho, and Er; dcd = 3,3-dimethylcyclopropane-1,2-dicarboxylate dianion), have been assembled from the unique Ln17 clusters and simple cliplike ligand H2dcd.

Structures and multiple properties of two polar metal-organic frameworks based on achiral N,O-coordinated ligands: toward multifunctional materials.

Two novel metal-organic frameworks (MOFs) [Cd3(padc)(Hpadc)(H2padc)(H2O)]n·nH2O (1, H3padc = pyrazole-3,5-dicarboxylic acid) and [Co4(pidc)2(Hpidc)4(H2O)3]n·12nH2O (2, H2pidc = pyridine-2,5-dicarboxylic acid), that both crystallize in polar space groups, were solvothermally synthesized by using achiral N,O-coordinated ligands. Compound 1 consists of trinuclear Cd(II)-based units that are further bridged by the backbone of H3padc ligands to form a three-dimensional (3-D) (4,6)-connected fsc topology network, while compound 2 features two types of double-helical tubes with different chiralities connecting with each other alternatively to construct a typical 2-D (3,6)-connected kgd topology network. Importantly, 1 exhibits combined properties of photoluminescence (PL) and second harmonic generation (SHG), and represents the first noncentrosymmetric H3padc-based MOF that was obtained without any ancillary ligands.

A comparison study of aliphatic and aromatic structure directing agents influencing the crystal and electronic structures, and properties of iodoplumbate hybrids: water induced structure conversion and visible light photocatalytic properties.

The introduction of the aliphatic amines en (ethylenediamine), aep (N-(2-aminoethyl)piperazine) and tepa (tetraethylenepentamine), and the aromatic species 2,2'-bipy (2,2'-bipyridine) and dpe (1,2-di(4-pyridyl)ethylene) as structure directing agents (SDAs) into inorganic iodoplumbates affords six hybrids, namely [(Hen)4(H2.5O)2I](PbI6) (1), Cs2n[Pb3I8(en)2]n (2), (H3tepa)n(PbI5)n (3), (H2aep)n(PbI4)n (4), (Et22,2'-bipy)n(Pb2I6)n (5) and (Et2dpe)n(Pb2I6)n (6). 1 contains a discrete octahedral (PbI6)(4-) anion generated under the direction of a novel co-template, [(Hen)4(H2.

Anhydrous lanthanide MOFs and direct photoluminescent sensing for polyoxometalates in aqueous solution.

New anhydrous lanthanide metal-organic frameworks (MOFs) [Pr(tip)1.5]2n (tip-Pr), [Nd(tip)1.5]2n (tip-Nd), [Eu-(tip)1.