Dimensional Reduction of Metal-Organic Frameworks for Photocatalytic Synthesis of Fused Tetracyclic Heterocycles.

Heterogeneous palladium catalysts with high efficiency, high Pd atom utilization, simplified separation, and recycle have attracted considerable attention in the field of synthetic chemistry. Herein, we reported a zirconium-based two-dimensional metal-organic framework (2D-MOF)-based Pd(II) photocatalyst (Zr-Ir-Pd) by merging the Ir photosensitizers and Pd(II) species into the skeletons of the 2D-MOF for the Pd(II)-catalyzed oxidation reaction. Morphological and structural characterization identified that Zr-Ir-Pd with a specific nanoflower-like structure consists of ultrathin 2D-MOF nanosheets (3.85 nm). Due to its excellent visible-light response and absorption capability, faster transfer and separation of photogenerated carriers, more accessible Pd active sites, and low mass transfer resistance, Zr-Ir-Pd exhibited boosted photocatalytic activity in catalyzing sterically hindered isocyanide insertion of diarylalkynes for the construction of fused tetracyclic heterocycles, with up to 12 times the Pd catalyst turnover number than the existing catalytic systems. In addition, Zr-Ir-Pd inhibited the competitive agglomeration of Pd(0) species and could be reused at least five times, owing to the stabilization of 2D-MOF on the single-site Pd and Ir sites. Finally, a possible mechanism of the photocatalytic synthesis of fused tetracyclic heterocycles catalyzed by Zr-Ir-Pd was proposed.

Imbalance of gut microbiota in gestational diabetes.

AIM: To investigate the differences in gut microbiota composition among nonpregnant women of reproductive age, healthy pregnant women, and gestational diabetes (GD) patients. METHODS: A total of 45 outpatients were enrolled and divided into three groups: nonpregnant women of reproductive age (control group, n = 23), healthy pregnant women (normal group, n = 10), and GD patients (GD group, n = 12). Faecal samples were collected and sequenced using 16S rRNA gene sequencing to analyse the microbial composition. RESULTS: (1) Pregnant patients exhibited an increase in the abundance of Streptococcus (Pnormal = 0.01286, PGD = 0.002965) and Blautia (Pnormal = 0.0003924, PGD = 0.000246) but a decrease in the abundance of Roseburia (Pnormal = 0.0361, PGD = 0.007075), Phascolarctobacterium (Pnormal = 0.0003906, PGD = 0.02499) and Lachnoclostridium (Pnormal = 0.0003906, PGD = 0.03866). (2) Compared with healthy pregnant women, GD patients had an excessive increase in Streptococcus abundance and decrease in Roseburia abundance. The increase in Blautia abundance and the decrease in Phascolarctobacterium and Lachnoclostridium abundance in GD patients were less than those in healthy pregnant women. (3) The abundance of Faecalibacterium prausnitzii decreased significantly in GD patients (PGD = 0.02985) but not in healthy pregnant patients (Pnormal = 0.1643). CONCLUSIONS: Abnormal increases and decreases in the abundances of gut microbiota components, especially Faecalibacterium prausnitzii, were observed in GD patients. TRIAL REGISTRATION: The cross-sectional research was conducted in accordance with the Declaration of Helsinki, and approved by Sir Run Run Shaw Hospital Clinical Trials and Biomedical Ethics Committee. The study has been registered in the Chinese Clinical Trial Registry (ChiCTR1900026164, 24/09/2019, http://www.chictr.org.cn/showproj.aspx?proj=43,455 ).

An efficient ß-nucleating agent with high lattice matching rate for plate-like crystallization of polypropylene random copolymer.

It is challenging to naturally produce large amounts of ß-crystals by directly adding a commercial ß-nucleating agent (ß-NA) into polypropylene random copolymer (PPR) at present. In this work, a novel rare earth ß-NA WBN-28 was directly introduced into PPR to prepare ß-PPR with high ß-crystal conversion. The results of differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) indicated that it is an efficient ß-NA for PPR. The ß-conversion rate (ß-CR) could surpass 85% when the nucleating agent content was mere 0.05%. With the further increment of nucleating agent, the ß-CR increased gradually, which could reach 89.5% and 86.9% respectively calculated by DSC and WAXD when the addition amount was 0.4%. The incredible high ß-CR delayed the ßα-recrystallization in isothermal crystallization. The fusion peak of α-crystal was unobserved below the isothermal crystallization temperature of 122 °C when the addition amount was more than 0.2%. Furthermore, there was a highly ordered structure in WBN-28 with the periodicity of 12.89 Å, which was approximately twice of the unit cell parameter in the c direction of ß-PP, indicating a high lattice matching rate between them. Intuitively observed by polarizing optical microscope (POM), the crystal grains of the blends with ß-NA were more refined and finally crystallized in a plate-like shape. The forming process of the plate-like ß crystalline regions were proposed by scanning electron microscope (SEM) and POM.

The Crystallization Morphology and Conformational Changes of Polypropylene Random Copolymer Induced by a Novel ß-Nucleating Agent.

The crystal morphology and conformational changes during crystallization of a polypropylene random copolymer (PPR) are the basis for understanding its crystallization process. In this work, novel rare-earth ß-nucleating agent WBN-28 was directly added into PPR to induce ß-crystallization. The results of differential scanning calorimetry (DSC) showed that it has an excellent ß-crystal-induced effect. The ß-crystal content could surpass 85%, calculated from wide-angle X-ray diffraction (WAXD) data. The morphology of the ß-crystal and α-crystal was intuitively observed via a polarizing optical microscope (POM). The ß-crystallites were interconnected to naturally develop plate-like crystalline regions possessing a certain size, and the α-crystallites with sufficient thicknesses possessed a cross-hatched phenomenon. The bundle-like supramolecular structure of the ß-crystal induced by WBN-28 was further observed via a scanning electron microscope (SEM). The conformational changes in the crystallization process of PPR were resolved via high-resolution infrared spectroscopy to understand its ß-crystallization in depth. The conformational changes during the crystallization of PPR were found to be different from those of the isotactic polypropylene homopolymer (PPH); they had their own characteristics. This will provide guidance for understanding the ß-crystallization of PPR in depth.

Development and validation of nomograms to predict clinical outcomes of preeclampsia.

Background: Preeclampsia (PE) is one of the most severe pregnancy-related diseases; however, there is still a lack of reliable biomarkers. In this study, we aimed to develop models for predicting early-onset PE, severe PE, and the gestation duration of patients with PE. Methods: Eligible patients with PE were enrolled and divided into a training (n = 253) and a validation (n = 108) cohort. Multivariate logistic and Cox models were used to identify factors associated with early-onset PE, severe PE, and the gestation duration of patients with PE. Based on significant factors, nomograms were developed and evaluated using the area under the curve (AUC) and a calibration curve. Results: In the training cohort, multiple gravidity experience (p = 0.005), lower albumin (ALB; p < 0.001), and higher lactate dehydrogenase (LDH; p < 0.001) were significantly associated with early-onset PE. Abortion history (p = 0.017), prolonged thrombin time (TT; p < 0.001), and higher aspartate aminotransferase (p = 0.002) and LDH (p = 0.003) were significantly associated with severe PE. Abortion history (p < 0.001), gemellary pregnancy (p < 0.001), prolonged TT (p < 0.001), higher mean platelet volume (p = 0.014) and LDH (p < 0.001), and lower ALB (p < 0.001) were significantly associated with shorter gestation duration. Three nomograms were developed and validated to predict the probability of early-onset PE, severe PE, and delivery time for each patient with PE. The AUC showed good predictive performance, and the calibration curve and decision curve analysis demonstrated clinical practicability. Conclusion: Based on the clinical features and peripheral blood laboratory indicators, we identified significant factors and developed models to predict early-onset PE, severe PE, and the gestation duration of pregnant women with PE, which could help clinicians assess the clinical outcomes early and design appropriate strategies for patients.

Highly efficient photosynthesis of hydrogen peroxide by a stable Zr(IV)-based MOF with a diamino-functionalized ligand.

Metal-organic frameworks (MOFs) have emerged as a promising class of materials for solar-driven hydrogen peroxide (H2O2) generation due to their porosity, large surface area and designable molecular building blocks; however, producing H2O2 from oxygen and water without sacrificial agents remains a major challenge. Herein, we have constructed two UiO-67-type MOFs, UiO-67-NH2 and UiO-67-(NH2)2, by a solvothermal method using 2-amino-4,4'-biphenyldicarboxylic acid and 2,2'-diamino-4,4'-biphenyldicarboxylic acid as ligands, respectively. A variety of photochemical measurements have shown that the introduction of diamino groups into UiO-67-(NH2)2 not only enhances its absorption ability for visible light, but also facilitates the separation of photogenerated electron/hole pairs. Consequently, compared to monoamino-functionalized UiO-67-NH2, UiO-67-(NH2)2 exhibits a 5.5 times higher H2O2 production rate in pure water for 1 h. A two-step one-electron oxygen reduction reaction pathway for photocatalytic H2O2 production was suggested based on a series of control experiments and active species trapping tests by electron paramagnetic resonance spectra. This work provides new insights into the regulation of functionalized MOF ligands at the molecular level and a catalytic mechanism towards MOF-based photocatalysts for H2O2 production with high activity.

Derivation and rogue waves of the fractional nonlinear Schrödinger equation for the Rossby waves.

The Cartesian coordinate system is not sufficient to study wave propagation on the coastline or in the sea where the terrain is extremely complicated, so it is necessary to study it in an unconventional coordinate system, fractals. In this paper, from the governing equations of fluid, the fractional nonlinear Schrödinger equation is derived to describe the evolution of Rossby waves in fractal by using multi-scale analysis and perturbation method. Based on the equation, the rogue-wave solution is obtained by the integral preserving transformation to explain some serious threats at sea.

Analysis of factors associated with abnormal thyroid function among medical staff in radiotherapy departments.

Objective: To understand abnormal thyroid function and its associated factors among medical staff in radiotherapy departments. Methods: Data related to medical staff in radiotherapy departments who met the inclusion and exclusion criteria were analyzed from September to December 2022 in Shenyang, Liaoning Province, including basic personal and lifestyle habits, work information, and scores on the Depression Self-Assessment Scale, Perception Stress Scale, and the Generalized Anxiety Scale. Data analysis was performed using the χ2 test and binary logistic regression. Results: Among 484 medical staff in the radiotherapy department, 147 (30.4%) had abnormal thyroid function. Binary logistic regression analysis showed that age, years of work, smoking, occupational exposure, smoking, late-night snacking habits, depression, and stress perception were factors associated with abnormal thyroid function among medical staff in radiotherapy departments; on the other hand, physical exercise was a protective factor. Conclusion: The positive rate of thyroid dysfunction among medical personnel in the radiology department is relatively high. It is necessary to strengthen health education and awareness among relevant practitioners and improve the coverage of occupational disease prevention and control education.

Template-Oriented Polyaniline-Supported Palladium Nanoclusters for Reductive Homocoupling of Furfural Derivatives.

Developing well-defined structures and desired properties for porous organic polymer (POP) supported catalysts by controlling their composition, size, and morphology is of great significance. Herein, we report a preparation of polyaniline (PANI) supported Pd nanoparticles (NPs) with controllable structure and morphology. The protocol involves the introduction of MnO2 with different crystal structures (α, ß, γ, δ, ϵ) serving as both the reaction template and the oxidant. The different forms of MnO2 each convert aniline to a PANI that contains a unique regular distribution of benzene and quinone. This leads to the Pd/PANI catalysts with different charge transfer properties between Pd and PANI, as well as different dispersions of the metal NPs. In this case, the Pd/ϵ-PANI catalyst greatly improves the turnover frequency (TOF; to 88.3 h-1 ), in the reductive coupling of furfural derivatives to potential bio-based plasticizers. Systematic characterizations reveal the unique oxidation state of the support in the Pd/ϵ-PANI catalyst and coordination mode of Pd that drives the formation of highly dispersed Pd nanoclusters. Density functional theory (DFT) calculations show the more electron rich Pd/PANI catalyst has the lower energy barrier in the oxidative addition step, which favors the C-C coupling reaction.

ß-Nucleated Polypropylene: Preparation, Nucleating Efficiency, Composite, and Future Prospects.

The ß-crystals of polypropylene have a metastable crystal form. The formation of ß-crystals can improve the toughness and heat resistance of a material. The introduction of a ß-nucleating agent, over many other methods, is undoubtedly the most reliable method through which to obtain ß-PP. Furthermore, in this study, certain newly developed ß-nucleating agents and their compounds in recent years are listed in detail, including the less-mentioned polymer ß-nucleating agents and their nucleation characteristics. In addition, the various influencing factors of ß-nucleation efficiency, including the polymer matrix and processing conditions, are analyzed in detail and the corresponding improvement measures are summarized. Finally, the composites and synergistic toughening effects are discussed, and three potential future research directions are speculated upon based on previous research.

Knowledge domain and research trends for Gestational Diabetes Mellitus and nutrition from 2011 to 2021: a bibliometric analysis.

Objective: Nutrient management and lifestyle changes are the frontlines of treatment for all pregnant women diagnosed with Gestational Diabetes Mellitus (GDM). This study aimed to identify the global research architecture, trends, and hotpots of GDM and nutrition. Methods: We obtained publications from the sub-databases of Science Citation Index Expanded and Social Science Citation Index sourced from the Web of Science Core Collection database on January 4, 2022, using publication years between 2011 and 2021. CiteSpace software, VOSviewer, and Microsoft Excel 2019 were used to conduct the bibliometric analyses. Results: A growing publication trend was observed for GDM and nutrition, and this field has great potential. More GDM and nutrition research has been conducted in developed countries than developing countries. The top three authors with a high publication frequency, co-citations, and a good h-index were from the United States. There were the four studies of randomized controlled trials (RCTs) or meta-analyses of RCTs, as well as one review in the top five items of cited literature. Keywords were categorized into four clusters based on the keywords visualization. Conclusion: It is important to strengthen the collaboration between nations of different economies to produce more high-quality research on GDM and nutrition. It may be beneficial to further study the etiology, diagnosis, and treatment of GDM based on current results to provide a new perspective on GDM and nutrition.

Tumor-Targeting NIRF/MR Dual-Modal Molecular Imaging Probe for Surgery Navigation.

Multimodality imaging recognized as a promising monitoring strategy can serve the needs of accurate diagnosis and treatment of cancer by providing molecular and anatomic information about tumor sites. However, the probes based on multiple imaging modalities for surgery navigation remain limited due to poor biocompatibility and tumor targeting specificity. Herein, we present a small-molecule near-infrared fluorescence/magnetic resonance (NIRF/MR) imaging probe, Gd-NMC-3, covalently coupled with DCDSTCY and Gd-DOTA via butane diamine, for precise detection and intraoperative visualization. The in vitro and in vivo studies demonstrated that Gd-NMC-3 could be effectively accumulated in tumor sites as a bimodal imaging molecule exhibiting significant fluorescence accumulation and reasonable relaxation property in tumors with low cytotoxicity and good biocompatibility. Furthermore, Gd-NMC-3 was successfully applied to provide real-time visual navigation in LM3 orthotopic and subcutaneous tumor models to guide the resection of tumors. Importantly, no more fluorescence was observed in mice after operation, implying the total removal of tumor tissues. In conclusion, Gd-NMC-3 has great potential to be applied in the clinic based on its high resolution and sensitivity in tumor imaging.

Metal-Organic Framework Surface Functionalization Enhancing the Activity and Stability of Palladium Nanoparticles for Carbon-Halogen Bond Activation.

Supported metal nanocatalyst is one of the efficient tools for organic transformations. However, catalyst deactivation caused by the migration, aggregation, and leaching of active metal species in the reaction process remains challenging. Herein, a metal-organic framework (MOF), MIL-101, was employed to covalently graft the PPh3 ligand on its surface and then supported palladium nanoparticles (Pd NPs), affording Pd/MIL-101-PPh3. A variety of spectral characterizations and DFT calculation reveal that there is an electron-donating effect of the MOF surface PPh3 toward Pd NPs, which markedly boosts the activation of the carbon-halogen bond in aryl halides. Consequently, Pd/MIL-101-PPh3 exhibits excellent activity for the three-component reaction of 2-iodoaniline, CO2, and isocyanide, as well as Suzuki-Miyaura and Heck coupling reactions, far exceeding amino-functionalized Pd/MIL-101-NH2, naked Pd/MIL-101, and other commercial-supported Pd catalysts. Furthermore, Pd/MIL-101-PPh3 can also frustrate the migration, aggregation, and leaching of reactive Pd species in the reaction process due to the molecular fence effect generated by MOF surface functionalization.

Visible light-driven efficient palladium catalyst turnover in oxidative transformations within confined frameworks.

Palladium catalyst turnover by reoxidation of a low-valent Pd species dominates the proceeding of an efficient oxidative transformation, but the state-of-the-art catalysis approaches still have great challenges from the perspectives of high efficiency, atom-economy and environmental-friendliness. Herein, we report a new strategy for addressing Pd reoxidation problem by the fabrication of spatially proximate IrIII photocatalyst and PdII catalyst into metal-organic framework (MOF), affording MOFs based Pd/photoredox catalysts UiO-67-Ir-PdX2 (X = OAc, TFA), which are systematically evaluated using three representative Pd-catalyzed oxidation reactions. Owing to the stabilization of single-site Pd and Ir catalysts by MOFs framework as well as the proximity of them favoring fast electron transfer, UiO-67-Ir-PdX2, under visible light, exhibits up to 25 times of Pd catalyst turnover number than the existing catalysis systems. Mechanism investigations theoretically corroborate the capability of MOFs based Pd/photoredox catalysis to regulate the competitive processes of Pd0 aggregation and reoxidation in Pd-catalyzed oxidation reactions.

LRSCnet: Local Reference Semantic Code learning for breast tumor classification in ultrasound images.

PURPOSE: This study proposed a novel Local Reference Semantic Code (LRSC) network for automatic breast ultrasound image classification with few labeled data. METHODS: In the proposed network, the local structure extractor is firstly developed to learn the local reference which describes common local characteristics of tumors. After that, a two-stage hierarchical encoder is developed to encode the local structures of lesion into the high-level semantic code. Based on the learned semantic code, the self-matching layer is proposed for the final classification. RESULTS: In the experiment, the proposed method outperformed traditional classification methods and AUC (Area Under Curve), ACC (Accuracy), Sen (Sensitivity), Spec (Specificity), PPV (Positive Predictive Values), and NPV(Negative Predictive Values) are 0.9540, 0.9776, 0.9629, 0.93, 0.9774 and 0.9090, respectively. In addition, the proposed method also improved matching speed. CONCLUSIONS: LRSC-network is proposed for breast ultrasound images classification with few labeled data. In the proposed network, a two-stage hierarchical encoder is introduced to learn high-level semantic code. The learned code contains more effective high-level classification information and is simpler, leading to better generalization ability.

Population-Wide Duchenne Muscular Dystrophy Carrier Detection by CK and Molecular Testing.

Carrier screening of Duchenne muscular dystrophy (DMD) has not been widely evaluated. To identify definite DMD female carriers prior to or in early pregnancy, we studied a large population of reproductive age females and provided informed reproductive options to DMD carriers. 37268 females were recruited from the Hangzhou Family Planning Publicity and Technology Guidance Station/Hangzhou Health Service Center for Children and Women, Hangzhou, China, between October 10, 2017, and December 16, 2018. CK activity was measured with follow-up serum DMD genetic testing in subjects with hyperCKemia, defined as CK > 200 U/L. The calculated upper reference limit (97.5th percentile) of serum creatine kinase (CK) for females aged 20-50 years in this study was near the reference limit recommended by the manufacturer (200 U/L), above which was defined as hyperCKemia. 427 females (1.2%) harbored initially elevated CK, among which 281 females (response rate of 65.8%) accepted CK retesting. DMD genetic testing was conducted on 62 subjects with sustained serum CK > 200 U/L and 16 females with a family history of DMD. Finally, 6 subjects were confirmed to be DMD definite carriers. The estimated DMD female carrier rate in this study was 1 : 4088 (adjusting for response rate), an underestimated rate, since only 50% to 70% of DMD female carriers manifest elevated serum CK, and carriers in this study may have been missed due to lack of follow-up or inability to detect all DMD pathogenic variants by current genetic testing.

Macrocyclization of 3-triflyloxybenzynes with tetrahydrofuran via an anionic thia-Fries rearrangement.

A novel and uncommon macrocyclization reaction between 3-triflyloxybenzynes and tetrahydrofuran has been developed for the first time, providing a direct method for the synthesis of a range of functionalized 19-membered polyether macrocycles in moderate to good yields. The process was proposed to proceed through an anionic thia-Fris rearrangement under transition metal-free conditions, leading to the formation of four new C-O bonds and one new C-S bond in a single step.

Palladium Catalysis for Aerobic Oxidation Systems Using Robust Metal-Organic Framework.

Described here is a new and viable approach to achieve Pd catalysis for aerobic oxidation systems (AOSs) by circumventing problems associated with both the oxidation and the catalysis through an all-in-one strategy, employing a robust metal-organic framework (MOF). The rational assembly of a PdII catalyst, phenanthroline ligand, and CuII species (electron-transfer mediator) into a MOF facilitates the fast regeneration of the PdII active species, through an enhanced electron transfer from in situ generated Pd0 to CuII , and then CuI to O2 , trapped in the framework, thus leading to a 10 times higher turnover number than that of the homogeneous counterpart for Pd-catalyzed desulfitative oxidative coupling reactions. Moreover, the MOF catalyst can be reused five times without losing activity. This work provides the first exploration of using a MOF as a promising platform for the development of Pd catalysis for AOSs with high efficiency, low catalyst loading, and reusability.

Enhanced Activity and Enantioselectivity of Henry Reaction by the Postsynthetic Reduction Modification for a Chiral Cu(salen)-Based Metal-Organic Framework.

Metal-organic frameworks (MOFs) imbedded privileged molecular catalysts are of particular interest due to their higher catalytic activities derived from the MOFs pore/channel confinement effect, improved lifetime through eliminating intermolecular deactivation pathway, and the recyclability based on their heterogeneity. In this work, a 3D chiral metallosalen-based MOF [Cd2(Cu(salen))(DMF)3]·DMF·3H2O (1) with a 1D open channel was synthesized and characterized by single-crystal X-ray diffraction and other physicochemical methods. Upon postsynthetic reduction modification with NaBH4, the conversion from imino to amino group on salen cores of 1 generates the reduction product 2 with a more flexible chiral group and more alkaline backbone, meanwhile still maintaining the original porous framework. 2 can be used as an efficient heterogeneous catalyst for the asymmetric Henry reaction with broad substrate applicability and exhibits higher activity and enantioselectivity (ee up to 98%) compared with the unreduced 1. Note that 2 can accelerate the Henry reaction of pyridine-2-carboxaldehyde possessing a potential coordination atom with excellent ee value; however, the homogeneous counterpart does not. In addition, the bulky aldehydes show a decrease in activity but almost the same enantioselectivity with an increase in the molecular size of substrates as a result of the chiral confinement effect of 2, indicating the size-dependent selectivity. To the best of our knowledge, this is the highest enantioselectivity for asymmetric Henry reaction catalyzed by MOF-based catalysts.