Flexible Hydrazone-Linked Metal-Covalent Organic Frameworks with Copper Clusters for Efficient Electrocatalytic Oxygen Evolution Reaction.

Despite the challenges associated with the synthesis of flexible metal-covalent organic frameworks (MCOFs), these offer the unique advantage of maximizing the atomic utilization efficiency. However, the construction of flexible MCOFs with flexible building units or linkages has rarely been reported. In this study, novel flexible MCOFs are constructed using flexible building blocks and copper clusters with hydrazone linkages. The heterometallic frameworks (Cu, Co) are prepared through the hydrazone linkage coordination method and evaluated as catalysts for the oxygen evolution reaction (OER). Owing to the spatial separation and functional cooperation of the heterometallic MCOF catalysts, the as-synthesized MCOFs exhibited outstanding catalytic activities with an overpotential of 268.8 mV at 10 mA cm-2 for the OER in 1 M KOH, which is superior to those of the reported covalent organic frameworks (COFs)-based OER catalysts. Theoretical calculations further elucidated the synergistic effect of heterometallic active sites within the linkages and frameworks, contributing to the enhanced OER activity. This study thus introduces a novel approach to the fundamental design of flexible MCOF catalysts for the OER, emphasizing their enhanced atomic utilization efficiency.

Clinical features of plastic bronchitis in children after congenital heart surgery.

BACKGROUND: Plastic bronchitis (PB) can occur in patients who have undergone congenital heart surgery (CHS). This study aimed to investigate the clinical features of PB in children after CHS. METHODS: We conducted a retrospective cohort study using the electronic medical record system. The study population consisted of children diagnosed with PB after bronchoscopy in the cardiac intensive care unit after CHS from May 2016 to October 2021. RESULTS: A total of 68 children after CHS were finally included in the study (32 in the airway abnormalities group and 36 in the right ventricular dysfunction group). All children were examined and treated with fiberoptic bronchoscopy. Pathogens were detected in the bronchoalveolar lavage fluid of 41 children, including 32 cases in the airway abnormalities group and 9 cases in the right ventricular dysfunction group. All patients were treated with antibiotics, corticosteroids (intravenous or oral), and budesonide inhalation suspension. Children with right ventricular dysfunction underwent pharmacological treatment such as reducing pulmonary arterial pressure. Clinical symptoms improved in 64 children, two of whom were treated with veno-arterial extracorporeal membrane oxygenation (ECMO) due to recurrent PB and disease progression. CONCLUSIONS: Children with airway abnormalities or right ventricular dysfunction after CHS should be alerted to the development of PB. Pharmacological treatment such as anti-infection, corticosteroids, or improvement of right ventricular function is the basis of PB treatment, while fiberoptic bronchoscopy is an essential tool for the diagnosis and treatment of PB. ECMO assistance is a vital salvage treatment for recurrent critically ill PB patients.

Novel missense mutation c.797T>C (p.Met266Thr) gives rise to the rare B(A) phenotype in a Chinese family.

BACKGROUND AND OBJECTIVES: B(A) phenotype is usually formed by nucleotide mutations in the ABO*B.01 allele, with their products exhibiting glycosyltransferases (GTs) A and B overlapping functionality. We herein report a B(A) allele found in a Chinese family. MATERIALS AND METHODS: The entire ABO genes of the probands, including flanking regulatory regions, were sequenced through PacBio third-generation long-read single-molecule real-time sequencing. 3D molecular models of the wild-type and mutant GTB were generated using the DynaMut web server. The effect of the mutation on the enzyme function was predicted by PROVEAN and PolyPhen2. The predictions of stability changes were performed using DynaMut and SNPeffect. RESULTS: Based on serological and sequencing features, we concluded the two probands as possible cases of the B(A) phenotype. Crystallization analysis showed that Thr266 substitution does not disrupt the hydrogen bonds. However, some changes in interatomic contacts, such as loss of ionic interactions and hydrophobic contacts, and addition of weak hydrogen bonds, may have affected protein stability to some extent. This mutation was predicted to have a benign effect on enzyme function and slightly reduce protein stability. CONCLUSION: The probands had the same novel B(A) allele with a c.797T>C (p.Met266Thr) mutation on the ABO*B.01 backbone.

Fabrication of attapulgite-based dual responsive composite hydrogel and its efficient adsorption for methyl violet.

In this work, attapulgite (ATP)-based dual sensitive poly (N-isopropylacrylamide-co-acrylic acid) composite hydrogel, P(NIPAM-co-AA)/ATP, was prepared by free radical polymerization. The prepared composite hydrogel was characterized via methods of scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), zeta potential analysis and Brunauer, Emmett, and Teller (BET) etc. The composite hydrogel showed pH and temperature sensitive behaviour, with lower critical solution temperature (LCST) of 35°C and highest swelling occurred at pH 8.0. The adsorption of methyl violet (MV) can be controlled by the hydrogel responsiveness, and 95.78% of MV can be removed at pH 8.0 and 35°C. The addition of a small amount of ATP (3 Wt%) can improve the swelling ratio and adsorption capacity. Kinetic analysis demonstrated that the experimental data were best fitted to the pseudo-second order model. Isotherm analysis showed that the equilibrium data followed Langmuir model with the adsorption capacity of 168.35 mg g-1. In addition, the composite hydrogel has high adsorption selectivity for cationic dyes, and MV-loaded hydrogel is easy to regenerate, which can be used for successive adsorption cycles. These results demonstrate that the composite hydrogel has potential application in dye wastewater treatment.

Phylogeny, biogeography, and character evolution in the fern family Hypodematiaceae.

The Old World fern genera Hypodematium and Leucostegia had long been placed in the families Dryopteridaceae and Davalliaceae, respectively, before the advent of molecular phylogenetics. Recent molecular studies confirmed the recognition of the family Hypodematiaceae composed of these two genera, but the relationships within each of these two genera have been unclear. In the present study we performed phylogenetic analyses (MP, ML, BI) based on DNA data from six plastid markers (atpB, atpB-rbcL, matK, rbcL, rps4 & rps4-trnS, and trnL & trnL-F) of 165 accessions representing 31 species in two genera of Hypodematiaceae as the ingroup and 26 accessions representing Cystopteridaceae, Didymochlaenaceae, Dryopteridaceae, Davalliaceae, Oleandraceae, and Woodsiaceae as the outgroups. Our analyses supported the monophyly of the currently defined Hypodematiaceae only including Hypodematium and Leucostegia and found that the family to be sister to the remaining eupolypods I. Our data resolved three taxa of Leucostegia into two clades. In Hypodematium, 28 taxa are resolved into seven strongly supported clades or single-accession clades. The evolution of important morphological characters are inferred in the phylogenetic context. Our dated phylogeny suggested a latest Jurassic-earliest Cretaceous origin of the family and Upper Cretaceous origin of two genera, with Hypodematiaceae originated from East Asia; extant lineages of Hypodematium originated from East Asia and subsequently into Africa, the Indian region, the Madagascar region, and Southeast Asia; and Leucostegia originated from East Asia and/or Southeast Asia.

Differential expression and bioinformatics analysis of epsin3 in colorectal cancer / 解剖学报

Objective To investigate the expression and significance of the adaptor protein epsin 3 (EPN3) in colorectal cancer in order to provide reference for further stud)' of EPN3. Methods GEPIA and GEDS were used to analyze the expression of EPN3 in colorectal cancer tissues and cells. SMART and cBioPortal databases were used to analyze the relationship between EPN3 gene metfrylation and cop)' number variation and its expression level. Metascape was used to complete analysis of gene ontology functional annotation and related pathways of EPN3 related genes and BioPlex was applied to construct a protein network in HCT116 cell. Thirteen pairs of colorectal cancer adjacent tissue and cancer tissue specimens were collected, and EPN3 mRNA expression were detected by Real-time PCR. The effect of abilities of cell proliferation, clone formation and migration via silencing EPN3 in HCT116 and HT29 were observed. Results GEPIA, GEDS, SMART and cBioPortal analyses showed that EPN3 was highly expressed in colorectal tumor tissues (P<0. 01), and was related to methylation and copy number variation. The enrichment result of EPN3 related genes showed that it was mainly related to cell adhesion. And a protein interaction network constructed by CCDC130, TNFAIP1, PHGDH, EPN2, etc. was related to protein ubiquitination. Real-time PCR result showed that EPN3 was highly expressed in tumor tissues (P<0. 05). Silencing EPN3 inhibited the proliferation, clony formation and migration abilities of HCT116 and HT29 cells. Conclusion EPN3 is highly expressed in colorectal cancer tissues and is related to cell adhesion and protein ubiquitination. Down-regulated EPN3 can inhibit abilities of proliferation, clony formation and migration of HCT116 and HT29 cells, and this could provide a reference for further research on EPN3.

Organic Thermometers Based on Aggregation of Difluoroboron ß-Diketonate Chromophores.

We report several novel thermometers resulting from the temperature-induced aggregation of difluoroboron ß-diketonate chromophores. These thermometers exhibit a much wider temperature-dependent fluorescence emission from 445 to 592 nm along with the color change from blue to red in a dilute chloroform solution. Spectroscopy measurements and theoretical calculations confirm that the thermochromic luminescence originates from the reversible change in the noncovalent intermolecular interactions and the abrupt volume shrinkage of the solvent at its melting point. The present work provides a new strategy for rationally designing high-performance thermometers having a wide emission property.

[Advances in the clinical research on acupuncture in treatment of respiratory diseases].

This article reviews the clinical studies on acupuncture in the treatment of asthma, chronic bronchitis, and acute exacerbation and stable phase of chronic obstructive pulmonary disease in China over the past 10 years, and the results suggest that acupuncture has a good clinical effect. At present, there are still several problems in related clinical studies, including lacking of standard operation procedure for acupuncture, unreasonable design of control group, and low quality of clinical research. Therefore, in the future, top-level design should be standardized and large-sample multicenter clinical studies should be conducted to provide stronger evidence of evidence-based medicine for acupuncture in the treatment of respiratory diseases.

Time-Dependent Afterglow Color in a Single-Component Organic Molecular Crystal.

An organic crystal of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (pCBP) exhibits time-dependent afterglow color from blue to orange over 1 s. Both experimental and computational data confirm that the color evolution results from well-separated, long-persistent thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP) with different but comparable decay rates. TADF is enabled by a small S1 -T1 energy gap of 0.7 kcal mol-1 . The good separation of TADF and RTP is due to a 11.8 kcal mol-1 difference in the S0 energies of the S1 and T1 structures, indicating that apart from the excited-state properties, tuning the ground state is also important for luminescence properties. This afterglow color evolution of pCBP allows its applications in anticounterfeiting and data encryption with high security levels.

Identification of ß-Sitosterol as in Vitro Anti-Inflammatory Constituent in Moringa oleifera.

ß-Sitosterol is a well known phytosterol in plants, but owing to its poor solubility in typical media, determining its cellular mechanisms has been proven to be difficult. In this study, we investigated the anti-inflammatory activity of ß-sitosterol (BSS) isolated from Moringa oleifera in two cell lines. Over a dose range of 7.5 to 30 µM, BSS dispersed well in the medium as nanoparticles with diameters of 50 ± 5 nm and suppressed the secretion of inflammatory factors from keratinocytes and macrophages induced by PGN, TNF-α, or LPS, such as TNF-α, IL-1ß, IL-6, IL-8, and ROS, separately. In addition, BSS significantly reduced the expression of NLRP3, a key component of NLRP3 inflammasomes, and inhibited the activation of caspase-1. There was partial inhibition of NF-κB in macrophages. This is the first study to report an increase in the solubility of nearly water-insoluble phytosterols via the formation of nanoparticles and to delineate the formulation's capacity to inhibit the signal transduction pathways of inflammation in macrophages.

Mechanism of the Visible-Light-Mediated Copper-Catalyzed Coupling Reaction of Phenols and Alkynes.

A recent experimental study reported a visible-light-mediated aerobic oxidative coupling reaction of phenol with alkynes that produces hydroxyl-functionalized aryl ketones using inexpensive CuCl as catalyst under mild conditions. Here we apply the complete active space self-consistent field (CASSCF) method and multistate second-order perturbation (MS-CASPT2) theory in combination with density functional theory (DFT) to systematically explore the entire photocatalytic reaction between phenol and phenylacetylene in acetonitrile solution in the presence of molecular oxygen and CuCl. Our main findings are as follows: (1) The visible-light-driven conversion of phenylacetylene to PhCCCu(I) occurs thermally because of efficient excited-state deactivation to the S0 state. (2) The single electron transfer from PhCCCu(I) to molecular oxygen that leads to the PhCCCu(II) cation takes place in the T1 state after an efficient S1 → T1 intersystem crossing. (3) During the initial oxidation of phenol, molecular oxygen prefers to attack the para position of the phenol radical intermediate to produce 1,4-benzoquinone, which further reacts with PhCCCu(II) to generate para-hydroxyl-substituted aryl ketones; this is the origin of the experimentally observed regioselectivity. (4) The C≡C bond of the phenylacetylene moiety is not activated by the triplet-state single electron transfer from PhCCCu(I) to molecular oxygen but is cleaved at a later stage, in the [2+2] cycloaddition between PhCCCu(II) and 1,4-benzoquinone. (5) The substrate phenol plays an active role in several hydrogen transfer and decarboxylation reactions; the barriers to these phenol-assisted reactions are lower than those for the corresponding direct or water-assisted reactions, which explains the experimental finding that adding water does not enhance the photocatalytic reaction yield. In summary, while supporting the general features of the experimentally proposed mechanism, our computational study provides detailed mechanistic insights that should be useful for understanding and further improving visible-light-induced copper-catalyzed coupling reactions.

Photophysics of a UV-B Filter 4-Methylbenzylidene Camphor: Intersystem Crossing Plays an Important Role.

4-Methylbenzylidene camphor (4MBC) is a frequently used ultraviolet (UV) filter in commercial sunscreens, which is experimentally found to undergo efficient intersystem crossing to triplet manifolds followed by predominant radiationless decay to the ground state. However, its photophysical mechanism is unclear. Herein, we have employed combined CASPT2 and CASSCF methods to study the spectroscopic properties, geometric and electronic structures, conical intersections and crossing points, and excited-state deactivation channels of 4MBC. We have found that the V(1 ππ*) state is populated with large probability in the Franck-Condon region. Starting from this state, there are two efficient nonradiative relaxation processes to populate the 3 ππ* state. In the first one, the V(1 ππ*) state decays to the V'(1 ππ*) state. The resultant V'(1 ππ*) state further jumps to the 1 nπ* state by internal conversion at the 1 ππ*/1 nπ* conical intersection. Then, the 1 nπ* state hops to the 3 ππ* state through an efficient 1 nπ*→3 ππ* intersystem crossing process. In the second one, the V(1 ππ*) state can diabatically relax along the photoisomerization reaction coordinate. In this process, a 1 ππ*/3 nπ* crossing point helps the 1 ππ* system decay to the 3 nπ* state, which further decays to the 3 ππ* state through internal conversion at the 3 nπ*/3 ππ* conical intersection. Once the 3 ππ* state is formed, a nearly barrierless relaxation path drives the 3 ππ* system to hop to the S0 state via the 3 ππ*/S0 crossing point. Our current work not only rationalizes recent experimental observations but also enriches our photophysical knowledge of UV filters.

A plastid phylogeny and character evolution of the Old World fern genus Pyrrosia (Polypodiaceae) with the description of a new genus: Hovenkampia (Polypodiaceae).

The Old World fern genus Pyrrosia (Polypodiaceae) offers a rare system in ferns to study morphological evolution because almost all species of this genus are well studied for their morphology, anatomy, and spore features, and various hypotheses have been proposed in terms of the phylogeny and evolution in this genus. However, the molecular phylogeny of the genus lags behind. The monophyly of the genus has been uncertain and a modern phylogenetic study of the genus based on molecular data has been lacking. In the present study, DNA sequences of five plastid markers of 220 accessions of Polypodiaceae representing two species of Drymoglossum, 14 species of Platycerium, 50 species of Pyrrosia, and the only species of Saxiglossum (subfamily Platycerioideae), and 12 species of other Polypodiaceae representing the remaining four subfamilies are used to infer a phylogeny of the genus. Major results and conclusions of this study include: (1) Pyrrosia as currently circumscribed is paraphyletic in relation to Platycerium and can be divided into two genera: Pyrrosia s.s. and Hovenkampia (gen. nov.), with Hovenkampia and Platycerium forming a strongly supported clade sister to Pyrrosia s.s.; (2) Subfamily Platycerioideae should contain three genera only, Hovenkampia, Platycerium, and Pyrrosia s.s.; (3) Based on the molecular phylogeny, macromorphology, anatomical features, and spore morphology, four major clades in the genus are identified and three of the four are further resolved into four, four, and six subclades, respectively; (4) Three species, P. angustissima, P. foveolata, and P. mannii, not assigned to any groups by Hovenkamp (1986) because of their unusual morphology, each form monospecific clades; (5) Drymoglossum is not monophyletic and those species previously assigned to this genus are resolved in two different subclades; (6) Saxiglossum is resolved as the first lineage in the Niphopsis clade; and (7) The evolution of ten major morphological characters in the subfamily is inferred based on the phylogeny and various morphological synapomorphies for various clades and subclades are identified.

Combination of three-gene immunohistochemical panel and magnetic resonance imaging-detected extramural vascular invasion to assess prognosis in non-advanced rectal cancer patients.

AIM: To identify a small, clinically applicable immunohistochemistry (IHC) panel that could be combined with magnetic resonance imaging (MRI)-detected extramural vascular invasion (EMVI) for assessment of prognosis concerning the non-advanced rectal cancer patients prior to operation. METHODS: About 329 patients with pathologically confirmed rectal carcinoma (RC) were screened in this research, all of whom had been examined via an MRI and were treatment-naïve from July 2011 to July 2014. The candidate proteins that were reported to be altered by RC were examined in tissues by IHC. All chosen samples were adopted from the fundamental cores of histopathologically confirmed carcinomas during the initial surgeries. RESULTS: Of the three proteins that were tested, c-MYC, PCNA and TIMP1 were detected with relatively significant expression in tumors, 35.9%, 23.7% and 58.7% respectively. The expression of the three proteins were closely connected with prognosis (P = 0.032, 0.003, 0.021). The patients could be classified into different outcome groups according to an IHC panel (P < 0.01) via these three proteins. Taking into consideration known survival covariates, especially EMVI, the IHC panel served as an independent prognostic factor. The EMVI combined with the IHC panel could categorize patients into different prognostic groups with distinction (P < 0.01). CONCLUSION: These studies argue that this three-protein panel of c-MYC, PCNA, coupled with TIMP1 combined with MRI-detected EMVI could offer extra prognostic details for preoperative treatment of RC.

Photodynamics of oxybenzone sunscreen: Nonadiabatic dynamics simulations.

Herein we have used combined static electronic structure calculations and "on-the-fly" global-switching trajectory surface-hopping dynamics simulations to explore the photochemical mechanism of oxybenzone sunscreen. We have first employed the multi-configurational CASSCF method to optimize minima, conical intersections, and minimum-energy reaction paths related to excited-state intramolecular proton transfer (ESIPT) and excited-state decays in the (1)ππ(∗), (1)nπ(∗), and S0 states (energies are refined at the higher MS-CASPT2 level). According to the mapped potential energy profiles, we have identified two ultrafast excited-state deactivation pathways for the initially populated (1)ππ(∗) system. The first is the diabatic ESIPT process along the (1)ππ(∗) potential energy profile. The generated (1)ππ(∗) keto species then decays to the S0 state via the keto (1)ππ(∗)/gs conical intersection. The second is internal conversion to the dark (1)nπ(∗) state near the (1)ππ(∗) /(1)nπ(∗) crossing point in the course of the diabatic (1)ππ(∗) ESIPT process. Our following dynamics simulations have shown that the ESIPT and (1)ππ(∗) → S0 internal conversion times are 104 and 286 fs, respectively. Finally, our present work demonstrates that in addition to the ESIPT process and the (1)ππ(∗) → S0 internal conversion in the keto region, the (1)ππ(∗) → (1)nπ(∗) internal conversion in the enol region plays as well an important role for the excited-state relaxation dynamics of oxybenzone.

Mechanistic Photochemistry of Methyl-4-hydroxycinnamate Chromophore and Its One-Water Complexes: Insights from MS-CASPT2 Study.

Herein we computationally studied the excited-state properties and decay dynamics of methyl-4-hydroxycinnamate (OMpCA) in the lowest three electronic states, that is, (1)ππ*, (1)nπ*, and S0 using combined MS-CASPT2 and CASSCF electronic structure methods. We found that one-water hydration can significantly stabilize and destabilize the vertical excitation energies of the spectroscopically bright (1)ππ* and dark (1)nπ* excited singlet states, respectively; in contrast, it has a much smaller effect on the (1)ππ* and (1)nπ* adiabatic excitation energies. Mechanistically, we located two (1)ππ* excited-state relaxation channels. One is the internal conversion to the dark (1)nπ* state, and the other is the (1)ππ* photoisomerization that eventually leads the system to a (1)ππ*/S0 conical intersection region, near which the radiationless internal conversion to the S0 state occurs. These two (1)ππ* relaxation pathways play distinct roles in OMpCA and its two one-water complexes (OMpCA-W1 and OMpCA-W2). In OMpCA, the predominant (1)ππ* decay route is the state-switching to the dark (1)nπ* state, while in one-water complexes, the importance of the (1)ππ* photoisomerization is significantly enhanced because the internal conversion to the (1)nπ* state is heavily suppressed due to the one-water hydration.