ABSTRACT
The maintenance of normal pregnancy requires appropriate maturation and transformation of various cells, which constitute the microenvironmental regulatory network at the maternal-fetal interface. Interestingly, changes in the cellular components of the maternal-fetal immune microenvironment and the regulation of epigenetic modifications of the genome have attracted much attention. With the development of epigenetics (DNA and RNA methylation, histone modifications, etc.), new insights have been gained into early embryonic developmental stages (e.g., maternal-to-zygotic transition, MZT). Understanding the various appropriate modes of transcriptional regulation required for the early embryonic developmental process from the perspective of epigenetic modifications will help us to provide new targets and insights into the pathogenesis of embryonic failure during further natural fertilization. This review focuses on the loci of action of epigenetic modifications from the perspectives of female germ cell development and embryo development to provide new insights for personalized diagnosis and treatment of abortion.
ABSTRACT
Achieving electronic/steric control and realizing selectivity regulation in nanocatalysis remains a formidable challenge, as the dynamic nature of metal-ligand interfaces, including dissolution (metal leaching) and structural reconstruction, poses significant obstacles. Herein, we disclose carboranyls (CBs) as unprecedented carbon-bonded functional ligands (Eads.CB-Au(111) = -2.90 eV) for gold nanoparticles (AuNPs), showcasing their exceptional stabilization capability that is attributed by strong Au-C bonds combined with B-Hâ¯Au interactions. The synthesized CB@AuNPs exhibit core(Aun)-satellite(CB2Au-) structure, showing high stability towards multiple stimuli (110oC, pH = 1-12, thiol etchants). In addition, different from conventional AuNP catalysts such as triphenylphosphine (PPh3) stabilized AuNPs, dissolution of catalytically active gold species was suppressed in CB@AuNPs under the reaction conditions. Leveraging these distinct features, CB@AuNPs realized outstanding p:o selectivities in aromatic bromination. Unbiased arenes including chlorobenzene (up to > 30:1), bromobenzene (15:1) and phenyl acrylate were examined using CB@AuNPs as catalysts to afford highly-selective p-products. Both carboranyl ligands and carboranyl derived counterions are crucial for such regioselective transformation. This work has provided valuable insights for AuNPs in realizing diverse regioselective transformations.
ABSTRACT
Selective catalytic oxidation of the hazardous DMF exhaust gas presents a significant challenge in balancing oxidation activity and products selectivity (CO, NOx, N2, etc.). It is found that Cu/H-MOR demonstrates superior performance for DMF oxidation compared to CuO on other supports (γ-Al2O3, HY, ZSM-5) in terms of product selectivity and stability. The geometric and electronic structures of CuO active sites in Cu/H-MOR have been regulated by CeO2 promoter, leading to an increase in the ratio of active CuO (highly dispersed CuO and Cu+ specie). As a result, the oxidation activity and stability of the Cu/H-MOR catalyst were enhanced for DMF selective catalytic oxidation. However, excessive CuO or CeO2 content led to decreased N2 selectivity due to over-high oxidation activity. It is also revealed that Ce3+ species, active CuO species, and surface acid sites play a critical role in internal selective catalytic reduction reaction during DMF oxidation. The 10Cu-Ce/H-MOR (1/4) catalyst exhibited both high oxidation activity and internal selective catalytic reduction activity due to its abundance of active CuO specie as well as Ce3+ species and surface acid sites. Consequently, the 10Cu-Ce/H-MOR (1/4) catalyst demonstrated the widest temperature window for DMF oxidation with high N2 selectivity. These findings emphasize the importance of surface active sites modification for DMF selective catalytic oxidation.
ABSTRACT
Natural organisms have evolved multi-scale wet gas sensing interfaces with optimized mass transport pathways in biological fluid environments, which sheds light on developing artificial counterparts with improved wet gas sensing abilities and practical applications. Herein, we highlighted current advances in wet gas sensing taking advantage of optimized mass transport pathways endowed by multi-scale interface design. Common moisture resistance (e.g., employing moisture resistant sensing materials, post-modifying moisture resistant coatings, physical heating for moisture resistance, and self-removing hydroxyl groups) and moisture absorption (e.g., employing moisture absorption sensing materials and post-modifying moisture absorption coatings) strategies for wet gas sensing were discussed. Then, the design principles of bioinspired multi-scale wet gas sensing interfaces were provided, including macro-level condensation mediation, micro/nano-level transport pathway adjustment and molecular level moisture-proof design. Finally, perspectives on constructing bioinspired multi-scale wet gas sensing interfaces were presented, which will not only deepen our understanding of the underlying principles, but also promote practical applications.
ABSTRACT
RATIONALE: Puerperal sepsis is a life-threatening condition caused by infection that can rapidly progress to multisystem infection and toxin-mediated shock. Symmetrical peripheral gangrene is defined as symmetrical distal ischemic damage in two or more sites in the absence of major vascular occlusive disease. The syndrome is devastating and rare. In this study, we introduce a case of puerperal septicemia complicated by symmetrical peripheral gangrene. PATIENT CONCERNS: A 23-year-old woman delivered a live female infant vaginally after cervical balloon dilatation at 39 weeks of gestation. Persistent hyperthermia developed on the first postpartum day. After experiencing ventricular fibrillation, acute liver failure, and acute pulmonary edema, she developed blackened extremities on the 5th postpartum day. DIAGNOSES: Puerperal septicemia complicated by symmetrical peripheral gangrene. INTERVENTIONS: Upon transfer to our hospital, the patient was enrolled in the intensive care unit and underwent anti-infective and amputation surgery. OUTCOMES: After the surgery, the patient recovered well and was successfully discharged from the hospital. LESSONS: Early detection and timely treatment is the best way to reduce the mortality and sequelae of puerperal sepsis. Physicians should be alert to the possibility of comorbid symmetrical peripheral gangrene when sepsis patients present with hepatic impairment.
Subject(s)
Gangrene , Shock, Septic , Humans , Female , Young Adult , Adult , Gangrene/etiology , Gangrene/surgery , Shock, Septic/complications , Shock, Septic/therapy , Extremities/surgery , Amputation, Surgical , Postpartum PeriodABSTRACT
Recurrent spontaneous abortion (RSA) has various causes, including chromosomal abnormalities, prethrombotic state, and abnormal uterine anatomical factors. However, the pathogenesis of RSA is still unclear. Surprisingly, non-coding RNA can stably express at the maternal-fetal interface and regulate immune cells' proliferation, apoptosis, invasion, metastasis, and angiogenesis. Accumulating evidence suggests that the competing endogenous RNA (ceRNA) regulatory network between non-coding RNAs complicates RSA's pathological process and maybe a new starting point for exploring RSA. In this review, we mainly discuss the regulatory network and potential significance of non-coding RNA in the immune microenvironment of RSA patients. In addition, the cellular interactions of non-coding RNA transported through vesicles were introduced from aspects of trophoblast function and immune regulation. Finally, we analyze previous studies and further discuss that the stable expression of non-coding RNA may be used as a biomarker of some disease states and a prediction target of RSA.
Subject(s)
Abortion, Habitual , Abortion, Spontaneous , Pregnancy , Female , Humans , Uterus/metabolism , Trophoblasts/metabolism , Chromosome Aberrations , RNA, Untranslated/genetics , RNA, Untranslated/metabolismABSTRACT
Advances in new ligands in the last decade facilitated in-depth studies on the property-relationship of gold nanoclusters and promoted the rational synthesis and related applications of such materials. Currently, more and more new ligands are being explored; thus, the ligand library of AuNCs is being expanded fast, which also enables investigation of ligand effects of AuNCs via direct comparison of different ligating shell with the identical gold core. It is now widely accepted that ligands influence the properties of AuNCs enormously including stability, catalysis, photoluminescence among others. These studies inspired ligand engineering of AuNCs. One of the goals for ligand engineering is to develop ligated AuNC catalysts in which the ligands are able to exert big-enough influence on electronic and steric control over catalysis as in a transition-metal or an enzyme system. Although increasing attention is paid to the further expansion of ligand library, the investigation of design principles and strategies regarding ligands are still in their infant stage. This review summarizes the ligands for AuNC synthesis, the ligand effects on stability and catalysis, and recently developed strategies in promoting AuNC catalytic performance via ligand manipulation.
ABSTRACT
Recurrent spontaneous abortion (RSA) has various causes, including chromosomal abnormalities, a prethrombotic state, and abnormal uterine anatomical factors. However, in about 50% of cases, the cause remains unknown and is referred to as unexplained recurrent spontaneous abortion (URSA). The fetus is protected from rejection by the maternal system, acting as an allogeneic gene, and immune tolerance serves as a crucial mechanism. The Th17/Treg cell paradigm's emergence as a new subpopulation of CD4+ T cells, interacting with one another, plays an essential role in the immune microenvironment and the body's defense system. This Th17/Treg cell model helps to explain the pathology of recurrent miscarriage that could not be accounted for by the original immune mechanism based on the Th1/Th2 model. Furthermore, the plasticity of Th17 and Treg cells holds innovative significance in autoimmunity and abortion. This paper reviews the role of Th17/Treg cellular immune response in the maintaining normal pregnancy and understanding unexplained recurrent spontaneous abortion.
ABSTRACT
The capping reagent plays an essential role in the functional properties of gold nanoparticles (AuNPs). Multiple stimuli-responsive materials are generated via diverse surface modification. The ability of the organic ligand shell on a gold surface to create a porous shell capable of binding small molecules is demonstrated as an approach to detect molecules, such as methane, that would be otherwise difficult to sense. Thiols are the most studied capping ligands of AuNPs used in chemiresistors. Phosphine capping groups are usually seen as stabilizers in synthesis and catalysis. However, by virtue of the pyramidal shape of triarylphosphines, they are natural candidates to create intrinsic voids within the ligand shell of AuNPs. In this work, surface-functionalized (capped) AuNPs with chelating phosphine ligands are synthesized via two synthetic routes, enabling chemiresistive methane gas detection at sub-100 ppm levels. These AuNPs are compared to thiol-capped AuNPs, and studies were undertaken to evaluate structure-property relationships for their performance in the detection of hydrocarbons. Polymer overcoatings applied to the conductive networks of the functionalized AuNP arrays were shown to reduce resistivity by promoting the formation of conduction pathways with decreased core-core distance between nanoparticles. Observations made in the context of developing methane sensors provide insight relevant to applications of phosphine or phosphine-containing surface groups in functional AuNP materials.
ABSTRACT
This work reports an unprecedented cascade cyclization of 1-arylethynyl-2-alkyl-o-carboranes promoted by magnesium-mediated sp3 C-H activation. Treatment of 1-arylethynyl-2-alkyl-o-carboranes with MeMgBr gives a series of carborane-fused cyclopentanes in very good yields. Deuterium labelling and control experiments suggest that HMgBr, resulting in situ from the nucleophilic substitution of cage B-H bonds with Grignard reagent, initiates the reaction, in which magnesium-promoted intramolecular sp3 C-H activation serves as a key step. This work not only offers a new route for the synthesis of carborane-fused cyclopentanes, but also sheds some light on Mg-mediated C-H activation and functionalization.
ABSTRACT
Vertex-specific functionalization of carboranes has received considerable research interest, due to the valuable application of carborane derivatives in medicine, coordination/organometallic chemistry and materials. In comparison with a protic cage C-H bond, cage B-H is hydridic and generally less polar, with a bond dissociation energy of ca. 108 kcal mol-1. These features make B-H activation quite different from that of the C-H bond. In addition, selectivity among ten very similar BH vertices in o-carborane is challenging yet crucial to the effective construction of carborane-based functional molecules. To address these issues, a brand new strategy of cage B-H nucleophilic substitution has recently been presented and developed for straightforward and regioselective cage B-H functionalization. The regioselectivity can be controlled by the electronic/steric properties of the cage carbon substituents. This Frontier article highlights the recent advancement in the nucleophilic cage B-H substitution of carboranes.
ABSTRACT
Connate topological superconductor (TSC) combines topological surface states with nodeless superconductivity in a single material, achieving effective p-wave pairing without interface complication. By combining angle-resolved photoemission spectroscopy and in-situ molecular beam epitaxy, we studied the momentum-resolved superconductivity in ß-Bi2Pd film. We found that the superconducting gap of topological surface state (ΔTSSâ¯â¼â¯3.8â¯meV) is anomalously enhanced from its bulk value (Δbâ¯â¼â¯0.8â¯meV). The ratio of 2ΔTSS/kBTcâ¯â¼â¯16.3, is substantially larger than the BCS value. By measuring ß-Bi2Pd bulk single crystal as a comparison, we clearly observed the upward-shift of chemical potential in the film. In addition, a concomitant increasing of surface weight on the topological surface state was revealed by our first principle calculation, suggesting that the Dirac-fermion-mediated parity mixing may cause this anomalous superconducting enhancement. Our results establish ß-Bi2Pd film as a unique case of connate TSCs with a highly enhanced topological superconducting gap, which may stabilize Majorana zero modes at a higher temperature.
ABSTRACT
Chiral fermions in solid state feature "Fermi arc" states, connecting the surface projections of the bulk chiral nodes. The surface Fermi arc is a signature of nontrivial bulk topology. Unconventional chiral fermions with an extensive Fermi arc traversing the whole Brillouin zone have been theoretically proposed in CoSi. Here, we use scanning tunneling microscopy/spectroscopy to investigate quasiparticle interference at various terminations of a CoSi single crystal. The observed surface states exhibit chiral fermion-originated characteristics. These reside on (001) and (011) but not (111) surfaces with p-rotation symmetry, spiral with energy, and disperse in a wide energy range from ~-200 to ~+400 mV. Owing to the high-energy and high-space resolution, a spin-orbit coupling-induced splitting of up to ~80 mV is identified. Our observations are corroborated by density functional theory and provide strong evidence that CoSi hosts the unconventional chiral fermions and the extensive Fermi arc states.
ABSTRACT
A new protocol for regioselective nucleophilic cage B-H substitution in o-carboranes has been proposed that is complementary to the strategies of transition metal catalysis and electrophilic substitution. Magnesium-mediated site-selective nucleophilic cage B(3,6)-H and B(9)-H substitution reactions of o-carboranes give a series of B(3,6)-dialkylated and B(9)-alkylated/arylated o-carboranes in high yields. Both steric and electronic factors of cage C substituents play crucial roles in controlling the site selectivity.
ABSTRACT
Poor graft function (PGF) is a life-threatening complication after allogeneic hematopoietic stem cell transplantation (allo-HSCT). Current treatment strategies include the use of growth factors, CD34+-selected stem cell boost, mesenchymal stem cell transfusion, and second allo-HSCT, but these treatments are not effective in all patients. Eltrombopag, an oral thrombopoietin receptor agonist, which showed promising results in severe aplasia anemia, may be an alternative choice for PGF patients. Therefore, we treated 12 patients who responded poorly to standard treatments for secondary PGF after allo-HSCT with eltrombopag. The median duration was 116 (35-1000) days from transplantation to PGF diagnosis and 59 (30-180) days from PGF diagnosis to eltrombopag treatment. Eltrombopag was started at a dose of 25 mg/d for 3 days and then increased to 50 or 75 mg/d. Median treatment duration was 8 (2-23) weeks. Ten patients (83.3%) responded to the treatment: 8 achieved complete response (CR), and the remaining 2 achieved partial response. In the 10 responding subjects, median platelet count was 18 (5-27) × 109/L vs 74 (30-117) × 109/L prior to and after treatment. Neutrophil count was 0.51 (0.28-0.69) × 109/L vs 1.84 (0.78-4.90) × 109/L. Hemoglobin was 88 (63-123) vs 101 (78-134) g/L. In the 8 patients who achieved CR, the time from eltrombopag initiation to achieving CR was 29 (10-49) days; the response lasted until the last follow-up in all 8 CR subjects (10-18 months). The 12-month overall survival rate was 83.3%. There was no treatment-related mortality and no evidence of cataract, thrombosis, or any other grade 3/4 toxicities.
Subject(s)
Benzoates/therapeutic use , Graft vs Host Disease/etiology , Hematopoietic Stem Cell Transplantation/methods , Hydrazines/therapeutic use , Pyrazoles/therapeutic use , Transplantation Conditioning/methods , Benzoates/pharmacology , Female , Humans , Hydrazines/pharmacology , Male , Pyrazoles/pharmacology , Transplantation, HomologousABSTRACT
Direct nucleophilic substitution reaction of cage B-H bonds of o-carboranes by Grignard reagents in the absence of any transition metals has been achieved for the first time, and leads to the regioselective synthesis of a series of 4-alkyl-1,2-diaryl-o-carboranes in very high yields. The presence of two electron-withdrawing aryl groups on the cage carbon atoms is crucial to realizing the reaction. The regioselectivity is controlled by both electronic and steric factors. This work represents a new strategy for the development of methods for carborane functionalization.
ABSTRACT
Pd-catalyzed carboxylic acid guided regioselective alkynylation of cage B(4)-H bonds in o-carboranes has been achieved for the first time using two different catalytic systems. In the presence of 5 mol% Pd(OAc)2 and 3 equiv. of AgOAc, the reaction of 1-COOH-2-R1-C2B10H10 with R3SiC[triple bond, length as m-dash]CBr in ClCH2CH2Cl gives 4-(R3SiC[triple bond, length as m-dash]C)-2-R1-o-C2B10H10 in moderate to high yields. This reaction is compatible with alkynes possessing sterically bulky silyl groups such as iPr3Si or t BuMe2Si. Meanwhile, another catalytic system of Pd(OAc)2/AgOAc/K2HPO4 can catalyze the direct B(4)-alkynylation of 1-COOH-2-R1-C2B10H10 with terminal alkynes R2C[triple bond, length as m-dash]CH in moderate to high yields. The latter has a broader substrate scope from bulky silyl to aromatic to carboranyl substituents. Desilylation of the resultant products affords carboranyl acetylene 4-(HC[triple bond, length as m-dash]C)-2-R1-o-C2B10H10 which can undergo further transformations such as Sonogashira coupling, dimerization and click reactions. It is suggested that the above two catalytic systems may proceed via Pd(ii)-Pd(iv)-Pd(ii) and Pd(ii)-Pd(0)-Pd(ii) catalytic cycles, respectively. In addition, the silver salt is found to promote the decarboxylation reaction and thereby controls the mono-selectivity.
ABSTRACT
A nickel-catalyzed arylation at the carbon center of o-carborane cages has been developed, thus leading to the preparation of a series of 1-aryl-o-carboranes and 1,2-diaryl-o-carboranes in high yields upon isolation. This method represents the first example of transition metal catalyzed C,C'-diarylation by cross-coupling reactions of o-carboranyl with aryl iodides.
Subject(s)
Boranes/chemistry , Carbon/chemistry , Iodides/chemistry , Nickel/chemistry , Catalysis , Molecular StructureABSTRACT
PURPOSE: To assess the clinical significance of WD40 repeat containing 62 (WDR62), a novel centrosome abnormalities-associated gene, in ovarian cancer. MATERIALS AND METHODS: In this study, WDR62 expression was assessed by western blot (6 ovarian cancer cell lines) and immunohistochemistry (primary epithelial ovarian cancer clinical specimens), and clinical variables were collected by retrospective chart review. Centrosome amplification was assessed by immunofluorescence staining in ovarian cancer cell lines, and by immunohistochemistry staining in ovarian cancer samples. RESULTS: Six ovarian cancer cell lines exhibited significant WDR62 protein overexpression, and amplification of centrosome. High-grade ovarian cancer specimens exhibited significantly stronger nuclear staining of WDR62 than low-grade ovarian carcinoma specimens (80.4% vs 41.3%; P<0.012). High WDR62 expression was strongly associated with supernumerary centrosome count in tumor cells (P < 0.001). CONCLUSION: Our findings suggest that WDR62 overexpression is related to centrosome amplification in ovarian cancer. It may be a novel useful differentiation biomarker and a potential therapy target for OC. Further assessment of WDR62 expression is highly warranted in large, prospective studies.
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Actinobacteria are widely distributed in the marine environment. To date, few studies have been performed to explore the coral-associated Actinobacteria, and little is known about the diversity of coral-associated Actinobacteria. In this study, the actinobacterial diversity associated with one soft coral Alcyonium gracllimum and one stony coral Tubastraea coccinea collected from the East China Sea was investigated using both culture-independent and culture-dependent approaches. A total of 19 actinobacterial genera were detected in these two corals, among which nine genera (Corynebacterium, Dietzia, Gordonia, Kocuria, Microbacterium, Micrococcus, Mycobacterium, Streptomyces, and Candidatus Microthrix) were common, three genera (Cellulomonas, Dermatophilus, and Janibacter) were unique to the soft coral, and seven genera (Brevibacterium, Dermacoccus, Leucobacter, Micromonospora, Nocardioides, Rhodococcus, and Serinicoccus) were unique to the stony coral. This finding suggested that highly diverse Actinobacteria were associated with different types of corals. In particular, five actinobacterial genera (Cellulomonas, Dermacoccus, Gordonia, Serinicoccus, and Candidatus Microthrix) were recovered from corals for the first time, extending the known diversity of coral-associated Actinobacteria. This study shows that soft and stony corals host diverse Actinobacteria and can serve as a new source of marine actinomycetes.