Activation of CO, CS, and COS by α-Diimine-Stabilized Gallylenes.

Several gallylenes [LGaM(THF)] stabilized by an α-diimine ligand (L=[(2,6-iPrCH)NC(Ph)] ; M=Li, n=3, 3-Li; M=Na, n=4, 3-Na; M=K, n=1, 3-K) were prepared, which display diverse reactivities toward carbon dioxide and its sulfurized analogues. The reaction of 3 with CO yielded a trimeric carbonate complex [{LGa(CO)}{μ-K(THF)}] (4) and a dinuclear oxo-carbonate complex [K(THF)][LGa(μ-CO)(μ-O)GaL] (5) in one pot through reductive disproportionation of CO. For CS, two ethenetetrathiolate gallium complexes, [M(Solv)][LGa(μ-CS)GaL] (M=Na, Solv=THF, 6; M=K, Solv=DME, 7), were obtained via reductive coupling of CS.

SPOP expression is associated with tumor-infiltrating lymphocytes in pancreatic cancer.

Background: Speckle Type POZ Protein (SPOP), despite its tumor type-dependent role in tumorigenesis, primarily as a tumor suppressor gene is associated with a variety of different cancers. However, its function in pancreatic cancer remains uncertain.

Methods: SPOP expression and the association between its expression and patient prognosis and immune function were evaluated using The Cancer Genome Atlas (TCGA), Genotype-Tissue Expression (GTEx), The Tumor Immune Estimation Resource 2.

Impact of exercise dosages based on American College of Sports Medicine recommendations on lipid metabolism in patients after PCI: a systematic review and meta-analysis of randomized controlled trials.

Background: The impact of exercise dosages based on American College of Sports Medicine(ACSM) recommendations on lipid metabolism in patients after PCI remains unclear. This study conducted a meta-analysis of reported exercise dosages from the literature to address this knowledge gap.

Methods: A comprehensive search of databases was conducted to identify eligible randomized controlled studies of exercise interventions in patients after PCI, following the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) statement.

Reduction of Ketones and Coupling of Ketyls by a Zn-Zn-Bonded Compound.

The α-diimine-ligated Zn-Zn-bonded compound [K(THF)][LZn-ZnL] (, L = [(2,6-PrCH)NC(Me)]) displays diverse reactivities toward a variety of ketones. In the reaction of with benzophenone or 4,4'-di--butylbenzophenone, a multielectron transfer process was observed to give bimetallic (Zn/K) complexes with both ketyl radical fragments and C-C coupled pinacolate moieties (products and ). In contrast, treating with 9-fluorenone only afforded pinacolate complex .

Activation of cyclopentadiene derivatives by an α-diimine-ligated Mg-Mg-bonded compound.

Heteroleptic, bimetallic (Mg/K) cyclopentadienyl complexes (2-4) were synthesized by the reaction of the Mg-Mg-bonded compound [K(THF)][LMg-MgL] (1, L = [(2,6-iPrCH)NC(CH)]) with cyclopentadiene derivatives, 6,6-dimethylfulvene, 6-(dimethylamino)fulvene, or 1,2,3,4-tetramethyl-1,3-cyclopentadiene. The reactions proceed through diverse pathways, including hydrogen abstraction, C-C coupling, and dehydrogenation, depending on the property of the polyene substrate, thus providing an access to alkali/alkaline earth metal cyclopentadienyl complexes.

Biomimetic Charge-Neutral Anion Receptors for Reversible Binding and Release of Highly Hydrated Phosphate in Water.

Control of phosphate capture and release is vital in environmental, biological, and pharmaceutical contexts. However, the binding of trivalent phosphate (PO ) in water is exceptionally difficult due to its high hydration energy. Based on the anion coordination chemistry of phosphate, in this study, four charge-neutral tripodal hexaurea receptors (L-L), which were equipped with morpholine and polyethylene glycol terminal groups to enhance their solubility in water, were synthesized to enable the pH-triggered phosphate binding and release in aqueous solutions.

Construction of Magnesium Phosphate Chemical Conversion Coatings with Different Microstructures on Titanium to Enhance Osteogenesis and Angiogenesis.

Titanium (Ti) and its alloys are widely used as hard tissue substitutes in dentistry and orthopedics, but their low bioactivity leads to undesirable osseointegration defects in the early osteogenic phase. Surface modification is an important approach to overcome these problems. In the present study, novel magnesium phosphate (MgP) coatings with controllable structures were fabricated on the surface of Ti using the phosphate chemical conversion (PCC) method.

Triplane technique for breast reconstruction after breast cancer surgery: A case series report.

Rationale: Implant-based breast reconstruction is an important method for post-mastectomy breast reconstruction. Currently, the most commonly used technique is the biplane technique. However, the high rate of postoperative complications, the inability of pockets to accommodate larger implants, and the expensive costs of biological mesh make the development of new surgical methods urgent.

Incorporation of an Anion-Coordinated Triple Helicate into a Thin Film for Choline Recognition in an Aqueous System.

Functional thin films, being fabricated by incorporating discrete supramolecular architectures, have potential applications in research areas such as sensing, energy storage, catalysis, and optoelectronics. Here, we have determined that an anion-coordinated triple helicate can be solution-processed into a functional thin film by incorporation into a polymethyl methacrylate (PMMA) matrix. The thin films fabricated by the incorporation of the anion-coordinated triple helicate show multiple optical properties, such as fluorescence, CD, and CPL.

One-Electron (2c/1e) Tin···Tin Bond Stabilized by -Phenylenediamido Ligands.

Odd-electron bonds, i.e., the two-center, three-electron (2c/3e), or one-electron (2c/1e) bonds, have attracted tremendous interest owing to their novel bonding nature and radical properties.

In Situ Photoisomerization of an Azobenzene-Based Triple Helicate with a Prolonged Thermal Relaxation Time.

The phosphate-coordination triple helicates A L (A=anion) with azobenzene-spaced bis-bis(urea) ligands (L) have proven to undergo a rare in situ photoisomerization (without disassembly of the structure) rather than the typically known, stepwise "disassembly-isomerization-reassembly" process. This is enabled by the structural self-adaptability of the "aniono" assembly arising from multiple relatively weak and flexible hydrogen bonds between the phosphate anion and bis(urea) units. Notably, the Z→E thermal relaxation rate of the isomerized azobenzene unit is significantly decreased (up to 20-fold) for the triple helicates compared to the free ligands.

pH-Dependent phosphate separation using a tripodal hexaurea receptor.

We demonstrate that a tripodal hexaurea receptor can selectively bind PO anions 12 hydrogen bonds with up to 3.8 × 10 M binding affinity in DMSO, which is 38-fold stronger than SO. This receptor facilitates the extraction of PO from strongly basic aqueous solutions into chloroform using liquid-liquid extraction, followed by its release as the HPO anion into an acidic solution.

Diverse Reactions of α-Diimine-Ligated Mg -Mg -Bonded Compound with Carbodiimides.

The α-diimine-ligated dimagnesium(I) compound [K(thf) ] [LMg-MgL] (1, L=[(2,6-iPr C H )NC(Me)] ) displays diverse reactivities toward carbodiimides (RN=C=NR) with different R substituents. In the reaction of 1 with Me SiNCNSiMe , one of the easily leaving trimethylsilyl groups is lost to yield the Me SiNCN moiety that either bridges two Mg centers (2) or terminally coordinated (3). In contrast, with the similarly bulky tBuNCNtBu, the carbodiimide inserts into Mg-Mg bond with accompanying C-H activation of a ligand or solvent (products 4 and 5).

Reactions of Low-Valent Gallium Species with Organic Azides: Formation of Imido-, Azoimido-, and Tetrazene Complexes.

The reactivity of two α-diimine-ligated digallanes, [LGa-GaL] (L = [(2,6-iPrCH)NC(CH)], dpp-dad, ; L = 1,2-[(2,6-iPrCH)NC]CH, dpp-bian, ), and a gallylene, [(L)GaNa(THF)] (), toward organic azides was studied. Reaction of digallane or with trimethylsilyl azide (MeSiN), 2-azido-benzonitrile (2-CNCHN), or tosylazide (TosN) results in imido-bridged complexes, [(L)Ga(μ-NSiMe)Ga(L)] () [(L)Ga(μ-NSiMe)Ga(L)] (), [(L)Ga(μ-2-CNCHN)Ga(L)] (), and [(L)Ga(μ-NTos)Ga(L)] (), with elimination of dinitrogen. Treatment of or with 1-adamantyl azide (1-AdN), on the other hand, affords the unsymmetrical dinuclear complexes [(L)Ga(NAd)(NAd)Ga(L)] () and [(L)Ga(NAd)(NAd)Ga(L)] (), which contain both imido and triazene bridges.

Assembly of an A L Anion Trigonal Antiprism and Binding of Glucopyranosides and Polyethylene Glycols (PEGs).

Anion-coordination-driven assembly (ACDA) has proven to be a very effective strategy for the construction of polyhedral structures. Here we demonstrate that variation of the "angle" of the backbone of C -symmetric tris-bis(urea) ligands, from triphenylamine to triphenylphosphine oxide, results in the change of the final construct from an A L tetrahedron to a higher-nuclearity, A L trigonal antiprism (A=anion, herein PO ; L=ligand). Most interestingly, this assembly features a huge hollow internal space that is divided into three compartments: one central cavity and two large outer pockets.

Anion-Coordination-Driven Assembly.

The assembly of discrete architectures has been an important subject in supramolecular chemistry because of their elegant structures and fascinating properties. During the last several decades, supramolecular chemists have developed manifold strategies for hierarchical assembly, which are normally classified by two main types of driving force: covalent and noncovalent interactions. Typical noncovalent interactions include metal coordination, hydrogen bonding, and other weak forces.

Health-related quality of life measured by EQ-5D-3L for the spouses of breast cancer patients.

To explore factors influencing the health-related quality of life of spouses of breast cancer patients and the suitable questionnaires for this purpose. A cross-sectional study was conducted in the Third Affiliated Hospital of Kunming Medical University. The spouses of breast cancer patients were included and evaluated face-to-face interviews.

Reactivity of Transition Metal Gallylene Complexes Toward Substrates with Multiple Carbon-Element Bonds.

Reactivity of transition metal complexes containing the redox-active gallylene (dpp-bian)Ga ligand (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) toward isocyanide, isocyanate, isothiocyanate, and ketene substrates is described. The reaction of [(dpp-bian)GaCr(CO)] () with tBuNC results in a dative complex [(dpp-bian)Ga(CNtBu)Cr(CO)] (), while compound [(dpp-bian)GaCr(CO)][Na(THF)] () reacts with tBuNC to give the coordination polymer [(dpp-bian)GaCr(CO)][Na(CNtBu)(THF)] (). Treatment of [(dpp-bian)GaCr(CO)][Na(THF)] with an excess of PhNCO results in trimerization of the latter and formation of complex [(dpp-bian)GaCr(CO)][Na(PhNCO)(EtO) (DME)] ().

Lipidomic analysis reveals altered lipid profiles of gingival tissues with periodontitis.

Aim: The role of lipids in periodontitis has not been well studied. Thus, this study aimed to explore periodontitis-associated lipid profile changes and identify differentially expressed lipid metabolites in gingival tissues.

Materials And Methods: Gingival tissues from 38 patients with periodontitis (periodontitis group) and 38 periodontally healthy individuals (control group) were collected.

Metaplastic breast cancer with chondrosarcomatous differentiation combined with concurrent bilateral breast cancer: A case report.

Background: Metaplastic breast carcinoma (MBC) is a rare subtype of invasive breast cancer comprising malignant epithelial and mesenchymal cells. Compared with other invasive breast cancers, MBC is not only histologically distinctly heterogeneous but also has a rapid and aggressive growth pattern, which leads to a significant risk of recurrence and mortality.

Case Summary: In this study, we report the case of a patient with a large left breast mass diagnosed with bilateral invasive ductal carcinoma in both breasts after a preoperative core needle aspiration biopsy of the bilateral breast mass.