Bridging 1,2-Bis(diphenylphosphino)methane Ligands Facilitate the Formation of Binuclear Complexes with Both Two-Coordinate and Three-Coordinate Gold(I) Ions.

Five new crystalline gold(I) complexes β-Au(μ-dppm)Br·2CHCl (), [Au(μ- dppm)Br]Br·2CHCl (), [Au(μ-dppm)Br](PF) (), [Au(μ-dppm)Cl](BPh)·3CHCl () and [Au(μ-dppm)]Cl(AsF)·2CHCl () (where dppm is bis(diphenylphosphino)methane) have been prepared and structurally characterized by single crystal X-ray diffraction. Colorless β-Au(μ-dppm)Br·2CHCl () has centrosymmetric structure with two three-coordinate gold(I) ions held in close proximity by the dppm ligands. Crystals of [Au(μ- dppm)Br]Br·2CHCl (), [Au(μ-dppm)Br](PF) (), and [Au(μ-dppm)Cl](BPh)·3CHCl () have a cation with an unusual arrangement that binds a two-coordinate gold(I) ion to a three-coordinate gold(I) ion through an aurophilic interaction.

Results of a Pilot Trial Assessing the Effects of Proper Oral Hygiene and a Probiotic Dietary Supplement on Oral Health in Volunteers with Oral Malodor.

Persistent malodor affects many people worldwide and is usually associated with poor dental hygiene. This pilot trial aimed to determine whether proper dental hygiene (DH) and a probiotic dietary supplement support oral health in volunteers with persistent malodor. Volunteers ( = 35) were randomly assigned to the probiotic or placebo cohort.

Molecular Flexibility in Solvated Crystals of the Dimer, Au(μ-1,2-bis(diphenylphosphino)ethane)I, with Three-Coordinate Gold(I).

We report the ability to trap the dimer Au(μ-dppe)I (dppe is 1,2-bis(diphenylphosphino)ethane) with different separations between the three-coordinate gold ions in crystalline solvates. All of these solvates ((Au(μ-dppe)I·4(CHCl) (), Au(μ-dppe)I·2(CHCl) (), the polymorphs α-Au(μ-dppe)I·2(HC(O)NMe) () and β-Au(μ-dppe)I·2(HC(O)NMe) (), and Au(μ-dppe)I·4(CHCl) ()) along with polymeric {Au(μ-dppe)I}·(CHCl) ()) originated from the same reaction, only the solvent system used for crystallization differed. In the different solvates of Au(μ-dppe)I, the Au···Au separation varied from 3.

Covalently linked thieno[2,3-]thiophene-fullerene dimers: synthesis and physical characterization.

Thienothiophene (TT) has received great attention in the fields of electronics and optoelectronics. Here we report a synthesis and characterization of fullerene-donor-fullerene triads linked to thieno[2,3-]thiophene as a donor. The photophysical and electrochemical properties of the new dumbbells were investigated using UV-vis spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and square wave voltammetry.

Open-cage fullerenes as ligands for metals.

The remarkable structures of open-cage fullerenes with functionalization on the outer surface and an accessible inner void make them interesting ligands for reactions with metal complexes. The behaviors of open-cage fullerenes in reactions with various metal complexes are examined and compared to the corresponding reactions with intact fullerenes. The structural results from X-ray diffraction are emphasized.

Structure and Luminescence Studies of Salts of the Helical Dication, [Au(μ-bis(diphenylphosphine)ethane)] and Comparison with Salts of [Au(μ-bis(diphenylphosphine)propane)].

Six salts ([Au(μ-dppe)](BF)·CHCl, [Au(μ-dppe)](BF)·1,2-ClCH, [Au(μ-dppe)](PF)·CHCl, [Au(μ-dppe)](PF), [Au(μ-dppe)](SbF), and [Au(μ-dppe)](OTf)·2CHCl), (dppe is bis(diphenylphosphine)ethane) containing the dication, [Au(μ-dppe)], have been prepared and structurally characterized by single-crystal X-ray crystallography. Unlike the three-coordinate dppe-bridged dimers, AuX(μ-dppe) (X = Br, I), which show considerable variation in the distance between the gold(I) ions over the range 3.0995(10) to 3.

Reactions of Thianthrene and 10-Phenylphenothiazine with the Lewis Acids─Titanium Tetrachloride, Titanium Tetrabromide, Tin(IV) Tetrachloride, or Antimony(V) Pentachloride: The Competition between Coordination and Oxidation.

The oxidation of thianthrene and 10-phenylphenothiazine into cation radicals has been examined using redox-active Lewis acids. The reaction of titanium(IV) tetrachloride with thianthrene in toluene produces a solution with an EPR spectrum indicative of oxidation of thianthrene to a cation radical, but the molecular compound () (μ-thianthrene)Ti(μ-Cl)Cl crystallized exclusively. Red crystalline () (μ-thianthrene)Ti(μ-Br)Br formed similarly from titanium(IV) tetrabromide.

Self-Assembled Encapsulation of CuX (X = Br, Cl) in a Gold Phosphine Box-like Cavity with Metallophilic Au-Cu Interactions.

Synthetic routes to the crystallization of two new box-like complexes, [Au(Triphos)(CuBr)](OTf)·(CHCl)·(CHOH)·(HO) () and [Au(Triphos) (CuCl)](PF)·(CHCl) () (triphos = bis(2-diphenylphosphinoethyl)phenylphosphine), have been developed. The two centrosymmetric cationic complexes have been structurally characterized through single-crystal X-ray diffraction and shown to contain a CuX (X = Br or Cl) unit suspended between two Au(I) centers without the involvement of bridging ligands. These colorless crystals display green luminescence (λ = 527 nm) for () and teal luminescence (λ = 464 nm) for ().

Patient-reported discrimination among limited-resourced cancer survivors: a brief report.

Purpose: Healthcare discrimination has been associated with health disparities including lower cancer screenings, higher medical mistrust, and strained patient-provider relationships. Our study sought to understand patient-reported discrimination among cancer survivors with limited resources living in the United States.

Design And Methods: We used cross-sectional survey data distributed by the Patient Advocate Foundation (PAF) in 12/2020 and 07/2021.

Metal-mediated rearrangement of 1,2-diphenylhydrazine to -semidine upon reaction with dichlorotris(triphenylphosphine)ruthenium(II).

Reaction between RuCl(PPh) and 1,2-diphenylhydrazine resulted in rearrangement and coordination of -semidine. The product, RuCl(PPh)(κ-NH-1,2-CH-NHPh), was characterized spectroscopically and the molecular structure was conclusively determined using X-ray crystallography. Computational chemistry was employed to probe the energetics surrounding the rearrangement reaction and product.

Dexmedetomidine Use in Infants Undergoing Cooling Due to Neonatal Encephalopathy (DICE Trial): A Randomized Controlled Trial: Background, Aims and Study Protocol.

Neonatal hypoxia-ischemia encephalopathy (HIE) is the leading cause of neonatal death and poor neurodevelopmental outcomes worldwide. Therapeutic hypothermia (TH), while beneficial, still leaves many HIE treated infants with lifelong disabilities. Furthermore, infants undergoing TH often require treatment for pain and agitation which may lead to further brain injury.

Direct Crystallization of Diamine Radical Cations: Carbon-Nitrogen Bond Formation from the Reaction of Triphenylamine with TiCl , TiBr , or SnCl versus Carbon-Carbon Bond Formation with SbCl.

Direct synthesis of diamine radical cations in crystalline form proceeding through oxidation of triphenylamine followed by the formation of a new C-N bond is reported. Although the oxidative coupling of triphenylamine is well studied, diamine products are rarely captured in their radical cation state. The neutral diamine most frequently obtained from this reaction pathway is N,N,N',N'-tetraphenylbenzidine.

Examining the association among fear of COVID-19, psychological distress, and delays in cancer care.

Background: Given the high risk of COVID-19 mortality, patients with cancer may be vulnerable to fear of COVID-19, adverse psychological outcomes, and health care delays.

Methods: This longitudinal study surveyed the pandemic's impact on patients with cancer (N= 1529) receiving Patient Advocate Foundation services during early and later pandemic. Generalized estimating equation with repeated measures was conducted to assess the effect of COVID-19 on psychological distress.

Introduction of a (PhP)Pt group into the rim of an open-cage fullerene by breaking a carbon-carbon bond.

Treatment of an open-cage fullerene, designated as MMK-9, with (PhP)Pt in toluene solution at room temperature allows a (PPh)Pt unit to be incorporated into the rim of the cage so that it becomes an integral part of the carbon cage skeleton. The structure of the adduct has been determined by single crystal X-ray diffraction and reveals that the platinum atom has planar PtCP coordination, rather than the usual η-bonding to an intact C-C double bond of the fullerene.

Financial toxicity in patients with gynecologic malignancies: a cross sectional study.

Objective: To evaluate financial toxicity and assess its risk factors among patients with gynecologic cancers.

Methods: This is a cross sectional study that included 2 survey tools, as well as patient demographics, disease characteristics, and treatment regimen. Financial toxicity is measured by validated Comprehensive Score for Financial Toxicity (COST) tool.

Synthesis and Electrochemistry of Novel Dumbbell-Shaped Bis-pyrazolino[60]fullerene Derivatives Formed Using Microwave Radiation.

The design of covalently linked [60]fullerene dimers has gained increased attention, as the linked electron donors or acceptors are in close proximity to the surface of the C, providing a valuable approach to novel molecular electronic devices. Herein, new compounds involving C dumbbells covalently connected by the π-conjugated system from azobenzene and diaryl ether linkers were synthesized following the bifunctional cycloaddition reactions to C using microwave radiation. The structural identity of the fullerene dimers has been determined using spectroscopic techniques including Fourier transform infrared (FT-IR), matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF), and NMR spectroscopy, and the photophysical and the electrochemical properties for the new dumbbells have been examined using UV-vis spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and square wave voltammetry.

Seeing luminescence appear as crystals crumble. Isolation and subsequent self-association of individual [(CHNC)Au] ions in crystals.

Non-luminescent, isostructural crystals of [(CHNC)Au](EF)·CH (E = As, Sb) lose benzene upon standing in air to produce green luminescent (E = As) or blue luminescent (E = Sb) powders. Previous studies have shown that the two-coordinate cation, [(CHNC)Au], self-associates to form luminescent crystals that contain linear or nearly linear chains of cations and display unusual polymorphic, vapochromic, and/or thermochromic properties. Here, we report the formation of non-luminescent crystalline salts in which individual [(CHNC)Au] ions are isolated from one another.

Patient perspectives on chemotherapy de-escalation in breast cancer.

Background: Given excellent survival outcomes in breast cancer, there is interest in de-escalating the amount of chemotherapy delivered to patients. This approach may be of even greater importance in the setting of the COVID-19 pandemic.

Methods: This concurrent mixed methods study included (1) interviews with patients and patient advocates and (2) a cross-sectional survey of women with breast cancer served by a charitable nonprofit organization.

A non-luminescent polymorph of [(cyclohexyl isocyanide)Au]PF that becomes luminescent upon grinding or exposure to dichloromethane vapor.

The discovery of a third, non-luminescent crystalline polymorph of [(C6H11NC)2Au]PF6 is reported. Remarkably, crystals of this polymorph are sensitive to mechanical pressure or to exposure to dichloromethane vapor. In both cases, the conversion produces the yellow, green luminescent polymorph of [(C6H11NC)2Au]PF6 and not the colorless, blue luminescent polymorph.

Quantifying treatment preferences and their association with financial toxicity in women with breast cancer.

Background: The objective of the current study was to understand treatment preferences and their association with financial toxicity in Patient Advocate Foundation clients with breast cancer.

Methods: This choice-based conjoint analysis used data from a nationwide sample of women with breast cancer who received assistance from the Patient Advocate Foundation. Choice sets created from 13 attributes of 3 levels each elicited patient preferences and trade-offs.