Synthesis, Characterization, and Nanomaterials Generated from 6,6'-(((2-Hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di- tert-butylphenol) Modified Group 4 Metal Alkoxides.

The impact on the morphology nanoceramic materials generated from group 4 metal alkoxides ([M(OR)4]) and the same precursors modified by 6,6'-(((2-hydroxyethyl)azanediyl)bis(methylene))bis(2,4-di- tert-butylphenol) (referred to as H3-AM-DBP2 (1)) was explored. The products isolated from the 1:1 stoichiometric reaction of a series of [M(OR)4] where M = Ti, Zr, or Hf; OR = OCH(CH3)2(OPr i); OC(CH3)3(OBu t); OCH2C(CH3)3(ONep) with H3-AM-DBP2 proved, by single crystal X-ray diffraction, to be [(ONep)Ti( k4( O,O',O'',N)-AM-DBP2)] (2), [(OR)M(µ( O)- k3( O',O'',N)-AM-DBP2)]2 [M = Zr: OR = OPr i, 3·tol; OBu t, 4·tol; ONep, 5·tol; M = Hf: OR = OBu t, 6·tol; ONep, 7·tol]. The product from each system led to a tetradentate AM-DBP2 ligand and retention of a parent alkoxide ligand. For the monomeric Ti derivative (2), the metal was solved in a trigonal bipyramidal geometry, whereas for the Zr (3-5) and Hf (6, 7) derivatives a symmetric dinuclear complex was formed where the ethoxide moiety of the AM-DBP2 ligand bridges to the other metal center, generating an octahedral geometry. High quality density functional theory level gas-phase electronic structure calculations on compounds 2-7 using Gaussian 09 were used for meaningful time dependent density functional theory calculations in the interpretation of the UV-vis absorbance spectral data on 2-7. Nanoparticles generated from the solvothermal treatment of the ONep/AM-DBP2 modified compounds (2, 5, 7) in comparison to their parent [M(ONep)4] were larger and had improved regularity and dispersion of the final ceramic nanomaterials.

Societal costs of localized renal cancer surgery.

INTRODUCTION: Hospital-related costs of renal cancer surgery have been described, but the societal costs of surgery-related lost productivity are poorly understood. We estimated the societal cost of renal cancer surgery by assessing surgery-related time off work (TOW) taken by patients and their caretakers. MATERIALS AND METHODS: A total of 413 subjects who underwent partial or radical nephrectomy enrolled in an IRB-approved prospective study received an occupational survey assessing employment status, work physicality, income, surgery-related TOW, and caretaker assistance. We excluded subjects with incomplete occupational information or metastatic disease. We estimated potential wages lost using individual income and TOW, and used logistic regression to evaluate for factors predictive of TOW > 30 days. RESULTS: Of the 219 subjects who responded, 138 were employed at time of surgery. Ninety-seven subjects returned to work, met the inclusion criteria, and were analyzed. Mean age was 54 and 56% of subjects had sedentary jobs. TOW ranged from 7 to 92 days; mean and median TOW was 35 and 33 days, respectively and 58% of subjects took > 30 days off. Mean potential wages lost for TOW was $10,152. Eighty-three percent of subjects had at least one caretaker take TOW (mean/median caretaker TOW: 11/7 days, respectively) to assist in recovery. Subjects with sedentary jobs were less likely to take > 30 days off (OR 0.30; 95% CI 0.09-0.99). CONCLUSIONS: Most renal cancer surgery patients take over 1 month off work. Recognizing the associated societal costs may allow better adjustment of patient expectations, and more comprehensive cost-effectiveness analyses in renal cancer care.

Coordination chemistry of N,N,N',N'-tetrakis(3,5-substituted benzyl-2-oxide)-2,2'-(ethylenedioxy)diethanamine modified Group 4 metal alkoxides.

The coordination behavior of a set of (ethylenedioxy)diethanamine-based tetraphenol ligands with a series of Group 4 metal alkoxides ([M(OR)(4)]) was determined. The ligands were synthesized from a modified Mannich reaction and fully characterized as N,N,N',N'-tetrakis(3,5-tert-butyl-benzyl-2-hydroxy)-2,2'-(ethylenedioxy)diethanamine, termed H(4)-OEA-DBP(4) (1), and N,N,N',N'-tetrakis(3,5-chloro-benzyl-2-hydroxy)-2,2'-(ethylenedioxy)diethanamine, termed H(4)-OEA-DCP(4) (2). The reaction of 1 with a set of [M(OR)(4)] [M = Ti, Zr, or Hf; OR = iso-propoxide (OPr(i)), neo-pentoxide (ONep), or tert-butoxide (OBu(t))] precursors led to the isolation of [(OPr(i))(2)Ti](2)(µ-OEA-DBP(4)) (3), [(ONep)(2)Ti](2)(µ-OEA-DBP(4)) (4), and [(OBu(t))(2)M](2)(µ-OEA-DBP(4)) where M = Ti (5), Zr (6), or Hf (7). In addition, the [(ONep)(2)Ti](2)(µ-OEA-DCP(4)) (4a) derivative was isolated from the reaction of 2 and [Ti(ONep)(4)], demonstrating the similarity of coordination behavior between the two OEA-R(4) ligands. For 3-7, the metal center adopts a slightly distorted octahedral geometry by binding the two O atoms of the phenoxide moiety, as well as one N and one O atom from the OEA moieties, while retaining two of the original OR ligands. Solution NMR demonstrates inequivalent protons for the majority of the bound OEA ligands, which argues for retention of structure in solution. The synthesis and characterization of these compounds are presented in detail.

Trends in Private Equity Acquisition of Dermatology Practices in the United States.

IMPORTANCE: Private equity (PE) firms invest in dermatology management groups (DMGs), which are physician practice management firms that operate multiple clinics and often acquire smaller, physician-owned practices. Consolidation of dermatology practices as a result of PE investment may be associated with changes in practice management in the United States. OBJECTIVE: To describe the scope of PE-backed dermatology practice acquisitions geographically over time. DESIGN, SETTING, AND PARTICIPANTS: This cross-sectional study examined acquisitions of dermatology practices by PE-backed DMGs in the United States. Acquisition and investment data through May 31, 2018, were compiled using information from 5 financial databases. Transaction data were supplemented with publicly available information from 2 additional financial databases, 2 financial news outlets, and press releases from DMGs. All dermatology practices acquired by PE-backed DMGs were included. Acquisitions were verified to be dermatology practices that provided medical, surgical, and/or cosmetic clinical care. Private equity financing data were included when available. The addresses of clinics associated with acquired practices were mapped using spatial analytics software. MAIN OUTCOMES AND MEASURES: The number and location of PE practice acquisitions over time were measured based on the date of deal closure, the geographic footprint of each DMG's acquisition, and the financing of each DMG. RESULTS: Seventeen PE-backed DMGs acquired 184 practices between May 1, 2012, and May 22, 2018. These acquired practices accounted for an estimated 381 dermatology clinics as of mid-2018 (assessment period from May 1 to August 31). The total number of PE-owned dermatology clinics in the United States was substantially larger because these data did not reflect DMGs that opened new clinics (organic growth); acquisitions data represented only the ownership transfer of existing practices from physician to PE-backed DMG. Practice acquisitions increased each year, from 5 in 2012 to 59 in 2017. An additional 34 acquisitions took place from January 1 to May 31, 2018. The number of financing rounds to sustain transactions mirrored the aforementioned trends in practice acquisitions. Clinics associated with acquired practices spanned at least 30 states, with 138 of 381 clinics (36%) located in Texas and Florida. CONCLUSION AND RELEVANCE: The study findings suggest that PE firms have a financial stake in an increasing number of dermatology practices throughout the United States. Further research is needed to assess whether and how PE-backed ownership influences clinical decision-making, health care expenditures, and patient outcomes.

New diamino-diheterophenol ligands coordinate iron(III) to make structural and functional models of protocatechuate 3,4-dioxygenase.

Three diamino, dihetero-phenol ligands were synthesized by sequential Mannich condensations. These ligands were combined with FeCl3 to produce three five-coordinate Fe(III) complexes that are structural models for the enzyme 3,4-PCD. The three Fe(III) complexes were characterized by elemental analysis, single crystal X-ray diffraction studies, UV-vis spectroscopy, and cyclic voltammetry. Combining the Fe(III) complexes with 3,5-di-t-butylcatechol and O2 resulted in oxidative cleavage similar to the function of 3,4-PCD.