Defining Stereochemistry in the Polymerization of Lactide by Aluminum Catalysts: Insights into the Dual-Stereocontrol Mechanism.

Aspects of the proposed pathway combining chain-end and enantiomorphic site control for the stereospecific polymerization of lactide (LA) were investigated through studies of aluminum complexes supported by enantiopure and racemic bipyrrolidine-based salan ligands, LigAlOBn and LigAlOBn. Spectroscopic analysis of stoichiometric initiation reactions and the definition of the stereochemistry of the selective formation of the "match" single-insertion products by X-ray crystallography led to key conclusions about the observed stereocontrol. Notably, it was determined to rely heavily on the preference for the trio of stereocenters around the metal to have a "match" formation (-ligand + -polymer), which works synergistically with the enantiomorphic site preference of the catalyst to ring-open next to a stereocenter of a monomer of the same chirality as that of the ligand, resulting in highly heterotactic or syndiotactic PLA from - or -LA, respectively.

Stereocomplexation of Stereoregular Aliphatic Polyesters: Change from Amorphous to Semicrystalline Polymers with Single Stereocenter Inversion.

Stereocomplexation is a useful strategy for the enhancement of polymer properties by the co-crystallization of polymer strands with opposed chirality. Yet, with the exception of PLA, stereocomplexes of biodegradable polyesters are relatively underexplored and the relationship between polymer microstructure and stereocomplexation remains to be delineated, especially for copolymers comprising two different chiral monomers. In this work, we resolved the two enantiomers of a non-symmetric chiral anhydride (CPCA) and prepared a series of polyesters from different combinations of racemic and enantiopure epoxides and anhydrides, via metal-catalyzed ring-opening copolymerization (ROCOP).

Defining the Macromolecules of Tomorrow through Synergistic Sustainable Polymer Research.

Transforming how plastics are made, unmade, and remade through innovative research and diverse partnerships that together foster environmental stewardship is critically important to a sustainable future. Designing, preparing, and implementing polymers derived from renewable resources for a wide range of advanced applications that promote future economic development, energy efficiency, and environmental sustainability are all central to these efforts. In this contribution, we take a comprehensive, integrated approach to summarize important and impactful contributions to this broad research arena.

Mechanistic insight into initiation and regioselectivity in the copolymerization of epoxides and anhydrides by Al complexes.

Pentacoordinate Al catalysts comprising bipyridine (bpy) and phenanthroline (phen) backbones were synthesized and their catalytic activity in epoxide/anhydride copolymerization was investigated and compared to (t-Busalph)AlCl. Stoichiometric reactions of tricyclic anhydrides with Al alkoxide complexes produced ring-opened products that were characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography, revealing key regio- and stereochemical aspects.

Catalytic Functionalization of C-H Bonds of Azulene by Carbene/Nitrene Incorporation.

The selective catalytic functionalization of the C-H bond of azulene upon incorporation of carbene or nitrene units with metal-based catalysts is described. Ethyl diazoacetate or ArI═NTs are employed as carbene or nitrene precursors, respectively. The azulene derivatives are subsequently employed as building blocks toward more complex structures with potential use as biodegradable materials.

Zinc Complexes of Sequential Tetradentate Monoanionic Ligands in the Isoselective Polymerization of rac-Lactide.

Zinc complexes of {ONNN}-type sequential tetradentate monoanionic ligands reacted with diethylzinc to give the mononuclear ethylzinc complexes. The benzyloxy complexes were formed readily and were found to be highly active as well as living/immortal catalysts for ring-opening polymerization of rac-lactic acid with a clear isospecific inclination. Chiral gas chromatography analysis revealed a mild preference for a given lactide enantiomer by the chiral catalysts.

The stereoselectivity of bipyrrolidine-based sequential polydentate ligands around Ru(ii).

The Ru(ii) coordination chemistry of the sequential hexadentate, tetradentate and the novel hybrid pentadentate ligands assembled around the chiral bipyrrolidine core and including bipyridyl and pyridyl periphery units is described. The bipyridine group exhibited priority in binding over the bipyrrolidine group, which led to a diastereomer mixture in the case of the hexadentate ligand 1. Employing only monopyridyl or a combination of monopyridyl and bipyridyl peripheral groups restored the chiral induction ability to the bipyrrolidine core resulting in predetermined chiral-at-metal complexes for the ligands 3 and 4.

Assembling Quasi-enantiomeric Octahedral Complexes of Different Metals via Quasi-racemate Crystallization.

Aiming at a general methodology for binary co-assembly of complexes of different metals through quasiracemate crystallization, the hexadentate ligand 1 comprised of the chiral bipyrrolidine core and two bipyridine peripheral arms is introduced. Ligand 1 was found to bind in a fully diastereoselective and uniform mode around Zn(II), Fe(II) and Cd(II) giving coordinatively inert octahedral "chiral-at-metal" complexes with the Δ4Λ2/Λ4 Δ2 wrapping mode. Equimolar mixtures of quasienantiomeric pairs of these complexes exhibited a clear tendency to pack as quasiracemates as was revealed from the crystallographic structures of [(R,R)-1-Zn](PF6)2/[(S,S)-1-Fe](PF6)2 and [(R,R)-1-Zn](PF6)2/[(S,S)-1-Cd](PF6)2, in an isomorphous fashion to that of the racemic compound [rac-1-Zn](PF6)2 in space group C2/c.

Impact of 18F-FDG PET/CT on target volume delineation in recurrent or residual gynaecologic carcinoma.

Background: To evaluate the impact of 18F-FDG PET/CT on target volume delineation in gynaecological cancer.

Methods: F-FDG PET/CT based RT treatment planning was performed in 10 patients with locally recurrent (n = 5) or post-surgical residual gynaecological cancer (n = 5). The gross tumor volume (GTV) was defined by 4 experienced radiation oncologists first using contrast enhanced CT (GTVCT) and secondly using the fused 18F-FDG PET/CT datasets (GTVPET/CT).

Toward the development of the direct and selective detection of nitrates by a bioinspired Mo-Cu system.

The development of a new platform for the direct and selective detection of nitrates is described. Two thioether-based chemosensors and the corresponding sulfoxides and sulfones were prepared, and their photophysical properties were evaluated. Upon selective sulfoxidation of these thioethers with nitrates via an oxygen-transfer reaction promoted by a bioinspired Mo-Cu system, significant fluorescence shifts were measured.

Selective sulfoxidation of thioethers and thioaryl boranes with nitrate, promoted by a molybdenum-copper catalytic system.

The catalytic reduction of nitrate by molybdo-enzymes plays a central role in the global biological cycle of nitrogen. However, the use of nitrates as oxidants in synthetic organic chemistry is very limited and typically requires very strong acidic and other extreme reaction conditions. We have developed a highly chemoselective and efficient catalytic process for the sulfoxidation of thioethers and arylthioethers containing boronic acid or boronic ester functional groups, using nitrate salts as oxidants.

High-dose-rate brachytherapy boost to the dominant intra-prostatic tumor region: hemi-irradiation of prostate cancer.

Background: To assess the feasibility, toxicity, and outcome of prostate hemi-irradiation with a high-dose-rate brachytherapy (HDR-BT) boost for patients presumed to harbor dominant intra-prostatic tumors in a single lobe.

Methods: After 3D conformal external radiotherapy (3DCRT) to 64-64.4 Gy, 77 patients with non-metastatic locally aggressive prostate cancer have been treated from 2000 to 2004, with HDR-BT using temporary open MRI-guided (192) Ir implants, to escalate the dose in the boost region.

Hypofractionated boost with high-dose-rate brachytherapy and open magnetic resonance imaging-guided implants for locally aggressive prostate cancer: a sequential dose-escalation pilot study.

Purpose: To evaluate the feasibility, tolerance, and preliminary outcome of an open MRI-guided prostate partial-volume high-dose-rate brachytherapy (HDR-BT) schedule in a group of selected patients with nonmetastatic, locally aggressive prostatic tumors.

Methods And Materials: After conventional fractionated three-dimensional conformal external radiotherapy to 64-64.4 Gy, 77 patients with nonmetastatic, locally aggressive (e.

Outcome of uterine clear cell carcinomas compared to endometrioid carcinomas and poorly-differentiated endometrioid carcinomas.

Objectives: Our aim was to compare the survival between patients with clear cell carcinoma (CC) and patients with endometrioid carcinoma (EC).

Methods: Through the population-based Geneva Cancer Registry, we identified 1,380 resident women diagnosed with uterine cancer between 1970 and 2000. We excluded those with papillary serous endometrial carcinoma and uterine sarcomas.

Absolute depth-dose-rate measurements for an 192Ir HDR brachytherapy source in water using MOSFET detectors.

Reported MOSFET measurements concern mostly external radiotherapy and in vivo dosimetry. In this paper, we apply the technique for absolute dosimetry in the context of HDR brachytherapy using an 192Ir source. Measured radial dose rate distributions in water for different planes perpendicular to the source axis are presented and special attention is paid to the calibration of the R and K type detectors, and to the determination of appropriate correction factors for the sensitivity variation with the increase of the threshold voltage and the energy dependence.

(144)Ce as a potential candidate for interstitial and intravascular brachytherapy.

Purpose: To investigate the suitability of (144)Ce for both interstitial and intravascular brachytherapy applications.

Methods And Materials: Monte Carlo calculations of radial dose rate distributions in water were performed for (144)Ce in a spring-shaped source and compared with two commonly used interstitial and intravascular sources, (192)Ir and (32)P. The numeric simulations were checked experimentally with a calibrated ionization chamber in a water phantom.

Fractionated stereotactic radiotherapy boost for gynecologic tumors: an alternative to brachytherapy?

Purpose: A brachytherapy (BT) boost to the vaginal vault is considered standard treatment for many endometrial or cervical cancers. We aimed to challenge this treatment standard by using stereotactic radiotherapy (SRT) with a linac-based micromultileaf collimator technique.

Methods And Materials: Since January 2002, 16 patients with either endometrial (9) or cervical (7) cancer have been treated with a final boost to the areas at higher risk for relapse.

Dosimetric characterization of radioactive sources employed in prostate cancer therapy.

Purpose: Three types of radiation sources are employed currently in the radiation treatment of prostate cancer, namely, external, implant, and high-dose-rate (HDR) sources using an afterloader method. The present article provides a detailed dosimetric characterization of several commercially available implant sources and an HDR source employing the same stochastic code and dataset.

Methods And Materials: The radioactive implants considered are (125)I seeds: models 6701, 6702 and 6711, (103)Pd seed: model 200, and a high-dose-rate (192)Ir source: microSelectron-HDR model V7.

Positive peritoneal cytology in early-stage endometrial cancer does not influence prognosis.

The aim of this study was to assess the prognostic importance of positive peritoneal cytology in early-stage endometrial cancer. All 278 stage I and 53 stage IIIA (without cervical involvement) endometrial cancer patients operated between 1980 and 1996, recorded at the Geneva Cancer registry, were included. Stage IIIA cancers were recategorised into 'cytological' stage IIIA (positive peritoneal cytology alone, n=33) and 'histological' stage IIIA (serosal or adnexal infiltration, n=20).

Prescribing, recording, and reporting in endovascular brachytherapy. Quality assurance, equipment, personnel and education.

Endovascular brachytherapy is a new, rapidly growing field of interest in radiotherapy for the prevention of neointimal hyperplasia after angioplasty in both coronary and peripheral arteries. Many physics aspects of these treatments have already been addressed in the report of the American Association of Physicists in Medicine task group on 'Intravascular brachytherapy', but up to now there are no generally accepted recommendations for recording and reporting radiation doses and volumes. The terminology to be used by all individuals involved in such treatments (radiation oncologists, physicists, and interventionalists) is not clearly defined.

Gamma-irradiation markedly inhibits the hydrated collagen gel contradiction by arterial smooth muscle cells.

Background: Vessel wall responses to percutaneous transluminal coronary angioplasty include neointimal proliferation and arterial remodeling. The contraction of a collagen gel is a good in vitro model of wound repair and vascular remodeling. Because irradiation is an important new therapeutic modality capable of preventing restenosis, the purpose of this study was to evaluate the effect of irradiation on the contraction of a collagen gel by smooth muscle cells (SMCs), on SMCs viability, and on DNA synthesis.

Endoluminal beta-radiation therapy for the prevention of coronary restenosis after balloon angioplasty. The Dose-Finding Study Group.

Background: Beta radiation is effective in reducing vascular neointimal proliferation in animals after injury caused by balloon angioplasty. However, the lowest dose that can prevent restenosis after coronary angioplasty has yet to be determined.

Methods: After successful balloon angioplasty of a previously untreated coronary stenosis, 181 patients were randomly assigned to receive 9, 12, 15, or 18 Gy of radiation delivered by a centered yttrium-90 source.

Mechanisms of neointima formation and remodeling in the porcine coronary artery.

Background: To characterize the cells responsible for neointima formation after porcine coronary artery wall injury, we studied the expression of smooth muscle cell (SMC) differentiation markers in 2 models: (1) self-expanding stent implantation resulting in no or little interruption of internal elastic lamina and (2) percutaneous transluminal coronary angioplasty (PTCA) resulting in complete medial rupture and exposure of adventitia to blood components.

Methods And Results: The expression of alpha-smooth muscle (SM) actin, SM myosin heavy chain isoforms 1 and 2, desmin, and smoothelin was investigated by means of immunohistochemistry and Western blots in tissues of the arterial wall collected at different time points and in cell populations cultured from these tissues. The expression of smoothelin, a marker of late SMC differentiation, was used to discriminate between SMCs and myofibroblasts.