A. Experimental part: general General Chemicals. IR-780 iodide (99%), 4-mercaptobenzoic acid (99%), yttrium(III) oxide (Y 2 O 3 , 99.99%), ytterbium (III) oxide (Yb 2 O 3, 99.9%), erbium (III) oxide (Er 2 O 3, 99.9%), trifluoroacetic acid (CF 3 COOH, 99%), sodium trifluoroacetate (CF 3 COONa, 98%), N,Ndimethylformamide (DMF, anhydrous, 99.8%), and chloroform (ACS spectrophotometric grade, ≥99.8%, with amylenes as stabilizer) were obtained from Aldrich. Oleylamine (C 18-content 80-90%) was purchased from Acros. Dichloromethane (DCM, AR grade) and diethyl ether (AR grade) were obtained from LAB-SCAN. Ethanol (absolute) was purchased from Merck. All chemicals were used as received. Lanthanide trifluoroacetate trihydrates (RE(CF 3 COO) 3 •3H 2 O) were prepared by a method described in the literature. [1] Instrumentation. 1 H and 13 C NMR spectra were recorded on a Varian AMX400 (400 and 100.59 MHz, respectively) using CDCl 3 as solvent at room temperature. Spectra were referenced to the solvent line (CHCl 3 : 7.26 ppm for 1 H, 77.0 ppm for 13 C) relative to tetramethylsilane. Data are reported as follows: chemical shifts, multiplicity (s = singlet, d = doublet, dd = doublet of doublets, t = triplet), coupling constants (Hz), and integration. FT-IR spectra were recorded on a Nicolet Nexus FT-IR spectrometer, using the SMART iTR for ATR measurements (diamond). Mass spectra were recorded on a LTQ Orbitrap XL (ESI+). Transmission electron microscopy (TEM) was performed on a Philips CM10 transmission electron microscope operating at an accelerating voltage of 100 kV. Images were recorded on a Gatan slow-scan CCD camera. UV-Vis absorption spectra were measured on a Perkin/Elmer Lambda 900 UV-Vis-NIR Spectrometer in chloroform in a quartz cuvette with a path length of 1 cm. Standard CW fluorescence measurements of solutions in chloroform were performed on a Fluorolog 3 (Jobin Yvon Horiba). For the up-conversion luminescence measurements, a Ti:Sapphire laser system (MIRA-900-F) was used as the excitation source. Luminescence spectra and lifetime measurements were performed in the cw and pulsed mode, respectively. In the latter case, the repetition rate was 76 MHz. The excitation light was focused into a 1 mm thick sample cell by a 75 mm focal length lens. This resulted in a focal spot of 120±10 μm full-width at half-maximum level. The excitation power was controlled by a gradient neutral density filter and set at 2 mW for all experiments with the exception of the power-dependence measurements. The emission was collected at the right-angle geometry via an f/2 collimating lens and subsequently focused by an f/4 lens onto the slit of the spectrograph. The (time-resolved) emission detection was performed by a streak camera system equipped with a spectrograph (Hamamatsu C5680) running with the vertical time axis sweep off while recording cw emission spectra.

No abstract

No abstract

Production of polyhydroxyalkanoate (PHA) biopolymers by mixed microbial cultures concurrent to wastewater treatment is a valorization route for residual organic material. This development has been at pilot scale since 2011 using industrial and municipal organic residuals. Previous experience was the basis for a PHA production demonstration project: PHARIO. PHARIO was centred on processing surplus activated sludge biomass from the Bath full-scale municipal wastewater treatment plant in the Netherlands to produce PHA. Full-scale surplus activated sludge was fed to a pilot facility to produce PHA rich biomass using fermented volatile fatty acid (VFA) rich liquors from industry or primary sludge sources. A PHA rich biomass with on average 0.41 gPHA/gVSS was obtained with reproducible thermal properties and high thermal stability. A routine kilogram scale production was established over 10 months and the polymer material properties and market potential were evaluated. Surplus full-scale activated sludge, over four seasons of operations, was a reliable raw material to consistently and predictably produce commercial quality grades of PHA. Polymer type and properties were systematic functions of the mean co-polymer content. The mean co-polymer content was predictably determined by the fermented feedstock composition. PHARIO polymers were estimated to have a significantly lower environmental impact compared to currently available (bio)plastics.

The half-sandwich zirconium and hafnium N,N-dimethylaminopropyl complexes Cp*M-[(CH 2 ) 3 NMe 2 ]Cl 2 (Cp* ) η 5 -C 5 Me 5 , M ) Zr, 1; Hf, 2) and Cp*M[(CH 2 ) 3 NMe 2 ] 2 Cl (M ) Zr, 3; Hf, 4) were synthesized by mono-or dialkylation of Cp*MCl 3 with the corresponding alkyllithium and Grignard reagents. Hydrogenolysis of the monoalkyl species resulted in the formation of the polyhydride complexes Cp* 3 M 3 (µ-H) 4 (µ-Cl) 2 Cl 3 (M ) Zr, 5; Hf, 6) and Cp*MCl 3 . A crystal structure determination of Cp* 3 Hf 3 H 4 Cl 5 (6) revealed a fully asymmetric trinuclear structure with three widely differing Hf‚‚‚Hf distances. Reaction of Cp* 3 M 3 H 4 Cl 5 with PMe 3 resulted in fragmentation of the cluster and ligand redistribution to give Cp*MCl 3 -(PMe 3 ) and the dimeric hydride complexes Cp* 2 M 2 (µ-H) 3 Cl 3 (PMe 3 ) (M ) Zr, 7; Hf, 8), structurally characterized for M ) Zr. The trinuclear polyhydride Cp* 3 Hf 3 H 4 Cl 5 reacts with 2,6-xylylisocyanide to give three distinct products, a µ-enediamide complex, [Cp*HfCl 2 ] 2 [µ-xyNCHdCHNxy] (11, xy ) 2,6-dimethylphenyl), which was structurally characterized, an imido complex, [Cp*Hf(µ-Nxy)Cl] 2 ( 12), and an azaallyl species, Cp*Hf(η 3 -CH 2 CHNxy)Cl 2 (13). The reactivity of 6 can be interpreted as proceeding through initial cleavage of the trinuclear complex into the fragments "Cp* 2 Hf 2 (µ-H) 3 Cl 3 " and "Cp*HfHCl 2 ", followed by the separate reactivity of these fragments.