Purpose: Organ motion can significantly affect the accurate delivery of radiation doses to the tumor, particularly for sites such as the breast, lung, abdomen, and pelvis. Managing this motion during treatment is crucial. One strategy employed to manage motion induced from respiration is breath-hold (BH), which enhances the geometric precision of dose delivery. Our institute is transitioning to using the ExacTrac Dynamic system to facilitate patient BH using surface-guided cameras. Only 20% of our linacs are equipped with surface guidance capabilities, and due to a high patient stereotactic throughput, the ability to perform in-bunker coaching for BH patients within the bunker is limited. To address this challenge, a time-of-flight camera (ToF) was developed to coach radiotherapy patients undergoing BH procedures, allowing them to gain confidence in the process outside of the bunker and before treatment. Methods: The camera underwent testing for absolute and relative accuracy, responsiveness under various environmental conditions, and comparison with the Elekta Active Breathing Coordinator (ABC) to establish correlation and testing on volunteers independently to assess usability. Results: The results showed that the absolute distance measured by the camera was nonlinear due to square light modulation, which was retrospectively corrected. Relative accuracy was tested with a QUASAR motion phantom, with results agreeing to within ± 2 mm. The camera response was found to be unaffected by changes in lighting or temperature, though it overresponded under extreme temperatures. The comparison with the Elekta ABC system yielded comparable results between lung volume and changes in surface distance during BH. All volunteers successfully followed instructions and maintained BH within ± 1 mm tolerance. Conclusions: This study demonstrates the feasibility of using a cost-effective ToF camera to coach patients before imaging/treatment, saving valuable LINAC linac and imaging system time.

This paper aims to provide guidance and a framework for commissioning tests and tolerances for the ExacTrac Dynamic image-guided and surface-guided radiotherapy (SGRT) system. ExacTrac Dynamic includes a stereoscopic X-ray system, a structured light projector, stereoscopic cameras, thermal camera for SGRT, and has the capability to track breath holds and internal markers. The system provides fast and accurate image guidance and intrafraction guidance for stereotactic radiosurgery and stereotactic ablative radiotherapy. ExacTrac Dynamic was commissioned on a recently installed Elekta Versa HD. Commissioning tests are described including safety, isocenter calibration, dosimetry, image quality, data transfer, SGRT stability, SGRT localization, gating, fusion, implanted markers, breath hold, and end-to-end testing. Custom phantom designs have been implemented for assessment of the deep inspiration breath-hold workflow, the implanted markers workflow, and for gating tests where remote-controlled movement of a phantom is required. Commissioning tests were all found to be in tolerance, with maximum translational and rotational deviations in SGRT of 0.3 mm and 0.4°, respectively, and X-ray image fusion reproducibility standard deviation of 0.08 mm. Tolerances were based on published documents and upon the performance characteristics of the system as specified by the vendor. The unique configuration of ExacTrac Dynamic requires the end user to design commissioning tests that validate the system for use in the clinical implementation adopted in the department. As there are multiple customizable workflows available, tests should be designed around these workflows, and can be ongoing as workflows are progressively introduced into departmental procedures.

Optically stimulated luminescence dosimetry is a relatively recent field of in-vivo dosimetry in clinical radiotherapy, developing over the last 20 years. As a pilot study, this paper presents a direct comparison between the sensitivity variance with use, stability of measurement and linearity of the current clinical standard Al2O3:C and a potential alternative, beryllium oxide. A set of ten optically stimulated luminescence dosimeters (OSLD), including five of each type, were used simultaneously and irradiated on a Versa HD linear accelerator. Having similar sensitivity, while Al2O3:C showed a relatively stable signal response from initial use, BeO was found to have a higher response to the same dose. However, BeO displayed a strong exponential decline from initial signal response following a model of $$Respons{e}_{BeO}=(0.55\pm 0.05){e}^{-\left(0.40\pm 0.05\right)x}+(0.54\pm 0.01)$$ , reaching stability after approximately 10 irradiation cycles. BeO was shown to have potentially higher accuracy than Al2O3:C, with less variation between individual doses. Both OSLD showed good linearity between 0.2–5.0 Gy. Between these bounds, Al2O3:C demonstrated a strong linear response following the trend $$Dose_{Al_{2}O_{3}, group(adj)}=(1.00\pm 0.09)x-(0.02\pm 0.04)\,{\text{Gy}}$$ , however beyond this showed deviation from linearity, resulting in a measured dose of $$12.0\pm 0.2$$ Gy at 10.0 Gy dose delivery. BeO showed strong linearity across the full examined range of 0.2–10.0 Gy with following a model of $$Dos{e}_{BeO, ind}=(0.98\pm 0.01)x+(0.04\pm 0.01)$$ Gy with a recorded dose at 10.0 Gy delivery as $$9.9\pm 0.1$$ Gy. In conclusion, BeO does show large variance in sensitivity between individual OSLD and a considerable initial variance and decline in dose–response, however after pre-conditioning and individual normalisation to offset OSLD specific sensitivity BeO provides not only a viable alternative to Al2O3:C, but potentially provide higher accuracy, precision and reproducibility for in-vivo dosimetry.

Healthcare relies upon the accurate and safe delivery of patient care. This is only achievable when systems are developed to ensure high quality, robust outcomes, for instance quality management systems. The concept of quality management can take on a different meaning depending on the context in which it is found. To add complication, the amount of education required for quality management will vary depending on one's exposure to the implementation of quality systems. In part to address these issues, the Australasian College of Physical Scientists and Engineers in Medicine (ACPSEM) Queensland Branch held a quality management webinar for members and non-members across Australia and New Zealand. The purpose of the webinar was to educate and facilitate discussion regarding the application of quality management principles for the ACPSEM profession. In conjunction, a pre- and post-webinar survey was conducted to gain an insight into existing knowledge and attitudes within the professions governed by the ACPSEM and students undertaking related studies. This paper authored by the webinar speakers reintroduces the quality management principles that were discussed in webinar, exemplifies the importance of quality management skills within the ACPSEM professions and presents the results of the surveys, promoting the need for more educational resources on quality management tools.

PURPOSE:Fiducial marker seeds are often used as a surrogate to identify and track the positioning of prostate volume in the treatment of prostate cancer. Tracking the movement of prostate seeds aids in minimizing the prescription dose spillage outside the target volume to reduce normal tissue complications. In this study, You Only Look Once (YOLO) v2™ (MathWorks™) convolutional neural network was employed to train ground truth datasets and develop a program in MATLAB that can visualize and detect the seeds on projection images obtained from kilovoltage (kV) X-ray volume imaging (XVI) panel (Elekta™).METHODS:As a proof of concept, a wax phantom containing three gold marker seeds was imaged, and kV XVI seed images were labeled and used as ground truth to train the model. The projection images were corrected for any panel shift using flex map data. Upon successful testing, labeled marker seeds and projection images of three patients were used to train a model to detect fiducial marker seeds. A software program was developed to display the projection images in real-time and predict the seeds using YOLO v2 and determine the centers of the marker seeds on each image.RESULTS:The fiducial marker seeds were successfully detected in 98% of images from all gantry angles; the variation in the position of the seed center was within ± 1 mm. The percentage difference between the ground truth and the detected seeds was within 3%.CONCLUSION:Our study shows that deep learning can be used to detect fiducial marker seeds in kV images in real time. This is an ongoing study, and work is underway to extend it to other sites for tracking moving structures with minimal effort.

Geometric distortions in magnetic resonance can introduce significant uncertainties into applications such as radiotherapy treatment planning and need to be assessed as part of a comprehensive quality assurance program. We report the design, fabrication, and imaging of a custom 3D printed unibody MR distortion phantom along with quantitative image analysis. Methods: The internal cavity of the phantom is an orthogonal three-dimensional planar lattice, composed of 3 mm diameter rods spaced equidistantly at a 20 mm centre-centre offset repeating along the X, Y, and Z axes. The phantom featured an overall length of 308.5 mm, a width of 246 mm, and a height of 264 mm with lines on the external surface for phantom positioning matched to external lasers. The MR phantom was 3D printed in Nylon-12 using an advancement on traditional selective laser sintering (SLS) (HP Jet Fusion 3D-4200 machine). The phantom was scanned on a Toshiba Aquilion CT scanner to check the integrity of the 3D print and correct for any resultant issues. The phantom was then filled with NiSO4 solution and scanned on a 3T PET-MR Siemens scanner for selected T1 and T2 sequences, from which distortion vectors were generated and analysed using in-house software written in Python. Results: All deviations of the node positions from the print design were less than 1 mm, with an average displacement of 0.228 mm. The majority of the deviations were smaller than the 0.692 mm pixel size for this dataset. Conclusion: A customised 3D printed MRI-phantom was successfully printed and tested for assessing geometric distortion on MRI scanners. 3D printed phantoms can be considered for clinics wishing to assess geometric distortions under specific conditions, but require resources for design, fabrication, commissioning, and verification.

Alanine chips exposed to high doses of radiation produces long lived free radicals that could be easily measured with electron paramagnetic resonance (EPR) spectrometers. In this study, the feasibility of using alanine dosimeters for performing rapid quality assurance of Leksell Gamma Knife (LGK) treatment plans was demonstrated. A 3D printed grid was placed inside the LGK spherical solid water phantom (SWP) for measurement of doses at isocentre and off-axis points. The EPR spectroscopy was performed on a Magnettech MS-5000 EPR/ESR spectrometer. A set of dose calibration curves were established prior to the use of alanine chips for LGK dosimetry. Absolute dose, transit dose and dose/timer linearity were performed with the alanine chips positioned at the centre of the LGK solid water phantom (SWP). Five patients of different sites were selected, and patient specific quality assurance (PSQA) was performed in the LGK SWP. The absolute dose measured with the EPR alanine dosimeter agreed well within 2% of the ion chamber results and PSQA results were within 2.1%. Alanine-based EPR dosimetry offers rapid dose measurement with high accuracy and can also be used as a dosimeter for Gamma Knife PSQA.

Melanin is the primary photoprotecting pigment in humans as well as being implicated in the development of deadly melanoma. The material also conducts electricity and has thus become a bioelectronic model for proton-to-electron transduction. Central to these phenomena are its spin properties-notably two linked species derived from carbon-centered and semiquinone radicals. Using a novel in situ photoinduced electron paramagnetic resonance technique with simultaneous electrical measurements, we have elucidated for the first time the distinct photoreactivity of the two different radical species. We find that the production of the semiquinone is light- and water-driven, explaining the electrical properties and revealing biologically relevant photoreactivity.

The synthesis, X-ray molecular structure, physico-chemical characterization and dual antioxidant activity (catalase and superoxide dismutase) of a new polymeric mixed valence Mn(III)Mn(II) complex, containing the ligand H2BPClNOL (N-(2-hydroxybenzyl)-N-(2-pyridylmethyl)[(3-chloro)(2-hydroxy)] propylamine) is described. The monomeric unit is composed of a dinuclear Mn(II)Mn(III) moiety, [Mn(III)(μ-HBPClNOL)(μ-BPClNOL)Mn(II)(Cl)](ClO4)·2H2O, 1, in which the Mn ions are connected by two different bridging groups provided by two molecules of the ligand H2BPClNOL, a phenoxide and an alkoxide group. In the solid state, this mixed valence dinuclear unit is connected to its neighbors through chloro bridges. Magnetic measurements indicated the presence of ferromagnetic [J = +0.076(13) cm−1] and antiferromagnetic [J = −5.224(13) cm−1] interactions. The compound promotes O2•- dismutation in aqueous solution (IC50 = 0.370 μmol dm−3, kcat = 3.6x106 M−1 s−1). EPR studies revealed that a high-valent Mn(III)-O-Mn(IV) species is involved in the superoxide dismutation catalytic cycle. Complex 1 shows catalase activity only in the presence of a base, e.g., piperazine or triethylamine. Kinetic studies were carried out in the presence of piperazine and employing two different methods, resulting in kcat values of 0.58 ± 0.03 s−1 (detection of O2 production employing a Clark electrode) and 2.59 ± 0.12 s−1 (H2O2 consuption recorded via UV-Vis). EPR and ESI-(+)-MS studies indicate that piperazine induces the oxidation of 1, resulting in the formation of the catalytically active Mn(III)-O-Mn(IV) species.

A new type of zeolitic imidazolate framework ZIF-8/TiO2 nanocomposites was developed for photocatalytic reduction of CO2 to CH4 and CO in a newly designed photoreactor under intentionally controlled pressure swing. The ZIF-8/TiO2 core-shell structure plays an important role in the adsorption of CO2 by ZIF-8 and subsequent in-situ photocatalytic reduction on TiO2. The introduction of pressure change in the reaction system facilitates the adsorption-desorption process of CO2 and reaction products, which consequently led to improved photoreduction performance. This approach highlights the importance of mass transfer and reactor design for improved photoreduction. (C) 2017 Elsevier B.V. All rights reserved.

In our previous studies, heme was bound into honeybee silk to generate materials that could function as nitric oxide sensors or as recoverable heterogeneous biocatalysts. In this study, we sought to increase the heme-binding capacity of the silk protein by firstly redesigning the heme binding site to contain histidine as the coordinating residue and secondly, by adding multiple histidine residues within the core of the coiled coil core region of the modified silk protein. We used detergent and a protein denaturant to confirm the importance of the helical structure of the silk for heme coordination. Aqueous methanol treatment, which was used to stabilize the materials, transformed the low-spin, six-coordinate heme to a five-coordinate high-spin complex, thus providing a vacant site for ligand binding. The optimal aqueous methanol treatment time that simultaneously maintains the helical protein structure and stabilizes the silk material without substantial leaching of heme from the system was determined.

Acetohydroxyacid synthase (AHAS) is the first enzyme in the biosynthesis pathway of the branched-chain amino acids, catalyzing the condensation of pyruvate with another molecule of pyruvate or with 2-ketobutyrate, to produce 2-acetolactate or 2-acetohydroxybutyrate, respectively. The catalytic subunit of the dimeric enzyme has thiamin diphosphate (ThDP), a divalent metal ion, flavin adenine dinucleotide (FAD), and two molecules of oxygen (O-2(I) and O-2(II)) as cofactors. Here, crystal structures of Saccharomyces cerevisiae AHAS in complex with pyruvate provide novel insights into the mechanistic features of this enzyme including: i) The precise position taken by pyruvate molecules as they enter the active site (i.e. prior to catalysis occurring) with conformations suitable for the transfer of electrons to/from O-2(I) and FAD; ii) The formation of ternary donor-acceptor-O-2(I) complexes and iii) The location of O-2(II) relative to the substrate showing that it plays a critical role in the organization of substrate for catalysis. These structural data, accompanied by electron paramagnetic resonance evidence that a radical is produced during AHAS catalysis, lead to the proposal that FAD and O-2 are involved in an indirect one-electron redox cycle. In this mechanism, the spatial configurations of O-2 and FAD in the active site can allow electrons to be exchanged with the substrates and catalytic intermediates to satisfy and control the overall AHAS catalyzed reaction.

Substituted semicarbazones/thiosemicarbazones and their copper complexes have been prepared and several single crystal structures examined. The copper complexes of these semicarbazone/thiosemicarbazones were prepared and several crystal structures examined. The single crystal X-ray structure of the pyridyl-substituted semicarbazone showed two types of copper complexes, a monomer and a dimer. We also found that the p-nitrophenyl semicarbazone formed a conventional 'magic lantern' acetate-bridged dimer. Electron Paramagnetic Resonance (EPR) of several of the copper complexes was consistent with the results of single crystal X-ray crystallography. The EPR spectra of the p-nitrophenyl semicarbazone copper complex in dimethylsulfoxide (DMSO) showed the presence of two species, confirming the structural information. Since thiosemicarbazones and semicarbazones have been reported to exhibit anticancer activity, we examined the anticancer activity of several of the derivatives reported in the present study and interestingly only the thiosemicarbazone showed activity while the semicarbazones were not active indicating that introduction of sulphur atom alters the biological profile of these thiosemicarbazones.

This study investigated how to control the rate of photoreduction of metastable AuCl2(-) at the solid-solution interface of large ZnO nanoparticles (NPs) (50-100 nm size). Band-gap photoexcitation of electronic charge in ZnO by 370 nm UV light yielded Au NP deposition and the formation of ZnO-Au NP hybrids. Au NP growth was observed to be nonepitaxial, and the patterns of Au photodeposition onto ZnO NPs observed by high-resolution transmission electron microscopy were consistent with reduction of AuCl2(-) at ZnO facet edges and corner sites. Au NP photodeposition was effective in the presence of labile oleylamine ligands attached to the ZnO surface; however, when a strong-binding dodecanethiol ligand coated the surface, photodeposition was quenched. Rates of interfacial electron transfer at the ZnO-solution interface were adjusted by changing the solvent, and these rates were observed to strongly depend on the solvent's permittivity (ε) and viscosity. From measurements of electron transfer from ZnO to the organic dye toluidine blue at the ZnO-solution interface, it was confirmed that low ε solvent mixtures (ε ≈ 9.5) possessed markedly higher rates of photocatalytic interfacial electron transfer (∼3.2 × 10(4) electrons·particle(-1)·s(-1)) compared to solvent mixtures with high ε (ε = 29.9, ∼1.9 × 10(4) electrons·particle(-1)·s(-1)). Dissolved oxygen content in the solvent and the exposure time of ZnO to band-gap, near-UV photoexcitation were also identified as factors that strongly affected Au photodeposition behavior. Production of Au clusters was favored under conditions that caused electron accumulation in the ZnO-Au NP hybrid. Under conditions where electron discharge was rapid (such as in low ε solvents), AuCl2(-) precursor ions photoreduced at ZnO surfaces in less than 5 s, leading to deposition of several small, isolated ∼6 nm Au NP on the ZnO host instead.

The active site of mammalian purple acid phosphatases (PAPs) have a dinuclear iron site in two accessible oxidation states (Fe(III)2 and Fe(III)Fe(II)), and the heterovalent is the active form, involved in the regulation of phosphate and phosphorylated metabolite levels in a wide range of organisms. Therefore, two sites with different coordination geometries to stabilize the heterovalent active form and, in addition, with hydrogen bond donors to enable the fixation of the substrate and release of the product, are believed to be required for catalytically competent model systems. Two ligands and their dinuclear iron complexes have been studied in detail. The solid-state structures and properties, studied by X-ray crystallography, magnetism, and Mössbauer spectroscopy, and the solution structural and electronic properties, investigated by mass spectrometry, electronic, nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and Mössbauer spectroscopies and electrochemistry, are discussed in detail in order to understand the structures and relative stabilities in solution. In particular, with one of the ligands, a heterovalent Fe(III)Fe(II) species has been produced by chemical oxidation of the Fe(II)2 precursor. The phosphatase reactivities of the complexes, in particular, also of the heterovalent complex, are reported. These studies include pH-dependent as well as substrate concentration dependent studies, leading to pH profiles, catalytic efficiencies and turnover numbers, and indicate that the heterovalent diiron complex discussed here is an accurate PAP model system.

Complexation studies of the dinucleating ligand H3 L (H3 L=2-{[bis(pyridin-2-ylmethyl)amino]methyl}-6-{[bis(6-pivaloylamidopyridin-2-ylmethyl)amino]methyl}-4-methylphenol), with metal-binding sites A and B, which both provide four donors to a metal ion; a tertiary amine; two pyridines (substituted with amide hydrogen-bond donors in site B), and a bridging phenolate, with Zn(II) , Cu(II) , and Ga(III) are reported. The titration of H3 L with the three metal ions in solution was monitored by NMR spectroscopy or EPR and UV/Vis/near-IR spectroscopy, as well as by ESI-MS to analyze the selectivity of the two metal-ion sites A and B of this model ligand for metallophosphatases; the spectroscopic assignments are supported by X-ray crystallography results. The first Zn(II) ion coordinates to site A with unsubstituted pyridine donors and, upon addition of a second equivalent of Zn(II) , this coordinates to the sterically less accessible site B. From a similar titration with Ga(III) , it emerges that only a mononuclear complex is obtained, with the Ga(III) center coordinated to site A. When one equivalent of Ga(III) is reacted with the mononuclear Zn(II) complex, Zn(II) is forced by Ga(III) to exchange the site; this results in a dinuclear complex with Ga(III) in site A and Zn(II) in site B. With Cu(II) , two isomers are observed: one with and the other without a bridging phenolate; these differ significantly in their spectroscopic and magnetic properties.

We report the first (55)Mn pulsed ENDOR studies on the S2 state multiline spin ½ centre of the oxygen evolving complex (OEC) in Photosystem II (PS II), at temperatures below 4.2 K. These were performed on highly active samples of spinach PS II core complexes, developed previously in our laboratories for photosystem spectroscopic use, at temperatures down to 2.5 K. Under these conditions, relaxation effects which have previously hindered observation of most of the manganese ENDOR resonances from the OEC coupled Mn cluster are suppressed. (55)Mn ENDOR hyperfine couplings ranging from ∼50 to ∼680 MHz are now seen on the S2 state multiline EPR signal. These, together with complementary high resolution X-band CW EPR measurements and detailed simulations, reveal that at least two and probably three Mn hyperfine couplings with large anisotropy are seen, indicating that three Mn(III) ions are likely present in the functional S2 state of the enzyme. This suggests a low oxidation state paradigm for the OEC (mean Mn oxidation level 3.0 in the S1 state) and unexpected Mn exchange coupling in the S2 state, with two Mn ions nearly magnetically silent. Our results rationalize a number of previous ligand ESEEM/ENDOR studies and labelled water exchange experiments on the S2 state of the photosystem, in a common picture which is closely consistent with recent photo-assembly (Kolling et al., Biophys. J. 2012, 103, 313-322) and large scale computational studies on the OEC (Gatt et al., Angew. Chem., Int. Ed. 2012, 51, 12025-12028, Kurashige et al. Nat. Chem. 2013, 5, 660-666).

Three synthetic analogues of westiallamide, H3L(wa), have previously been synthesized (H3L(1-3)) that have a common backbone (derived from l-valine) with H3L(wa) but differ in their heterocyclic rings (imidazole, oxazole, thiazole, and oxazoline). Herein we explore in detail through high-resolution pulsed electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) spectroscopy in conjunction with density functional theory (DFT) the geometric and electronic structures of the mono- and dinuclear Cu(II) complexes of these cyclic pseudo hexapeptides. Orientation-selective hyperfine sublevel correlation, electron nuclear double resonance, and three-pulse electron spin echo envelope modulation spectroscopy of [Cu(II)(H2L(1))(MeOH)2](+) reveal delocalization of the unpaired electron spin onto the ligating and distal nitrogens of the coordinated heterocyclic rings and that they are magnetically inequivalent. DFT calculations confirm this and show similar spin densities on the distal heteroatoms in the heterocyclic rings coordinated to the Cu(II) ion in the other cyclic pseudo hexapeptide [Cu(II)(H2L(2,3,wa))(MeOH)2](+) complexes. The magnetic inequivalencies in [Cu(II)(H2L(1))(MeOH)2](+) arise from different orientations of the heterocyclic rings coordinated to the Cu(II) ion, and the delocalization of the unpaired electron onto the distal heteroatoms within these N-methylimidazole rings depends upon their location with respect to the Cu(II) d(x(2)-y(2)) orbital. A systematic study of DFT functionals and basis sets was undertaken to examine the ability to reproduce the experimentally determined spin Hamiltonian parameters. Inclusion of spin-orbit coupling (SOC) using MAG-ReSpect or ORCA with a BHLYP/IGLO-II Wachters setup with SOC corrections and ∼38% Hartree-Fock exchange gave the best predictions of the g and A((63)Cu) matrices. DFT calculations of the (14)N hyperfine and quadrupole parameters for the distal nitrogens of the coordinated heterocyclic rings in [Cu(II)(H2L(1))(MeOH)2](+) with the B1LYP functional and the SVP basis set were in excellent agreement with the experimental data, though other choices of functional and basis set also provided reasonable values. MCD, EPR, mass spectrometry, and DFT showed that preparation of the dinuclear Cu(II) complex in a 1:1 MeOH/glycerol mixture (necessary for MCD) resulted in the exchange of the bridging methoxide ligand for glycerol with a corresponding decrease in the magnitude of the exchange coupling.

In recent times the Cu(I)-catalyzed click reaction between azides and alkynes has been extensively utilized in the preparation of polymers proposed for the use in biomedical applications. There is a potential for some Cu residues to remain in the polymers, and there has been discussion about whether this renders the polymers unsuitable for medical applications. It is well known that the presence of Cu(II) complexed to ester groups can accelerate their hydrolysis. The question then arises as to whether residual Cu(II) from the click reaction can catalyze the hydrolysis of polyesters. In this work the role of residual Cu(II) in the hydrolysis of copolymer hydrogels containing ester groups is elucidated. The copper(I)-catalyzed "click" reaction was used to synthesize a hyperbranched Boltornbased polyester macromer which was then used in the preparation of a series of copolymer hydrogels formed with PEG diacrylate. Trace amounts of Cu(II) residues were found by AAS and EPR to remain in the hydrogels, even after extensive washing with EDTA solutions. The effect of these residues on the hydrolytic degradation of the hydrogels has been investigated and the presence of complexed Cu(II) was found to accelerate the hydrolysis of the hydrogels and to contribute also to the formation of pits in the pore walls of the hydrogels at intermediate degradation times.

A mixed-valence complex, [Fe(III)Fe(II)L1(μ-OAc)(2)]BF(4)·H(2)O, where the ligand H(2)L1 = 2-{[[3-[((bis(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzyl](pyridin-2-ylmethyl)amino]methyl]phenol}, has been studied with a range of techniques, and, where possible, its properties have been compared to those of the corresponding enzyme system purple acid phosphatase. The Fe(III)Fe(II) and Fe(III)(2) oxidized species were studied spectroelectrochemically. The temperature-dependent population of the S = 3/2 spin states of the heterovalent system, observed using magnetic circular dichroism, confirmed that the dinuclear center is weakly antiferromagnetically coupled (H = -2JS(1)·S(2), where J = -5.6 cm(-1)) in a frozen solution. The ligand-to-metal charge-transfer transitions are correlated with density functional theory calculations. The Fe(III)Fe(II) complex is electron paramagnetic resonance (EPR)-silent, except at very low temperatures (<2 K), because of the broadening caused by the exchange coupling and zero-field-splitting parameters being of comparable magnitude and rapid spin-lattice relaxation. However, a phosphate-bound Fe(III)(2) complex showed an EPR spectrum due to population of the S(tot) = 3 state (J= -3.5 cm(-1)). The phosphatase activity of the Fe(III)Fe(II) complex in hydrolysis of bis(2,4-dinitrophenyl)phosphate (k(cat.) = 1.88 × 10(-3) s(-1); K(m) = 4.63 × 10(-3) mol L(-1)) is similar to that of other bimetallic heterovalent complexes with the same ligand. Analysis of the kinetic data supports a mechanism where the initiating nucleophile in the phosphatase reaction is a hydroxide, terminally bound to Fe(III). It is interesting to note that aqueous solutions of [Fe(III)Fe(II)L1(μ-OAc)(2)](+) are also capable of protein cleavage, at mild temperature and pH conditions, thus further expanding the scope of this complex's catalytic promiscuity.