When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky.

The mixed molybdenum/tungsten Keggin-type polyoxometalate (POM) hybrid (TBA)4[PW9Mo2O39{Sn(C6H4I)}] (TBA = tert-butylammonium) has been prepared by the reaction between [α-PW9Mo2O39]7- and [Cl3Sn(C6H4I)] in dried acetonitrile, in the presence of tetra-n-butylammonium bromide. A further coupling reaction affords the ferrocenyl derivative (TBA)4[PW9Mo2O39{Sn(C6H4)C≡C(C6H4)Fc}]. The POM hybrids have been thoroughly characterized by NMR and IR spectroscopies. Electrochemical analysis confirms their ease of reduction compared to the all-W analogue, albeit with a second reduction process occurring at a lower potential than in the all-Mo species. It is noteworthy that the second reduction is accompanied by an unusual red shift of the electronic absorption spectrum. Whereas there is no doubt that the first reduction deals with Mo, the location of the second electron in the bireduced species, on the second Mo or on W, has thus been the subject of a cross-investigation by spectroelectrochemistry, electron spin resonance, and theoretical calculations. Finally, it came out that the second reduction is also Mo-centered with two unpaired and antiferromagnetically coupled extra electrons.

Photoelectric Conversion System Composed of Gene-Recombined Photosystem I and Platinum Nanoparticle Nanosheet.

Photosynthesis is one of the most vital processes in nature, which consists of two main photoreaction centers called photosystem I and photosystem II. The high quantum yield of photosystem I (PSI) makes it attractive for bioelectronic applications. However, the native PSI (N-PSI) loses its robust photochemical properties once fabricated into devices. This property degradation results from the difficulty in controlling the orientation of PSI. With the optimal orientation of PSI, photoexcited electrons can easily reach the electrode, yielding good photoelectric conversion efficiency. We developed a novel photoelectrode by integrating a newly designed gene-recombined PSI (G-PSI) with platinum nanoparticles (PtNPs) on substrates using a simple stacking method, which can control the orientation of PSI on the electrode. The target orientation of the attached G-PSI toward the substrate was confirmed by the absorption spectra of polarized light. An approximately 2-fold increase in the internal quantum yield (IQY) was observed for the G-PSI-attached electrode under 680 nm irradiation compared with that of the N-PSI-modified electrode. In addition, a 4-fold enhancement of the IQY was detected for cytochrome c (Cyt c) stacking on the G-PSI because of the electrostatic interaction, suggesting that Cyt c successfully secured the electron-transfer pathway.

Hierarchical Self-Assembly of Polyoxometalate-Based Organo Palladium(II) Metallomacrocycles via Electrostatic Interactions.

The design and synthesis of a supramolecular square composed of polyoxometalate-based hybrid donors and ethylenediamine palladium(II) nodes are reported. The structure of the metallomacrocycle scaffold was inferred by diffusion NMR, small-angle X-ray scattering (SAXS), and molecular modeling. The metallomacrocycle scaffold that contains negatively and positively charged subunits can further self-assemble owing to a competition between the solvation energy of the discrete species and intermolecular electrostatic interactions. When the dissociating character of the solvent was lowered or when in the presence of a protic solvent, different types of multiscale organizations (vesicles and pseudo-1D structures) were selectively formed and were characterized by SAXS and transmission electron microscopy.

Exploring the self-assembly of dumbbell-shaped polyoxometalate hybrids, from molecular building units to nanostructured soft materials.

The formation of hierarchical nanostructures using preformed dumbbell-like species made of covalent organic-inorganic polyoxometalate (POM)-based hybrids is herein described. In this system, the presence of charged subunits (POM, metal linkers, and counter ions) in the complex molecular architecture can drive their aggregation, which results from a competition between the solvation energy of the discrete species and intermolecular electrostatic interactions. We show that the nature of the POM and the charge of the metal linker are key parameters for the hierarchical nanoorganization. The experimental findings were corroborated with a computational investigation combining DFT and molecular dynamics simulation methods, which outlines the importance of solvation of the counter ion and POM/counter ion association in the aggregation process. The dumbbell-like species can also form gels, in the presence of a poorer solvent, displaying similar nanoorganization of the aggregates. We show that starting from the designed molecular building units whose internal charges can be controlled by redox trigger we can achieve their implementation into soft nanostructured materials through the control of their supramolecular organization.

Photosensing System Using Photosystem I and Gold Nanoparticle on Graphene Field-Effect Transistor.

In this study, a light sensor is fabricated based on photosystem I (PSI) and a graphene field-effect transistor (FET) that detects light at a high quantum yield under ambient conditions. We immobilized PSI on a micrometer-sized graphene FET using Au nanoparticles (AuNPs) and measured the I-V characteristics of the modified graphene FET before and after light irradiation. The source-drain current (Isd) increased upon illumination, exhibiting a photoresponsivity of 4.8 × 102 A W-1, and the charge neutrality point of graphene shifted by -12 mV. This system represents the first successful photosensing system based on proteins and a solution-gated graphene FET. The probable mechanism of this negative shift can be explained by the increase in negative charge carriers in graphene induced by a hole trap in the AuNP resulting from electron transfer from the AuNP to PSI. Photoresponses were only observed in the presence of two surface-active agents, n-hexyltrimethylammonium bromide and sodium dodecylbenzenesulfonate, because they caused the formation of a hydrophobic environment on the surface of the graphene. The lipid layer of these agents caused dissociation of ascorbate ions from the graphene sheet, thereby expanding the Debye screening length of the electrolyte solution. The hydrophobic environment above graphene also enhanced hole storage in the AuNP through electron transfer from the AuNP to PSI.

Comparison of 68Ga PET/CT to Other Imaging Studies in Medullary Thyroid Cancer: Superiority in Detecting Bone Metastases.

Context: Persistent disease after surgery is common in medullary thyroid cancer (MTC), requiring lifelong radiological surveillance. Staging workup includes imaging of neck, chest, abdomen, and bones. A study integrating all sites would be ideal. Despite the established use of gallium-68 (68Ga) positron emission tomography (PET)/CT with somatostatin analogues in most neuroendocrine tumors, its efficacy is controversial in MTC. Objective: Evaluate the efficacy of 68Ga PET/CT in detecting MTC lesions and evaluate tumor expression of somatostatin receptors (SSTRs) associated with 68Ga PET/CT findings. Methods: Prospective study evaluating 30 patients with MTC [group 1 (n = 16), biochemical disease; group 2 (n = 14), metastatic disease]. Patients underwent 68Ga PET/CT, bone scan, CT and ultrasound of the neck, CT of the chest, CT/MRI of the abdomen, and MRI of the spine. 68Ga PET/CT findings were analyzed by disease site as positive or negative and as concordant or discordant with conventional studies. Sensitivity and specificity were calculated using pathological or cytological analysis or unequivocal identification by standard imaging studies. Immunohistochemical analysis of SSTRs was compared with 68Ga PET/CT findings. Results: In both groups, 68Ga PET/CT was inferior to currently used imaging studies except for bone scan. In group 2, 68Ga PET/CT sensitivities were 56%, 57%, and 9% for detecting neck lymph nodes, lung metastases, and liver metastases, respectively, and 100% for bone metastases, superior to the bone scan (44%). Expression of SSTRs, observed in 44% of tumors, was not associated with 68Ga-DOTATATE uptake. Conclusions: 68Ga PET/CT does not provide optimal whole-body imaging as a single procedure in patients with MTC. However, it is highly sensitive in detecting bone lesions and could be a substitute for a bone scan and MRI.