Platinum-based anticancer drugs are the mainstay of chemotherapy regimens in clinic. Nevertheless, the efficacy of platinum drugs is badly affected by serious systemic toxicities and drug resistance, and the pharmacokinetics of most platinum drugs is largely unknown. In recent years, a keen interest in functionalizing platinum complexes with bioactive molecules, targeting groups, photosensitizers, fluorophores, or nanomaterials has been sparked among chemical and biomedical researchers. The motivation for functionalization comes from some of the following demands: to improve the tumor selectivity or minimize the systemic toxicity of the drugs, to enhance the cellular accumulation of the drugs, to overcome the tumor resistance to the drugs, to visualize the drug molecules in vitro or in vivo, to achieve a synergistic anticancer effect between different therapeutic modalities, or to add extra functionality to the drugs. In this Account, we present different strategies being used for functionalizing platinum complexes, including conjugation with bisphosphonates, peptides, receptor-specific ligands, polymers, nanoparticles, magnetic resonance imaging contrast agents, metal chelators, or photosensitizers. Among them, bisphosphonates, peptides, and receptor-specific ligands are used for actively targeted drug delivery, polymers and nanoparticles are for passively targeted drug delivery, magnetic resonance imaging contrast agents are for theranostic purposes, metal chelators are for the treatment or prevention of Alzheimer's disease (AD), and photosensitizers are for photodynamic therapy of cancers. The rationales behind these designs are explained and justified at the molecular or cellular level, associating with the requirements for diagnosis, therapy, and visualization of biological processes. To illustrate the wide range of opportunities and challenges that are emerging in this realm, representative examples of targeted drug delivery systems, anticancer conjugates, anticancer theranostic agents, and anti-AD compounds relevant to functionalized platinum complexes are provided. All the examples exhibit new potential of platinum complexes for future applications in biomedical areas. The emphases of this Account are placed on the functionalization for targeted drug delivery and theranostic agents. In the end, a general assessment of various strategies has been made according to their major shortcomings and defects. The original information in this Account comes entirely from literature appearing since 2010.
Light-driven CO 2 reduction into high value-added product is a potential route to convert and store solar energy. Here, using the hydroxyls on an oxyhydroxide photocatalyst, CoGeO 2 (OH) 2 , as solid-state proton source to reduce the CO 2 into CH 4 is proposed. It is found that under irradiation, the lattice hydroxyls on surface of CoGeO 2 (OH) 2 are oxidized by photogenerated holes, resulting in the generation of oxygen vacancies (O Vs ) and protons. The photoinduced O Vs (Lewis acid) and its proximal surface hydroxyls (Lewis base) are more likely to form the frustrated Lewis acid-base pairs, which can capture, activate, and reduce CO 2 with the assistance of protons into CH 4 . The surface lattice hydroxyls are able to regenerate when the catalyst is exposed to the water molecule-containing atmosphere, thus achieving a sustainable CO 2 conversion. The proposed CO 2 reduction by self-breathing surface hydroxyls may open a new avenue to use photocatalysis for energy conversion.
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