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Exploration of the Medical Periodic Table: Towards New Targets Nicolas P

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Exploration of the Medical Periodic Table: Towards New Targets Nicolas P Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2013 Exploration of the medical periodic table: towards new targets Nicolas P. E. Barry and Peter J. Sadler* Supporting Information Table S1. Some examples of uses of the elements in therapy and diagnosis. These entries have guided our colour-coding in Fig.1, which is illustrative only and not comprehensive. Z Symbol Element Some medically-relevant uses Essential element; pH tightly controlled but variable: blood ~7.4, lysomes 4–5, tumour tissue 6–7, 1 H Hydrogen endosomes (transferrin) 5.5; duodenum 6–6.5, large intestine 5.5–7, stomach 1–3; 2H for kinetic control of organic drugs; 3H as radiotracer. He-O ; for treatment of chronic obstructive 2 He Helium 2 pulmonary disease; hyperpolarised 3He for MRI. 3 Li Lithium Li2CO3: drug for treatment of bipolar disorders. Compounds can provoke severe immune response 4 Be Beryllium (chronic beryllium disease). Boromycin: bacteriocidal polyether-macrolide antibiotic. Boronophenylalanine-based Boron 5 B Boron Neutron Capture Therapy in combination with Cetuximab in clinical Phase I trials for head and neck cancer treatments. Essential element; body produces 3-6 mL CO per 6 C Carbon day- suppresses organ rejection, ‘neurotransmitter’; 11C, 14C used in radiopharmaceuticals. Essential element; NO is a muscle relaxant, 7 N Nitrogen vasodilator, hypotensive, ‘neurotransmitter’; 13N used in radiopharmaceuticals. Essential element; Reactive oxygen species (ROS), 8 O Oxygen 1 - - e.g. O2, O2 , H2O2, O3, ONO2 . Essential element; Toughens tooth enamel as 9 F Fluorine component of (fluoro)apatite; 18F labelling, positron emission, radioimaging, PET scans. 10 Ne Neon Essential element; ca. 0.14 M in blood; excessive 11 Na Sodium NaCl intake increases arterial hypertension. Essential element; MgII is a laxative (sulphate, 12 Mg Magnesium Epsom Salts); Mg(OH)2 (milk of magnesia) antacid; II Mg (aspartate)2 dietary supplement. Added to some vaccines as an adjuvant; 13 Al Aluminium Al(OH)3 antacid. 14 Si Silicon Essential element; Role in connective tissue? Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2013 Silicates essential to prevent Al toxicity? Silicon phthalocyanine 4 photosensitizer for photodynamic therapy. Essential element; Polyphosphate abundant in all cells; oral sodium phosphate for bowel cleansing; 15 P Phosphorus phytate (inositol hexaphosphate) in plants can modulate metal uptake (e.g. Zn2+). Essential element; H S as signalling molecule 16 S Sulfur 2 (vasodilator and regulator of blood pressure). Essential element; Defect in membrane Cl- transport 17 Cl Chlorine in cystic fibrosis (CFTR gene); HOCl/OCl-, generated by myeloperoxidase in neutrophils. Ionized argon gas (plasma) - coagulation to control 18 Ar Argon bleeding from lesions in gastrointestinal tract. Essential element; natural radioisotope 40K 0.012% 19 K Potassium 9 emitter, t1/2 1.3 × 10 y. Essential element; CaCO antacid; Ca 20 Ca Calcium 3 oxalate/phosphate/carbonate kidney stones. 21 Sc Scandium 44Sc, positron emitter, potential for PET imaging. Budotitane and Cp2TiCl2 clinical anticancer trials 22 Ti Titanium abandoned; new Cp derivatives in development; Utilisation as inert material for implants. Essential element; Insulin-enhancing drugs, VIV 23 V Vanadium bis(2-ethyl-3-hydroxy-4-pyronato) in clinical trials for type-2 diabetes. CrIII tris(picolinate) sold as nutritional supplement; 24 Cr Chromium essentiality of Cr unclear. Essential element; SOD mimetics (e.g. MnIII salen chloride), MnII macrocyles for treatment of pain, 25 Mn Manganese neuroprotection; MnII dipyridoxyl diphosphate (MnDPDP) clinical MRI contrast agent. Essential element; FeII compounds for Fe deficiency (succinate, fumarate), also FeIII with Eo < –324 mV at pH 7 (dextran, dextrin); ferroquine in clinical 26 Fe Iron Phase II trials as antimalarial agent; superparamagnetic iron oxide MRI contrast agent; II Na2[Fe (CN)5NO] hypotensive. Essential element; Coenzyme Vitamin B12 essential (2-3 µg/day); treatment of pernicious anaemia; CTC- 96 CoIII bis(2-methylimidazole) acacen derivative 27 Co Cobalt (Doxovir) has completed clinical Phase I trials for ophthalmic herpetic keratitis and adenoviral conjunctivitis and clinical Phase II trials for herpes labialis. Essential element; Potential allergen (ear rings); used 28 Ni Nickel in trace mineral supplements; role in body poorly understood. Essential element; CuII bis(histidine) for Menke’s 29 Cu Copper disease; 64Cu PET/CT scans in clinical Phase II trials Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2013 for cervical cancer imaging; Cu-Algesic approved as anti-inflammatory agent for horses and dogs. II Essential element; Zn (gluconate)2 dietary 30 Zn Zinc supplement; ZnO skin ointment; ZnII citrate antiplaque (toothpastes). 67Ga γ-ray radioimaging; 66/68Ga PET; III [Ga (malolate)3] and [Ga(hydroxyquinolinate)3] NKP-2235 in Phase I clinical trials; 68Ga- 31 Ga Gallium DOTATATE PET/CT scans in clinical development (NCT01524016) for imaging in mesenchymal tumours, and oncogenic osteomalacia, and in clinical Phase I trials for neuroendocrine cancer imaging. 32 Ge Germanium Possible use of Ge nanoparticles as radiosensitizers. As2O3 approved drug for treatment of leukaemia and in clinical Phase II trials for lung cancers; arsenobetaine in marine organisms; Roxarsone (3- nitro-4-hydroxyphenyl arsenic acid) growth promoter in poultry. Darinaparsin approved drug for 33 As Arsenic peripheral T-cell lymphoma treatment, and in clinical Phase I clinical trials for solid tumours treatments. GSAO in clinical Phase I trials for advanced solid tumours that have not responded to therapy. Essential element; Human selenoproteome consists of 25 selenoproteins; selenocysteine tRNA; SeIV 34 Se Selenium sulfide active ingredient in some anti-dandruff shampoos (antifungal). Daily dietary intake of bromide ca 2 - 8 mg (fish, grains and nuts). Concentration in blood 10 – 100 35 Br Bromine µM; substrate for eosinophil peroxidase Br/H2O2 → HOBr. Potential for hyperpolarised 83Kr in MR imaging of 36 Kr Krypton airways 82Rb, positron emitter, PET e.g. in cardiac 37 Rb Rubidium sarcoidosis. SrCl in toothpastes (for sensitive teeth); 89Sr, β 38 Sr Strontium 2 emitter, therapeutic radionuclide. 90Y, β emitter, therapeutic radionuclide; 86Y, 39 Y Yttrium positron emitter, PET. 89Zr, positron emitter, PET imaging; ‘Aluminium zirconium tetrachlorohydrex gly’ 40 Zr Zirconium (Zr4+/Al3+ OH/Cl/glycine complexes) used in antiperspirants; zirconia (ZrO2) ceramics for orthopaedic surgery Heteropolyniobates [SiNb O ]16- can immobilise 41 Nb Niobium 12 40 viruses. 2- Essential element; MoO4 transport pathways; Tetrathiomolybdate [MoS ]2-: copper chelator for 42 Mo Molybdenum 4 overload (e.g. Wilson’s) diseases and in clinical Phase II trials for both breast cancer and esophageal Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2013 carcinoma treatments. 99mTc γ-ray radioimaging-ATSM in clinical Phase II trials for cervical cancer treatment; Cardiolite (99mTc-sestamibi) and Neurite (99mTc-disicate) approved for folate-receptor positive tumours 43 Tc Technetium imaging; Etarfolatide (EC20-99mTc) in clinical Phase III trials for folate-receptor positive tumours imaging; 99mTc-MIP-1404 in clinical Phase II trials for prostate cancer imaging. Trials of 94mTc (positron emitter) for PET. Two tetrachloride bis(N-heterocycle) RuIII 44 Ru Ruthenium complexes in clinical trials as anticancer and antimetastatic agents. 105Rh, β emitter, therapeutic radionuclide; dinuclear 45 Rh Rhodium RhII anticancer; photochemotherapeutic complexes. 103Pd, electron capture, radiotherapy; Palladium bacteriopherophorbide photosensitizer TOOKAD in 46 Pd Palladium Phase III clinical trials for localised prostate cancer treatment, and in Phase I/II for predetermined small renal tumour targets treatment. Antimicrobial; treatment of burnwounds; sulfadiazine, carbene complexes, nanoparticles; 47 Ag Silver Acticoat absorbant™ silver eluting dressing in clinical Phase IV trials for prevention of lower extremity revascularization wound complications. Induces metallothionein synthesis (detoxification); 48 Cd Cadmium cadmium carbonic anhydrase active in marine diatoms. 49 In Indium 111In γ-ray radioimaging. Essential element; Little known about biochemistry as essential element; SnIV ethyl etiopurpurin 50 Sn Tin (Purlytin) photosensitizer for photodynamic therapy of psoriasis and restenosis (Phase II). Antileishmanial SbV drugs: meglumine antimoniate 51 Sb Antimony (Glucantime) and sodium stibogluconate (Pentostam). Ammonium trichloro (dioxoethylene-O,O') tellurate 52 Te Tellurium is an immunomodulator Essential element; Thyroid hormones; iodo-organics 53 I Iodine as X-ray contrast agents; 123I, 125I radioimaging; 131I radiotherapy. Anaesthetic; hyperpolarised 129Xe as MRI contrast 54 Xe Xenon agent. 55 Cs Cesium 131Cs, electron capture, prostate brachytherapy. BaSO (barium sulphate meal) for radiographs of 56 Ba Barium 4 oesophagus, stomach and duodenum. La CO approved drug Oct 2004 (Fosrenol) for 57 La Lanthanum 2 3 hyperphosphatemia. 58 Ce Cerium Flammacerium (cerium(III) nitrate-silver Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2013 sulphadiazine) for treatment of burn wounds; CeIV
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