Imperial College London

DrPhilipMiller

Faculty of Natural SciencesDepartment of Chemistry

Senior Lecturer
 
 
 
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Contact

 

+44 (0)20 7594 2847philip.miller Website

 
 
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Location

 

501kMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Publication Type
Year
to

51 results found

Miller P, Apps S, Long N, 2019, Cobalt(-I) triphos dinitrogen complexes: activation and silyl-functionalisation of N2, Chemical Communications, Vol: 55, Pages: 6579-6582, ISSN: 1359-7345

The cobalt dinitrogen complexes [{(EP3Ph)Co(μ-N2)}2Mg(THF)4], with triphos ligand scaffolds (EP3Ph, E = N or CMe), were prepared via two electron reductions of the Co(I) precursors [CoCl(EP3Ph)]. Both complexes showed high degrees of N2 activation owing to the formation of a rare M–NN–Mg–NN–M bridging-magnesium core. These systems showed further N2 functionalisation reactivity by silylation, forming silyldiazenido complexes [(EP3Ph)Co(NNSiMe3)].

Journal article

Green SP, Payne AD, Wheelhouse KM, Hallett JP, Miller PW, Bull JAet al., 2019, Diazo transfer reagent 2-azido-4,6-dimethoxy-1,3,5-triazine (ADT) Displays highly exothermic decomposition comparable to tosyl azide, The Journal of Organic Chemistry, Vol: 84, Pages: 5893-5898, ISSN: 0022-3263

2-Azido-4,6-dimethoxy-1,3,5-triazine (ADT) was reported recently as a new “intrinsically safe” diazo-transfer reagent. This assessment was based on differential scanning calorimetry data indicating that ADT exhibits endothermic decomposition. We present DSC data on ADT that show exothermic decomposition with an initiation temperature (Tinit) of 159 °C and an enthalpy of decomposition (ΔHD) of −1135 J g–1 (−207 kJ mol–1). We conclude that ADT is potentially explosive and must be treated with caution, being of comparable exothermic magnitude to tosyl azide (TsN3). A maximum recommended process temperature for ADT is 55 °C.

Journal article

Cooper S, Yue T, Miller P, Ma M, Long Net al., 2019, Tripodal N-centred phosphine ligands: Towards a novel donor set for Tc-99m and Re-186/188 radiopharmaceutical formulation, Publisher: WILEY, Pages: S295-S296, ISSN: 0362-4803

Conference paper

Zhang J, Chen J, Peng S, Peng S, Zhang Z, Tong Y, Miller PW, Yan X-Pet al., 2019, Emerging porous materials in confined spaces: from chromatographic applications to flow chemistry., Chem Soc Rev

Searching for porous materials that can be employed as solid stationary phases for chromatographic separations, porous membrane matrixes and solid supports for catalysis has become an active research area. Strategies for embedding emerging porous materials in columnar systems and their subsequent applications (separation and catalysis) have been developed, which benefit from the remarkable progress in the discovery and development of porous materials based on metal-organic coordination or dynamic covalent bonding such as metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), porous organic cages, and porous organic polymers. In this review, porous materials that have been confined within capillary columns as packed, monolithic and open tubular columns are discussed. Progress in chromatographic separation and continuous flow catalytic synthesis is reviewed according to three major strategies. Applications of porous materials in membrane-separation fibre membrane systems and microfluidic devices with various functions are also highlighted.

Journal article

Fu R, Carroll L, Yahioglu GK, Aboagye E, Miller Pet al., 2018, Antibody fragment and affibody immunoPET imaging agents: radiolabelling strategies and applications, ChemMedChem, Vol: 13, Pages: 2466-2478, ISSN: 1860-7187

Antibodies have long been recognised as potent vectors for carrying diagnostic medical radionuclides, contrast agents and optical probes to diseased tissue for imaging. The area of ImmunoPET combines the use of positron emission tomography (PET) imaging with antibodies to improve the diagnosis, staging and monitoring of diseases. Recent developments in antibody engineering and PET radiochemistry have led to a new wave of experimental ImmunoPET imaging agents that are based on a range of antibody fragments and affibodies. In contrast to full antibodies, engineered affibody proteins and antibody fragments such as minibodies, diabodies, singleā€chain variable region fragments (scFvs), and nanobodies are much smaller but retain the essential specificities and affinities of full antibodies in addition to more desirable pharmacokinetics for imaging. Herein, recent key developments in the PET radiolabelling strategies of antibody fragments and related affibody molecules are highlighted, along with the main PET imaging applications of overexpressed antigenā€associated tumours and immune cells.

Journal article

Apps SL, White AJP, Miller PW, Long NJet al., 2018, Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex, Dalton Transactions, Vol: 47, Pages: 11386-11396, ISSN: 1477-9234

The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH2PPh2)3, NP3Ph) are reported. Reaction of N-triphos with [MoX3(THF)3] (X = Cl, Br, I) gave the Mo(III) complex [MoX3(κ2-NP3Ph)(THF)] (1), where bidentate N-triphos coordination was observed. Reduction of this complex in the presence of dppm (bis(diphenylphosphino)methane) gave the dinitrogen complex [Mo(N2)(dppm)(κ3-NP3Ph)] (2), which exhibits moderate dinitrogen activation. An additional hydride complex, [Mo(H)2(dppm)(κ3-NP3Ph)] (4), was produced either as a minor side product during the reduction step, or as a major product by direct hydrogenation of the dinitrogen complex 2. The reactivity of the dinitrogen complex 2 with a range of Lewis acids was also investigated. At low temperatures, protic or borane Lewis acids (H+, BBr3 and tris(pentafluorophenyl)borane (BCF)) were found to coordinate to the apical nitrogen atom of the N-triphos ligand, with no conclusive evidence of any functionalisation of the dinitrogen ligand. Alkali metal Lewis acid addition to 2 resulted in the unexpected rearrangement of the N-triphos ligand to form [Mo(dppm)(PMePh2)(PCP)][B(C6F5)4] (7), where PCP, [Ph2PCNHCH2PPh2] is the carbenic ligand formed upon rearrangement from the reaction of 2 with M[B(C6F5)4] (M = Li, Na or K). Single crystal X-ray diffraction of complexes 1, 2, 4 and 7 provided structural confirmation of the N-triphos molybdenum complexes described.

Journal article

Haywood T, Cesarec S, Kealey S, Plisson C, Miller Pet al., 2018, Ammonium [11C]thiocyanate: revised preparation and reactivity studies of a versatile nucleophile for carbon-11 radiolabelling, MedChemComm, Vol: 9, Pages: 1311-1314, ISSN: 2040-2503

Herein we report the preparation of ammonium [11C]thiocyanate via the reaction of [11C]CS2 with ammonia. The [11C]SCN− ion is demonstrated as a potent nucleophile that can be used to readily generate a range of 11C-labelled thiocyanate molecules in high conversions. Furthermore, novel 11C-labelled thiazolone molecules can be easily prepared from the intermediate α-thiocyanatophenones via an acid mediated cyclisation reaction.

Journal article

Rasekh M, Ahmad Z, Cross R, Hernandez-Gil J, Wilton-Ely JDET, Miller PWet al., 2017, Facile Preparation of Drug-Loaded Tristearin Encapsulated Superparamagnetic Iron Oxide Nanoparticles Using Coaxial Electrospray Processing, MOLECULAR PHARMACEUTICS, Vol: 14, Pages: 2010-2023, ISSN: 1543-8384

Naturally occurring polymers are promising biocompatible materials that have many applications for emerging therapies, drug delivery systems, and diagnostic agents. The handling and processing of such materials still constitutes a major challenge, which can limit the full exploitation of their properties. This study explores an ambient environment processing technique: coaxial electrospray (CO-ES) to encapsulate genistein (an isoflavonoid and model drug), superparamagnetic iron oxide nanoparticles (SPIONs, 10–15 nm), and a fluorophore (BODIPY) into a layered (triglyceride tristearin shell) particulate system, with a view to constructing a theranostic agent. Mode mapping of CO-ES led to an optimized atomization engineering window for stable jetting, leading to encapsulation of SPIONs within particles of diameter 0.65–1.2 μm and drug encapsulation efficiencies of around 92%. Electron microscopy was used to image the encapsulated SPIONs and confirm core–shell triglyceride encapsulation in addition to further physicochemical characterization (AFM, FTIR, DSC, and TGA). Cell viability assays (MTT, HeLa cells) were used to determine optimal SPION loaded particles (∼1 mg/mL), while in vitro release profile experiments (PBS, pH = 7.4) demonstrate a triphasic release profile. Further cell studies confirmed cell uptake and internalization at selected time points (t = 1, 2, and 4 h). The results suggest potential for using the CO-ES technique as an efficient way to encapsulate SPIONs together with sensitive drugs for the development of multimodal particles that have potential application for combined imaging and therapy.

Journal article

Omoruyi U, Page S, Hallett J, Miller PWet al., 2016, Homogeneous Catalyzed Reactions of Levulinic Acid: To γ-Valerolactone and Beyond, Chemsuschem, Vol: 9, Pages: 2037-2047, ISSN: 1864-564X

Platform chemicals derived from lignocellulosic plant biomass are viewed as a sustainable replacement for crude oil-based feedstocks. Levulinic acid (LA) is one such biomass-derived chemical that has been widely studied for further catalytic transformation to γ-valerolactone (GVL), an important ‘green’ fuel additive, solvent, and fine chemical intermediate. Although the transformation of LA to GVL can be achieved using heterogeneous catalysis, homogeneous catalytic systems that operate under milder reactions, give higher selectivities and can be recycled continuously are attracting considerable attention. A range of new homogeneous catalysts have now been demonstrated to efficiently convert LA to GVL and to transform LA directly to other value-added chemicals such as 1,4-pentanediol (1,4-PDO) and 2-methyltetrahydrofuran (2-MTHF). This Minireview covers recent advances in the area of homogeneous catalysis for the conversion of levulinic acid and levulinic ester derivatives to GVL and chemicals beyond GVL.

Journal article

Merchant S, Allott L, Carroll L, Tittrea V, Kealey S, Witney TH, Miller PW, Smith G, Aboagye EOet al., 2016, Synthesis and pre-clinical evaluation of a [<sup>18</sup>F]fluoromethyl-tanaproget derivative for imaging of progesterone receptor expression, RSC Advances, Vol: 6, Pages: 57569-57579, ISSN: 2046-2069

The estrogen receptor (ER) and progesterone receptor (PR) are over-expressed in ∼50% of breast cancer lesions, and used as biomarkers to stratify patients for endocrine therapy. Currently, immunohistochemical (IHC) assessment of these lesions from a core-needle biopsy in deep-sited metastases has limitations associated with sampling error and lack of standardization. An alternative solution is positron emission tomography (PET)-based probes, which are inherently quantitative and capable of imaging the entire tumor, including metastases. This work features the synthesis and biological evaluation of a novel fluorinated derivative of tanaproget, a high affinity non-steroidal PR ligand, as a candidate for imaging PR expression in vivo. Radiolabeling of the candidate was achieved in a 15% ± 4 radiochemical yield (non-decay corrected) in one step from [18F]fluoromethyltosylate in 30 min. Cell uptake studies showed a significant difference between the radioligand uptake in PR+ and PR- cell lines; however, in vivo imaging was confounded by defluorination hypothesized to occur via iminium salt formation. Investigation into high affinity, metabolically stable non-steroidal PR ligands is currently ongoing.

Journal article

Phanopoulos A, Long NJ, Miller PW, 2016, Triphosphine ligands: coordination chemistry and recent catalytic applications, The Chemical Bond III, Editors: Mingos, Publisher: Springer, Pages: 31-61

Phosphines are a long established class of ligand that are known to form a vast array of transition metal complexes. They behave as neutral electron pair donors, or Lewis bases, that alter the solubility and stereoelectronic properties of the metal centre. A key motivation for their continued development is for homogeneous catalysis. For over five decades, transition metal–phosphine complexes have been used for catalytic reactions, mainly exploiting monodentate or bidentate phosphine ligands. Multidentate phosphines by comparison have received much less attention in part because they tend to form more stable complexes with a saturated coordination environment around the metal centre. Recent developments in the areas of catalytic reduction of carboxylic acid derivatives using molecular hydrogen and in the field of biomass up-conversion have exploited catalysts based on tridentate phosphines. This chapter highlights the use of these multidentate phosphines for synthesis of coordination complexes and discusses some of their recent applications in homogeneous catalysis.

Book chapter

Phanopoulos A, White AJP, Long NJ, Miller PWet al., 2016, Insight into the stereoelectronic parameters of N-triphos ligands via coordination to tungsten(0), Dalton Transactions, Vol: 45, Pages: 5536-5548, ISSN: 1477-9226

A series of new N-triphos tungsten complexes have been synthesised and structurally characterised. The coordination behaviour of a range of N-triphos (N(CH2PR2)3, NP3R) ligands, and a mixed-arm diphosphine-pyridyl (PPNCyh) ligand were explored. The steric and electronic parameters of five N-triphos ligands: NP3Ph, NP3iPr, NP3Cyp, NP3Cyh and NP3PhF2, and the carbon-centred triphos ligand, CH3C(CH2PPh2)3 (MeCP3Ph), were established. Steric parameters were evaluated by analysing the cone angles calculated from X-ray crystal structures, whilst the electron-donating ability of the ligands was determined from 31P–77Se NMR coupling constants of selenium derivatives and the IR carbonyl stretching frequencies across a series of tungsten–carbonyl complexes. In general, electron-rich phosphines formed bidentate complexes while less electron-rich ligands coordinated in a tridentate mode, regardless of steric bulk. An indirect interaction between the apical nitrogen of the ligand and metal centre is implicated for tridentate complexes and is supported through DFT calculations and analysis of N-protonated complexes. Complexes 1, 3, 4, 6–8 and 10 were characterised by single-crystal X-ray crystallography.

Journal article

Miller P, Phanopoulos A, Long N, 2015, Direct conversion of levulinic acid to 2-methyltetrahydrofuran using discrete Ru and Rh N-triphos catalysts, Publisher: AMER CHEMICAL SOC, ISSN: 0065-7727

Conference paper

Miller PW, 2015, Production and Reaction of [11C]Carbon Disulfide for the Synthesis of [11C]Dithiocarbamates, Radiochemical Syntheses, Volume 2 Further Radiopharmaceuticals for Positron Emission Tomography and New Strategies for Their Production, Editors: Scott, Publisher: John Wiley & Sons, Pages: 177-183, ISBN: 9781118237847

Book chapter

Haywood T, Kealey S, Sanchez-Cabezas S, Hall J, Allott L, Smith G, plisson C, Miller PWet al., 2015, Carbon-11 Radiolabelling of Organosulfur Compounds: 11C Synthesis of the Progesterone Receptor Agonist Tanaproget, Chemistry-A European Journal, Vol: 21, Pages: 9034-9038, ISSN: 1521-3765

Herein a new 11C radiolabelling strategy for the fast and efficient synthesis of thioureas and related derivatives using the novel synthon, 11CS2, is reported. This approach has enabled the facile labelling of a potent progesterone receptor (PR) agonist, [11C]Tanaproget, by the intramolecular reaction of the acyclic aminohydroxyl precursor with 11CS2, which has potential applications as a positron emission tomography radioligand for cancer imaging.

Journal article

Phanopoulos A, Miller PW, Long NJ, 2015, Beyond Triphos - New hinges for a classical chelating ligand, Coordination Chemistry Reviews, Vol: 299, Pages: 39-60, ISSN: 1873-3840

Branched triphosphine ligands have been less widely studied than mono- and bi-dentate analogues. The most studied ligand of this type is TriphosPh (CH3C(CH2PPh2)3). Substitution of the apical Csingle bondCH3 moiety with boron, silicon, tin, nitrogen or phosphorus fragments has generated a new family of ligands, in some cases displaying varying coordination chemistry and reactivity to the parent carbon-based system. This review includes the synthetic strategies implemented to afford these ligands, as well as derivatives by way of varying the phosphine substituents. Although not exhaustive, relevant types of reported complexes featuring these ligands are discussed, as well as their reactivity and catalytic applications. Through critical analysis, common themes and chemical trends across this family of apical heteroatomic, branched triphosphines can be identified, leading to improvements in current chemical applications, as well as new areas that remain underdeveloped.

Journal article

Phanopoulos A, Long N, Miller P, 2015, The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphos(Ph) Complexes, JOVE-JOURNAL OF VISUALIZED EXPERIMENTS, ISSN: 1940-087X

Journal article

Phanopoulos A, White AJ, Long NJ, Miller PWet al., 2015, Catalytic Transformation of Levulinic Acid to 2-Methyltetrahydrofuran Using Ruthenium–N-Triphos Complexes, ACS Catalysis

Journal article

Liu H, Feng J, Zhang J, Miller PW, Chen L, Su C-Yet al., 2015, A catalytic chiral gel microfluidic reactor assembled via dynamic covalent chemistry, Chemical Science, Vol: 6, Pages: 2292-2296, ISSN: 2041-6539

Journal article

Miller PW, Kato K, Langstrom B, 2015, Carbon-11, Nitrogen-13 and Oxygen-15 Chemistry, The Chemistry of Molecular Imaging, Editors: Long, Wong, Pages: 79-99, ISBN: 978-1-118-09327-6

Book chapter

Luo W, Zhu Y, Zhang J, He J, Chi Z, Miller PW, Chen L, Su C-Yet al., 2014, A dynamic covalent imine gel as a luminescent sensor, CHEMICAL COMMUNICATIONS, Vol: 50, Pages: 11942-11945, ISSN: 1359-7345

Journal article

Lin M, Liu H, Miller PW, Zhang J, Su CYet al., 2014, Surface modification of supramolecular nanotubes and selective guest capture, New Journal of Chemistry

Journal article

Phanopoulos A, Brown NJ, White AJP, Long NJ, Miler PWet al., 2014, Synthesis, Characterization, and Reactivity of Ruthenium Hydride Complexes of N-Centered Triphosphine Ligands, INORGANIC CHEMISTRY, Vol: 53, Pages: 3742-3752, ISSN: 0020-1669

Journal article

Kealey S, Gee A, Miller PW, 2014, Transition metal mediated [C-11] carbonylation reactions: recent advances and applications, JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS, Vol: 57, Pages: 195-201, ISSN: 0362-4803

Journal article

Haywood T, Miller PW, 2014, Microfluidic Hydrogenation Reactions by using a Channel-Supported Rhodium Catalyst, Chemcatchem, Vol: 6, Pages: 1199-1203

Journal article

Miller PW, Bender D, 2012, [11C]Carbon Disulfide: A Versatile Reagent for PET Radiolabelling, CHEMISTRY-A EUROPEAN JOURNAL, Vol: 18, Pages: 433-436, ISSN: 0947-6539

Journal article

Gong X, Miller PW, Gee AD, Long NJ, deMello AJ, Vilar Ret al., 2012, Gas–Liquid Segmented Flow Microfluidics for Screening Pd-Catalyzed Carbonylation Reactions, Chemistry: A European Journal, Vol: 18, Pages: 2768-2772

Journal article

Hanton MJ, Tin S, Boardman B, Miller Pet al., 2011, Ruthenium-catalysed hydrogenation of esters using tripodal phosphine ligands, JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, Vol: 346, Pages: 70-78, ISSN: 1381-1169

Journal article

Buscemi G, Miller PW, Kealey S, Gee AD, Long NJ, Passchier J, Vilar Ret al., 2011, Ultra-rapid carbonylation using palladium(I) dimer precatalysts applied to 11CO-radiolabelling for PET, Org. Biomol. Chem., Vol: 9, Pages: 3499-3503, ISSN: 1477-0520

Journal article

Child CR, Kealey S, Jones H, Miller PW, AJP W, Gee AD, Long NJet al., 2011, Binding and photodissociation of CO in iron(II) complexes for application in positron emission tomography (PET) radiolabelling, Dalton Transactions, Vol: 40, Pages: 6210-6215

Journal article

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