Mathias O. Senge

Mathias O. Senge
Trinity College Dublin | TCD · School of Chemistry

Dipl.-Chem., Dr. rer. nat.

About

600
Publications
95,082
Reads
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13,441
Citations
Introduction
Synthetic organic chemistry; development of new synthetic methods; photochemistry; Bioorganic, bioinorganic and biological chemistry; molecular function of enzymes; medicinal chemistry, esp. photodynamic cancer therapy and photomedicine; photobiology, photosynthesis; crystallography, structure determination and conformational analysis of coordination compounds; porphyrins and tetrapyrroles. Optical materials and functional 2D materials. History and philosophy of chemistry and photomedicine.
Additional affiliations
January 2007 - present
St. James's Hospital
Position
  • PI
January 2005 - present
Trinity College Dublin
Position
  • Chair of Organic Chemistry
May 2001 - December 2004
Universität Potsdam
Position
  • Professor fuer Organische Chemie

Publications

Publications (600)
Article
Full-text available
Tetrapyrrole-containing proteins are one of the most fundamental classes of enzymes in nature and it remains an open question to give a chemical rationale for the multitude of biological reactions that can be catalyzed by these pigment-protein complexes. There are many fundamental processes where the same (i.e., chemically identical) porphyrin cofa...
Article
Full-text available
Heavy atom-free BODIPY-anthracene dyads (BADs) upon photoexcitation generate locally excited triplet excited states by way of photoinduced electron transfer (PeT), followed by recombination of the resulting charge-separated states (CSS). Subsequent quenching of the triplet states by molecular oxygen produces singlet oxygen (1O2), which reacts with...
Article
Full-text available
For the first time, free base and N-methylated porphyrins have been utilized as bifunctional organocatalysts in Michael additions and it was found that distortion of the macrocycle is a vital prerequisite for their catalytic activity. Conformational design has been used to tailor the properties of nonplanar porphyrins with regards to availability o...
Article
Full-text available
The selectivity and functional variability of porphyrin cofactors are typically based on substrate binding of metalloporphyrins wherein the pyrrole nitrogen units only serve to chelate the metal ions. Yet, using the free base porphyrin inner core system for other functions is possible through conformational engineering. As a first step towards porp...
Article
Full-text available
Porphyrins feature prominently in nature, be it as enzymatic cofactors, electron and exciton shuffles, as photoactive dyes, or as signaling substances. Their involvement in the generation, storage and use of oxygen is pivotal to life, while their photochemical properties are central to the biochemical functioning of plants. When complexed to metals...
Preprint
Full-text available
Within this work we review the metal coordination effect on the photophysics of metal dipyrrinato complexes. Dipyrrinato complexes are promising candidates in the search for alternative transition metal photosensitizers for application in photodynamic therapy (PDT). These complexes can be activated by irradiation with light of a specific wavelength...
Article
Porphyrins are variously substituted tetrapyrrolic macrocycles, with wide-ranging biological and chemical applications derived from metal chelation in the core and the 18π aromatic surface. Under suitable conditions, the porphyrin framework can deform significantly from regular planar shape, owing to steric overload on the porphyrin periphery or st...
Article
Full-text available
This review follows the research, development and clinical applications of the photosensitizer 5,10,15,20‐tetra(m‐hydroxyphenyl)chlorin (mTHPC, temoporfin) in photodynamic (cancer) therapy (PDT) and other medical applications. Temoporfin is the active substance in the medicinal product Foscan® authorized in the EU for the palliative treatment of he...
Article
The intrinsic challenge of large molecules to cross the cell membrane and reach intracellular targets is a major obstacle for the development of new medicines. We report how rotation along a single C–C bond, between separable atropisomers, of a drug in clinical trials improves cell uptake and therapeutic efficacy. The atropisomers of redaporfin (a...
Article
Full-text available
Two graphene oxide nanoassemblies using 5-(4-(aminophenyl)-10,15,20-triphenylporphyrin (TPPNH2) were fabricated by two synthetic methods: covalent (GO-CONHTPP) and noncovalent bonding. GO-CONHTPP was achieved through amide formation at the periphery of GO sheets and the hybrid material was fully characterized by FTIR, XPS, Raman spectroscopy, and S...
Article
The number of drug-resistant bacteria is increasing significantly. To combat such issues, antimicrobial PDT (aPDT) provides an efficient way to eliminate these species efficiently, cost-effectively, and more importantly, without the associated mechanism of resistance. The hemisynthesis and synthesis of photosensitizers such as polyaminated chlorin-...
Chapter
Porphyrin is the ligand that encapsulates iron in heme, the active site of the red blood cell protein hemoglobin. In plants, porphyrins in the form of magnesium complexes are the key players in photosynthesis. Porphyrin colors are also encountered in daily life. Many colors around us are related to porphyrin biosynthesis and catabolism. The early d...
Chapter
The chapter reviews past and current ways of naming and classifying synthetic and natural porphyrinoids and covers the older Fischer and modern IUPAC‐IUB nomenclature. The latter provides a convenient system of naming standard porphyrin derivatives, but has not kept pace with the explosive development of new classes of porphyrins with altered macro...
Chapter
The synthesis and functionalization of porphyrins is a long‐established but still burgeoning field. It has seen many advances, from studies on the fundamental natural heme and chlorophyll systems, to an ever‐expanding array of complex tetrapyrroles that are used in a multitude of modern applications ranging from biochemistry to catalysis, medicine...
Article
BODIPYs have been extensively used for biological imaging owing to their high fluorescent quantum yields of stability toward photobleaching. In this work, zwitterionic groups were introduced into trimethoxyphenyl-BODIPY derivatives to improve their water-solubility. The impact of the substitution pattern of the methoxy groups in the phenyl motif an...
Article
Full-text available
Recently prochiral solvating agents (pro-CSA) became a spotlight for the detection of enantiopurity by NMR. Chemical shift non-equivalency in achiral hosts introduced by the presence of chiral guests yields observable resonance signal splitting (Δδ) correlating to the enantiomeric excess (e.e.). In this work, symmetry is our lens to explain porphyr...
Article
Photodynamic therapy (PDT) is a multi-component therapy which relies on the delivery of a photosensitizer drug and light in the presence of oxygen to mediate a therapeutic anti-cancer or anti-microbial effect. As a multi-component therapy, a multidisciplinary research approach is required to achieve success with the application of PDT. The POLYTHEA...
Article
Full-text available
Photodynamic therapy (PDT) is a cancer treatment, which exploits a photosensitizing drug and light to produce reactive oxygen species that can cause selective damage to target tissue. The second generation photosensitizer 5,10,15,20‐tetrakis( m ‐hydroxyphenyl)chlorin ( m‐ THPC) is a widely used, clinically tested, and commercially available drug wi...
Article
Full-text available
Free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin stands for the class of powerful porphyrin photosensitizers for singlet oxygen generation and light-harvesting. The atomic level selectivity of dynamic UV pump - N K-edge probe X-ray absorption spectroscopy in combination with time-dependent density functional theory (TD-DFT) gives direct...
Article
Flüssigkristalle als responsive Materialien etwa in der organischen Elektronik, erste Nanogürtel mit Acencharakter, direkt aus der Atmosphäre entferntes CO2, Disauerstoff wird organokatalytisch zu Wasserstoffperoxid, und Chinazolinone lassen sich biokatalytisch herstellen.
Preprint
Recently prochiral solvating agents (pro-CSA) became a spotlight for the detection of enantiopurity by NMR. Chemical shift non-equivalency in achiral hosts introduced by the presence of chiral guest yields observable resonance signal splitting correlating to the enantiomeric excess (e.e.). In this work, symmetry is our lens to explain porphyrin-bas...
Article
Full-text available
Inspired by the rigidified architecture of ‘picket-fence’ systems, we propose a strategy utilizing strain to impose intramolecular tension in already peripherally overcrowded structures leading to selective atropisomeric conversion. Employing this approach, tuneable shape-persistent porphyrin conformations were acquired exhibiting distinctive supra...
Preprint
Aromaticity is an established and widely used concept for the prediction of the reactivity of organic molecules. However, in on-surface chemistry – where the interaction with the substrate can significantly alter the electronic and geometric structure of the adsorbates – the role of aromaticity is not understood. Here we investigate how aromaticity...
Article
Porphyrin-based oligomers were synthesized from the condensation of adsorbed 4-benzaldehyde-substituted porphyrins through the formation of C=C linkages, following a McMurry-type coupling scheme. Scanning tunneling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy data evidence both the dissociation of aldehyde g...
Article
Full-text available
A Langmuir film of cubane-bridged bisporphyrin (H2por-cubane-H2por) at the air/water interface was developed and characterized. The floating film was successfully employed for the chiral discrimination between l- and d-histidine. The enantioselective behavior persisted after the deposition of the film on a solid support using the Langmuir–Schaefer...
Article
Full-text available
Environmental pollution with chiral organic compounds is an emerging problem requiring innovative sensing methods. Amino-functionalized thioureas, such as 2-(dimethylamino)cyclo-hexyl-(3,5-bis(trifluoromethyl)phenyl)thiourea (Takemoto's catalyst), are widely used organocata-lysts with virtually unknown environmental safety data. Ecotoxicity studies...
Article
Full-text available
Tetraphenylethylene (TPE) and its derivatives exhibit excellent aggregation-induced emission (AIE) properties. The TPE unit is easily accessible and many functional groups can be introduced in a facile manner to yield effective luminescent materials in both solution and the solid-state. It is because of this, several TPE-based compounds have been d...
Article
Full-text available
Heavy‐atom‐free sensitizers forming long‐living triplet excited states via the spin‐orbit charge transfer intersystem crossing (SOCT‐ISC) process have potential to replace transition metal complexes in photonic applications. The efficiency of SOCT‐ISC in BODIPY donor‐acceptor dyads can be tuned by structural modification. Predicting the triplet sta...
Article
Full-text available
The inner core system of metal-free (‘free base’) porphyrins has continually served as a ligand for various metal ions, but it was only recently studied in organocatalysis due its highly tunable basicity. Highly conjugated porphyrin systems offer spectrophotometric sensitivity toward geometrical and/or electronic changes and, thus, utilizing the po...
Article
Full-text available
The development of new antimicrobial strategies that act more efficiently than traditional antibiotics is becoming a necessity to combat multidrug-resistant pathogens. Here we report the efficacy of laser-light-irradiated 5,10,15,20-tetrakis(m-hydroxyphenyl)porphyrin (mTHPP) loaded onto an ethylcellulose (EC)/chitosan (Chs) nanocomposite in eradica...
Article
Porphyrins have long been recognized as sensors for various analytes. However, this involves mostly metalloporphyrins and there are still limitations with regard to discrimination and sensitivity. Here we illustrate that metal-free metal-free (‘free base’) porphyrins can be re-engineered via conformational design to make the core N-H units accessib...
Article
Full-text available
Base-modification can occur throughout a transfer RNA molecule; however, elaboration is particularly prevalent at position 34 of the anticodon loop (the wobble position), where it functions to influence protein translation. Previously, we demonstrated that the queuosine modification at position 34 can be substituted with an artificial analogue via...
Article
Full-text available
Metal-organic frameworks (MOFs) encompass a rapidly expanding class of materials with diverse potential applications including gas storage, molecular separation, sensing and catalysis. So-called ‘rod MOFs’, which comprise infinitely extended 1D secondary building units (SBUs), represent an underexplored subclass of MOF. Further, porphyrins are cons...
Article
Full-text available
The use of halogens in the crystal engineering of supramolecular porphyrin assemblies has been a topic of strong interest over the past decades. With this in mind we have characterized a series of direct meso-halogenated porphyrins using single crystal X-ray crystallography. This is accompanied by a detailed conformational analysis of all deposited...
Article
Full-text available
The generation of bio-targetable photosensitisers is of utmost importance to the emerging field of photodynamic therapy and antimicrobial (photo-)therapy. A synthetic strategy is presented in which chelating dipyrrin moieties are used to enhance the known photoactivity of iridium(III) metal complexes. Formed complexes can thus be functionalized in...
Article
Full-text available
Coordination complexes of iridium(III) are potential candidates for photodynamic therapy. Phenylpyridyl‐ and Cp*‐containing (dipyrrinato)iridium(III) complexes with a multitude of functional groups at the dipyrrin moieties were synthesized and the phototoxic activity of the complexes evaluated in tumor and bacterial cell assays. The Cp*‐containing...
Article
Full-text available
Traditional 'picket fence' porphyrin systems have been a topic of interest for their capacity to direct steric shielding effects selectively to one side of the macrocycle. Sterically overcrowded porphyrin systems that adopt macrocycle deformations have recently drawn attention for their applications in organocatalysis and sensing. Here we explore t...
Article
Full-text available
Porphyrin molecules are a widely exploited biochemical moiety, with uses in medicinal chemistry, sensing and materials science. The shape of porphyrins, as an aromatic unit, is reductively imagined to be approximately flat, with regular, rigid shape, owing to the popular depiction as a simplified skeletal model. While this regular conformation does...
Preprint
Heavy-atom-free sensitizers forming long-living triplet excited states via the spin-orbit charge transfer intersystem crossing (SOCT-ISC) process have recently attracted attention due to their potential to replace costly transition metal complexes in photonic applications. The efficiency of SOCT-ISC in BODIPY donor-acceptor dyads, so far the most t...
Preprint
Full-text available
The use of halogens in the crystal engineering of porphyrin scaffolds has been a topic of strong interest over the past decades. Previously, this was focused on the introduction of a variety of halogens on the meso-phenyl groups of the porphyrin. However, investigations into the effects of direct halogenation of porphyrins at the meso-position on t...
Article
Full-text available
The crystal structures of three intermediate compounds in the synthesis of 8-bromo-2,3,4,5-tetrahydro-1,3,3-trimethyldipyrrin are reported; 4-bromo-2-formyl-1-tosyl-1H-pyrrole, C12H10BrNO3S, (E)-4-bromo-2-(2-nitrovinyl)-1-tosyl-1H-pyrrole, C13H11BrN2O4S, and 6-(4-bromo-1-tosylpyrrol-2-yl)-4,4-dimethyl-5-nitrohexan-2-one, C19H23BrN2O5S. The compound...
Article
Full-text available
Bicyclo[1.1.1]pentane (BCP) is studied extensively as a bioisosteric component of drugs. Not found in nature, this molecular unit approximates the distance of a para-disubstituted benzene which is replaced in medicines as a method of improving treatments. Predicting interactions of these drugs with specific active sites requires knowledge of the no...
Cover Page
Full-text available
The Cover Feature shows artist Ella Marushenko′s view of the docking between an iodinated bicyclo(1.1.1)pentane (BCP) derivative and 1,4‐diazabicyclo[2.2.2]octane (DABCO). It illustrates noncovalent interactions of the BCP scaffold and how they can be used for the precise assembly of molecular components in chemical space. More information on BCP i...
Article
We report the structural, photophysical, and photobiological properties of a promising BODIPY‐anthracene dyad (BAD) that was previously shown to induce a therapeutic effect against MDA‐MB‐468 cells. The BODIPY was synthesized and its crystal structure was elucidated. We further investigate the potential of this molecule as a versatile photosensitiz...
Preprint
Full-text available
Traditional 'picket fence' porphyrin systems have been a topic of interest for their capacity to direct steric shielding effects selectively to one side of the macrocycle. Sterically overcrowded porphyrin systems that adopt macrocycle deformations have recently drawn attention for their applications in organocatalysis and sensing. Here we explore t...
Preprint
Traditional ‘picket fence’ porphyrin systems have been a topic of interest for their capacity to direct steric shielding effects selectively to one side of the macrocycle. Sterically overcrowded porphyrin systems that adopt macrocycle deformations have recently drawn attention for their applications in organocatalysis and sensing. Here we explore t...
Article
Full-text available
The nucleophilic substitution of aromatic moieties (S N Ar) has been known for over 150 years and found wide use for the functionalization of (hetero)aromatic systems. At current, several 'types' of S N Ar reactions have been established and notably the area of porphyrinoid macrocycles has seen many uses thereof. Herein we detail the S N Ar reactio...
Article
Full-text available
Atropisomerism is a fundamental feature of substituted biaryls resulting from rotation around the biaryl axis. Different stereoisomers are formed due to restricted rotation about the single bond, a situation often found in substituted porphyrins. Previously NMR determination of porphyrin atropisomers proved difficult, if not almost impossible to ac...
Article
The bicyclo[1.1.1]pentane (BCP) unit is under scrutiny as a bioisostere in drug molecules. We employed methodologies for the synthesis of different BCP triazole building blocks from one precursor, 1-azido-3-iodobicyclo[1.1.1]pentane, by “click” reactions and integrated cycloaddition–Sonogashira coupling reactions. Thereby, we accessed 1,4-disubstit...
Article
Full-text available
Photodynamic therapy (PDT) is a promising cancer treatment which involves a photosensitizer (PS), light at a specific wavelength for PS activation and oxygen, which combine to elicit cell death. While the illumination required to activate a PS imparts a certain amount of selectivity to PDT treatments, poor tumor accumulation and cell internalizatio...
Article
Full-text available
Bench-stable meso-substituted di(p/m-benzi)homoporphyrins were synthesized through acid-catalyzed condensation of dipyrrole derivatives with aryl aldehydes. The insertion of a 1,1,2,2-tetraphenylethene (TPE) or but-2-ene-2,3-diyldibenzene unit in the porphyrin framework results in the formation of dibenzihomoporphyrins, merging the features of hydr...
Article
The remarkable structural and electronic properties of rigid non-conjugated hydrocarbons afford attractive opportunities to design molecular building blocks for both medicinal and material applications. The bridgehead positions provide the possibility to append diverse functional groups at specific angles and in specific orientations. The current r...
Preprint
The bicyclo[1.1.1]pentane (BCP) unit exhibits special physical and chemical properties and is under scrutiny as a bioisostere in drug molecules. We employed methodologies for the synthesis of different BCP triazole building blocks from one precursor, 1-azido-3-iodobicyclo[1.1.1]pentane, by Cu(I)-catalyzed 1,3-dipolar cycloaddition (“click”) reactio...
Preprint
Full-text available
The bicyclo[1.1.1]pentane (BCP) unit exhibits special physical and chemical properties and is under scrutiny as a bioisostere in drug molecules. We employed methodologies for the synthesis of different BCP triazole building blocks from one precursor, 1-azido-3-iodobicyclo[1.1.1]pentane, by Cu(I)-catalyzed 1,3-dipolar cycloaddition ("click") reactio...
Article
The ability to cover the face of a porphyrin macrocycle selectively is an attractive feature for concepts such as catalysis and anion binding that is reliant on porphyrin core interactions. Herein, we have synthesized a family of mono-urea functionalized porphyrin complexes with intent to investigate their potential to form core···π interactions se...
Article
Full-text available
Chlorins that bear a gem ‐dimethyl group, which attributes their resistance to oxidation, are of interest for applications in photomedicine. Herein, we present the synthesis and the photophysical properties of two geminal ‐dimethyl chlorins (dihydroporphyrins) and their free base counterparts that act as efficient singlet oxygen generators and thus...