RESUMEN
Novel approaches to modify the spectral output of the sun have seen a surge in interest recently, with triplet-triplet annihilation driven photon upconversion (TTA-UC) gaining widespread recognition due to its ability to function under low-intensity, noncoherent light. Herein, four diphenylanthracene (DPA) dimers are investigated to explore how the structure of these dimers affects upconversion efficiency. Also, the mechanism responsible for intramolecular upconversion is elucidated. In particular, two models are compared using steady-state and time-resolved simulations of the TTA-UC emission intensities and kinetics. All dimers perform TTA-UC efficiently in the presence of the sensitizer platinum octaethylporphyrin. The meta-coupled dimer 1,3-DPA2 performs best yielding a 21.2% upconversion quantum yield (out of a 50% maximum), which is close to that of the reference monomer DPA (24.0%). Its superior performance compared to the other dimers is primarily ascribed to the longer triplet lifetime of this dimer (4.7 ms), thus reinforcing the importance of this parameter. Comparisons between simulations and experiments reveal that the double-sensitization mechanism is part of the mechanism of intramolecular upconversion and that this additional pathway could be of great significance under specific conditions. The results from this study can thus act as a guide not only in terms of annihilator design but also for the design of future solid-state systems where intramolecular exciton migration is anticipated to play a major role.
RESUMEN
Nine metal-organic frameworks have been prepared with the hexagon-shaped linker 1,2,3,4,5,6-hexakis(4-carboxyphenyl)benzene (H6cpb) by solvothermal reactions in dimethylformamide (dmf) or dimethylacetamide (dmac) with acetic acid or formic acid as modulators: [Bi2(cpb)(acetato)2(dmf)2]·2dmf CTH-6 forms a rtl-net; 2(H2NMe2)[Cu2(cpb)] CTH-7 forms a kgd-net; [Fe4(cpb)(acetato)2(dmf)4] CTH-8 and [Co4(cpb)(acetato)2(dmf)4] CTH-9 are isostructural and form yav-nets; 2(HNEt3)[Fe2(cpb)] CTH-10 and the two polymorphs of 2(H2NMe2)[Zn2(cpb)]·1.5dmac, Zn-MOF-888 and CTH-11, show kgd-nets; [Cu2(cpb)(acetato)2(dmf)2]·2dmf, CTH-12, forms a mixed coordination and hydrogen-bonded sql-net; and 2(H2NMe2)[Zn2(cpb)] CTH-13, a similarly mixed yav-net. Surface area values (Brunauer-Emmett-Teller, BET) range from 34 m2 g-1 for CTH-12 to 303 m2 g-1 for CTH-9 for samples activated at 120 °C in dynamic vacuum. All compounds show normal (10-fold higher) molar CO2 versus N2 uptake at 298 K, except the 19-fold CO2 uptake for CTH-12 containing Cu(II) dinuclear paddle-wheels. We also show how perfect hexagons and triangles can combine to a new 3D topology laf, a model of which gave us the idea of foldable network topologies, as the laf-net can fold into a 2D form while retaining the local geometry around each vertex. Other foldable nets identified are cds, cds-a, ths, sqc163, clh, jem, and tfc covering the basic polygons and their combinations. The impact of this concept on "breathing" MOFs is discussed. I2 sorption, both from gas phase and from MeOH solution, into CTH-7 were studied by time of flight secondary ion mass spectrometry (ToF-SIMS) on dried crystals. I2 was shown to have penetrated the crystals, as layers were consecutively peeled off by the ion beam. We suggest ToF-SIMS to be a method for studying sorption depth profiles of MOFs.
RESUMEN
Hybridizing graphene and molecules possess a high potential for developing materials for new applications. However, new methods to characterize such hybrids must be developed. Herein, the wet-chemical non-covalent functionalization of graphene with cationic π-systems is presented and the interaction between graphene and the molecules is characterized in detail. A series of tricationic benzimidazolium salts with various steric demand and counterions was synthesized, characterized and used for the fabrication of graphene hybrids. Subsequently, the doping effects were studied. The molecules are adsorbed onto graphene and studied by Raman spectroscopy, XPS as well as ToF-SIMS. The charged π-systems show a p-doping effect on the underlying graphene. Consequently, the tricationic molecules are reduced through a partial electron transfer process from graphene, a process which is accompanied by the loss of counterions. DFT calculations support this hypothesis and the strong p-doping could be confirmed in fabricated monolayer graphene/hybrid FET devices. The results are the basis to develop sensor applications, which are based on analyte/molecule interactions and effects on doping.
RESUMEN
The triplet pair is the key functional unit in triplet-triplet annihilation photon upconversion. The same molecular properties that stabilize the triplet pair also allow dimers to form on the singlet energy surface, creating an unwanted energy relaxation pathway. Here we show that excimer formation most likely is a consequence of a triplet dimer formed before the annihilation event. Polarity-dependent studies were performed to elucidate how to promote wanted emission pathways over excimer formation. Furthermore, we show that the yield of triplet-triplet annihilation is increased in higher-viscosity solvents. The results will bring new insights in how to increase the upconversion efficiency and how to avoid energy-loss channels.
RESUMEN
The analysis of small polar compounds with ToF-SIMS and MALDI-ToF-MS have been generally hindered by low detection sensitivity, poor ionization efficiency, ion suppression, analyte in-source fragmentation, and background spectral interferences from either a MALDI matrix and/or endogenous tissue components. Chemical derivatization has been a well-established strategy for improved mass spectrometric detection of many small molecular weight endogenous compounds in tissues. Here, we present a devised strategy to selectively derivatize and sensitively detect catecholamines with both secondary ion ejection and laser desorption ionization strategies, which are used in many imaging mass spectrometry (IMS) experiments. Chemical derivatization of catecholamines was performed by a reaction with a synthesized permanent pyridinium-cation-containing boronic acid molecule, 4-( N-methyl)pyridinium boronic acid, through boronate ester formation (boronic acid-diol reaction). The derivatization facilitates their sensitive detection with ToF-SIMS and LDI-ToF mass spectrometric techniques. 4-( N-Methyl)pyridinium boronic acid worked as a reactive matrix for catecholamines with LDI and improved the sensitivity of detection for both SIMS and LDI, while the isotopic abundances of the boron atom reflect a unique isotopic pattern for derivatized catecholamines in MS analysis. Finally, the devised strategy was applied, as a proof of concept, for on-tissue chemical derivatization and GCIB-ToF-SIMS (down to 3 µm per pixel spatial resolution) and LDI-ToF mass spectrometry imaging of dopamine, epinephrine, and norepinephrine in porcine adrenal gland tissue sections. MS/MS using collision-induced dissociation (CID)-ToF-ToF-SIMS was subsequently employed on the same tissue sections after SIMS and LDI mass spectrometry imaging experiments, which provided tandem MS information for the validation of the derivatized catecholamines in situ. This methodology can be a powerful approach for the selective and sensitive ionization/detection and spatial localization of diol-containing molecules such as aminols, vic-diols, saccharides, and glycans along with catecholamines in tissue sections with both SIMS and LDI/MALDI-MS techniques.
Asunto(s)
Ácidos Borónicos/química , Catecolaminas/química , Espectrometría de Masas/métodos , Piridinas/químicaRESUMEN
As a part of their sun-protective strategy, cyanobacteria produce the natural UV-screener scytonemin. Its accumulation in the extracellular sheaths allows the bacteria to thrive in inhospitable locations highly exposed to solar radiation. Scytonemin is often referred to as photostable and has been reported to be non-fluorescent. Taken together, these properties indicate inherently fast non-radiative relaxation processes. Despite these interesting traits, the photophysics of scytonemin is as yet almost completely unexplored. In this study, we have compared the steady-state photophysics of scytonemin itself and four derivatives thereof. Furthermore, the in vitro photostability of scytonemin was studied in different solvents using a solar simulation system. Scytonemin and the investigated derivatives demonstrated a more rapid photoinduced decay in comparison with two commercial UV-screening agents. The photostability could be modulated by varying the solvent, with the protic solvent ethanol providing the most stabilizing environment.
Asunto(s)
Indoles/química , Fenoles/química , Protectores Solares/química , Cianobacterias/química , Fotólisis , Rayos UltravioletaRESUMEN
Design of Experiments (DoE) has been used to optimize a diversity oriented palladium catalyzed cascade Heck-Suzuki reaction for the construction of 3-alkenyl substituted cyclopenta[b]indole compounds. The obtained DoE model revealed a reaction highly dependent on the ligand. Guided by the model, an optimal ligand was chosen that selectively delivered the desired products in high yields. The conditions were applicable with a variety of boronic acids and were used to synthesize a library of 3-alkenyl derivatized compounds. Focusing on inhibition of kinases relevant for combating melanoma, the library was used in an initial structure-activity survey. In line with the observed kinase inhibition, cellular studies revealed one of the more promising derivatives to inhibit cell proliferation via an apoptotic mechanism.
Asunto(s)
Diseño de Fármacos , Indoles/farmacología , Leucocitos Mononucleares/efectos de los fármacos , Fenoles/farmacología , Fosfotransferasas/antagonistas & inhibidores , Inhibidores de Proteínas Quinasas/síntesis química , Apoptosis/efectos de los fármacos , Catálisis , Proliferación Celular/efectos de los fármacos , Relación Dosis-Respuesta a Droga , Humanos , Indoles/síntesis química , Indoles/química , Estructura Molecular , Paladio/química , Fenoles/síntesis química , Fenoles/química , Fosfotransferasas/metabolismo , Inhibidores de Proteínas Quinasas/química , Relación Estructura-ActividadRESUMEN
Photocontact allergy is a well-known side effect of topical preparations of the nonsteroidal anti-inflammatory drug ketoprofen. Photocontact allergy to ketoprofen appears to induce a large number of photocross allergies to both structurally similar and structurally unrelated compounds. Contact and photocontact allergies are explained by structural modification of skin proteins by the allergen. This complex is recognized by the immune system, which initiates an immune response. We have studied ketoprofen's interaction with amino acids to better understand ketoprofen's photoallergenic ability. Irradiation of ketoprofen and amino acid analogues resulted in four different ketoprofen photodecarboxylation products (6-9) together with a fifth photoproduct (5). Dihydroquinazoline 5 was shown to be a reaction product between the indole moiety of 3-methylindole (Trp analogue) and the primary amine benzylamine (Lys analogue). In presence of air, dihydroquinazoline 5 quickly degrades into stable quinazolinone 12. The corresponding quinazolinone (17) was formed upon irradiation of ketoprofen and the amino acids N-acetyl-l-Trp ethyl ester and l-Lys ethyl ester. The formation of these models of an immunogenic complex starts with the ketoprofen-sensitized formation of singlet oxygen, which reacts with the indole moiety of Trp. The formed intermediate subsequently reacts with the primary amino functionality of Lys, or its analogue, to form a Trp-Lys adduct or a mimic thereof. The formation of a specific immunogenic complex that does not contain the allergen but that can still induce photocontact allergy would explain the large number of photocross allergies with ketoprofen. These allergens do not have to be structurally similar as long as they can generate singlet oxygen. To the best of our knowledge, there is no other suggested explanation for ketoprofen's photoallergenic properties that can account for the observed photocross allergies. The formation of a specific immunogenic complex that does not contain the allergen is a novel hypothesis in the field of contact and photocontact allergy.
Asunto(s)
Aminoácidos/efectos de la radiación , Antiinflamatorios no Esteroideos/efectos de la radiación , Cetoprofeno/efectos de la radiación , Rayos Ultravioleta , Antiinflamatorios no Esteroideos/efectos adversos , Dermatitis Fotoalérgica/etiología , Cetoprofeno/efectos adversos , FotólisisRESUMEN
BACKGROUND: Reports of positive patch test and photopatch test reactions to the chemical ultraviolet filter octocrylene have increased during the last decade. Little is known about the reason for octocrylene's allergenic activity. OBJECTIVES: To present and discuss the results of patch tests and photopatch tests with octocrylene, and to investigate the possible cause of its allergenic properties. METHODS: Results of patch tests and photopatch tests with octocrylene in patients with adverse skin reactions to sunscreen products and/or ketoprofen were collected. The allergenic potency of octocrylene was investigated in the murine local lymph node assay (LLNA). Chemical reactivity assays were used to mimic octocrylene's interaction with biomolecules. RESULTS: We report 23 cases of positive test reactions to octocrylene (5 patch test and 18 photopatch). Notably, many of these patients also had positive photopatch test reactions to ketoprofen and benzophenone-3. Octocrylene was shown to be a moderate sensitizer in the LLNA, and it reacted with amines such as lysine, but not with thiols such as cysteine. CONCLUSIONS: The clinical studies show that octocrylene is both a photocontact allergen and a contact allergen. Octocrylene's ability to cause contact allergy is probably attributable to its reactivity towards lysine. To be able to understand why octocrylene causes photocontact allergy, further studies are needed.
Asunto(s)
Acrilatos/efectos adversos , Dermatitis Alérgica por Contacto/etiología , Protectores Solares/efectos adversos , Acrilatos/metabolismo , Adulto , Anciano , Animales , Benzofenonas/efectos adversos , Niño , Preescolar , Dermatitis Fotoalérgica/etiología , Femenino , Humanos , Cetoprofeno/efectos adversos , Ensayo del Nódulo Linfático Local , Lisina/metabolismo , Masculino , Ratones , Persona de Mediana Edad , Pruebas del Parche/métodos , Piel/metabolismo , Adulto JovenRESUMEN
This perspective will focus on the mechanistic aspects of singlet and triplet excitation energy transfer. Well defined donor-bridge-acceptor systems specifically designed for investigating the distance and energy gap dependencies of the energy transfer reactions are discussed along with some recent developments in computational modeling of the electronic coupling.
RESUMEN
This article presents the first evidence that the DNA base analogue 1,3-diaza-2-oxophenoxazine, tC(O), is highly fluorescent, both as free nucleoside and incorporated in an arbitrary DNA structure. tC(O) is thoroughly characterized with respect to its photophysical properties and structural performance in single- and double-stranded oligonucleotides. The lowest energy absorption band at 360 nm (epsilon = 9000 M(-1) cm(-1)) is dominated by a single in-plane polarized electronic transition and the fluorescence, centred at 465 nm, has a quantum yield of 0.3. When incorporated into double-stranded DNA, tC(O) shows only minor variations in fluorescence intensity and lifetime with neighbouring bases, and the average quantum yield is 0.22. These features make tC(O), on average, the brightest DNA-incorporated base analogue so far reported. Furthermore, it base pairs exclusively with guanine and causes minimal perturbations to the native structure of DNA. These properties make tC(O) a promising base analogue that is perfectly suited for e.g. photophysical studies of DNA interacting with macromolecules (proteins) or for determining size and shape of DNA tertiary structures using techniques such as fluorescence anisotropy and fluorescence resonance energy transfer (FRET).
Asunto(s)
Sondas de ADN/química , Colorantes Fluorescentes/química , Oxazinas/química , ADN/química , ADN de Cadena Simple/química , Fluorescencia , Polarización de Fluorescencia , Sondas de Oligonucleótidos/química , Espectrometría de FluorescenciaRESUMEN
The Aurora family of kinases is closely involved in regulating cell division. Inhibition of Aurora A and B with small molecules is currently being investigated in clinical trials for the treatment of different cancers. It has also been evaluated as a treatment option against different autoimmune diseases in preclinical studies. Here, we present a cyclopenta[b]indole derivative capable of inhibiting Aurora B selectively in kinase assays. To evaluate the Aurora B inhibition capacity of the compound, we used a kinase IC50 assay as well as a suppression assay of proliferating primary cells. In addition, we examined if the cells had gained a phenotype characteristic for Aurora B inhibition after treatment with the compound. We found that the compound selectively inhibited Aurora B (IC50 = 1.4 µM) over Aurora A (IC50 > 30 µM). Moreover, the compound inhibited proliferating PBMCs with an IC50 = 4.2 µM, and the cells displayed reduced phosphorylation of histone H3 as well as tetraploidy, consistent with Aurora B inhibition.
RESUMEN
In this work we examine the trapping and conversion of visible light energy into chemical energy using a supramolecular assembly. The assembly consists of a light-absorbing antenna and a porphyrin redox center, which are covalently attached to two complementary 14-mer DNA strands, hybridized to form a double helix and anchored to a lipid membrane. The excitation energy is finally trapped in the lipid phase of the membrane as a benzoquinone radical anion that could potentially be used in subsequent chemical reactions. In addition, in this model complex, the hydrophobic porphyrin moiety acts as an anchor into the liposome positioning the DNA construct on the lipid membrane surface. The results show the suitability of our system as a prototype for DNA-based light-harvesting devices, in which energy transfer from the aqueous phase to the interior of the lipid membrane is followed by charge separation.
Asunto(s)
ADN/química , Fuentes Generadoras de Energía , Membrana Dobles de Lípidos/química , Benzoquinonas/química , Dicroismo Circular , Electrones , Transferencia de Energía , Fluoresceínas/química , Polarización de Fluorescencia , Interacciones Hidrofóbicas e Hidrofílicas , Metaloporfirinas/química , Modelos Moleculares , Conformación de Ácido Nucleico , Oligonucleótidos/síntesis química , Oligonucleótidos/química , Oxidación-Reducción , Procesos Fotoquímicos , Porfirinas/químicaRESUMEN
One of the most frequently observed photoallergens today is the sunscreen agent 4-tert-butyl-4'-methoxy dibenzoylmethane (1a). The structurally similar compound, 4-isopropyldibenzoylmethane (1b), was a common cause of sunscreen allergy in the eighties and early nineties but was removed from the market in 1993 and replaced with dibenzoylmethane 1a. We have studied the photodegradation of the dibenzoylmethane 1a, to better understand how these substances cause an immune reaction. Several expected degradation products were formed and identified. Of these, arylglyoxals and benzils were of particular interest because they were unexplored as potential contact allergens. The allergenic potential of photodegraded 1a was evaluated by screening the formed arylglyoxals and benzils for their sensitizing capacity in the murine local lymph node assay. The arylglyoxals were found to be strong sensitizers. They were also found to be highly reactive toward the nucleophile arginine, which indicates that the immunogenic hapten-protein complex could be formed via an electrophilic-nucleophilic pathway. By varying the electron-withdrawing or -donating capacity of the substituent in the para position of the arylglyoxal, the electronic effects were shown to have no significant impact on either the sensitizing or the electrophilic power of arylglyoxals. Thus, a change in the substitution pattern of the parent dibenzoylmethane will not influence the sensitizing capacity of the products formed from them upon photodegradation. Furthermore, the combined studies of benzils, using the local lymph node assay and a cell proliferation assay, indicate that the benzils are cytotoxic rather than allergenic. Taken together, this study presents strong indication that photocontact allergy to dibenzoylmethanes is caused by the arylglyoxals that are formed upon photodegradation.
Asunto(s)
Chalconas/química , Dermatitis Alérgica por Contacto/etiología , Protectores Solares/química , Alérgenos/química , Animales , Línea Celular , Chalconas/síntesis química , Chalconas/toxicidad , Cromatografía Líquida de Alta Presión , Humanos , Ensayo del Nódulo Linfático Local , Ratones , Fotólisis , Propiofenonas , Espectrometría de Masa por Ionización de Electrospray , Protectores Solares/síntesis química , Protectores Solares/toxicidad , Rayos UltravioletaRESUMEN
A series of donor--bridge--acceptor (D--B--A) systems with varying donor-acceptor distances have been studied with respect to their triplet energy transfer properties. The donor and acceptor moieties, zinc(II), and free-base porphyrin, respectively, were separated by 2-5 oligo-p-phenyleneethynylene units (OPE) giving rise to edge-to-edge separations ranging between 12.7 and 33.4 A. The study was performed in 2-MTHF at 150 K and it was established that triplet excitation energy transfer occurs with high efficiency in all of the studied D--B--A systems. The distance dependence was exponential with an attenuation factor, beta, equal to 0.45 +/- 0.015 A(-1). The experimental study was also supported by quantum mechanical DFT and TD-DFT calculations on a series of closely related model systems. A thorough analysis of the OPE-bridge conformational dynamics led to an equation that quantitatively models the distance dependence of the electronic coupling found in the experimental study.
RESUMEN
Gold porphyrins are often used as electron-accepting chromophores in artificial photosynthetic constructs. Because of the heavy atom effect, the gold porphyrin first-excited singlet state undergoes rapid intersystem crossing to form the triplet state. The lowest triplet state can undergo a reduction by electron donation from a nearby porphyrin or another moiety. In addition, it can be involved in triplet-triplet energy transfer interactions with other chromophores. In contrast, little has been known about the short-lived singlet excited state. In this work, ultrafast time-resolved absorption spectroscopy has been used to investigate the singlet excited state of Au(III) 5,15-bis(3,5-di-t-butylphenyl)-2,8,12,18,-tetraethyl-3,7,13,17-tetramethylporphyrin in ethanol solution. The excited singlet state is found to form with the laser pulse and decay with a time constant of 240 fs to give the triplet state. The triplet returns to the ground state with a life-time of 400 ps. The lifetime of the singlet state is comparable with the time constants for energy and photoinduced electron transfer in some model and natural photosynthetic systems. Thus, it is kinetically competent to take part in such processes in suitably designed supermolecular systems.
Asunto(s)
Porfirinas/química , Transporte de Electrón , Oro/química , Modelos Biológicos , Fotobiología , Fotoquímica , FotosíntesisRESUMEN
A series of Ru(II) compounds and salts have been synthesized: [Ru(6-carboxylato-bpy)(2)] (5), [Ru(6-carboxylato-bpy)(tpy)]PF(6) (9), [Ru(tpy)(2)](PF(6))(2) (8), and [Ru(bpy)(2)(Pic)]PF(6) (11), where 6-carboxy-bpy (1) = 6-carboxy-2,2'-bipyridine, tpy (2) = 2,2':6',2"-terpyridine, and Pic = 2-carboxylatopyridine. The compounds have been characterized by NMR, electrospray mass spectrometry (ESI-MS), cyclic voltammetry, absorption and emission spectroscopy (at 100, 140, and 298 K), and single-crystal X-ray diffraction (complex 5). Complex 5 crystallizes in the monoclinic system, space group P2(1)/n, formula RuC(22)H(14)N(4)O(4).C(2)H(5)OH, with a = 11.088(3) Å, b = 11.226(3) Å, c = 35.283(9) Å, beta = 91.41(2) degrees, and Z = 8. A linear dependence on the number of coordinated carboxylato groups and the electrochemical redox potentials was found, ca. 0.4 V lower reduction potential for the oxidation step (Ru(II/III)) per carboxylate group. Also, to the best of our knowledge, these are the first examples (9, 11) of mononuclear Ru(II) complexes containing a carboxypyridine-ruthenium moiety displaying any luminescence emission.
RESUMEN
The first total synthesis of the mitotic spindle poison nostodione A is described. The inherent oxidative sensitivity of indoles is utilized for a late introduction of a second carbonyl to the cyclopent[b]indole-2-one system. The tricyclic system is prepared from indole-3-acetic acid and O-silylated 4-ethynylphenol, using a stereoselective intramolecular reductive Heck cyclization as the key transformation.
Asunto(s)
Alcaloides Indólicos/síntesis química , Cianobacterias/metabolismo , Ciclización , Alcaloides Indólicos/química , Alcaloides Indólicos/farmacología , Modelos Moleculares , Estructura Molecular , Oxidación-Reducción , EstereoisomerismoRESUMEN
Octocrylene is an organic UV filter, commonly used in sunscreens and cosmetics, which can give rise to both contact and photocontact allergy. Our aim was to investigate octocrylene's interaction with amino acid analogs in the presence of UV radiation to better understand the reason for octocrylene's photoallergenic capacity. The amino acid analogs were photolysed in presence and absence of octocrylene for 1 h in cyclohexane. The rate of degradation was considerably slower for all amino acid analogs when octocrylene was present in the mixture. Benzylamine, the lysine analog, did react with octocrylene during the photolysis and the corresponding amide was formed in an acylation reaction. By varying the benzylamine concentration and keeping the octocrylene concentration fixed the reaction rate was shown to be independent of the amine concentration. The same type of acylation reaction took place when octocrylene alone was photolysed in ethanol in which the ethyl ester was formed from octocrylene and ethanol. Our results suggest that octocrylene's ability to cause photocontact allergy could be due to its photoinduced reactivity toward primary amines and alcohols.
Asunto(s)
Acrilatos/química , Alérgenos/química , Aminoácidos/química , Cosméticos/química , Protectores Solares/química , Bencilaminas/química , Cromatografía Líquida de Alta Presión , Ciclohexanos/química , Interacciones Farmacológicas , Etanol/química , Humanos , Cinética , Espectroscopía de Resonancia Magnética , Imitación Molecular , Fenoles/química , Fotólisis , Escatol/química , Soluciones , Compuestos de Sulfhidrilo/química , Rayos UltravioletaRESUMEN
A binding pocket consisting of two zinc porphyrins self assembled by Watson-Crick base pairing is presented. The porphyrin binding pocket is located in the confined environment of a lipid membrane whereas the DNA is located in the water phase. Bidentate electron accepting ligands are shown to coordinate in-between the two porphyrins.