Platinum(II) and palladium(II) complexes with 2-Acetyl pyridine 4N-ethyl thiosemicarbazone able to overcome the cis-Platin resistance. Structure, antibacterial activity and DNA strand breakage

The reactions of Pd(II) and Pt(II) with 2-Acetyl Pyridine N(4)-Ethyl-Thiosemicarbazones, HAc4Et and 2-Acetyl Pyridine N(4)-1-(2-pyridyl)-piperazinyl Thiosemicarbazone, HAc4PiPiz and 2-Formyl Pyridine N(4)-1-(2-pyridyl)-piperazinyl Thiosemicarbazone, HFo4PiPiz afforded the complexes, [Pd(Ac4Et)], 1, [Pd(HAc4Et)₂]Cl₂, 2 and [Pd(Ac4Et)₂], 3[Pt(Ac4Et)], 4, [Pt(HAc4Et)₂]Cl₂, 5, [Pt(Ac4Et)₂], 6 and [Pd(Fo4PipePiz)Cl], 7, [Pd(Fo4PipePiz)₂], 8, [Pd(Ac4PipePiz)Cl], 9 and [Pd(Ac4PipePiz)₂], 10. The crystal structure of the complex [Pt(Ac4Et)₂], 6 has been solved. The platinum(II) atom is in a square planar environment surrounded by two cis nitrogen atoms and two cis sulfur atoms. The ligands are not equivalent, one being tridentate with (N,N,S) donation, the other being monodentate using only the sulfur atom to coordinate to the metal. The tridentate ligand shows a Z, E, Z configuration while the monodentate ligand shows an E, E, Z. Inter-molecular hydrogen bonds stabilize the structure, while the crystal packing is determined by –, and Pt – C interactions. The antibacterial effect of Pd(II) and Pt(II) complexes were studied in vitro. The complexes were found to have effect on Gram(+) bacteria, while the same complexes showed no bactericidal effect on Gram(–) bacteria. The effect of the Pd(II) and Pt(II) complexes on the in vitro DNA strand breakage was studied by agarose gel electrophoresis. The complexes 1-6 were found to exhibit a cytotoxic potency in a very low micromolar range and to be able to overcome the cisplatin resistance of A2780/Cp8 cells (Kovala-Demertzi et al. 2000).     

Effect of Pt and Sn on the adsorption of n-heptane in γ-Al2O3 catalyst models

The Grand Canonical Monte-Carlo (GCMC) method has been used to carry out simulations of the adsorption of n-heptane in models of naphtha-reforming catalysts. Models used in the study differed in the number and distribution of metal atoms—Pt and Sn. The number of adsorbed n-heptane molecules grows linearly with increasing number of metal atoms. The effect of Pt content on the adsorption of n-heptane molecules is most distinct at approximately 100 kPa and within the lower range of the temperatures investigated. In the models of bimetallic catalysts, the effect of the two metals is additive.Figure Effect of Pt and Sn on number of n-heptane molecules adsorbed in Al₂O₃ catalyst in 773 K and 1000 kPa.      

Effect of thiol-functionalised silica on cisplatin adsorption

This study contributes to the investigation related to guest–host interactions between the chemotherapeutic agent cisplatin and a functionalised silica matrix in order to improve and find new materials such as drug carriers. The adsorption of cisplatin and its complexes, cis-[PtCl(NH₃)₂]⁺ and cis-[Pt(NH₃)₂]²⁺, on a SH-functionalised SiO₂(111) surface has been studied by the atom superposition and electron delocalisation method. The adiabatic energy curves for the adsorption of the drug and its products on the delivery system were considered. The electronic structure and bonding analysis were also performed. The molecule and their complex are adsorbed on the functionalised surface resulting in a major absorption of the cis-[Pt(NH₃)₂]²⁺ complex. The molecule–surface interactions are formed via –SH group. The molecule/complexes SH electron-donating effect plays an important role in the catalytic reaction. The more important drug–carrier interactions occur through the Cl–H bond for the adsorption of cis-[PtCl₂(NH₃)₂] and cis-[PtCl(NH₃)₂]⁺, and through the Pt–S and Pt–H interactions for cis-[Pt(NH₃)₂]²⁺ adsorption. When the new interactions are formed, the functionalised carrier maintains their matrix properties while the molecule is the most affected after adsorption. The Pt atomic orbitals present the most important changes during adsorption.     

Modeling the interaction between anti-cancer drug penicillamine and pristine and functionalized carbon nanotubes for medical applications: density functional theory investigation and a molecular dynamics simulation

Abstract

The present study focuses on the prediction and investigation of binding properties of penicillamine with pure (5,5) single-walled carbon nanotube (SWCNT) and functionalized SWCNT (f-SWCNT) through the B3LYP and M06-2X functionals using the 6-31G** basis set. The electronic and structural properties, adsorption energy and frontier molecular orbitals of various configurations are examined. Our theoretical results indicated that the interaction of the nanotubes with penicillamine molecule is weak so that the drug adsorption process is typically physisorption. Also, results of theoretical calculations show that the adsorption of the drug molecule on f-SWCNT is stronger with shorter intermolecular distances in comparison to pure SWCNT. The natural bond orbital (NBO) analysis of studied systems demonstrates that the charge is transferred from penicillamine molecule to the nanotubes. Furthermore, molecular dynamics (MD) simulation is employed to evaluate the dynamic and diffusion behavior of drug molecule on SWCNT and f-SWCNT. Energy results show that drug molecule spontaneously moves toward the carriers, and the van der Waals energy contributions in drug adsorption are more than electrostatic interaction. The obtained results from MD simulation confirm that the functionalization of SWCNT leads to increase in the solubility of the carrier in aqueous solution.

Communicated by Ramaswamy H. Sarma     

Modeling of adsorption in nanopores

Adsorption in nonporous materials has been studied using Grand Canonical Monte Carlo simulations. We discuss three types of materials: (a) a model of cylindrical pores with smooth walls, representing MCM-41 like materials, (b) a model of cylindrical pores with regular structured walls (model of carbon nanotubes) and (c) a material with crystalline wall structure (zeolites). Typical problems related to the stability of adsorbed layers have been analyzed. We have shown that the mechanism of adsorption is strongly dependent on the structure of the pore walls. In the case of amorphous walls it may lead to metastable configurations. In nanotubes, the ordered corrugation structure of walls determines the low temperature structure of the adsorbed system. In 3D ordered porous system, such as zeolites, the mechanism of adsorption is mostly determined by characteristic sites of adsorption.Figure Adsorbed atoms and energy fluctuations at the pressure of the first layer formation of krypton atoms: (a) instantaneous numbers of adsorbed atoms (per nm² of the pore wall) as a function of the time of simulation (Monte Carlo steps) observed in a relatively long run, (b) the bimodal distribution of the energy fluctuations is a consequence of the behavior of the systems as shown in (a).     

A simple dilute-and-shoot procedure for the determination of platinum in human pleural effusions using HR-CS GF-AAS

BackgroundHigh-resolution continuum source AAS is an emerging technique for the determination of trace elements in clinical analysis. We aimed to develop a method for the direct determination of platinum (Pt) in pleural effusions that could deepen the understanding of the dynamics of intrapleural Pt concentration during cytostatic therapy.Materials and methodsSamples were collected by thoracic drainage from five patients with lung cancer undergoing platinum based chemotherapy. A simple dilute-and-shoot method for Pt determination in the pleural effusions was developed. Ashing of the sample in an oxygen flow in a graphite tube allowed for direct analysis without prior mineralization. The trueness of the method was verified using an independent technique (ICP-MS). As platinum derivatives are only active in its free form (not bound to proteins), Pt in samples was further divided into free and protein-bound forms by means of ultrafiltration.ResultsUsing the proposed method, Pt contents (free and total) were determined in samples collected at different times after the intravenous application of the Pt derivative. The concentration of total Pt reached values of up to 5,000 μg/L and different patterns of its dynamics in intrapleural fluid were observed.ConclusionsThe developed method enables the fast and simple determination of Pt in biological fluids. It may be applied on a large scale to improve the understanding of Pt dynamics during cytostatic therapy, and also to determine the optimal timing of both thoracic drainage and administration of systemic chemotherapy.     

Tuning the electronic and photophysical properties of platinum(II) complexes through ancillary ligand modification: a theoretical study

In this work, six Pt(II) complexes have been studied via density functional theory (DFT)/time-dependent DFT caculations to explore the influence of different ancillary ligand on electron structures, photophysical properties and radiative decay processes. Moreover, the self-consistent spin–orbit coupling TDDFT was used to calculate zero-field splitting, radiative rate and radiative lifetime to unveil the radiative deactivation processes for these complexes. The results indicated that [Pt(ppy)(ppz)] (ppy = 2-phenylpyridine and ppz = 5-(2-pyridyl)-pyrazole) has a higher radiative decay rate constant and a smaller nonradiative decayrate constant than that of [Pt(ppy)(acac)] (acac = acetylacetonate). Furthermore, complex 5, with dimesityboron added on the 3′-position of the pyrazole ring in [Pt(ppy)(ppz)], shows great potential to serve as an efficient blue-green light emitter in OLED.     

Adsorption of gold(III), platinum(IV) and palladium(II) onto glycine modified crosslinked chitosan resin

The adsorption of Au(III), Pt(IV) and Pd(II) onto glycine modified crosslinked chitosan resin (GMCCR) has been investigated. The parameters studied include the effects of pH, contact time, ionic strength and the initial metal ion concentrations by batch method. The optimal pH for the adsorption of Au(III), Pt(IV) and Pd(II) was found to range from 1.0 to 4.0 and the maximum uptake was obtained at pH 2.0 for Au(III), Pt(IV) and Pd(II). The results obtained from equilibrium adsorption studies are fitted in various adsorption models such as Langmuir and Freundlich and the model parameters have been evaluated. The maximum adsorption capacity of GMCCR for Au(III), Pt(IV) and Pd(II) was found to be 169.98, 122.47 and 120.39mg/g, respectively. The kinetic data was tested using pseudo-first-order and pseudo-second-order kinetic models and an intraparticle diffusion model. The correlation results suggested that the pseudo-second-order model was the best choice among all the kinetic models to describe the adsorption behavior of Au(III), Pt(IV) and Pd(II) onto GMCCR. Various concentrations of HCl, thiourea and thiourea-HCl solutions were used to desorb the adsorbed precious metal ions from GMCCR. It was found that 0.7M thiourea-2M HCl solution provided effectiveness of the desorption of Au(III), Pt(IV) and Pd(II) from GMCCR. The modification of glycine on crosslinked chitosan resin (CCR) was studied by Fourier transform infrared spectrometry (FTIR) and scanning electron microscopy (SEM).     

Solid Supported Vesicles for Bactericide Delivery

Abstract

Cationic and anionic liposomes have been prepared by extrusion from dipalmitoylphosphatidylcholine (DPPC) and its mixtures with cholesterol and dimethyldioctadecyltrimethylammonium bromide (DDAB) and with phosphatidylinositol (PI) respectively covering a range of composition from 0 to 19 mole % DDAB and PI. The adsorption of liposomal lipid from the liposome dispersion onto particles of silica and titanium dioxide in suspension has been studied as a function of liposome composition and concentration. The adsorption isotherms have been fitted using a Langmuir equation from which the binding constants and maximum surface coverage were obtained. The Gibbs energies of adsorption for the cationic liposomes were on average -61.0 ± 2.1 kJ mol^?1 (on silica) and -50.6 ± 2.9 kJ mol^?1 (on titanium dioxide). On average saturation adsorption is equivalent to 3 to 10 lipid monolayers on silica and 3 to 7 on titanium dioxide. Using liposomes encapsulating D-glucose it is demonstrated that there is almost no release of glucose on adsorption of the lipid, indicating that the liposomes are adsorbed intact to form a liposome monolayer on the particle surfaces. Adsorption of intact liposomes to form a close-packed liposome monolayer of solid supported vesicles (SSV) is shown to be equivalent to on average 7.0 ± 0.2 phospholipid monolayers. The SSVs are shown to have increased stability to disruption by surfactants and when carrying the oil-soluble bactericide, Triclosan?, to be capable of inhibiting the growth of oral bacteria from immobilised biofilms.     

An Investigation of Adsorption-Induced Smoothing Mechanisms in Pt/Pt(111) Homoepitaxy

Abstract

We report the results of a molecular dynamics study of the deposition of Pt atoms on a Pt(111) surface. The interatomic potential in our study is generated from Corrected Effective Medium theory. The transient mobility, the interaction between an atom and a ascending step edge, and the incorporation of an atom into a descending step edge have been investigated. No significant transient mobility is observed. Adatoms exchange with atoms at the descending step edges rather than jumping over the edges, and the exchange can involve two or more atoms. Our simulations indicate that the exchange is assisted by instantaneous momentum transfer between the impinging atom and the island atoms.     

Modeling of Platinum Clusters in H-Mordenite

The size, location and structure of Pt clusters in H-mordenite have been investigated by molecular mechanics energy minimization and molecular dynamics simulation techniques using the Catalysis software of Molecular Simulations (MSI). Lattice energy minimizations are performed to study the effects of the specific framework aluminum positions on the location and stability of monoatomic Pt sites in H-mordenite. The lattice energies relative to the siliceous platinum-aluminosilicate structure reveal that the stability of a single Pt atom in H-mordenite is remarkably influenced by the specific location of the Al atoms in the lattice. At the studied Si/Al ratio of two Al ions per unit cell, a stabilization of the H-mordenite lattice upon Pt deposition is obtained. Moreover, lattice energy calculations on Pt/aluminosilicate mordenites of different metal contents per unit cell have been performed. An optimum size for the aggregate confined to the 12-ring main channel that is almost independent of the Pt content per mordenite unit cell has been found. The structural features of the resulting clusters at the end of molecular dynamics simulations on Pt/alumina-mordenites reflect a strong metal-zeolite interaction. The present results are consistent with a previous molecular dynamics simulation study on the structure of platinum deposited on SiO₂ surfaces.     

Mitochondrial dysfunction,autophagy stimulation and non-apoptotic cell death caused by nitric oxide-inducing Pt-coated Au nanoparticle in human lung carcinoma cells

BackgroundReactive oxygen species (ROS)-mediated cancer therapeutic has been at higher appreciation than those mediated by reactive nitrogen species. Cytotoxic mechanism of a novel nitric oxide (NO) inducing-Pt coated Au nanoparticle (NP) has been comparatively studied with the well-established ROS inducing Pt-based anticancer drug cisplatin in human lung A549 carcinoma cells.MethodsCytotoxicity was evaluated by MTT assay, lactate dehydrogenase (LDH) release, thiobarbituric acid substances (TBARS) and C11-Boron dipyrromethene (BODIPY). ROS (O^2·− and H₂O₂) was measured with dihydroethidium (DHE) and H₂O₂-specific sensor. Nitric oxide (NO) and mitochondrial dysfunction were evaluated respectively by NO-specific probe DAR-1 and JC-1. Autophagy was determined by lysotracker (LTR) and monodansylcadaverine (MDC) applied tandemly whereas apoptosis/necrosis by Hoechst/PI and caspase 3 activity.ResultsIC50 (concentration that inhibited cell viability by 50%) of Pt coated Au NP came to be 0.413 μM whereas IC50 of cisplatin came out to 86.5 μM in A549 cells treated for 24 h meaning NPs toxicity was over 200 times higher than cisplatin. However, no significant stimulation of intracellular ROS was observed at the IC50 of Pt coated Au NPs in A549 cells. However, markers like LDH release, TBARS, BODIPY and ROS were significantly higher due to cisplatin in comparison to Pt coated Au NP.ConclusionsPt coated Au NP caused NO-dependent mitochondrial dysfunction and autophagy. Mode of cell death due to NP was much different from ROS-inducing cisplatin.General significancePt coated Au NP offer promising opportunity in cancer therapeutic and warrants advanced study in vivo models of cancer.     

Molecular-Dynamics Simulation of the Surface Diffusion of n-Alkanes on Pt(111)

Abstract

In the present study, the equilibrium adsorption and the dynamics of surface diffusion in a model of ethane and n-butane on a Pt(111) surface were simulated with molecular dynamics. At low temperatures, we found that both admolecules adsorb in a specific binding site. Through analysis of the trajectories, several features of the dynamics were resolved. At low temperature, we observed that diffusion occurs through a nearest-neighbor hopping mechanism involving both lateral rotation and axial translation. At high temperatures, the admolecule makes multiple-site hops and nonlocalized long flights. The temperature dependence of the diffusion coefficients was analyzed and was found to exhibit good Arrhenius behavior. The apparent diffusion coefficients follow trends seen in related experimental studies. In the case of ethane, a comparison between the diffusion barrier measured in the molecular-dynamics simulations and the theoretical barrier predicted by transition-state theory indicates that the simulated barrier is larger than the theoretical value. This finding is consistent with conclusions in recent studies of metal-atom diffusion on metal surfaces, where it was found that systems with low corrugation exhibit a non-unique relationship between the dynamical diffusion barrier and the potential-energy-surface topology.     

Surface-modified magnetite nanoparticles affect lysozyme amyloid fibrillization

BackgroundThe surface of nanoparticles (NPs) is an important factor affecting the process of poly/peptides' amyloid aggregation. We have investigated the in vitro effect of trisodium citrate (TC), gum arabic (GA) and citric acid (CA) surface-modified magnetite nanoparticles (COAT-MNPs) on hen egg-white lysozyme (HEWL) amyloid fibrillization and mature HEWL fibrils.MethodsDynamic light scattering (DLS) was used to characterize the physico-chemical properties of studied COAT-MNPs and determine the adsorption potential of their surface towards HEWL. The anti-amyloid properties were studied using thioflavin T (ThT) and tryptophan (Trp) intrinsic fluorescence assays, and atomic force microscopy (AFM). The morphology of amyloid aggregates was analyzed using Gwyddion software. The cytotoxicity of COAT-MNPs was determined utilizing Trypan blue (TB) assay.ResultsAgents used for surface modification affect the COAT-MNPs physico-chemical properties and modulate their anti-amyloid potential. The results from ThT and intrinsic fluorescence showed that the inhibitory activities result from the more favorable interactions of COAT-MNPs with early pre-amyloid species, presumably reducing nuclei and oligomers formation necessary for amyloid fibrillization. COAT-MNPs also possess destroying potential, which is presumably caused by the interaction with hydrophobic residues of the fibrils, resulting in the interruption of an interface between β-sheets stabilizing the amyloid fibrils.ConclusionCOAT-MNPs were able to inhibit HEWL fibrillization and destroy mature fibrils with different efficacy depending on their properties, TC-MNPs being the most potent nanoparticles.General significanceThe study reports findings regarding the general impact of nanoparticles' surface modifications on the amyloid aggregation of proteins.     

Mixtures of Associating and Non-associating Chains on Activated Surfaces: A Monte Carlo Approach

Abstract

The behavior of mixtures of associating and non-associating chains confined in pores with activated surfaces is studied by means of molecular simulation. The fluid molecules are modeled as a chain of four tangent Lennard-Jones spheres. Some of the chains have an additional associating square-well site placed in an end sphere. The activated surfaces of the slit pore are modeled via an integrated Lennard-Jones (10-4-3) potential with specific association sites protruding from the surface. We present Gibbs ensemble Monte Carlo simulation results for the partitioning of mixtures of chains in the bulk and confined phases for this particular model. The chain-wall association governs the adsorption behavior of the system. The preferential adsorption of associating chains is seen to strongly depend on temperature and pore width. Selectivities obtained are in the range of those seen in experiments of alkane-alkanol mixtures.     

Poly(methylmetacrylate) (PMMA) core-shell nanospheres act as efficient pharmacophores for the antiproliferative [PtCl3(NH3)] complex by forming ionic couples

Polymer-based, covalently linked drug-delivery systems have been shown to improve the therapeutic index of effective but toxic anticancer agents, such as cisplatin, by exploiting the peculiar features of tumour blood and lymphatic circulation. In the present study, positively charged poly(methylmetacrylate) core-shell nanospheres (ZN2) were used as pharmacophores for anionic platinum-containing moieties (PtA). The antitumor effect of the resulting non-covalent adduct (PtA-ZN2) was assessed in C57BL/6 mice bearing B16 murine melanoma. PtA-ZN2 was significantly more effective than cisplatin in inhibiting B16 tumour growth when both agents were used at their respective maximum tolerated doses; importantly, mice receiving PtA-ZN2 exhibited no signs of significant general toxicity. Tumour growth in mice treated with unconjugated PtA did not significantly differ from that observed in control animals. As expected, the in vivo efficacy of PtA-ZN2, cisplatin and PtA was found to correlate with Pt intratumour accumulation. In vitro cytotoxicity assays on cultured B16 cells also evidenced a superior efficacy for PtA-ZN2 as compared with unconjugated PtA. This was associated with higher intracellular levels of Pt in cells treated with PtA-ZN2, suggesting that the pharmacophore may facilitate Pt accumulation in tumour cells, even when blood circulation and lymphatic drainage are not an issue.     

Molecular Dynamics Studies of Electrolyte Solution/Metal Interfaces

Abstract

The results of Molecular Dynamics simulations of pure water near a Pt(100) and a mercury surface as well as an aqueous LiI solution in contact with the Pt(100) surface are reported. The flexible BJH water model is employed in the simulations and the metal-water, ion-water and platinum-ion potentials are derived from molecular orbital calculations. It is shown that the structural and dynamical properties of water and the ions in the adsorbed water layer are significantly different from those in the bulk region.     

Adsorption/Condensation of Xenon in a Disordered Silica Glass Having a Mixed (Micro a Mixed and Meso) Porosity

Abstract

We have studied adsorption of xenon in a mixed (micro and meso) porosity silica controlled porous glass (CPG) by means of grand canonical Monte-Carlo (GCMC) simulation. A numerical sample of the CPG adsorbent has been obtained by using an off-lattice reconstruction method recently introduced to reproduce topological and morphological properties of correlated disordered mesoporous materials. The off-lattice functional of (100m²/g)-Vycor is applied to a simulation box containing silicon and oxygen atoms of orthorhombic silicalite zeolite with an homothetic reduction of factor 2.5 so as to obtain a CPG sample exhibiting both micro and meso porosity. A realistic surface chemistry is then obtained by saturating all oxygen dangling bonds in the mesoporosity with hydrogen. The Xe adsorption/desorption isotherms is calculated at 195 K. It is shown that in the particular case of xenon, the difference of energetics between zeolitic micropores and CPG mesopores lead to two distinct adsorption processes which occur consecutively. As a consequence, both the microporosity and the mesoporosity can be calculated independently.     

Selective adsorption and recovery of precious metal ions using protein-rich biomass as efficient adsorbents

Various types of protein-rich biomass were examined as selective and environment-friendly adsorbents for precious metal ions. In the presence of base metal ions, Au³⁺, Pd²⁺ and Pt⁴⁺ ions were selectively adsorbed to samples of protein-rich biomass. Among the biomass samples tested, egg-shell membrane exhibited the highest adsorption ability and had high selectivity for Au, Pd and Pt ions. The maximum adsorption amount of Au, Pd and Pt ions to egg-shell membrane was approximately 250, 110 and 50 mg/g, respectively, in the presence of 0.1 M HCl. Microscopic observations and metal-ion desorption studies suggested that the precious metal ions were adsorbed and a portion of them was reduced to form metal nanoparticles on the egg-shell membrane, leading to high adsorption ratios. Investigations using glycoproteins indicated the importance of sugar chains in the adsorption of Au ions to the egg-shell membrane. Successful recovery of Au, Pd and Pt ions from industrial waste solutions was also demonstrated using egg-shell membrane. Biomass sheets (1 mm thick) made from egg-shell membrane also exhibited adsorption abilities for precious metal ions.     

Reactivity of an extremenly sterically crowded monofunctional Pt complex, [Pt(1-MeC-N3)3(H2O)]2+ (1-MeC=1-methylcytosine), toward model nucleobases and selectivity toward guanine in single- and double-stranded deoxyoligonucleotides

 Reactions of [Pt(1-MeC-N3)₃Cl]NO₃ (1-MeC-N3=1-methylcytosine, bound to Pt via N3) and the respective aqua species [Pt(1-MeC-N3)₃(H₂O)]²⁺ with the model nucleobases 9-ethylguanine (9-EtGH), 9-methyladenine (9-MeA), single-stranded 5′d(T₃GT₃), and double-stranded [5′d(GAGA₂GCT₂CTC)]₂ have been studied in solution by means of ¹H NMR spectroscopy, HPLC, and electrospray ionization mass spectrometry. Reactions are generally slow, in particular with the chloro species, and guanine is the only reactive base in the oligonucleotides. However, unlike (dien)Pt^II, which binds randomly to the guanines in the ds dodecamer, (1-MeC-N3)₃Pt^II binds selectively to the terminal guanine only, probably because base fraying takes place at the duplex ends. The X-ray crystal structures of [Pt(1-MeC-N3)₃(9-EtG-N7)]ClO₄·8H₂O (1b) and of [Pt(1-MeC-N3)₃(9-MeA-N7)](ClO₄)₂·0.5H₂O as well as NMR spectroscopic studies of [Pt(1-MeC-N3)₃(9-EtGH-N7)] (NO₃)₂·H₂O (1a) are reported. The tetrakis(nucleobase) complexes adopt a head-tail-head orientation of the three 1-MeC bases and an orientation of the fourth base (purine) that permits a maximum of intracomplex H bonds between exocyclic groups. As far as the guanine adduct (1a, 1b) is concerned, relative orientations of the four bases are identical in the model and in the oligonucleotide adduct. Received: 19 June 1998 / Accepted: 1 October 1998