Ines Corral

Ines Corral
Universidad Autónoma de Madrid | UAM · Department of Chemistry

PhD

About

105
Publications
5,592
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1,489
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February 2010 - present
Universidad Autónoma de Madrid
Position
  • Professor (Assistant)

Publications

Publications (105)
Article
Full-text available
There is significant interest in developing suitable nucleoside analogs exhibiting high fluorescence and triplet yields to investigate the structure, dynamics, and binding properties of nucleic acids and promote selective photosensitized damage to DNA/RNA, respectively. In this study, steady-state, laser flash photolysis, time-resolved IR luminesce...
Article
Full-text available
The cooperative action of the acetate ligand, the 2-pyridyl sulfonyl (SO2Py) directing group on the alkyne substrate, and the palladium catalyst has been shown to be crucial for controlling reactivity, regioselectivity, and stereoselectivity in the acetoxylation of unsymmetrical internal alkynes under mild reaction conditions. The corresponding alk...
Article
Full-text available
We present the synthesis, photophysical properties, and biological application of nontoxic 3-azo-conjugated BODIPY dyes as masked fluorescent biosensors of hypoxia-like conditions. The synthetic methodology is based on an operationally simple N═N bond-forming protocol, followed by a Suzuki coupling, that allows for a direct access to simple and und...
Article
Full-text available
Oxo and amino substituted purines and pyrimidines have been suggested as protonucleobases participating in ancient pre-RNA forms. Considering electromagnetic radiation as a key environmental selection pressure on early Earth, the investigation of the photophysics of modified nucleobases is crucial to determine their viability as nucleobases' ancest...
Article
Full-text available
Small structural alterations of the purine/pyrimidine core have been related to important photophysical changes, such as the loss of photostability. Similarly to canonical nucleobases, solute-solvent interactions can lead to a change in the excited state lifetimes and/or to the interplay of different states in the photophysics of these modified nuc...
Article
Full-text available
Low-valent group 2 (E = Be and Mg) stabilized compounds have been long synthetically pursued. Here we discuss the electronic structure of a series of Lewis base-stabilized Be and Mg compounds. Despite the accepted zero(0) oxidation state nature of the group 2 elements of some recent experimentally accomplished species, the analysis of multireferenc...
Article
Full-text available
Subphthalocyanines (SubPcs) chemistry has been limited so far by their high sensitivity toward strong nucleophiles. In particular, the substitution of the axial chlorine atom by a nucleophilic group in the case of less reactive SubPcs, such as those bearing electron‐withdrawing peripheral substituents, presents some limitations and requires harsh c...
Article
High-level single and multireference ab initio calculations show that the Be4 cluster behaves as a very efficient Lewis acid when interacting with conventional Lewis bases such as ammonia, water or hydrogen fluoride, to the point that the corresponding acid-base interaction triggers a sequential dissociation of all the bonds of the Lewis base. Nota...
Article
In this study, the working mechanism of the first light-driven rotary molecular motors used to control an eight-base-pair DNA hairpin has been investigated. In particular, this linker was reported to have promising photophysical properties under physiological conditions, which motivated our work at the quantum mechanical level. Cis–trans isomerizat...
Article
The structure, stability, and bonding of the complexes formed by the interaction of Mg4 clusters and first row Lewis bases, namely, ammonia, water, and hydrogen fluoride, have been investigated through the use of high-level G4 single-reference and CASPT2 multireference formalisms. The adducts formed reflect the high electrophilicity of the Mg4 clus...
Article
This work investigates the photophysics of barbituric acid at different pH conditions using ab initio methods. Our calculations ascribe the most intense bands at ca. 260 nm at neutral pH and 210 nm at acidic pH conditions in the absorption spectra of this chromophore to the lowest lying ππ* transitions. Consistently with the ultrashort excited stat...
Article
The substitution of canonical nucleobases by thiated analogues in natural DNA has been exploited in pharmacology, photochemotherapy, and structural biology. Thionucleobases react with adjacent thymines leading to 6-4 pyrimidine-pyrimidone photoproducts (6-4PPs), which are a major source of DNA photodamage, in particular intrastrand cross-linked pho...
Article
Full-text available
Chemical bonds are traditionally assigned as electron‐sharing or donor‐acceptor/dative. External criteria such as the nature of the dissociation process, energy partitioning schemes or quantum chemical topology are invoked to assess the bonding situation. However, for systems with marked multi‐reference character, this binary categorization might n...
Article
Full-text available
Die konventionelle Bindungsanalyse unterscheidet zwei Situationen: Elektronenpaarbindung und Donor‐Akzeptor. Jedoch ist ein drittes Szenario möglich, bei dem die Bindung einer Spinpolarisation unterliegt. Hier wird der Fall von NaBH3⁻ erörtert, das als Molekül mit spinpolarisierter Bindung klassifiziert werden kann. Ein einfaches Modell zur Untersc...
Article
Isolated Be2 is a typical example of a weakly bound system, but interaction with other systems may give rise to surprising bonding features. The interactions between Be2 and a set of selected neutral Cn Hn (n=2-8) π-systems have been analyzed through the use of G4 and G4MP2 ab initio methods, along with multireference CASPT2//CASPT2 calculations. O...
Article
Today’s genetic composition is the result of continual refinement processes on primordial heterocycles present in prebiotic Earth and at least partially regulated by ultraviolet radiation. Femtosecond transient absorption spectroscopy and state-of-the-art ab initio calculations are combined to unravel the electronic relaxation mechanism of pyrimidi...
Article
The Cover Feature illustrates competing deactivation photophysical routes in the parent BODIPY molecule: Internal conversion, intersystem crossing and fluorescence. Rational functionalization can quench radiative and non‐radiative decay to the ground state while increasing population transfer to the triplet states. This study maps the landscape of...
Article
This work scrutinizes the relaxation mechanism of 2-oxopurine. Contrary to its ancestor, purine, which is a UVC chromophore, 2-oxopurine shows a red-shifted absorption spectrum centered in the UVA region. In 2-oxopurine, relaxation from the spectroscopic state directs the population from the FC region of a ππ* state towards a minimum, which acts as...
Article
A study on C9‐imide acridinium photocatalysts with enhanced photoredox catalytic activity with respect to the well‐established C9‐mesityl acridinium salt is presented. The differences observed rely on the diverse accessibility of singlet charge‐transfer excited states, which have been proven by CASPT2/CASSCF calculations, fluorescence and quenching...
Article
This work describes the decay mechanism of photoexcited thiourea, both in gas phase and in solution, from the information inferred from the topography of the excited and ground state potential energy surfaces and mixed singlet/triplet quantum classical molecular dynamics simulations. Our gas phase results reveal T1/S0 intersystem crossing as the do...
Article
The pentafluorophenyl (PFP) moiety is an important and versatile substituent in the chemistry of BODIPYs, porphyrins and corroles. The widespread use of PFP meso-substituted compounds, as intermediates in the synthesis of more complex pyrrole derivatives, is the motivation behind this work, which investigates the optical properties of the meso-PFP-...
Article
Here we present a computational investigation of the excited state dynamics of 5 different active medical substances (aspirin, ibuprofen, carprofen, suprofen, indomethacin) which belong to the family of nonsteroidal anti-inflammatory drugs (NSAIDs). The nonadiabatic dynamics simulations were performed using the surface hopping method, with electron...
Preprint
Full-text available
This work describes the decay mechanism of photoexcited thiourea, both in gas phase and in solution, from the information inferred from the topography of the excited and ground state potential energy surfaces and mixed singlet/triplet quantum classical molecular dynamics simulations. Our gas phase results reveal T1/S0 intersystem crossing as the do...
Preprint
Full-text available
Here we present a computational investigation of the excited state dynamics of 5 different active medical substances (aspirin, ibuprofen, carprofen, suprofen, indomethacin) which belong to the family of nonsteroidal anti-inflammatory drugs (NSAIDs). The nonadiabatic dynamics simulations were performed using the surface hopping method, with electron...
Article
The presence of nonadiabatic effects during the interaction of small molecules with metals has been observed experimentally for the last decades. Specially remarkable are the effects found for NO/Au, where experiments have suggested the presence of very strong vibronic coupling during the molecular scattering. However, the accurate inclusion of the...
Article
The potential tunability of the properties of the BODIPY parent dye by suitable functionalization is attractive for a number of applications. The remarkable fluorescence of the parent compound, which competes with intersystem crossing to the triplet states, can be reverted by the structural tuning of the BODIPY core, leading to BODIPY derivatives s...
Article
Full-text available
H₂ has been proposed as a long-term non-fossil fuel to be used in a future ideal carbon neutral energetic economy. However, its low volumetric energy density hinders its storage and transportation. MOFs represent very promising materials for this purpose, due to their very extended surface areas. Azolates and, in particular tetrazolates, are togeth...
Article
The electronic structure of complexes formed by the interaction of Be2 with radical ligands (L:Be-Be:L) has been studied by means of the high-level theoretical protocol, CCSD(T)/cc-pVTZ. At this level of theory, no matter the nature of the ligand, the Be-Be bond becomes up to 300 times stronger compared to isolated Be2, indicating that this kind of...
Article
The F–, Cl–, CN–, NO2–, NO3–, SO4= anion affinities of 4,5-bis(BeX)-fluorene (X = H, F, Cl, CN, NC, OCH3) derivatives have been calculated at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p) level of theory. The reliability of this approach was assessed using, for some suitable cases, the accurate G4MP2 ab initio composite method as a reference. The va...
Article
Full-text available
Interest in understanding the photophysics and photochemistry of thiated nucleobases has been awakened because of their possible involvement in primordial RNA or their potential use as photosensitizers in medicinal chemistry. The interpretation of the photodynamics of these systems, conditioned by their intricate potential energy surfaces, requires...
Article
The theoretical description of core-hole and core-hole excited (shake-up) states resulting from the interaction of a molecule with X-ray free electron lasers, attosecond pulses and synchrotron radiation is a challenging task, as these states lie in the ionization continuum and, therefore, are subject to variational collapse. Although much effort ha...
Article
The theoretical description of observables in attosecond pump-probe experiments requires a representation of the system’s ionization continuum. For polyelectronic molecules, however, this is still a challenge, due to the complicated short-range structure of correlated electronic wave functions. Whereas quantum chemistry packages (QCP) implementing...
Article
Photosensitization of DNA by thionucleosides is a promising photo-chemotherapeutic treatment option for a variety of malignancies. DNA metabolization of thiated prodrugs can lead to cell death upon exposure to a low dose of UVA light. The exact mechanisms of thionucleoside phototoxicity are still not fully understood. In this work, we have combined...
Article
Low-lying p vacancies of the beryllium atoms inserted in 1,8-di(BeX)naphthalene (X=H, F, Cl, CN, CF3, C(CF3)3) frameworks confer on these derivatives enhanced anion affinities that surpass those of some of the strongest neutral single Lewis acids reported. This enhanced ability to bind anions permits these compounds to be considered as good anion r...
Article
Full-text available
Elucidating the photophysical mechanisms in sulfur-substituted nucleobases (thiobases) is essential for designing prospective drugs for photo-and chemotherapeutic applications. Although it has long been established that the phototherapeutic activity of thiobases is intimately linked to efficient intersystem crossing into reactive triplet states, th...
Data
Supplementary Figures 1-8, Supplementary Tables 1-7, Supplementary Notes 1-3 and Supplementary References
Article
Through the use of high-level ab initio and density functional calculations we have shown that 1,8-diBeX-naphthalene (X = H, F, Cl, CN, CF₃, C(CF₃)₃) derivatives behave as anion sponges, very much as 1,8-bis(dimethylamino)naphthalene derivatives behave as proton sponges. The electron deficient nature of the BeX substituents, which favors strong cha...
Poster
Full-text available
We analyze the effect of a Beryllium bond in the homolytic dissociation of several systems (YZ) using high-level multiconfigurational methods. For all the systems examined we find that, in contrast to natural dissociation, Be interaction results in an exothermic process, leading to the formation of neutral products: XBeY + XZ (X= H,Cl). Interesting...
Article
High-level ab initio calculations show that the formation of radicals, by the homolytic bond fission of Y−R (Y=F, OH, NH2; R=CH3, NH2, OH, F, SiH3, PH2, SH, Cl, NO) bonds is dramatically favored by the association of the molecule with BeX2 (X=H and Cl) derivatives. This finding is a consequence of two concomitant effects, the significant activation...
Article
High-level ab initio calculations show that the formation of radicals, by the homolytic bond fission of Y-R (Y=F, OH, NH2 ; R=CH3 , NH2 , OH, F, SiH3 , PH2 , SH, Cl, NO) bonds is dramatically favored by the association of the molecule with BeX2 (X=H and Cl) derivatives. This finding is a consequence of two concomitant effects, the significant activ...
Article
Full-text available
Nonadiabatic processes play a fundamental role in the understanding of photochemical processes in excited polyatomic molecules. A particularly important example is that of radiationless electronic relaxation at conical intersections (CIs). We discuss new opportunities for controlling coupled electron–nuclear dynamics at CIs, offered by the advent o...
Article
A new synthetic one-step approach to perform the axial ligand exchange reaction in subphthalocyanines that employs trimethylsilyl-protected nucleophiles as starting materials is reported. Theoretical calculations indicate that the exchange reaction proceeds through a similar 4-centered σ-bond metathesis transition state as the substitution with phe...
Article
Full-text available
In this contribution, equilibrium geometries and potential energy curves computed at the CASSCF level of theory for the core hole and shake up superexcited states of small size molecules will be presented. The effect of dynamic correlation on the description of these species will be discussed based on preliminary multireference configuration intera...
Article
Full-text available
We present a theoretical study of the vibrationally resolved core photoionization of the water molecule up to high photon energies. In order to understand the role of the coupled electron-nuclear motion in polyatomic molecules, we thus have implemented a new methodology to describe all vibrational modes of a polyatomic molecule. We show our prelimi...
Article
Full-text available
An interface between quantum chemistry electronic structure and scattering electronic theory was developed for representing the ionization of molecules. This description is achieved by creating a mix of Gaussian and B-spline functions (GABS) for the ejected electron and standard multiconfigurational methodology for the remaining bounded ones
Article
Full-text available
To study the photoionization of polyelectronic systems by attosecond pulses, we take advantage of existing quantum chemistry packages for the description of correlated electronic states, and of hybrid Gaussian- B-splines basis for the representation of continuum orbitals. In our approach, a short-range region, which can host all the interacting ele...
Article
The direct reaction between [Cu(OAc)2·(H2O)]2 and n-butyldithiocarboxylic acid affords two copper(I) aggregates with dithiocarboxylato, [Cu(S2C-n-butyl)]4 (1), and perthiocarboxylato ligands, [Cu(S3C-n-butyl)]4 (2), in which the oxidation of dithiocarboxylato ligand is triggered by the CuII centers. The activation of the S–S bond in 2 by two reduci...
Article
Small molecular probes able to act as sensors are of enormous interest thanks to their multiple applications. Here, we report on the development of a novel supramolecular dual viscosity and polarity probe based on the foldamer concept, which increases the resolution limits of traditional probes at low viscosity values (0-4 mPa·s). The applicability...
Article
The excited-state dynamics of the purine free base and 9 methylpurine are investigated using experimental and theoretical methods. Femtosecond broadband transient absorption experiments reveal that excitation of these purine derivatives in aqueous solution at 266 nm results primarily in ultrafast conversion of the S2(ππ*) state to the vibrationally...
Article
A synergistic approach combining high-level multiconfigurational static calculations and full-dimensional ab initio surface hopping dynamics has been employed to gain insight into the photochemistry of endoperoxides. Electronic excitation of endoperoxides triggers two competing pathways, cycloreversion and O-O homolysis, that result in the generati...
Article
We present a density functional theory and ab initio (MP2) study of stereoisomer discrimination between the homochiral and heterochiral dimers of the form M(XYYX')2, where M is a cationic metal (Li, Ca2+, Zn2+, Cu+, Cu2+) complexing chalcogen-chalcogen bridges (H2O2, H2S2, H2Se2, and their corresponding methyl and dimethyl derivatives). The heteroc...
Article
We provide here an insight into the mechanism of the axial ligand exchange reaction between chlorosubphthalocyanines and phenols. Our combined experimental and theoretical results support a bimolecular σ-bond metathesis mechanism in which the phenolic proton assists in weakening the boron-halogen bond concomitantly with substitution at the boron ce...
Article
In this paper we simulate the deactivation dynamics of photoexcited 6-thioguanine, a cytotoxic analogue of the canonical DNA/RNA base guanine, using a direct surface hopping dynamics approach. Our aim is to investigate the mechanism for triplet population, which was found to take place on a similar time scale as internal conversion. The surface hop...
Article
The suitability of di-thiosubstituted derivatives of formic acid dimer, both in hydroxyl and carbonyl position, as possible hydrogen-bonded electron transfer linkers in a hypothetical donor–acceptor dyad for photovoltaic cells and artificial photosynthesis reactors has been studied from a theoretical point of view. To this purpose, the valence sing...
Article
The present study is aimed at elucidating the factors governing the organization on surfaces of some aromatic alcohol molecules. The ability to self-assemble on an Au (111) surface monolayer structures of three different polyalcohols with trigonal symmetry, 1,3,5-trihydroxybenzene (THB), 1,3,5-tris(4-hydroxyphenyl)benzene (THPB), and 2,3,6,7,10,11-...
Article
Getackert: Die kleinsten Mitglieder einer Familie von Kohlenstoff‐Nanowendeln (CNCs) mit fixierter helikaler Struktur wurden durch Einführung einer oder zweier ,,Klammern“ in o‐Phenylenethinylen‐Oligomere synthetisiert. Die chiroptischen Antworten der Systeme mit enantiomerenreinen, von L‐Tartrat abgeleiteten Klammern bestätigen die induzierte Heli...
Article
Spring loaded: The smallest members of a family of carbon nanocoils (CNCs), adopting a fixed helical structure, have been synthesized by introduction of one or two staples in o-phenylene ethynylene oligomers. The chiroptical responses of the systems having enantiopure L-tartrate-derived staples confirmed the induced helicity. Theoretical studies su...
Article
We present a combined experimental and theoretical study focused on the ionic states of the N2O4 molecule. Experimental results regarding photoionization induced by the synchrotron radiation SOLEIL in the 13.5-15.5 eV energy range were obtained using the electron-ion velocity vector correlation method. The potential energy curves for the dissociati...
Article
The structure, relative stability, and anharmonic vibrational frequencies of the most stable complexes between glycine, serine, and cysteine with Ca2+ have been calculated by means of DFT approaches. The global minimum of the potential energy surface for glycine‐Ca2+ complex corresponds to the salt‐bridge (SB) form, whereas for serine‐ and cysteine...
Article
The deactivation mechanism of the cytotoxic 6-thioguanine, the 6-sulfur-substituted analogue of the canonical DNA base, is unveiled by ab initio calculations. Oxygen-by-sulfur substitution leads to efficient population of triplet states-the first step for generating singlet oxygen-which is responsible for its cytotoxicity.
Article
Full-text available
Oxygenation mechanisms of phenylhalocarbenes in vacuum are investigated through the use of density functional theory and CASSCF-PT2 approaches. Reactions with both substituted and unsubstituted phenylhalocarbenes are strongly exothermic. The reactions with nitrosubstituted halocarbenes are predicted to be spin allowed due to the practical degenerac...
Article
The performance of Time-Dependent Density Functional Theory (TD-DFT) in the prediction of the low-energy region of the electronic absorption spectrum of a model aromatic endoperoxide (anthracene-9,10-endoperoxide, APO) has been assessed against accurate MS-CASPT2//CASSCF transition energies and oscillator strengths for comparison. This survey inclu...
Article
Doubly charged species in the gas phase have been an oddity for many years, but the possibility of generating and detecting them with the new available experimental techniques has faced the scientific community with challenging questions regarding their stability, bonding and reactivity. In this paper we analyze, mainly from a theoretical perspecti...
Article
Ab initio surface-hopping dynamics calculations have been performed to simulate the intramolecular excited state hydrogen transfer dynamics of ortho-nitrobenzaldehyde (o-NBA) in the gas phase from the electronic S(1) excited state. Upon UV excitation, the hydrogen is transferred from the aldehyde substituent to the nitro group, generating o-nitroso...
Article
High-level single-reference CCSD(T) and multireference MS-CASPT2/CASSCF ab initio calculations have been carried out to determine the electronic structure and the lifetimes of GaX(2+) (X = N, F) doubly charged diatomic systems. Lifetimes were evaluated using the Exterior Complex Scaling (ECS) method implemented with basis sets of B-spline functions...
Article
o-Nitrobenzaldehyde is photolabile because of an irreversible phototautomerization, whereas comparable aromatic compounds function as photoprotectors because the tautomerization is reversible. In this experimental and theoretical study we track down the cause of this difference to the electronic changes that occur during the tautomerization.
Article
The electronic structure, stability, and lifetime of GaO2+ have been investigated using high-level ab initio calculations. The potential energy curves have been calculated at the CCSD(T)/aug-cc-pV5Z and at the MS-CASPT2/ANO-RCC levels of theory. Lifetimes were evaluated using the Exterior Complex Scaling (ECS) method and B-spline basis functions. O...
Article
In a joint experimental and theoretical study, the UV/Vis absorption spectra of the three isomers (ortho, meta, para) of nitrobenzaldehyde (NBA) were analyzed. Absorption spectra are reported for NBA vapors, cyclohexane and acetonitrile solutions. All spectra are poor in vibronic structure and hardly affected in shape by the surroundings (vapor or...