Alberto Lesarri

Alberto Lesarri
Universidad de Valladolid | UVA · Department of Physical Chemistry and Inorganic Chemistry

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272
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Introduction
PChem Professor at the University of Valladolid (Spain)
Skills and Expertise

Publications

Publications (272)
Article
Full-text available
Self-aggregation of sevoflurane, an inhalable, fluorinated anesthetic, provides a challenge for current state-of-the-art high-resolution techniques due to its large mass and the variety of possible hydrogen bonds between monomers. Here we present the observation of sevoflurane trimer by chirped-pulse Fourier transform microwave spectroscopy, identi...
Article
Full-text available
Weakly-bound intermolecular clusters constitute reductionist physical models for non-covalent interactions. Here we report the observation of the monomer, the dimer and the monohydrate of 2-adamantanol, a secondary alcohol with a bulky ten-carbon aliphatic skeleton. The molecular species were generated in a supersonic jet expansion and characterize...
Article
Furfuryl alcohol and thenyl alcohol contain a labile torsional chiral center, producing transiently chiral enantiomers interconverting in the nanosecond time-scale. We explored chiral molecular recognition using the weakly-bound intermolecular dimers of both alcohols, freezing stereomutation. Supersonic jet broadband microwave spectroscopy revealed...
Article
Methyl vinyl ketone is one of the major oxidation products of isoprene, and therefore, an important precursor of secondary organic aerosol. Understanding its interactions with water is relevant to gain insight into aerosol formation and improve the predictive power of atmospheric chemistry models. The molecular complex formed between methyl vinyl k...
Article
Dinitriles with a saturated hydrocarbon skeleton and a –C≡N group at each end can have large electric dipole moments. Their formation can be related to highly reactive radicals such as CH2CN, C2N, or CN. Thus, these saturated dinitriles are potential candidates to be observed in the interstellar medium. In this work, two members of this family, hex...
Article
We have characterized the homochiral (2R, 3R) and heterochiral meso (2R,3S) isomers of 2,3-butanedithiol, using rotational spectroscopy at centimeter and millimeter-wave frequencies. The microwave experiment used jet-cooled chirped-pulsed fast-passage excitation in the range 2–8 GHz, while the millimeter-wave measurements in the regions 75–129 and...
Article
Chirality is determinant for sphingosine biofunctions and pharmacological activity, yet the reasons for the biological chiral selection are not well understood. Here, we characterized the intra- and intermolecular interactions at the headgroup of the cytotoxic anhydrophytosphingosine jaspine B, revealing chirality-dependent correlations between the...
Article
Molecular aggregation is of paramount importance in many chemical processes, including those in living beings. Thus, characterization of the intermolecular interactions is an important step in its understanding. We describe here the aggregation of benzyl alcohol at the molecular level, a process governed by a delicate equilibrium between OH⋯O and O...
Article
Plausible methods for accurate determination of equilibrium structures of intermolecular clusters have been assessed for the van der Waals dimer N2O⋯CO. In order to assure a large initial dataset of rotational parameters, we first measured the microwave spectra of the ¹⁵N2O⋯¹²CO and ¹⁵N2O⋯¹³CO isotopologs, expanding previous measurements. Then, an...
Article
The conformational landscape of the cyclohexanolSO2 cluster was revealed in the gas phase using chirped-pulsed broadband rotational spectroscopy and quantum chemical calculations. Four isomers stabilized by a dominant SO chalcogen bond and cooperative C-HO[double bond, length as m-dash]S and O-HO[double bond, length as m-dash]S secondary weak hydro...
Article
2-Chloro-4-fluorotoluene was investigated using a combination of molecular jet Fourier transform microwave spectroscopy in the frequency range from 5 to 21 GHz and quantum chemistry. The molecule experiences an internal rotation of the methyl group, which causes fine splittings of all rotational transitions into doublets with separation on the orde...
Article
We used jet-cooled broadband rotational spectroscopy to explore the balance between π-stacking and hydrogen-bonding interactions in the self-aggregation of thiophenol. Two different isomers were detected for the thiophenol dimer, revealing dispersion-controlled π-stacked structures anchored by a long S-H···S sulfur hydrogen bond. The weak intermole...
Article
We characterized the bis-quinolizidine tetracyclic alkaloid (5S, 6S, 7R, 11R)-matrine in a supersonic jet expansion, using chirped-pulsed broadband microwave spectroscopy. Previous crystal diffraction analyses suggested 16 diastereoisomers associated with matrine's four carbon stereocenters but were inconclusive whether the lactamic nitrogen atom w...
Chapter
Noncovalent interactions comprise an array of long-range interactions loosely classified as hydrogen bonds and van der Waals forces. These interactions are unique since their effect spans through long distances, therefore controlling many physical and chemical processes, such as formation of aerosols, crystals, condensation or even aggregation of m...
Article
Epigenetic marks are modest chemical modifications on DNA and histone proteins that regulate the activation or silencing of genes, through modulation of the intermolecular interactions between the DNA strands and the protein machinery. The process is complex and not always well understood. One of the systems studied in greater detail is the epigene...
Article
The rotational spectrum of the 1:1 complex pyridine–chlorotrifluoromethane shows that the two moieties are held together through a linear C-Cl···N halogen bond (RCl···N = 2.909(5) Å). The quadrupolar effects of the ³⁵Cl (or ³⁷Cl) and ¹⁴N nuclei combined with the high density of the rotational transitions give rise to a very congested spectrum. The...
Article
The monohydrates of thenyl alcohol and thenyl mercaptan have been generated in a supersonic jet expansion and probed using chirped-pulsed and Fabry-Perot Fourier-transform microwave spectroscopy. The rotational spectra revealed a single isomer for each of the dimers. The thenyl alcohol hydrate is stabilized by an O-H···Ow hydrogen bond between the...
Article
The cyclohexanol homodimer is a delicate test model of the role of dispersion forces in intermolecular association. While phenol produces a single dimer, suppression of π interactions and larger conformational flexibility in cyclohexanol results in multiple isomerism, as six competing dimers of the free molecule are observed in a supersonic jet exp...
Article
The cyclohexanol homodimer is a delicate test model of the role of dispersion forces in intermolecular association. While phenol produces a single dimer, suppression of π interactions and larger conformational flexibility in cyclohexanol results in multiple isomerism, as six competing dimers of the free molecule are observed in a supersonic jet exp...
Article
We studied the impact of the aliphatic side chain in the stability and conformational landscape of the local anaesthetics benzocaine, butamben and isobutamben, combining high resolution rotational spectroscopy in the...
Article
The jet-cooled rotational spectrum of 1,2-butanedithiol was observed in the frequency region 2–8 GHz. Two conformers were detected for the molecule, corresponding to anti- and gauche-carbon molecular skeletons, both featuring a gauche arrangement of the two thiol groups. All ¹³C and ³⁴S monosubstituted isotopologues were additionally assigned in na...
Article
The rotational spectrum of benzyl mercaptan (parent and four isotopologues) has been assigned in a supersonic jet expansion using chirped-pulsed Fourier transform microwave spectroscopy. The spectrum is characterized by torsional tunneling doublings, strongly perturbed by Coriolis interactions. The experimental rotational constants reveal that the...
Article
Molecular Aggregation The forest of non‐covalent interactions, dominated by the centenary hydrogen bond (HB), has more trees than expected. In the Minireview on page 11402 ff., Lesarri and co‐workers outline the role played by supersonic‐jet rotational spectroscopy to discern self‐aggregation, molecular recognition, and recently evidenced interacti...
Article
Cresyl and phenyl saligenin phosphate have been probed in a jet expansion by broadband chirp-excitation microwave spectroscopy, revealing the most stable conformation and its structural properties. The rotational parameters offer...
Article
The symmetrically substituted diallyl disulfide adopts a non-symmetric conformation in the gas-phase, as observed with supersonic-jet rotational spectroscopy. The determination of the equilibrium structure with a predicate mixed estimation illustrates...
Article
Understanding the conformational preferences of carbohydrates is crucial to explain the interactions with their biological targets and to improve their use as therapeutic agents. We present experimental data resolving the conformational landscape of the monosaccharide D-lyxose, for which quantum mechanical (QM) calculations offer model dependent re...
Article
Nearly-free internal rotation produces huge (>1 GHz)tunneling splittings in the rotational spectrum of meta-chlorotoluene. Additionally, the simultaneous presence of two chlorine ( ³⁵ Cl and ³⁷ Cl)isotopologues results in dense spectra with complicated hyperfine patterns, hampering the spectral analysis by conventional spectroscopic techniques. Sub...
Article
Full-text available
In a recent article (ACS Catal. 2018, 8, 11119−11133), a comprehensive catalytic mechanism is proposed to explain the effects of residual water on the reactivity and regioselectivity of tris(pentafluorophenyl)borane catalyst in the ring-opening reaction of 1,2-epoxyoctane by 2-propanol. Using it as a representative example of a common trend followed...
Article
In the last decade experiment and theory have expanded our vision of non‐covalent interactions, shifting the focus from the conventional hydrogen bond to new bridging interactions involving a variety of weak donor/acceptor partners. While most experimental data originates from condensed phases, the introduction of broadband (chirped‐pulse) microwav...
Article
The Cover Feature presents an investigation of the equilibrium structure of diphenyl disulfide with the chemically relevant ‐S‐S‐ bridge, using supersonic jet rotational spectroscopy and ab initio methods. More information can be found in the Article by J. Demaison et al. on page 366 in Issue 3, 2019 (DOI: 10.1002/cphc.201800973).
Article
The disulfide bridge (–S–S–) is an important structural motif in organic and protein chemistry, but only a few accurate equilibrium structures are documented. We report the results of supersonic‐jet microwave spectroscopy experiments on the rotational spectra of diphenyl disulfide, C6H5–S–S–C6H5 (including all 13C and 34S monosubstituted isotopolog...
Article
Two conformers of cyclohexanol and the cyclohexanol-water adduct have been characterized in a jet expansion using rotational spectroscopy. Cyclohexanol adopts in the gas phase an equatorial position for the hydroxyl group, with the two conformers differing in the orientation of the hydroxylic hydrogen, either gauche or trans with respect to the ali...
Article
Weaker intermolecular forces permit expanded isomerization alternatives for molecular aggregation, as observed for the prototype models of the aniline trimer (An3) and the monohydrated aniline dimer (An2‐W) when compared to the phenol trimer. These isolated trimers were generated in a jet‐cooled neon expansion and probed using broadband (chirped‐pu...
Article
Weaker intermolecular forces permit expanded isomerization alternatives for molecular aggregation, as observed for the prototype models of the aniline trimer (An3) and the monohydrated aniline dimer (An2‐W) when compared to the phenol trimer. These isolated trimers were generated in a jet‐cooled neon expansion and probed using broadband (chirped‐pu...
Article
We report on a mass-resolved IR spectrosopic study on propofol-benzocaine aggregates. This is a complex system, due to the several conformational isomers that both monomers may adopt and to the combination of functional grups they present, which allow the molecules to interact in many possible ways. However, our results demonstrate that a single co...
Article
Molecular aggregates or condensed phase?: Aggregation of aniline is a complex process, guided by many interactions of similar strength, N−H⋅⋅⋅N, N−H⋅⋅⋅p, C−H⋅⋅⋅N, C−H⋅⋅⋅p and p⋅⋅⋅p, which produce an increasing number of (quasi) isoenergetic structures, connected by low energy barriers. Thus, aniline pentamer formed in jets already presents the IR s...
Article
We deal here with the controlled nucleation of aniline from the isolated molecule until formation of a moderately large aggregate: aniline nonamer. The structure of the cluster at each step of the nucleation was unravelled combining mass‐resolved IR spectroscopy and computational chemistry, demonstrating that aggregation is primarily guided by form...
Article
The microwave rotational spectrum of 2,3-difluorotoluene has been studied by pulsed supersonic jet using Fourier transform microwave spectroscopy. The tunneling splitting due to the methyl internal rotation in the ground torsional state could be unambiguously identified and the three-fold (V3) potential barrier hindering the internal rotation of th...
Article
Hydrogen bond strengths depend on the electronegativity of donor and acceptor groups. The figure illustrates a 3D map of electronegativities, emphasizing the differences between the oxygen and sulfur atoms. In this experiment a jet expansion was used to generate the monohydrates of furfuryl mercaptan and furfuryl alcohol in the gas phase, also depi...
Article
Full-text available
The rotational spectrum of 2,4-difluorotoluene in the region 5–25 GHz has been studied by pulsed supersonic jet using Fourier transform microwave spectroscopy. The tunneling splitting due to the methyl internal rotation in the ground torsional state could be unambiguously identified and the threefold (V3) potential barrier hindering the internal ro...
Article
The conformational landscape of the bicyclic molecule 2-decalone has been studied in a jet-cooled expansion by using rotational spectroscopy. The investigation covered the frequency region 7–19 GHz using broadband fast-passage IMPACT Fourier-transform microwave techniques. The introduction of the asymmetric carbonyl substituent in the double-chair...
Article
Full-text available
An experimental-computational methodology combining rotational data, high-level ab initio calculations and predicate least-squares fitting is applied to the axial–equatorial isomerism and semiexperimental equilibrium structure determination of fluorocyclohexane. New supersonic-jet microwave measurements of the rotational spectra of the two molecula...
Article
Invited for the cover of this issue are the groups of Natalja Vogt at the University of Ulm, Alberto Lesarri at the University of Valladolid and Emilio J. Cocinero at the University of Pais Vasco. The image depicts the family tree of tropane alkaloids, to which pseudopelletierine belongs, and their occurrence in nature. Read the full text of the ar...
Article
Pseudopelletierine is a natural compound belonging to the tropane alkaloids family which has different pharmacological properties. Here, we address the structure of the two conformers unambiguously identified in the gas phase. The possible connections of the axial/equatorial (ax/eq) isomerism with its biological role have motivated the study of the...
Article
A rotational spectroscopy investigation has resolved the conformational equilibrium and structural properties of the alkaloid pseudopelletierine. Two different conformers originated by the inversion of the N-methyl group from axial to equatorial position have been unambiguously identified in the gas phase, and nine independent isotopologues have be...
Article
Invited for the cover of this issue is the group of Emilio J. Cocinero at the University of the Basque Country. The image depicts a fight between two biomolecules, cotinine and nicotine. Read the full text of the article at 10.1002/chem.201700023.
Article
The microwave spectrum of 2,5-difluorotoluene was investigated in a pulsed Molecular Beam Fourier Transform Microwave (MB-FTMW) spectrometer in the frequency region 4.5 – 24 GHz. Rotational lines show large internal rotation splittings indicating that the potential barrier hindering internal rotation of the methyl group is comparatively low. The to...
Article
The ultimate battle has begun: The two opponents will pit their skills against each other in terms of ring puckering, intra-molecular interactions and internal rotation. The battlefield: the interaction-free environment of a supersonic expansion where both nicotinoids display their intrinsic properties. The referee: high resolution microwave spectr...
Article
Nicotinoids are agonists of the acetylcholine receptor (nAChR) and play important biochemical and pharmacological roles. Here we report on the structural and conformational landscape of cotinine, and compare its molecular properties with the nicotine prototype, from which it only differs in the addition of a carbonyl group. The investigation of cot...
Article
Upon supersonic expansion, formic acid and cyclobutanone (CBU) form a molecular cluster in which the two constituent molecules, linked by OHO and CHO hydrogen bonds, undergo a rapid interconversion between two equivalent forms. The tunneling motion takes place through the rupture and reformation of the C-HO hydrogen bond between the carbonyl oxygen...
Article
The rotational spectrum of the tropane alkaloid scopine has been detected by Fourier transform microwave spectroscopy in a pulsed supersonic jet. A non-conventional method for bringing the molecules intact into the gas phase was used, mixing scopine syrup with glycine powder and vaporizing the solid mixture with an UV ultrafast laser beam. Laser va...
Article
Previous ambiguities in the conformational and structural landscape of the volatile anesthetic enflurane have been solved combining microwave spectroscopy in a jet expansion and ab initio calculations. The broadband (2-18 GHz) rotational spectra identified three different rotamers, sharing a common trans ether skeleton but differing in the ±gauche/...
Article
Fructose and deoxyribose (24 and 19 atoms, respectively) are too large for determining accurate equilibrium structures, either by high-level ab initio methods or by experiments alone. We show in this work that the semiexperimental (SE) mixed estimation (ME) method offers a valuable alternative for equilibrium structure determinations in moderate-si...
Article
The hydration of 2-fluoropyridine with one water molecule has been studied with a pulsed jet Fourier transform microwave technique. The rotational spectra of five isotopologues of the 1:1 complex have revealed the formation of a single most stable isomer. The observed cluster is characterized by an O−H⋅⋅⋅N hydrogen bond and a C−H⋅⋅⋅O weak hydrogen...
Article
This is the first investigation of an isolated ribofuranose unit in the gas phase, revealing the intrinsic conformational landscape of the biologically active sugar form. We report the rotational spectra of two conformers of methyl β-D-ribofuranoside in a supersonic jet expansion. Both conformers adopt a twisted (3T2) ring conformation with the met...
Article
The potential energy surface (PES) of the general anesthetic fluoroxene (2,2,2-trifluoroethyl vinyl ether) was probed in a supersonic jet expansion using broadband chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy and theoretical calculations. The PES is dominated by a single conformation, as other stable minima are shown to kinetica...
Article
Histone-DNA interactions were probed computationally at a molecular level, by characterizing the bimolecular clusters constituted by selected amino acid derivatives, with polar (asparagine and glutamine), non-polar (alanine, valine and isoleucine) and charged (arginine) side chains and methylated pyrimidinic (1-methylcytosine and 1- methylthymine)...
Article
Full-text available
Pure six-fold symmetry (V6) internal rotation poses significant challenges to experimental and theoretical determination, as the very low torsional barriers result in huge tunneling splittings difficult to identify and to model. Here we resolved the methyl group internal rotation dynamics of 2,6- and 3,5-difluorotoluene using a newly developed comp...
Article
Exo-2,3-epoxynorbornane is studied in the gas phase by pulsed jet Fourier transform microwave spectroscopy in the 4-18 GHz region. Six isotopologues were observed and characterized in their natural abundance. The experimental substitution and effective structures were obtained. Comparison with the structure of norbornane shows significant differenc...
Article
Full-text available
We have examined the stereoselectivity of molecular recognition between two molecules of the anesthetic sevoflurane using broadband rotational spectroscopy. The transient axial chirality of sevoflurane is revealed on formation of the dimer, as two different diastereoisomers made of either homo- or heterochiral species are detected in a supersonic j...
Article
Broadband chirped-pulse Fourier transform microwave (CP-FTMW) spectrometers have increased the sensitivity for molecular rotational spectroscopy. The measurement dynamic range is often large enough that isotopologues of the molecular species with the highest transition strength will also be detectable. In order to analyze the complex spectra from t...
Article
The rotational spectra of two isotopologues of the 1:1 complex between chlorotrifluoromethane and formaldehyde have been recorded and analyzed by using Fourier-transform microwave spectroscopy. Only one rotamer was detected, with the two constituent molecules held together through a Cl⋅⋅⋅O halogen bond (RCl⋅⋅⋅O =3.048 Å). The dimer displays two sim...
Article
Reported is the hydration of nanomicelles in the gas-phase using spectroscopic methods and quantum chemical calculations. A fine-tuning of the experimental conditions allowed formation of a propofol trimer and tetramer with a water molecule and to determine the structure of the aggregates. Their electronic and IR spectra were obtained using mass-re...