Platelet bioenergetic profiling uncovers a metabolic pattern of high dependency on mitochondrial fatty acid oxidation in type 2 diabetic patients who developed in-stent restenosis.

Although platelet bioenergetic dysfunction is evident early in the pathogenesis of diabetic macrovascular complications, the bioenergetic characteristics in type 2 diabetic patients who developed coronary in-stent restenosis (ISR) and their effects on platelet function remain unclear. Here, we performed platelet bioenergetic profiling to characterize the bioenergetic alterations in 28 type 2 diabetic patients with ISR compared with 28 type 2 diabetic patients without ISR (non-ISR) and 28 healthy individuals. Generally, platelets from type 2 diabetic patients with ISR exhibited a specific bioenergetic alteration characterized by high dependency on fatty acid (FA) oxidation, which subsequently induced complex III deficiency, causing decreased mitochondrial respiration, increased mitochondrial oxidant production, and low efficiency of mitochondrial ATP generation. This pattern of bioenergetic dysfunction showed close relationships with both α-granule and dense granule secretion as measured by surface P-selectin expression, ATP release, and profiles of granule cargo proteins in platelet releasates. Importantly, ex vivo reproduction of high dependency on FA oxidation by exposing non-ISR platelets to its agonist mimicked the bioenergetic dysfunction observed in ISR platelets and enhanced platelet secretion, whereas pharmaceutical inhibition of FA oxidation normalized the respiratory and redox states of ISR platelets and diminished platelet secretion. Further, causal mediation analyses identified a strong association between high dependency on FA oxidation and increased angiographical severity of ISR, which was significantly mediated by the status of platelet secretion. Our findings, for the first time, uncover a pattern of bioenergetic dysfunction in ISR and enhance current understanding of the mechanistic link of high dependency on FA oxidation to platelet abnormalities in the context of diabetes.

Probing the Electronic Structure of [B10H10]2- Dianion Encapsulated by an Octamethylcalix[4]pyrrole Molecule.

Despite being an important closo-borate in condensed phase boron chemistry, isolated [B10H10]2- is electronically unstable and has never been detected in the gas phase. Herein, we report a successful capture of this fleeting species through binding with an octamethylcalix[4]pyrrole (omC4P) molecule to form a stable gaseous omC4P·[B10H10]2- complex and its characterizations utilizing negative ion photoelectron spectroscopy (NIPES). The recorded NIPE spectrum, contributed by both omC4P and [B10H10]2-, is deconvoluted by subtracting the omC4P contribution to yield a [B10H10]2- spectrum. The obtained [B10H10]2- spectrum consists of four major bands spanning the electron binding energy (EBE) range from 1 to 5 eV, with the EBE gaps matching excellently with the energy intervals of computed high-lying occupied molecular orbitals of the [B10H10]2- dianion. This study showcases a generic method to utilize omC4P to capture unstable multiply charged anions in the gas phase for experimental determination of their electronic structures.

Deprotonated sulfamic acid and its homodimers: Does sulfamic acid adopt zwitterion during cluster growth?

We present a joint experimental and computational study on the geometric and electronic structures of deprotonated sulfamic acid (SA) clusters [(SA)n-H]- (n = 1, 2) employing negative ion photoelectron spectroscopy and high-level ab initio calculations. The photoelectron spectra provide the vertical/adiabatic detachment energy (VDE/ADE) of the sulfamate anion (SM-) H2N●SO3- at 4.85 ± 0.05 and 4.58 ± 0.08 eV, respectively, and the VDE and ADE of the SM-●SA dimer at 6.41 ± 0.05 and 5.87 ± 0.08 eV, respectively. The significantly increased electron binding energies of the dimer confirm the enhanced electronic stability upon the addition of one SA molecule. The CCSD(T)-predicted VDEs/ADEs agree excellently with the experimental data, confirming the identified structures as the most stable ones. Two types of dimer isomers possessing different hydrogen bonding (HB) motifs are identified, corresponding to SM- binding to a zwitterionic SA (SM-●SAz) and a canonical SA (SM-●SAc), respectively. Two N-H⋯O HBs and one superior O-H⋯O HB are formed in the lowest-lying SM-●SAc, while SM-●SAz has three moderate N-H⋯O HBs, with the former being 4.71 kcal/mol more stable. Further theoretical analyses reveal that the binding strength advantage of SM-●SAc over SM-●SAz arises from its significant contributions of orbital interactions between fragments, illustrating that sulfamate strongly interacts with its parent SA acid and preferably chooses the canonical SA in the subsequent cluster formations. Given the prominent presence of SA, this study provides the first evidence that the canonical dimer model of sulfamic acid should exist as a superior configuration during cluster growth.

Observation of a super-tetrahedral cluster of acetonitrile-solvated dodecaborate dianion via dihydrogen bonding.

We launched a combined negative ion photoelectron spectroscopy and multiscale theoretical investigation on the geometric and electronic structures of a series of acetonitrile-solvated dodecaborate clusters, i.e., B12H122-·nCH3CN (n = 1-4). The electron binding energies of B12H122-·nCH3CN are observed to increase with cluster size, suggesting their enhanced electronic stability. B3LYP-D3(BJ)/ma-def2-TZVP geometry optimizations indicate each acetonitrile molecule binds to B12H122- via a threefold dihydrogen bond (DHB) B3-H3 ⁝⁝⁝ H3C-CN unit, in which three adjacent nucleophilic H atoms in B12H122- interact with the three methyl hydrogens of acetonitrile. The structural evolution from n = 1 to 4 can be rationalized by the surface charge redistributions through the restrained electrostatic potential analysis. Notably, a super-tetrahedral cluster of B12H122- solvated by four acetonitrile molecules with 12 DHBs is observed. The post-Hartree-Fock domain-based local pair natural orbital- coupled cluster singles, doubles, and perturbative triples [DLPNO-CCSD(T)] calculated vertical detachment energies agree well with the experimental measurements, confirming the identified isomers as the most stable ones. Furthermore, the nature and strength of the intermolecular interactions between B12H122- and CH3CN are revealed by the quantum theory of atoms-in-molecules and the energy decomposition analysis. Ab initio molecular dynamics simulations are conducted at various temperatures to reveal the great kinetic and thermodynamic stabilities of the selected B12H122-·CH3CN cluster. The binding motif in B12H122-·CH3CN is largely retained for the whole halogenated series B12X122-·CH3CN (X = F-I). This study provides a molecular-level understanding of structural evolution for acetonitrile-solvated dodecaborate clusters and a fresh view by examining acetonitrile as a real hydrogen bond (HB) donor to form strong HB interactions.

Organic Molecules Mimic Alkali Metals Enabling Spontaneous Harpoon Reactions with Halogens.

The harpoon mechanism has been a milestone in molecular reaction dynamics. Until now, the entity from which electron harpooning occurs has been either alkali metal atoms or non-metallic analogs in their excited states. In this work, we demonstrate that a common organic molecule, octamethylcalix[4] pyrrole (omC4P), behaves just like alkali metal atoms, enabling the formation of charge-separated ionic bonding complexes with halogens omC4P+ ⋅ X- (X=F-I, SCN) via the harpoon mechanism. Their electronic structures and chemical bonding were determined by cryogenic photoelectron spectroscopy of the corresponding anions and confirmed by theoretical analyses. The omC4P+ ⋅ X- could be visualized to form from the reactants omC4P+X via electron harpooning from omC4P to X at a distance defined by the energy difference between the ionization potential of omC4P and electron affinity of X.

Anion-Activated Bases and Nucleophiles Characterized by Photoelectron Spectroscopy.

Negative ion photoelectron spectra at 20 K along with ab initio [CCSD(T)] and M06-2X density functional theory calculations are reported for a series of six basic and nucleophilic pyridine derivatives with an anionic substituent [i.e., 3- and 4-PyrBX3-, where X = F, 4-t-BuC6H4, 4-MeOC6H4, and 3,5-(MeO)2C6H3]. Vertical detachment energies (VDEs) of these charge-activated reagents span from 4.50-5.85 eV and are well reproduced by M06-2X/aug-cc-pVTZ and CCSD(T)/maug-cc-pVTZ computations. Surprisingly, the VDEs are found to correlate with the SN2 reactivity of the PPh4+ salts of the substituted pyridine anions with 1-iodooctane in dichloromethane. This provides an experimental measure of the nucleophilicity of these charge-activated anions, which represent a new class of chemical reagent.

Locking water molecules via ternary O-H⋯O intramolecular hydrogen bonds in perhydroxylated closo-dodecaborate.

A multitude of applications related to perhydroxylated closo-dodecaborate B12(OH)122- in the condensed phase are inseparable from the fundamental mechanisms underlying the high water orientation selectivity based on the base B12(OH)122-. Herein, we directly compare the structural evolution of water clusters, ranging from monomer to hexamer, oriented by functional groups in the bases B12H122-, B12H11OH2- and B12(OH)122- using multiple theoretical methods. A significant revelation is made regarding B12(OH)122-: each additional water molecule is locked into the intramolecular hydrogen bond B-O-H ternary ring in an embedded form. This new pattern of water cluster growth suggests that B-(H-O)⋯H-O interactions prevail over the competition from water-hydrogen bonds (O⋯H-O), distinguishing it from the behavior observed in B12H122- and B12H11OH2- bases, in which competition arises from a mixed competing model involving dihydrogen bonds (B-H⋯H-O), conventional hydrogen bonds (B-(H-O)⋯H-O) and water hydrogen bonds (O⋯H-O). Through aqueous solvation and ab initio molecular dynamics analysis, we further demonstrate the largest water clusters in the first hydrated shell with exceptional thermodynamic stability around B12(OH)122-. These findings provide a solid scientific foundation for the design of boron cluster chemistry incorporating hydroxyl-group-modified borate salts with potential implications for various applications.

How generic is iodide-tagging photoelectron spectroscopy: An extended investigation on the Gly·X- (Gly = glycine, X = Cl or Br) complexes.

We report a joint negative ion photoelectron spectroscopy (NIPES) and quantum chemical computational study on glycine-chloride/bromide complexes (denoted Gly·X-, X = Cl/Br) in close comparison to the previously studied Gly·I- cluster ion. Combining experimental NIPE spectra and theoretical calculations, various Gly·X- complexes were found to adopt the same types of low-lying isomers, albeit with different relative energies. Despite more congested spectral profiles for Gly·Cl- and Gly·Br-, spectral assignments were accomplished with the guidance of the knowledge learned from Gly·I-, where a larger spin-orbit splitting of iodine afforded well-resolved, recognizable spectral peaks. Three canonical plus one zwitterionic isomer for Gly·Cl- and four canonical conformers for Gly·Br- were experimentally identified and characterized in contrast to the five canonical ones observed for Gly·I- under similar experimental conditions. Taken together, this study investigates both genericity and variations in binding patterns for the complexes composed of glycine and various halides, demonstrating that iodide-tagging is an effective spectroscopic means to unravel diverse ion-molecule binding motifs for cluster anions with congested spectral bands by substituting the respective ion with iodide.

Beyond Duality: Rationalizing Repulsive Coulomb Barriers in Host-Guest Cyclodextrin-Dodecaborate Complexes.

The repulsive Coulomb barrier (RCB), an intrinsic potential energy barrier along electron detachment or charge-separation coordinates in multiply charged anions (MCAs), provides dynamic stability to MCAs whose electronic and thermodynamic stabilities are largely dictated by strong internal Coulomb repulsions. Spectroscopic and theoretical characterizations of the RCB have been focused on isolated MCAs. In this work, we extend the RCB investigation beyond the previous scope by including noncovalent host-guest cyclodextrin-closo-dodecaborate dianionic complexes χCD·B12X122- (χ = α, ß, γ; X = H, F-I). Photodechment photoelectron spectroscopy reveals the existence of two distinctly different RCBs, derived from detaching electrons from the guest dianions (RCB1) or ionizing the host neutrals (RCB2), respectively, with the latter being substantially smaller than the former. Theoretical calculations support the duality of RCBs in these complexes and further exhibit highly anisotropic nature of the RCBs.

Photogeneration of singlet oxygen catalyzed by hexafluoroisopropanol for selective degradation of dyes.

Singlet oxygen (1O2) shows great potential for selective degradation of dyes in environmental remediation of wastewater. In this study, we showcased that 1O2 can be effectively generated from an anion complex composed of deprotonated hexafluoroisopropanol anion ([HFIP-H]‒) with hydroperoxyl radical (⋅HO2) via ultraviolet (UV) photodetachment. Electronic structure calculations and cryogenic negative ion photoelectron spectroscopy unveil critical proton transfer upon complex formation and electron ejection, effectively photoconverting prevalent triplet ground state 3O2 to long-lived excited 1O2, stabilized by nearby HFIP. Inspired by this spectroscopic study, a novel "photogeneration" strategy is proposed to produce 1O2 with the incorporation of atmospheric O2 and HFIP, acting as a catalyst. Conceptually, the designed catalytic cycle upon UV irradiation and electron injection is able to achieve different degradations of dye molecules in a controllable fashion from decolorization to complete mineralization, shedding new light on potential water purification.

The primary gas phase hydration shell of hydroxide.

The number of water molecules in hydroxide's primary hydration shell has been long debated to be three from the interpretation of experimental data and four from theoretical studies. Here, we provide direct evidence for the presence of a fourth water molecule in hydroxide's primary hydration shell from a combined study based on high-resolution cryogenic experimental photoelectron spectroscopy and high-level quantum chemical computations. Well-defined spectra of OH-(H2O)n clusters (n = 2 to 5) yield accurate electron binding energies, which are, in turn, used as key signatures of the underlying molecular conformations. Although the smaller OH-(H2O)3 and OH-(H2O)4 clusters adopt close-lying conformations with similar electron binding energies that are hard to distinguish, the OH-(H2O)5 cluster clearly has a predominant conformation with a four-coordinated hydroxide binding motif, a finding that unambiguously determines the gas phase coordination number of hydroxide to be four.

Influence of surface and intermolecular interactions on the properties of supported polyoxometalates.

Polyoxometalates (POMs) with localized radical or open-shell metal sites have the potential to be used as transformative electronic spin based molecular qubits (MQs) for quantum computing (QC). For practical applications, MQs have to be immobilized in electronically or optically addressable arrays which introduces interactions with supports as well as neighboring POMs. Herein, we synthesized Keggin POMs with both tungsten (W) and vanadium (V) addenda atoms. Ion soft landing, a highly-controlled surface modification technique, was used to deliver mass-selected V-doped POMs to different self-assembled monolayer surfaces on gold (SAMs) without the solvent, counterions, and contaminants that normally accompany deposition from solution. Alkylthiol, perfluorinated, and carboxylic-acid terminated monolayers were employed as representative model supports on which different POM-surface and POM-POM interactions were characterized. We obtained insights into the vibrational properties of supported V-doped POMs and how they are perturbed by interactions with specific surface functional groups using infrared reflection absorption and scattering-type scanning near-field optical microscopy, as well as tip enhanced Raman spectroscopy. Different functional groups on SAMs and nanoscale heterogeneity are both shown to modulate the observed spectroscopic signatures. Spectral shifts are also found to be dependent on POM-POM interactions. The electronic structure of the V-doped POMs was determined in the gas phase using negative ion photoelectron spectroscopy and on surfaces with scanning Kelvin probe microscopy. The chemical functionality and charge transfer properties of the SAMs are demonstrated to exert an influence on the charge state and electronic configuration of supported V-doped POMs. The geometric and electronic structure of the POMs were also calculated using density functional theory. Our joint experimental and theoretical findings provide insight into how V substitution as well as POM-surface and POM-POM interactions influence the vibrational properties of POMs.

Properties of Gaseous Deprotonated L-Cysteine S-Sulfate Anion [cysS-SO3]-: Intramolecular H-Bond Network, Electron Affinity, Chemically Active Site, and Vibrational Fingerprints.

L-cysteine S-sulfate, Cys-SSO3H, and their derivatives play essential roles in biological chemistry and pharmaceutical synthesis, yet their intrinsic molecular properties have not been studied to date. In this contribution, the deprotonated anion [cysS-SO3]- was introduced in the gas phase by electrospray and characterized by size-selected, cryogenic, negative ion photoelectron spectroscopy. The electron affinity of the [cysS-SO3]• radical was determined to be 4.95 ± 0.10 eV. In combination with theoretical calculations, it was found that the most stable structure of [cysS-SO3]- (S1) is stabilized via three intramolecular hydrogen bonds (HBs); i.e., one O-H⋯⋯N between the -COOH and -NH2 groups, and two N-H⋯⋯O HBs between -NH2 and -SO3, in which the amino group serves as both HB acceptor and donor. In addition, a nearly iso-energetic conformer (S2) with the formation of an O-H⋯⋯N-H⋯⋯O-S chain-type binding motif competes with S1 in the source. The most reactive site of the molecule susceptible for electrophilic attacks is the linkage S atom. Theoretically predicted infrared spectra indicate that O-H and N-H stretching modes are the fingerprint region (2800 to 3600 cm-1) to distinguish different isomers. The obtained information lays out a foundation to better understand the transformation and structure-reactivity correlation of Cys-SSO3H in biologic settings.

Quantitative Descriptions of Dewar-Chatt-Duncanson Bonding Model: A Case Study of Zeise and Its Family Ions.

Historically, Dewar-Chatt-Duncanson (DCD) model is a heuristic device to advance the development of organometallic chemistry and deepen our understanding of the metal-ligand bonding nature. Zeise's ion, the first man-made organometallic compound and a quintessential transition metal-olefin complex, was qualitatively explained using the DCD bonding scheme in 1950s. In this work, we quantified the explicit contributions of the σ donation and π back-donation to the metal-ligand bonding in Zeise and its family ions, [PtX3 L]- (X=F, Cl, Br, I, and At; L=C2 H4 , CO, and N2 ), using state-of-the-art quantum chemical calculations and energy decomposition analysis. The relative importance of the σ donation and π back-donation depends on both X and L, with [PtCl3 (C2 H4 )]- being a critical case in which the σ donation is marginally weaker than the π back-donation. The changes along this series are controlled by the energy levels of the correlated molecular orbitals of PtX3 - and ligand L. This study deepens our understanding of the bonding properties for transition metal complexes beyond the qualitative description of the DCD model.

Highly Structured Water Networks in Microhydrated Dodecaborate Clusters.

We report a combined photoelectron spectroscopy and theoretical investigation of a series of size-selected hydrated closo-dodecaborate clusters B12X122-·nH2O (X = H, F, or I; n = 1-6). Distinct structural arrangements of water clusters from monomer to hexamer can be achieved by using different B12X122- bases, illustrating the evident solute specificity. Because B-H···H-O dihydrogen bonds are stronger than O···H-O hydrogen bonds in water, the added water molecules are arranged in a unified binding mode by forming highly structured water networks manipulated by B12H122-. As a comparison, the hydrated B12F122- clusters display similar water evolution for n values of 1 and 2 but different binding modes for larger clusters, while water networks in B12I122- share similarities with the free water clusters. This finding provides a consistent picture of the structural diversity of hydrogen bonding networks in microhydrated dodecaborates and a molecular-level understanding of microsolvation dynamics in aqueous borate chemistry.

Li2[SeC2Se]·2NH3: A Crystalline Ammoniate with a -Se-C≡C-Se- Dianion.

Reaction of Li2C2 with elemental selenium in a molar ratio of 1:2 in liquid ammonia led to the formation of the ammoniate Li2[SeC2Se]·2NH3. Its crystal structure was solved and refined from high-resolution synchrotron powder diffraction data (P21/c, Z = 4). It contains the -Se-C≡C-Se- anion, unprecedented in a crystalline material, whose existence was corroborated by IR/Raman spectra and electronic-structure theory, showing an almost perfect agreement with calculated spectra. Elaborated magnetic-bottle and velocity-map imaging photoelectron spectroscopic investigations show that the -Se-C≡C-Se• radical anion can be transferred to the gas phase, where it was analyzed by NIPE (Negative Ion Photoelectron) and VMI (Velocity-Map Imaging) spectra, which correlate nicely with simulated spectra based on 2Πu → 3Σg- and 2Πu → 1Σg+ transitions including spin-orbit couplings.

Inhibition of mitochondrial complex I leading to NAD+/NADH imbalance in type 2 diabetic patients who developed late stent thrombosis: Evidence from an integrative analysis of platelet bioenergetics and metabolomics.

Type 2 diabetes mellitus (T2DM) is a strong indicator of late stent thrombosis (LST). Platelet bioenergetic dysfunction, although critical to the pathogenesis of diabetic macrovascular complications, remains uncharacterized in T2DM patients who developed LST. Here, we explored the mechanistic link between the alterations in platelet bioenergetics and LST in the setting of T2DM. Platelet bioenergetics, metabolomics, and their interactomes were analyzed in a nested case-control study including 15 T2DM patients who developed LST and 15 matched T2DM patients who did not develop LST (non-LST). Overall, we identified a bioenergetic alteration in T2DM patients with LST characterized by an imbalanced NAD+/NADH redox state resulting from deficient mitochondrial complex I (NADH: ubiquinone oxidoreductase) activity, which led to reduced ATP-linked and maximal mitochondrial respiration, increased glycolytic flux, and platelet hyperactivation compared with non-LST patients. Congruently, platelets from LST patients exhibited downregulation of tricarboxylic acid cycle and NAD+ biosynthetic pathways as well as upregulation of the proximal glycolytic pathway, a metabolomic change that was primarily attributed to compromised mitochondrial respiration rather than increased glycolytic flux as evidenced by the integrative analysis of bioenergetics and metabolomics. Importantly, both bioenergetic and metabolomic aberrancies in LST platelets could be recapitulated ex vivo by exposing the non-LST platelets to a low dose of rotenone, a complex I inhibitor. In contrast, normalization of the NAD+/NADH redox state, either by increasing NAD+ biosynthesis or by inhibiting NAD+ consumption, was able to improve mitochondrial respiration, inhibit mitochondrial oxidant generation, and consequently attenuate platelet aggregation in both LST platelets and non-LST platelets pretreated with low-dose rotenone. These data, for the first time, delineate the specific patterns of bioenergetic and metabolomic alterations for T2DM patients who suffer from LST, and establish the deficiency of complex I-derived NAD+ as a potential pathogenic mechanism in platelet abnormalities.

Sodium Cationization Enables Exotic Deprotonation Sites on Gaseous Mononucleotides.

We report observation and photoelectron spectroscopic characterization of sodium cationization on four doubly deprotonated mononucleotide dianions Na+·[dNMP-2H]2- (N = A, G, C, or T) in the gas phase. Multiple tautomers with distinct deprotonated sites are identified, in which Na+ enables novel double deprotonation patterns and folds the resultant mononucleotide dianions. The most stable isomer for the whole family is derived from detaching one proton from the phosphate and the other from the nucleobase (amino group for N = A, G, and C, but nitrogen atom for T), whereas high-lying isomers with protons detached separately from the phosphate and the hydroxy group of sugar coexist. Particularly, an exotic deprotomer with both protons deprived from guanosine is populated as well. This work thus displays a remarkably diverse binding landscape enabled by sodium cationization, a potentially critical element in developing a general formulism to better model metal cation and nucleotide interactions.

Annihilating Actinic Photochemistry of the Pyruvate Anion by One and Two Water Molecules.

Photochemical behaviors of pyruvic acid in multiple phases have been extensively studied, while those of its conjugate base, the pyruvate anion (CH3COCOO-, PA-) are less understood and remain contradictory in gaseous versus aqueous phases. Here in this article, we report a joint experimental and theoretical study combining cryogenic, wavelength-resolved negative ion photoelectron spectroscopy (NIPES) and high-level quantum chemical computations to investigate PA- actinic photochemistry and its dependence on microsolvation in the gas phase. PA-·nH2O (n = 0-5) clusters were generated and characterized, with their low-lying isomers identified. NIPES conducted at multiple wavelengths across the PA- actinic regime revealed the PA- photochemistry extremely sensitive to its hydration extent. While bare PA- anions exhibit active photoinduced dissociations that generate the acetyl (CH3CO-), methide (CH3-) anions, their corresponding radicals, and slow electrons, one single attached water molecule results in significant suppression with a subsequent second water being able to completely block all dissociation pathways, effectively annihilating all PA- photochemical reactivities. The underlying dissociation mechanisms of PA-·nH2O (n = 0-2) clusters are proposed involving nπ* excitation, dehydration, decarboxylation, and further CO loss. Since the photoexcited dihydrate does not have sufficient energy to overcome the full dehydration barrier before PA- could fragmentate, the PA- dissociation pathway is completely blocked, with the energy most likely released via loss of one water and internal electronic and vibrational relaxations. The insight unraveled in this work provides a much-needed critical link to connect the seemingly conflicting PA- actinic chemistry between the gas and condensed phases.

Manifesting Direction-Specific Complexation in [HFIP-H·H2O2]-: Exclusive Formation of a High-Lying Conformation.

Size-selective, negative ion photoelectron spectroscopy in conjunction with quantum chemical calculations is employed to investigate the geometric and electronic structures of a protype system in catalytic olefin epoxidation research, that is, deprotonated hexafluoroisopropanol ([HFIP-H]-) complexed with hydrogen peroxide (H2O2). Spectral assignments and molecular electrostatic surface analyses unveil a surprising prevalent existence of a high-lying isomer with asymmetric dual hydrogen-bonding configuration that is preferably formed driven by influential direction-specific electrostatic interactions upon H2O2 approaching [HFIP-H]- anion. Subsequent inspections of molecular orbitals, charge, and spin density distributions indicate the occurrence of partial charge transfer from [HFIP-H]- to H2O2 upon hydrogen-bonding interactions. Accompanied with electron detachment, a proton transfer occurs to form the neutral complex of [HFIP·HOO•] structure. This work conspicuously illustrates the importance of directionality encoded in intermolecular interactions involving asymmetric and complex molecules, while the produced hydroperoxyl radical HOO• offers a possible new pathway in olefin epoxidation chemistry.