GMP affected assembly behaviors of phosphatidylethanolamine monolayers elucidated by multi-resolved SFG-VS and BAM.

The interaction between nucleotide molecules and lipid molecules plays important roles in cell activities, but the molecular mechanism is very elusive. In the present study, a small but noticeable interaction between the negatively charged phosphatidylethanolamine (PE) and Guanosine monophosphate (GMP) molecules was observed from the PE monolayer at the air/water interface. As shown by the sum frequency generation (SFG) spectra and Pi-A isotherm of the PE monolayer, the interaction between the PE and GMP molecules imposes very small changes to the PE molecules. However, the Brewster angle microscopy (BAM) technique revealed that the assembly conformations of PE molecules are significantly changed by the adsorption of GMP molecules. By comparing the SFG spectra of PE monolayers after the adsorption of GMP, guanosine and guanine, it is also shown that the hydrogen bonding effect plays an important role in the nucleotide-PE interactions. These results provide fundamental insight into the structure changes during the nucleotide-lipid interaction, which may shed light on the molecular mechanism of viral infection, DNA drug delivery, and cell membrane curvature control in the brain or neurons.

Interfacial carbonyl groups of propylene carbonate facilitate the reversible binding of nitrogen dioxide.

The interaction of NO2 with organic interfaces is critical in the development of NO2 sensing and trapping technologies, and equally so to the atmospheric processing of marine and continental aerosol. Recent studies point to the importance of surface oxygen groups in these systems, however the role of specific functional groups on the microscopic level has yet to be fully established. In the present study, we aim to provide fundamental information on the interaction and potential binding of NO2 at atmospherically relevant organic interfaces that may also help inform innovation in NO2 sensing and trapping development. We then present an investigation into the structural changes induced by NO2 at the surface of propylene carbonate (PC), an environmentally relevant carbonate ester. Surface-sensitive vibrational spectra of the PC liquid surface are acquired before, during, and after exposure to NO2 using infrared reflection-absorption spectroscopy (IRRAS). Analysis of vibrational changes at the liquid surface reveal that NO2 preferentially interacts with the carbonyl of PC at the interface, forming a distribution of binding symmetries. At low ppm levels, NO2 saturates the PC surface within 10 minutes and the perturbations to the surface are constant over time during the flow of NO2. Upon removal of NO2 flow, and under atmospheric pressures, these interactions are reversible, and the liquid surface structure of PC recovers completely within 30 min.

Structural evolution of water-in-propylene carbonate mixtures revealed by polarized Raman spectroscopy and molecular dynamics.

The liquid structure of systems wherein water is limited in concentration or through geometry is of great interest in various fields such as biology, materials science, and electrochemistry. Here, we present a combined polarized Raman and molecular dynamics investigation of the structural changes that occur as water is added incrementally to propylene carbonate (PC), a polar, aprotic solvent that is important in lithium-ion batteries. Polarized Raman spectra of PC solutions were collected for water mole fractions 0.003 ≤ χwater ≤ 0.296, which encompasses the solubility range of water in PC. The novel approach taken herein provides additional hydrogen bond and solvation characterization of this system that has not been achievable in previous studies. Analysis of the polarized carbonyl Raman band in conjunction with simulations demonstrated that the bulk structure of the solvent remained unperturbed upon the addition of water. Experimental spectra in the O-H stretching region were decomposed through Gaussian fitting into sub-bands and comparison to studies of dilute HOD in D2O. With the aid of simulations, we identified these different bands as water arrangements having different degrees of hydrogen bonding. The observed water structure within PC indicates that water tends to self-aggregate, forming a hydrogen bond network that is distinctly different from the bulk and dependent on concentration. For example, at moderate concentrations, the most likely aggregate structures are chains of water molecules, each with two hydrogen bonds.

Array-Based Machine Learning for Functional Group Detection in Electron Ionization Mass Spectrometry.

Mass spectrometry is a ubiquitous technique capable of complex chemical analysis. The fragmentation patterns that appear in mass spectrometry are an excellent target for artificial intelligence methods to automate and expedite the analysis of data to identify targets such as functional groups. To develop this approach, we trained models on electron ionization (a reproducible hard fragmentation technique) mass spectra so that not only the final model accuracies but also the reasoning behind model assignments could be evaluated. The convolutional neural network (CNN) models were trained on 2D images of the spectra using transfer learning of Inception V3, and the logistic regression models were trained using array-based data and Scikit Learn implementation in Python. Our training dataset consisted of 21,166 mass spectra from the United States' National Institute of Standards and Technology (NIST) Webbook. The data was used to train models to identify functional groups, both specific (e.g., amines, esters) and generalized classifications (aromatics, oxygen-containing functional groups, and nitrogen-containing functional groups). We found that the highest final accuracies on identifying new data were observed using logistic regression rather than transfer learning on CNN models. It was also determined that the mass range most beneficial for functional group analysis is 0-100 m/z. We also found success in correctly identifying functional groups of example molecules selected from both the NIST database and experimental data. Beyond functional group analysis, we also have developed a methodology to identify impactful fragments for the accurate detection of the models' targets. The results demonstrate a potential pathway for analyzing and screening substantial amounts of mass spectral data.

New Insights into Cation- and Temperature-Driven Protein Adsorption to the Air-Water Interface through Infrared Reflection Studies of Bovine Serum Albumin.

The chemistry and structure of the air-ocean interface modulate biogeochemical processes between the ocean and atmosphere and therefore impact sea spray aerosol properties, cloud and ice nucleation, and climate. Protein macromolecules are enriched in the sea surface microlayer and have complex adsorption properties due to the unique molecular balance of hydrophobicity and hydrophilicity. Additionally, interfacial adsorption properties of proteins are of interest as important inputs for ocean climate modeling. Bovine serum albumin is used here as a model protein to investigate the dynamic surface behavior of proteins under several variable conditions including solution ionic strength, temperature, and the presence of a stearic acid (C17COOH) monolayer at the air-water interface. Key vibrational modes of bovine serum albumin are examined via infrared reflectance-absorbance spectroscopy, a specular reflection method that ratios out the solution phase and highlights the aqueous surface to determine, at a molecular level, the surface structural changes and factors affecting adsorption to the solution surface. Amide band reflection absorption intensities reveal the extent of protein adsorption under each set of conditions. Studies reveal the nuanced behavior of protein adsorption impacted by ocean-relevant sodium concentrations. Moreover, protein adsorption is most strongly affected by the synergistic effects of divalent cations and increased temperature.

Identification of Ion Pairs in Aqueous NaCl and KCl Solutions in Combination with Raman Spectroscopy, Molecular Dynamics, and Quantum Chemical Calculations.

This work summarizes a theoretical analysis of the perturbation on Raman spectra in aqueous NaCl and KCl solutions with the aim to detect ion pairs. The experimental Raman spectra, both polarized and depolarized, are perturbed by these ions to a comparable extent or somewhat less by KCl than NaCl. This result appears to be contrary to the molecular dynamics (MD) simulation showing that the isolated and separated ions of KCl should have a larger perturbation than NaCl, as the solvation shell of K+ is larger than that of Na+. The apparent discrepancy signifies the ion pair formation which is more substantial for KCl than NaCl. The MD simulations and quantum chemical calculations revealed that KCl forms ion pairs more than NaCl and that the ion pair formation reduces the perturbation on the Raman spectra more for KCl. The present analysis shows that the perturbed Raman spectra provide a useful sign to evaluate the ion pair formation in aqueous solutions.

Recognition competes with hydration in anion-triggered monolayer formation of cyanostar supra-amphiphiles at aqueous interfaces.

The triggered self-assembly of surfactants into organized layers at aqueous interfaces is important for creating adaptive nanosystems and understanding selective ion extraction. While these transformations require molecular recognition, the underlying driving forces are modified by the local environment in ways that are not well understood. Herein, we investigate the role of ion binding and ion hydration using cyanosurf, which is composed of the cyanostar macrocycle, and its binding to anions that are either size-matched or mis-matched and either weakly or highly hydrated. We utilize the supra-amphiphile concept where anion binding converts cyanosurf into a charged and amphiphilic complex triggering its self-organization into monolayers at the air-water interface. Initially, cyanosurf forms aggregates at the surface of a pure water solution. When the weakly hydrated and size-matched hexafluorophosphate (PF6 -) and perchlorate (ClO4 -) anions are added, the macrocycles form distinct monolayer architectures. Surface-pressure isotherms reveal significant reorganization of the surface-active molecules upon anion binding while infrared reflection absorption spectroscopy show the ion-bound complexes are well ordered at the interface. Vibrational sum frequency generation spectroscopy shows the water molecules in the interfacial region are highly ordered in response to the charged monolayer of cyanosurf complexes. Consistent with the importance of recognition, we find the smaller mis-matched chloride does not trigger the transformation. However, the size-matched phosphate (H2PO4 -) also does not trigger monolayer formation indicating hydration inhibits its interfacial binding. These studies reveal how anion-selective recognition and hydration both control the binding and thus the switching of a responsive molecular interface.

La3+ and Y3+ interactions with the carboxylic acid moiety at the liquid/vapor interface: Identification of binding complexes, charge reversal, and detection limits.

Specific interactions of yttrium and lanthanum ions with a fatty acid Langmuir monolayer were investigated using vibrational sum frequency spectroscopy. The trivalent ions were shown to interact with the charged form of the carboxylic acid group from nanomolar concentrations (<300 nM). Analysis of the spectral features from both the symmetric and the asymmetric carboxylate modes reveals the presence of at least three distinct coordination structures linked to specific binding configurations. Although the same species were identified for both La3+ and Y3+, they display a different concentration dependence, highlighting the ion-specificity of the interaction. From the analysis of the response of interfacial water molecules, the reversal of the surface charge, as well as the formation of yttrium hydroxide complexes, were detected upon increasing the amount of salt in solution. The binding interaction and kinetics of absorption are sensitive to the solution pH, showing a distinct ion speciation in the interfacial region when compared to the bulk. Changing the subphase pH or adding a monovalent background electrolyte that promotes deprotonation of the carboxylic acid headgroup could further improve the detection limit of La3+ and Y3+ to concentrations < 100 nM. These findings demonstrate that nM concentrations of trace metals contaminants, typically found on monovalent salts, can significantly influence the binding structure and kinetics in Langmuir monolayers.

Hydration and Hydrogen Bond Order of Octadecanoic Acid and Octadecanol Films on Water at 21 and 1 °C.

The temperature-dependent hydration structure of long-chain fatty acids and alcohols at air-water interfaces has great significance in the fundamental interactions underlying ice nucleation in the atmosphere. We present an integrated theoretical and experimental study of the temperature-dependent vibrational structure and electric field character of the immediate hydration shells of fatty alcohol and acid headgroups. We use a combination of surface-sensitive infrared reflection-absorption spectroscopy (IRRAS), surface potentiometry, and ab initio molecular dynamics simulations to elucidate detailed molecular structures of the octadecanoic acid and octadecanol (stearic acid and stearyl alcohol) headgroup hydration shells at room temperature and near freezing. In experiments, the alcohol at high surface concentration exhibits the largest surface potential; yet we observe a strengthening of the hydrogen-bonding for the solvating water molecules near freezing for both the alcohol and the fatty acid IRRAS experiments. Results reveal that the hydration shells for both compounds screen their polar headgroup dipole moments reducing the surface potential at low surface coverages; at higher surface coverage, the polar headgroups become dehydrated, which reduces the screening, correlating to higher observed surface potential values. Lowering the temperature promotes tighter chain packing and an increase in surface potential. IRRAS reveals that the intra- and intermolecular vibrational coupling mechanisms are highly sensitive to changes in temperature. We find that intramolecular coupling dominates the vibrational relaxation pathways for interfacial water determined by comparing the H2O and the HOD spectra. Using ab initio molecular dynamics (AIMD) calculations on cluster systems of propanol + 6H2O and propionic acid + 10H2O, a spectral decomposition scheme was used to correlate the OH stretching motion with the IRRAS spectral features, revealing the effects of intra- and intermolecular coupling on the spectra. Spectra calculated with AIMD reproduce the red shift and increase in intensity observed in experimental spectra corresponding to the OH stretching region of the first solvation shell. These findings suggest that intra- and intermolecular vibrational couplings strongly impact the OH stretching region at fatty acid and fatty alcohol water interfaces. Overall, results are consistent with ice templating behavior for both the fatty acid and the alcohol, yet the surface potential signature is strongest for the fatty alcohol. These findings develop a better understanding of the complex surface potential and spectral signatures involved in ice templating.

Role of Hydration in Magnesium versus Calcium Ion Pairing with Carboxylate: Solution and the Aqueous Interface.

The binding of group II metal cations such as Ca2+ and Mg2+ has been largely categorized as electrostatic or ionic using carboxylate symmetric and asymmetric stretching frequency assignments that have been historically used with little regard for the solvation environment of aqueous solutions. However, given the importance of these cations and their binding mechanisms related to biological function and in revealing surface enrichment factors for ocean to marine aerosol transfer, it is imperative that a deeper understanding be sought to include hydration effects. Here, infrared reflection-absorption and Raman spectra for surface and solution phase carboxylate binding information, respectively, are compared against bare (unbound) carboxylate and bidentate Zn2+:carboxylate spectral signatures. Spectral non-coincidence effect analysis, temperature studies, and spectral and potential of mean force calculations result in a concise interpretation of binding motifs that include the role of mediating water molecules, that is, contact and solvent-shared ion pairs. Calcium directly binds to the carboxylate group in contact ion pairs where magnesium rarely does. Moreover, we reveal the dominance of the solvent-shared ion pair of magnesium with carboxylate at the air-water interface and in solution.

Vibrational exciton delocalization precludes the use of infrared intensities as proxies for surfactant accumulation on aqueous surfaces.

Surface-sensitive vibrational spectroscopy is a common tool for measuring molecular organization and intermolecular interactions at interfaces. Peak intensity ratios are typically used to extract molecular information from one-dimensional spectra but vibrational coupling between surfactant molecules can manifest as signal depletion in one-dimensional spectra. Through a combination of experiment and theory, we demonstrate the emergence of vibrational exciton delocalization in infrared reflection-absorption spectra of soluble and insoluble surfactants at the air/water interface. Vibrational coupling causes a significant decrease in peak intensities corresponding to C-F vibrational modes of perfluorooctanoic acid molecules. Vibrational excitons also form between arachidic acid surfactants within a compressed monolayer, manifesting as signal reduction of C-H stretching modes. Ionic composition of the aqueous phase impacts surfactant intermolecular distance, thereby modulating vibrational coupling strength between surfactants. Our results serve as a cautionary tale against employing alkyl and fluoroalkyl vibrational peak intensities as proxies for concentration, although such analysis is ubiquitous in interface science.

Calcium bridging drives polysaccharide co-adsorption to a proxy sea surface microlayer.

Saccharides comprise a significant mass fraction of organic carbon in sea spray aerosol (SSA), but the mechanisms through which saccharides are transferred from seawater to the ocean surface and eventually into SSA are unclear. It is hypothesized that saccharides cooperatively adsorb to other insoluble organic matter at the air/sea interface, known as the sea surface microlayer (SSML). Using a combination of surface-sensitive infrared reflection-absorption spectroscopy and all-atom molecular dynamics simulations, we demonstrate that the marine-relevant, anionic polysaccharide alginate co-adsorbs to an insoluble palmitic acid monolayer via divalent cationic bridging interactions. Ca2+ induces the greatest extent of alginate co-adsorption to the monolayer, evidenced by the ∼30% increase in surface coverage, whereas Mg2+ only facilitates one-third the extent of co-adsorption at seawater-relevant cation concentrations due to its strong hydration propensity. Na+ cations alone do not facilitate alginate co-adsorption, and palmitic acid protonation hinders the formation of divalent cationic bridges between the palmitate and alginate carboxylate moieties. Alginate co-adsorption is largely confined to the interfacial region beneath the monolayer headgroups, so surface pressure, and thus monolayer surface coverage, only changes the amount of alginate co-adsorption by less than 5%. Our results provide physical and molecular characterization of a potentially significant polysaccharide enrichment mechanism within the SSML.

Insight into the Ionizing Surface Potential Method and Aqueous Sodium Halide Surfaces.

Complementing the microscopic picture of the surface structure of electrolyte solutions set out by previous theoretical and experimental studies, the ionizing surface potential technique offers a unique approach to quantifying the impact of aqueous inorganic ions upon the interfacial electric field of the air-aqueous interface. In this Feature Article, we review the vulnerability of theoretical and empirically derived χwater values as a normative reference for aqueous ion surface potentials. Instead, we recognize and evaluate aqueous ion surface potentials relative to well-known ionic surfactants cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS). Additionally, we also explore factors that impact the magnitude of the measured surface potentials using the ionizing method, particularly in the type of reference electrode and ionizing gas environment. With potential measurements of sodium halide solutions, we show that iodide has a dominant effect on the air-aqueous electric field. Compared to chloride and bromide, iodide is directly observed with a net negatively charged surface electric field at all salt concentrations measured (0.2 to 3.0 mol/kg water). Also, above the 2 M region, bromide is observed with a net negatively charged surface. Although several scenarios contribute to this effect, it is most likely due to the surface enrichment of bromide and iodide. While the results of this study are pertinent to determining the specific interfacial reactivity of aqueous halides, these anions seldom transpire as single-halide systems in the natural environment. Therefore, we also provide an outlook on future research concerning surface potential methods and more complex aqueous electrolyte systems.

Functional Group Identification for FTIR Spectra Using Image-Based Machine Learning Models.

Fourier transform infrared spectroscopy (FTIR) is a ubiquitous spectroscopic technique. Spectral interpretation is a time-consuming process, but it yields important information about functional groups present in compounds and in complex substances. We develop a generalizable model via a machine learning (ML) algorithm using convolutional neural networks (CNNs) to identify the presence of functional groups in gas-phase FTIR spectra. The ML models reduce the amount of time required to analyze functional groups and facilitate interpretation of FTIR spectra. Through web scraping, we acquire intensity-frequency data from 8728 gas-phase organic molecules within the NIST spectral database and transform the data into spectral images. We successfully train models for 15 of the most common organic functional groups, which we then determine via identification from previously untrained spectra. These models serve to expand the application of FTIR measurements for facile analysis of organic samples. Our approach was done such that we have broad functional group models that infer in tandem to provide full interpretation of a spectrum. We present the first implementation of ML using image-based CNNs for predicting functional groups from a spectroscopic method.

Structural Effects of Cation Binding to DPPC Monolayers.

Ions at the two sides of the plasma membrane maintain the transmembrane potential, participate in signaling, and affect the properties of the membrane itself. The extracellular leaflet is particularly enriched in phosphatidylcholine lipids and under the influence of Na+, Ca2+, and Cl- ions. In this work, we combined molecular dynamics simulations performed using state-of-the-art models with vibrational sum frequency generation (VSFG) spectroscopy to study the effects of these key ions on the structure of dipalmitoylphosphatidylcholine. We used lipid monolayers as a proxy for membranes, as this approach enabled a direct comparison between simulation and experiment. We find that the effects of Na+ are minor. Ca2+, on the other hand, strongly affects the lipid headgroup conformations and induces a tighter packing of lipids, thus promoting the liquid condensed phase. It does so by binding to both the phosphate and carbonyl oxygens via direct and water-mediated binding modes, the ratios of which depend on the monolayer packing. Clustering analysis performed on simulation data revealed that changes in area per lipid or CaCl2 concentration both affect the headgroup conformations, yet their effects are anticorrelated. Cations at the monolayer surface also attract Cl-, which at large CaCl2 concentrations penetrates deep to the monolayer. This phenomenon coincides with a radical change in the VSFG spectra of the phosphate group, thus indicating the emergence of a new binding mode.

Molecular Recognition and Hydration Energy Mismatch Combine To Inform Ion Binding Selectivity at Aqueous Interfaces.

There is a critical need for receptors that are designed to enhance anion binding selectivity at aqueous interfaces in light of the growing importance of separation technologies for environmental sustainability. Here, we conducted the first study of anion binding selectivity across a series of prevalent inorganic oxoanions and halides that bind to a positively charged guanidinium receptor anchored to an aqueous interface. Vibrational sum frequency generation spectroscopy and infrared reflection absorption spectroscopy studies at the water-air interface reveal that the guanidinium receptor binds to an oxoanion series in the order SO42- > H2PO4- > NO3- > NO2- while harboring very weak interactions with the halides in the order I- > Cl- ≈ Br-. In spite of large dehydration penalties for sulfate and phosphate, the more weakly hydrated guanidinium receptor was selective for these oxoanions in contradiction to predictions made from ion partitioning alone, like the Hofmeister series and Collins's rules. Instead, sulfate binding is likely favored by the suppression of dielectric screening at the interface that consequently boosts Coulombic attractions, and thus helps offset the costs of anion dehydration. Geometric factors also favor the oxoanions. Furthermore, the unique placement of iodide in our halide series ahead of the stronger hydrogen-bond acceptors (Cl-, Br-) suggests that the binding interaction also depends upon single-ion surface partitioning from bulk water to the interface. Knowledge of the anion binding preferences displayed by a guanidinium receptor sheds light on the receptor architectures needed within designer interfaces to control selectivity.

Relating Structure and Ice Nucleation of Mixed Surfactant Systems Relevant to Sea Spray Aerosol.

Ice nucleating particles (INPs) influence weather and climate by their effect on cloud phase state. Fatty alcohols present within aerosol particles confer a potentially important source of ice nucleation activity to sea spray aerosol produced in oceanic regions. However, their interactions with other aerosol components and the influence on freezing were previously largely unknown. Here, we report quantitative measurements of fatty alcohols in model sea spray aerosol and examine the relationships between the composition and structure of the surfactants and subphase in the context of these measurements. Deposited mixtures of surfactants retain the ability to nucleate ice, even in fatty acid-dominant compositions. Strong refreezing effects are also observed, where previously frozen water-surfactant samples nucleate more efficiently. Structural sources of refreezing behavior are identified as either kinetically trapped film states or three-dimensional (3D) solid surfactant particles. Salt effects are especially important for surfactant INPs, where high salt concentrations suppress freezing. A simple water uptake model suggests that surfactant-containing aerosol requires either very low salt content or kinetic trapping as solid particles to act as INPs in the atmosphere. These types of INPs could be identified through comparison of different INP instrument responses.

One-Pot Aldol Cascade for the Preparation of Isospiropyrans, Flavylium Salts, and bis-Spiropyrans.

We probed tandem aldol condensations of sixteen o-hydroxyacetophenones, carrying electron-withdrawing and -donating groups at positions 4 and 5, using five molar equivalents of SiCl4 in anhydrous ethanol. Substrates carrying electron-withdrawing groups (EWGs) (0 < ∑σ > 0.63) populated the equilibria with isospiropyrans (12-74% yield), while those carrying electron-donating groups (EDGs) (∑σ < -0.31) gave flavylium salts (50-80%) or thermochromic bis-spiropyrans (73%). The results are of interest for developing novel organic materials possessing switchable photochromic and thermochromic characteristics.

Thermodynamic Signatures of the Origin of Anti-Hofmeister Selectivity for Phosphate at Aqueous Interfaces.

The selectivities and driving forces governing phosphate recognition by charged receptors at prevalent aqueous interfaces is unexplored relative to the many studies in homogeneous solutions. Here we report on electrostatic binding versus hydrogen-bond-assisted electrostatic binding of phosphate (H2PO4-) for two important receptor classes in the unique microenvironment of the air-water interface. We find that the methylated ammonium receptor (U-Ammo+) is dominated by electrostatic binding to phosphate anions and fails to be selective for phosphate binding over chloride, whereas the highly phosphate-selective guanidinium receptor (U-Guan+) provides synergistic hydrogen-bonding and electrostatic interactions. Apparent binding constants were evaluated in situ for U-Ammo+ and U-Guan+ using temperature-controlled infrared reflection-absorption spectroscopy with Langmuir-type fitting. Thermodynamic quantities showed enthalpically driven binding affinities of U-Guan+ and U-Ammo+ receptors (ΔH°b = -71 (±9) kJ/mol and ΔH°b = -155 (±13) kJ/mol, respectively). U-Guan+ revealed a nearly fourfold smaller entropic barrier to binding (ΔS°b = -132 (±34) J/mol K) than the U-Ammo+ receptor (ΔS°b = -440 (±45) J/mol K), attributed to hydration differences. The larger entropic penalty for the U-Ammo+ receptor is correlated with a molecular expansion shown in surface pressure-area isotherms, whereas the smaller entropic penalty of the U-Guan+ receptor conversely correlated with no expansion. The U-Guan+ receptor also revealed anti-Hofmeister selectivity for phosphate over chloride, while the non-hydrogen-bonding U-Ammo+ receptor followed Hofmeister selectivity. Our results indicate that hydrogen bonding is an integral chemical design element for achieving anti-Hofmeister selectivity for phosphate.

An easily accessible isospiropyran switch.

In the presence of SiCl4, three molecules of 5'-bromo-2'-hydroxyacetophenone underwent an unexpected tandem aldol condensation to give a novel isospiropyran switch (69%), with X-ray crystallography confirming its structure. The strong Brønsted acid CH3SO3H turned the colorless isospiropyran into its protonated and open form possessing red color. This process was reversed using the Et3N base, with the acid/base toggling repeatable for at least six times (UV-Vis). When printed on a silica plate, however, the isospiropyran formed a blue-colored product due to, as posited, its stabilization by hydrogen bonding (HB) to silica. An exposure to HB-competing ethyl acetate temporarily "erased" the print only to be brought back by subjecting the plate to a higher temperature for evaporating the solvent. The isospiropyran described here is an easily accessible, chromic, modular and switchable compound that one can incorporate into dynamic materials or use for building chemosensors, molecular machines and organic electronic devices.