Laser spectroscopy

Hydrogen bonding interactions play an important role in many chemical and physical processes occurring in bulk liquids and at interfaces. In this study, hydrous species (H₂O and Si-OH) on nano-porous alteration layers (gels) formed on a boroaluminosilicate glass called International Simple Glass corroded in aqueous solutions at pH 7 and pH 9, and initially saturated with soluble silicon-containing species were analyzed using linear and non-linear vibrational spectroscopy in combination with molecular dynamics simulations. The simulation results revealed various possible types of hydrogen bonds among these hydrous species in nanoconfinement environments with their populations depending on pore-size distribution. The nano-porous gels formed on corroded glass surfaces enhance hydrogen bond strength between hydrous species as revealed by attenuated total reflectance infrared spectroscopy. Sum frequency generation spectroscopy showed some significant differences in hydrogen bonding interactions on alteration layers formed at pH 7 and pH 9. The glass dissolution under the leaching conditions used in this study has been known to be ten times faster at pH 7 in comparison to that at pH 9 due to unknown reasons. The simulation and experimental results obtained in this study indicate that the water mobility in the gel formed at pH 9 could be slower than that in the gel formed at pH 7, and as a result, the leaching rate at pH 9 is slower than that at pH 7.

A thin film of poly(4-methylpentene-1) (P4MP1) was prepared on a quartz substrate, which was a model system of an interface in filler-reinforced semicrystalline polymer composites. Grazing-incidence wide-angle X-ray diffraction measurements revealed that P4MP1 in the thin film after isothermal crystallization formed a Form I crystal polymorph composed of a tetragonal unit cell with a 7₂ helix, in which the chain axis was oriented along the direction parallel to the quartz interface. Combining sum-frequency generation vibrational spectroscopy with molecular dynamics simulation enabled us to gain access to the local conformation of P4MP1 chains at the quartz interface and the changes that occurred with isothermal crystallization. Finally, the way in which the initial chain orientation at the substrate interface impacted the crystalline structure in the thin film was discussed.

Charged defects at the surface of the organic–inorganic perovskite active layer are detrimental to solar cells due to exacerbated charge carrier recombination. Here we show that charged surface defects can be benign after passivation and further exploited for reconfiguration of interfacial energy band structure. Based on the electrostatic interaction between oppositely charged ions, Lewis-acid-featured fullerene skeleton after iodide ionization (PCBB-3N-3I) not only efficiently passivates positively charged surface defects but also assembles on top of the perovskite active layer with preferred orientation. Consequently, PCBB-3N-3I with a strong molecular electric dipole forms a dipole interlayer to reconfigure interfacial energy band structure, leading to enhanced built-in potential and charge collection. As a result, inverted structure planar heterojunction perovskite solar cells exhibit the promising power conversion efficiency of 21.1% and robust ambient stability. This work opens up a new window to boost perovskite solar cells via rational exploitation of charged defects beyond passivation.

We have studied the chemical composition of the epoxy and amine components, HDGEBA and CBMA, of an epoxy resin in close proximity to a copper interface by using ADXPS in conjunction with SFG vibrational spectroscopy. A bilayer sample of epoxy resin and copper was first prepared on a solid substrate before etching the copper layer just before the interface with Ar+ beams. Using ADXPS, in which an incident X-ray was guided from the copper surface, it was found that the CBMA component was preferentially segregated at the copper interface, with the segregation extending over ~10 nm. SFG spectroscopy was used to confirm the above observation. Postulating that copper ions diffused from the metal copper into the internal phase during the curing process and reacted with amine groups to form copper complexes, the interfacial segregation of CBMA can be understood. This knowledge should be useful for understanding and controlling the adhesive properties of epoxy resins.

Electrochemical actuators directly converting electrical energy to mechanical energy are critically important for artificial intelligence. However, their energy transduction efficiency is always lower than 1.0% because electrode materials lack active units in microstructure, and their assembly systems can hardly express the intrinsic properties. Here, we report a molecular-scale active graphdiyne-based electrochemical actuator with a high electro-mechanical transduction efficiency of up to 6.03%, exceeding that of the best-known piezoelectric ceramic, shape memory alloy and electroactive polymer reported before, and its energy density (11.5 kJ m⁻³) is comparable to that of mammalian skeletal muscle (~8 kJ m⁻³). Meanwhile, the actuator remains responsive at frequencies from 0.1 to 30 Hz with excellent cycling stability over 100,000 cycles. Furthermore, we verify the alkene–alkyne complex transition effect responsible for the high performance through in situ sum frequency generation spectroscopy. This discovery sheds light on our understanding of actuation mechanisms and will accelerate development of smart actuators.

Significant questions remain in respect to cellulose’s structure and polymorphs, particularly the cellulose surface layers and the bulk crystalline core as well as the conformational differences. Total Internal Reflection Sum Frequency Generation Vibrational Spectroscopy (TIR-SFG-VS) combined with conventional SFG-VS (non-TIR) enables selectively characterizing the molecular structures of surface layers and the crystalline core of cellulose, revealing their differences for the first time. From the SFG spectra in the C-H and O-H regions, we found that the surface layers of Avicel are essentially amorphous while the surface layers of Iβ cellulose are crystalline but with different structural and spectroscopic signatures compared with its crystalline core. The differences between hydrogen bonding networks of cellulose surface and crystalline core were also shown by the SFG signal. The discovery here represents yet another instance of the importance of spectroscopic observations in transformative advances to understand the structure of the cellulosic biomass.

Sum frequency generation vibrational spectroscopy (SFG-VS) has become one of the most appealing technologies to characterize molecular structures at interfaces. In this focal point review, we focus on SFG-VS studies at buried polymer interfaces and review many of the recent publications in the field. We also cover the essential theoretical background of SFG-VS and discuss the experimental implementation of SFG-VS.

Poly(methyl methacrylate) (PMMA) terminated with elemental blocks containing polyhedral oligomeric silsesquioxane (POSS), hereafter referred to as PPMP, was synthesized by living anionic polymerization. Combining modern interfacial-sensitive spectroscopy with traditional contact angle measurements, static and dynamic structures at the surface of PPMP films in water were examined. The surface of the well-annealed PPMP films, where the POSS end groups were preferentially segregated, was flat at the sub-nanometer level. Once the PPMP film was immersed in water, the surface was reorganized, and the rate was much slower for PPMP than for the conventional PMMA. This implies that the POSS units hindered the interfacial dynamics of the polymer segments. Then, platelet-adhesion tests were performed on the PPMP films. The number of platelets adhered to the PPMP film was dependent on the pre-immersion time in phosphate-buffered saline before the platelet seeding, whereas that of the reference PMMA film was unaffected by the pre-immersion time. These results could be explained in terms of the aggregation states of water at the interface.

Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there have been many progresses in the development of methodology and instrumentation in the SFG-VS toolbox that have significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, some of the controversial issues that have been puzzling the community are discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS.

Understanding interactions of calcium with lipid membranes at the molecular level is of great importance in light of their involvement in calcium signaling, association of proteins with cellular membranes, and membrane fusion. We quantify these interactions in detail by employing a combination of spectroscopic methods with atomistic molecular dynamics simulations. Namely, time-resolved fluorescent spectroscopy of lipid vesicles and vibrational sum frequency spectroscopy of lipid monolayers are used to characterize local binding sites of calcium in zwitterionic and anionic model lipid assemblies, while dynamic light scattering and zeta potential measurements are employed for macroscopic characterization of lipid vesicles in calcium-containing environments. To gain additional atomic-level information, the experiments are complemented by molecular simulations that utilize an accurate force field for calcium ions with scaled charges effectively accounting for electronic polarization effects. We demonstrate that lipid membranes have substantial calcium-binding capacity, with several types of binding sites present. Significantly, the binding mode depends on calcium concentration with important implications for calcium buffering, synaptic plasticity, and protein-membrane association.