Tunable wavelength lasers

We investigate anionic [Co,CO₂,nH₂O]⁻ clusters as model systems for the electrochemical activation of CO₂ by infrared multiple photon dissociation (IRMPD) spectroscopy in the range of 1250–2234 cm⁻¹ using an FT-ICR mass spectrometer. We show that both CO₂ and H₂O are activated in a significant fraction of the [Co,CO₂,H₂O]⁻ clusters since it dissociates by CO loss, and the IR spectrum exhibits the characteristic C−O stretching frequency. About 25 % of the ion population can be dissociated by pumping the C−O stretching mode. With the help of quantum chemical calculations, we assign the structure of this ion as Co(CO)(OH)₂⁻. However, calculations find Co(HCOO)(OH)⁻ as the global minimum, which is stable against IRMPD under the conditions of our experiment. Weak features around 1590–1730 cm⁻¹ are most likely due to higher lying isomers of the composition Co(HOCO)(OH)⁻. Upon additional hydration, all species [Co,CO₂,nH₂O]⁻, n≥2, undergo IRMPD through loss of H₂O molecules as a relatively weakly bound messenger. The main spectral features are the C−O stretching mode of the CO ligand around 1900 cm⁻¹, the water bending mode mixed with the antisymmetric C−O stretching mode of the HCOO⁻ ligand around 1580–1730 cm⁻¹, and the symmetric C−O stretching mode of the HCOO⁻ ligand around 1300 cm⁻¹. A weak feature above 2000 cm⁻¹ is assigned to water combination bands. The spectral assignment clearly indicates the presence of at least two distinct isomers for n ≥2.

We use vibrational sum-frequency generation (VSFG) spectroscopy to study the structure of hen egg-white lysozyme (HEWL) aggregates adsorbed to DOPG/D₂O and air/D₂O interfaces. We find that aggregates with a parallel and antiparallel β-sheet structure together with smaller unordered aggregates and a denaturated protein are adsorbed to both interfaces. We demonstrate that to retrieve this information, fitting of the VSFG spectra is essential. The number of bands contributing to the VSFG spectrum might be misinterpreted, due to interference between peaks with opposite orientation and a nonresonant background. Our study identified hydrophobicity as the main driving force for adsorption to the air/D₂O interface. Adsorption to the DOPG/D₂O interface is also influenced by hydrophobic interaction; however, electrostatic interaction between the charged protein’s groups and the lipid’s headgroups has the most significant effect on the adsorption. We find that the intensity of the VSFG spectrum at the DOPG/D₂O interface is strongly enhanced by varying the pH of the solution. We show that this change is not due to a change of lysozyme’s and its aggregates’ charge but due to dipole reorientation at the DOPG/D₂O interface. This finding suggests that extra care must be taken when interpreting the VSFG spectrum of proteins adsorbed at the lipid/water interface.

As the development of oxygen evolution co-catalysts (OECs) is being actively undertaken, the tailored integration of those OECs with photoanodes is expected to be a plausible avenue for achieving highly efficient solar-assisted water splitting. Here, we demonstrate that a black phosphorene (BP) layer, inserted between the OEC and BiVO₄ can improve the photoelectrochemical performance of pre-optimized OEC/BiVO₄ (OEC: NiOOH, MnO_x, and CoOOH) systems by 1.2∼1.6-fold, while the OEC overlayer, in turn, can suppress BP self-oxidation to achieve a high durability. A photocurrent density of 4.48 mA·cm⁻² at 1.23 V vs reversible hydrogen electrode (RHE) is achieved by the NiOOH/BP/BiVO₄ photoanode. It is found that the intrinsic p-type BP can boost hole extraction from BiVO₄ and prolong holes trapping lifetime on BiVO₄ surface. This work sheds light on the design of BP-based devices for application in solar to fuel conversion, and also suggests a promising nexus between semiconductor and electrocatalyst.

We investigate the photodissociation of helium-solvated cesium dimer cations using action spectroscopy and quantum chemical calculations. The spectrum of Cs₂He⁺ shows three distinct absorption bands into both bound and dissociative states. Upon solvation with further helium atoms, considerable shifts of the absorption bands are observed, exceeding 0.1 eV (850 cm⁻¹) already for Cs₂He₁₀⁺, along with significant broadening. The shifts are highly sensitive to the character of the excited state. Our calculations show that helium atoms adsorb on the ends of Cs₂⁺. The shifts are particularly pronounced if the excited state orbitals extend to the area occupied by the helium atoms. In this case, Pauli repulsion leads to a deformation of the excited state orbitals, resulting in the observed blue shift of the transition. Since the position of the weakly bound helium atoms is ill defined, Pauli repulsion also explains the broadening.

Multimodal imaging with photoacoustic microscopy (PAM) and optical coherence tomography (OCT) can be an effective method to evaluate the choroidal and retinal microvasculature. To improve the efficiency for visualizing capillaries, colloidal gold nanoparticles (AuNPs) have been applied as a multimodal contrast agent for both OCT and PAM imaging by taking advantage of the strong optical scattering and the strong optical absorption of AuNPs due to their surface plasmon resonance. Ultra-pure AuNPs were fabricated by femtosecond laser ablation, capped with polyethylene glycol (PEG), and administered to 13 New Zealand white rabbits and 3 Dutch Belted pigmented rabbits. The synthesized PEG-AuNPs (20.0 ± 1.5 nm) were demonstrated to be excellent contrast agents for PAM and OCT, and do not demonstrate cytotoxicity to bovine retinal endothelial cells in cell studies. The image signal from the retinal and choroidal vessels in living rabbits was enhanced by up to 82% for PAM and up to 45% for OCT, respectively, by the administered PEG-AuNPs, which enables detection of individual blood vessels by both imaging modalities. The biodistribution study demonstrated the AuNP accumulated primarily in the liver and spleen. Histology and TUNEL staining did not indicate cell injury or death in the lung, liver, kidney, spleen, heart, or eyes up to seven days after AuNP administration. PEG-AuNPs offer an efficient and safe contrast agent for multimodal ocular imaging to achieve improved characterization of microvasculature.

Hydrated singly charged magnesium ions [Mg(H₂O)_n]⁺ are thought to consist of an Mg²⁺ ion and a hydrated electron for n > 15. This idea is based on mass spectra, which exhibit a transition from [MgOH(H₂O)_n−1]⁺ to [Mg(H₂O)_n]⁺ around n = 15–22, black-body infrared radiative dissociation, and quantum chemical calculations. Here, we present photodissociation spectra of size-selected [Mg(H₂O)_n]⁺ in the range of n = 20–70 measured for photon energies of 1.0–5.0 eV. The spectra exhibit a broad absorption from 1.4 to 3.2 eV, with two local maxima around 1.7–1.8 eV and 2.1–2.5 eV, depending on cluster size. The spectra shift slowly from n = 20 to n = 50, but no significant change is observed for n = 50–70. Quantum chemical modeling of the spectra yields several candidates for the observed absorptions, including five- and six-fold coordinated Mg²⁺ with a hydrated electron in its immediate vicinity, as well as a solvent-separated Mg²⁺/e⁻ pair. The photochemical behavior resembles that of the hydrated electron, with barrierless interconversion into the ground state following the excitation.

Joint high-resolution multimodal photoacoustic microscopy (PAM) and optical coherence tomography (OCT) was developed to improve the efficiency for visualizing newly developed retinal neovascularization (RNV) and to monitor the dynamic changes of retinal vein occlusion (RVO) in living rabbits. The RNV and RVO models were created in New Zealand rabbits by Rose Bengal laser-induced RVO. Dual modalities imaging equipment, including color fundus photography, fluorescein angiography (FA), OCT, and PAM, was used to image and assess the changes of retinal vasculature. In vivo experimental results exhibited that not only the treatment boundaries and the position of the occluded vasculature but also the structure of individual RNV were markedly observed using PAM platform with great resolution and high image contrast. The laser light energy of 80 nJ was used to induce photoacoustic signal, which is approximately half the energy of the American National Standards Institute safety limit. A cross-sectional structure of RNV was identified with the OCT modality. Furthermore, vibrant transformations in the RNV and the retinal morphology were examined at different times after laser occlusion: days 4, 28, 35, 49, and 90. PAM revealed high contrast and high resolution vascular imaging of the retina and choroid with amplified penetration depth. Through the present custom-built imaging system, both RNV and RVO can be reconstructed and observed in two and three dimensions. A unique dual modality A unique dual modality PAM and OCT can help precisely visualize and distinguish individual microvessels, microvessel depth, and the surrounding anatomy. Thus, the proposed multimodal ocular imaging platform may offer a potential equipment to enhance classification of microvasculature in a reliable and proficient manner in larger rabbit eyes.

Mid-infrared (MIR) microscopy provides rich chemical and structural information about biological samples, without staining. Conventionally, the long MIR wavelength severely limits the lateral resolution owing to optical diffraction; moreover, the strong MIR absorption of water ubiquitous in fresh biological samples results in high background and low contrast. To overcome these limitations, we propose a method that employs photoacoustic detection highly localized with a pulsed ultraviolet laser on the basis of the Grüneisen relaxation effect. For cultured cells, our method achieves water-background suppressed MIR imaging of lipids and proteins at ultraviolet resolution, at least an order of magnitude finer than the MIR diffraction limits. Label-free histology using this method is also demonstrated in thick brain slices. Our approach provides convenient high-resolution and high-contrast MIR imaging, which can benefit the diagnosis of fresh biological samples.

Light is an exceptional external stimulus for establishing precise control over the properties and functions of chemical and biological systems, which is enabled through the use of molecular photoswitches. Ideal photoswitches are operated with visible light only, show large separation of absorption bands and are functional in various solvents including water, posing an unmet challenge. Here we show a class of fully-visible-light-operated molecular photoswitches, Iminothioindoxyls (ITIs) that meet these requirements. ITIs show a band separation of over 100 nm, isomerize on picosecond time scale and thermally relax on millisecond time scale. Using a combination of advanced spectroscopic and computational techniques, we provide the rationale for the switching behavior of ITIs and the influence of structural modifications and environment, including aqueous solution, on their photochemical properties. This research paves the way for the development of improved photo-controlled systems for a wide variety of applications that require fast responsive functions.

The functionality of organic semiconductor devices crucially depends on molecular energies, namely the ionisation energy and the electron affinity. Ionisation energy and electron affinity values of thin films are, however, sensitive to film morphology and composition, making their prediction challenging. In a combined experimental and simulation study on zinc-phthalocyanine and its fluorinated derivatives, we show that changes in ionisation energy as a function of molecular orientation in neat films or mixing ratio in blends are proportional to the molecular quadrupole component along the π-π-stacking direction. We apply these findings to organic solar cells and demonstrate how the electrostatic interactions can be tuned to optimise the energy of the charge-transfer state at the donor−acceptor interface and the dissociation barrier for free charge carrier generation. The confirmation of the correlation between interfacial energies and quadrupole moments for other materials indicates its relevance for small molecules and polymers.