The selective detection of crystalline cellulose in biomass was demonstrated with sum-frequency-generation (SFG) vibration spectroscopy. SFG is a second-order nonlinear optical response from a system where the optical centrosymmetry is broken. In secondary plant cell walls that contain mostly cellulose, hemicellulose, and lignin with varying concentrations, only certain vibration modes in the crystalline cellulose structure can meet the noninversion symmetry requirements. Thus, SFG can be used to detect and analyze crystalline cellulose selectively in lignocellulosic biomass without extraction of noncellulosic species from biomass or deconvolution of amorphous spectra. The selective detection of crystalline cellulose in lignocellulosic biomass is not readily achievable with other techniques such as XRD, solid-state NMR, IR, and Raman analyses. Therefore, the SFG analysis presents a unique opportunity to reveal the cellulose crystalline structure in lignocellulosic biomass.

The presence of leachable alkali ions, or their hydrated sites in the glass, is believed to be a determining factor for the interfacial water structure at the glass surface, influencing the surface properties of glass. The interfacial water structure on soda‐lime silicate glass in humid ambience at room temperature was analyzed with sum‐frequency‐generation (SFG) vibration spectroscopy, which can probe the interfacial water layer without spectral interferences from the gas phase water. The soda‐lime glass surface exposed to water vapor shows three sharp SFG peaks at 3200, 3430, and 3670 cm−1 in SFG, which is drastically different from the SFG spectra of the water layers on the fused quartz glass surface and the liquid water/air interface. The sharp peak at 3200 cm−1 is believed to be associated with the hydronium ions in the Na+‐leached silicate glass surface. The 3200 cm−1 peak intensity varies with the relative humidity, indicating its equilibrium with the gas phase water. It is proposed that the hydronium ions in the Na+‐leached sites produce compressive stress in the silicate glass surface; thus the growth of hydronium ions with increasing humidity might be responsible for the increased wear resistance of soda‐lime glass surfaces in near‐saturation humidity conditions.

No abstract

Janus particles are colloidal analogues of molecular amphiphiles that can self-assemble to form diverse suprastructures, exhibit motility under appropriate catalytic reactions, and strongly adsorb to fluid-fluid interfaces to stabilize multiphasic fluid mixtures. The chemistry of Janus particles is the fundamental parameter that controls their behavior and utility as colloid surfactants in bulk solution and at fluid interfaces. To enable their widespread utilization, scalable methods that allow for the synthesis of Janus particles with diverse chemical compositions and shapes are highly desirable. Here, we develop clickable Janus particles that can be modified through thiol-yne click reactions with commercially available thiols. Janus particles are modified to be amphiphilic by introducing either carboxyl, hydroxyl, or amine moieties. We also demonstrate that regulating the extent of the modification can be used to control the particle morphology, and thus the type of emulsion stabilized, as well as to fabricate composite Janus particles through sequential click reactions. Modifying Janus particles through thiol-yne click chemistry provides a fast-reacting, scalable synthesis method for the fabrication of diverse Janus particles.

No abstract