Exploring the Role of Surface States in Emissive Carbon Nanodots: Analysis at Single-Particle Level

Fluorescent carbon nanodots (CDs) have been highlighted as promising semiconducting materials due to their outstanding chemical and optical properties. However, the intrinsic heterogeneity of CDs has impeded a clear understanding of the mechanisms behind their photophysical properties. In this study, as-prepared CDs are fractionated via chromatography to reduce their structural and chemical heterogeneity and analyzed through ensemble and single-particle spectroscopies. Many single particles reveal fluorescence intensity fluctuations between two or more discrete levels with bi-exponential decays. While the intrinsic τ₁ components are uniform among single particles, the τ₂ components from molecule-like emissions spans a wider range of lifetimes, reflecting the inhomogeneity of the surface states. Furthermore, it is concluded that the relative population and chemical states of surface functional groups in CDs have a significant impact on emissive states, brightness, blinking, stability, and lifetime distribution of photoluminescence.     

Distinguishing Protein Chemical Topologies Using Supercharging Ion Mobility Spectrometry-Mass Spectrometry

A technique combining ion mobility spectrometry-mass spectrometry (IMS-MS) and supercharging electrospray ionization (ESI) has been demonstrated to differentiate protein chemical topology effectively. Incorporating as many charges as possible into proteins via supercharging ESI allows the protein chains to be largely unfolded and stretched, revealing their hidden chemical topology. Different chemical topologies result in differing geometrical sizes of the unfolded proteins due to constraints in torsional rotations in cyclic domains. By introducing new topological indices, such as the chain-length-normalized collision cross-section (CCS) and the maximum charge state (z_M) in the extensively unfolded state, we were able to successfully differentiate various protein chemical topologies, including linear chains, ring-containing topologies (lasso, tadpole, multicyclics, etc.), and mechanically interlocked rings, like catenanes.     

Colloidal rotation near the colloidal glass transition

We compare, using single-particle optical imaging, trajectories of rotation and translation for micron-sized spheres in index-matched colloidal suspensions near their glass transition. Rotational trajectories, while they show intermittent caged behavior associated with supercooled and glassy behavior, explore a sufficiently wider phase space such that in the averaged mean-square angular displacement there appears no plateau regime, but instead sub-Fickian angular diffusion that follows an apparent power law in time. We infer translation and rotation time constants, the former being the time to diffuse a particle diameter and the latter being the time to rotate a full revolution. Correlation between time constants increases with increasing volume fraction, but unlike the case for molecular glasses, the rotation time constant slows more weakly than the translation time.     

Materials Space-Tectonics: Atomic-level Compositional and Spatial Control Methodologies for Synthesis of Future Materials

Reactions occurring at surfaces and interfaces necessitate the creation of well-designed surface and interfacial structures. To achieve a combination of bulk material (i.e., framework) and void spaces, a meticulous process of “nano-architecting” of the available space is necessary. Conventional porous materials such as mesoporous silica, zeolites, and metal–organic frameworks lack advanced cooperative functionalities owing to their largely monotonous pore geometries and limited conductivities. To overcome these limitations and develop functional structures with surface-specific functions, the novel materials space-tectonics methodology has been proposed for future materials synthesis. This review summarizes recent examples of materials synthesis based on designing building blocks (i.e., tectons) and their hybridization, along with practical guidelines for implementing materials syntheses and state-of-the-art examples of practical applications. Lastly, the potential integration of materials space-tectonics with emerging technologies, such as materials informatics, is discussed.     

Single-particle tracking of janus colloids in close proximity

We describe algorithms and an experimental method based on differential interference contrast microscopy to discriminate optically anisotropic colloidal spheres under situations where diffraction owing to their close proximity causes overlapping images. The data analysis is applied to modulated optical nanoprobes (MOONs) that are coated with metal on one hemisphere. These methods enable single-particle tracking of rotation in addition to translation not only in concentrated suspensions but also in dilute suspensions when particles come into transient hydrodynamic contact. An illustrative example is given.     

Aerogel nanoarchitectonics based on cellulose nanocrystals and nanofibers from eucalyptus pulp: preparation and comparative study

Cellulose - Nanocellulose-based materials have attracted significant attention because of their attractive advantages. Particularly, aerogel, a porous nanocellulose material, have been used in...     

Single-particle colloid tracking in four dimensions

Coating a close-packed fluorescent colloid monolayer with a nanometer-thick metal film followed by sonication in liquid produces modulated optical nanoprobes. The metal coating modulates the fluorescence as these structures rotate in suspension, enabling the use of these particles as probes to monitor both rotational and center-of-mass (translational) dynamics in complex environments. Here, we demonstrate methods to simultaneously measure two translational and two rotational degrees of freedom, with excellent agreement to theory. The capability to determine two angles of rotation opens several new avenues of future research.     

Synthesis and photocatalytic activity of TiO2 nanoparticles prepared by chemical vapor condensation method with different precursor concentration and residence time

Nanosized TiO(2) photocatalysts were synthesized using a chemical vapor condensation method under a range of synthesis conditions (precursor vapor concentration and residence time in a tubular electric furnace). X-ray diffraction showed that the prepared TiO(2) powders consisted mainly of anatase (>94%) with a small amount of rutile. The mean particle diameter from the Brunauer-Emmett-Teller surface area and transmission electron microscopy measurements ranged from 9.4 to 16.6 nm. The specific surface area (92.5-163.5 m(2) g(-1)) of the prepared TiO(2) powders was found to be dependent on the synthesis conditions. The content of hydroxyl groups on the surface of the prepared TiO(2) sample was higher than those on commercial TiO(2), resulting in increased photocatalytic oxidation. The photocatalytic activity of the TiO(2) samples prepared in a methylene blue solution was strongly dependent on the crystallinity and specific surface area, which were affected by the TTIP vapor concentration and residence time.     

Time-discretized steady compressible Navier–Stokes equations with inflow and outflow boundaries

The time-discretized steady compressible Navier–Stokes equations in n-dimensional bounded domains with the velocity specified only at the inflow boundary are considered. The existence and uniqueness of L ^p solutions are proved for p > n. For time-discretized steady flows, results of Kweon and Kellogg and of Kweon and Song are extended in a manner that allows for more general domains and for density-dependent viscosity coefficients. Moreover, we only require p > n which is a critical barrier in the previous works.     

Methyl substituent effects for methyltryptophans in 13C nmr

The ¹³C and ¹H nmr spectra of methyltryptophans 2–5 in 0.1 N sodium deuteroxide methanol-d₄ were assigned based on 1-D and 2-D nmr techniques, including COSY, inverse-detected direct (HMQC) and long-range (HMBC) correlation. Methyl substituent effects in chemical shifts (SCS) for the indole ring of tryptophan were calculated and compared with those of indole. The correlations were linear except for 4-methyltryptophan, which suggest structural changes in the indole ring of 4-methyltryptophan and 4-methylindole. The results of molecular modeling and NOE experiments supported that suggestion.