We report the first mass-specific absorption and extinction cross sections for size- and mass-selected laboratory-generated soot aerosol. Measurement biases associated with aerosols possessing multiple charges were eliminated using mass selection to isolate singly charged particles for a specified electrical mobility diameter. Aerosol absorption and extinction coefficients were measured using photoacoustic and cavity ring-down spectroscopy techniques, respectively, for lacey and compacted soot morphologies. The measurements show that the mass-specific absorption cross sections are proportional to particle mass and independent of morphology, with values between 5.7 and 6 m(2) g(-1). Mass-specific extinction cross sections were morphology dependent and ranged between 12 and 16 m(2) g(-1) for the lacey and compact morphologies, respectively. The resulting single-scattering albedos ranged from 0.5 to 0.6. Results are also compared to theoretical calculations of light absorption and scattering from simulated particle agglomerates. The observed absorption is relatively well modeled, with minimum differences between the calculated and measured mass absorption cross sections ranging from ∼ 5% (lacey soot) to 14% (compact soot). The model, however, was unable to satisfactorily reproduce the measured extinction, underestimating the single-scattering albedo for both particle morphologies. These discrepancies between calculations and measurements underscore the need for validation and refinement of existing models of light scattering and absorption by soot agglomerates.

Optical absorption spectra of laboratory generated aerosols consisting of black carbon (BC) internally mixed with non-absorbing materials (ammonium sulfate, AS, and sodium chloride, NaCl) and BC with a weakly absorbing brown carbon surrogate derived from humic acid (HA) were measured across the visible to near-IR (550 nm to 840 nm). Spectra were measured in-situ using a photoacoustic spectrometer and step-scanning a supercontinuum laser source with a tunable wavelength and bandwidth filter. BC had a mass-specific absorption cross section (MAC) of 7.89 ± 0.25 m2 g−1 at λ = 550 nm and an absorption Ångström exponent (AAE) of 1.03 ± 0.09 (2σ). For internally mixed BC, the ratio of BC mass to the total mass of the mixture was chosen as 0.13 to mimic particles observed in the terrestrial atmosphere. The manner in which BC mixed with each material was determined from transmission electron microscopy (TEM). AS/BC and HA/BC particles were fully internally mixed and the BC was both internally and externally mixed for NaCl/BC particles. The AS/BC, NaCl/BC and HA/BC particles had AAEs of 1.43 ± 0.05, 1.34 ± 0.06 and 1.91 ± 0.05, respectively. The observed absorption enhancement of mixed BC relative to the pure BC was wavelength dependent for AS/BC and decreased from 1.5 at λ = 550 nm with increasing wavelength while the NaCl/BC enhancement was essentially wavelength independent. For HA/BC, the enhancement ranged from 2 to 3 and was strongly wavelength dependent. Removal of the HA absorption contribution to enhancement revealed that the enhancement was ≈ 1.5 and independent of wavelength.

The mobility of a nonspherical particle is a function of both particle shape and orientation. In turn, the higher magnitude of electric field causes nonspherical particles to align more along the field direction, increasing their mobility or decreasing their mobility diameter. In previous works, Li et al. developed a general theory for the orientation-averaged mobility and the dynamic shape factor applicable to any axially symmetric particles in an electric field, and applied it to the specific cases of nanowires and doublets of spheres. In this work, the theory for a nanowire is compared with experimental results of gold nanorods with known shape determined by TEM images. We compare the experimental measured mobility sizes with the theoretical predicted mobility in the continuum, free molecular, and the transition regime. The mobility size shift trends in the electric fields based on our model, expressed both in the free molecular regime and in the transition regime, are in good agreement with the experimental results. For rods of dimension: width d r = 17 nm and length L r = 270 nm, where one length scale is smaller than the mean free path and one larger, the results clearly show that the flow regime of a slender rod is mostly controlled by the diameter of the rod (i.e., the smallest dimension). In this case, the free molecule transport properties best represented our nanorod. Combining both theory and experiment we show how, by evaluating the mobility as a function of applied electric field, we can extract both rod length and diameter.

Cisplatin-complexed gold nanoparticles (Pt-AuNP) provide a promising strategy for chemo-radiation-based anticancer drugs. Effective design of such platforms necessitates reliable assessment of surface engineering on a quantitative basis and its influence on drug payload, stability, and release. In this paper, poly(ethylene glycol) (PEG)-stabilized Pt-AuNP was synthesized as a model antitumor drug platform, where Pt is attached via a carboxyl-terminated dendron ligand. Surface modification by PEG and its influence on drug loading, colloidal stability, and drug release were assessed. Complexation with Pt significantly degrades colloidal stability of the conjugate; however, PEGylation provides substantial improvement of stability in conjunction with an insignificant trade-off in drug loading capacity compared with the non-PEGylated control (<20% decrease in loading capacity). In this context, the effect of varying PEG concentration and molar mass was investigated. On a quantitative basis, the extent of PEGylation was characterized and its influence on dispersion stability and drug load was examined using electrospray differential mobility analysis (ES-DMA) hyphenated with inductively coupled plasma mass spectrometry (ICP-MS) and compared with attenuated total reflectance-FTIR. Using ES-DMA-ICP-MS, AuNP conjugates were size-classified based on their electrical mobility, while Pt loading was simultaneously quantified by determination of Pt mass. Colloidal stability was quantitatively evaluated in biologically relevant media. Finally, the pH-dependent Pt release performance was evaluated. We observed 9% and 16% Pt release at drug loadings of 0.5 and 1.9 Pt/nm, respectively. The relative molar mass of PEG had no significant influence on Pt uptake or release performance, while PEGylation substantially improved the colloidal stability of the conjugate. Notably, the Pt release over 10 days (examined at 0.5 Pt/nm drug loading) remained constant for non-PEGylated, 1K-PEGylated, and 5K-PEGylated conjugates.

Mass absorption coefficient spectra were measured between λ = 500 nm and 840 nm for nine forms of highly-absorbing carbonaceous aerosol: five samples generated from gas-, liquid-and solid-fueled flames; spark-discharge fullerene soot; graphene and reduced graphene oxide (rGO) crumpled nanosheets; and fullerene (C 60 ) assemblies. Aerosol absorption spectra were measured for size-and mass-selected particles and found to be dependent on fuel type and formative conditions. Flame-generated particles had morphologies consistent with freshly emitted black carbon (BC) with mass absorption coefficients (MAC) ranging between 3.8 m 2 g -1 and 8.6 m 2 g -1 at λ = 550 nm. Absorption Ångström exponents (AAE) -i.e. MAC spectral dependence -ranged between 1.0 and 1.3 for flame-generated particles and up to 7.5 for C 60 . The dependence of MAC and AAE on mobility diameter and particle morphology was also investigated. Lastly, the current data were compared to all previously published MAC measurements of highly-absorbing carbonaceous aerosol. Mass absorption coefficient spectra were measured between λ = 500 nm and 840 nm for nine 13 forms of highly-absorbing carbonaceous aerosol: five samples generated from gas-, liquid-and 14 solid-fueled flames; spark-discharge fullerene soot; graphene and reduced graphene oxide (rGO) 15 crumpled nanosheets; and fullerene (C 60 ) assemblies. Aerosol absorption spectra were measured 16 for size-and mass-selected particles and found to be dependent on fuel type and formative 17 conditions. Flame-generated particles had morphologies consistent with freshly emitted black 18 carbon (BC) with mass absorption coefficients (MAC) ranging between 3.8 m 2 g -1 and 8.6 m 2 g -1 19at λ = 550 nm. Absorption Ångström exponents (AAE) -i.e. MAC spectral dependence -ranged 20 between 1.0 and 1.3 for flame-generated particles and up to 7.5 for C 60 . The dependence of MAC 21 and AAE on mobility diameter and particle morphology was also investigated. Lastly, the current 22 M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT 2 data were compared to all previously published MAC measurements of highly-absorbing 23 carbonaceous aerosol. 24

Large planetary seedlings, comets, microscale pharmaceuticals, and nanoscale soot particles are made from rigid, aggregated subunits that are compacted under low compression into larger structures spanning over 10 orders of magnitude in dimensional space. Here, we demonstrate that the packing density (θ f ) of compacted rigid aggregates is independent of spatial scale for systems under weak compaction. The θ f of rigid aggregated structures across six orders of magnitude were measured using nanoscale spherical soot aerosol composed of aggregates with ∼17-nm monomeric subunits and aggregates made from uniform monomeric 6-mm spherical subunits at the macroscale. We find θ f = 0.36 ± 0.02 at both dimensions. These values are remarkably similar to θ f observed for comet nuclei and measured values of other rigid aggregated systems across a wide variety of spatial and formative conditions. We present a packing model that incorporates the aggregate morphology and show that θ f is independent of both monomer and aggregate size. These observations suggest that the θ f of rigid aggregates subject to weak compaction forces is independent of spatial dimension across varied formative conditions. M any systems are comprised of elementary subunits packed within a defined volume. The simplest 3D system consists of uniform spheres, and despite its apparent simplicity, a rigorous mathematical description eluded researchers for nearly four centuries dating back to Kepler's conjecture in 1611. In 2005, Hales provided a definitive mathematical proof confirming the observed experimental maximum packing density of 74% (1). Packing of more complex structures is far more mathematically challenging and instead relies on empirical studies (2-9). One of the most ubiquitous packing systems in the universe are rigid aggregates composed of a collection of monomeric units joined together into a fractal structure and subsequently densified through omnidirectional applied force, as shown in Fig. 1 (10).The formation and compaction mechanism of disordered aggregates is presumed to be independent of dimension, composition, and spatial scale, and has been observed in a diverse range of materials and conditions, such as the accretion of material in interstellar space and the formation and compaction of aerosol in the Earth's atmosphere. Many interstellar formations comprise nano-or microscale dust particles that begin as disordered monomeric subunits, which electrostatically aggregate to form fractal (lacey) agglomerates that serve as foundries for comets and planetary seedlings (10-16). Soot, ubiquitous in the Earth's troposphere, is also comprised of nanometer sized carbonaceous monomers aggregated in a disordered lacey structure. Compaction into spheres occurs after trace gas and/or liquid adsorption and evaporation. In both cases, the resulting structure is constrained by aggregate rigidity (17).The systems described above are similarly constructed from single-unit building blocks assembled into larger disordered structures. The final structure ...

We propose bionanoparticles as a candidate reference material for determining the mobility of nanoparticles over the range of 6 × 10(-8)-5 × 10(-6) m(2)V(-1)s(-1). Using an electrospray differential mobility analyzer (ES-DMA), we measured the empirical distribution of several bionanoparticles. All of them show monomodal distributions that are more than two times narrower than the currently used calibration particles for mobility larger than 6 × 10(-8) m(2)V(-1)s(-1) (diameters less than 60 nm). We also present a numerical method to calculate corrected distributions of bionanoparticles by separating the contribution of the diffusive transfer function. The corrected distribution is about 20% narrower than the empirical distributions. Even with the correction, the reduced width of the mobility distribution is about a factor of 2 larger than the diffusive transfer function. The additional broadening could result from the nonuniform conformation of bionanoparticles and from the presence of volatile impurities or solvent adducts. The mobilities of these investigated bionanoparticle are stable over a range of buffer concentration and molarity, with no evidence of temporal degradation over several weeks.

For a nonspherical particle, a standard differential mobility analyzer (DMA) measurement yields a mobility-equivalent spherical diameter, but provides no information about the degree of sphericity. However, given that the electrical mobility for nonspheres is orientation-dependent, and that orientation can be manipulated using electric fields of varying strength, one can, in principle, extract some type of shape information through a systematic measurement of mobility as a function of particle orientation. Here, we describe the development of a pulsed-field differential mobility analyzer (PFDMA) which enables one to change the peak E-field experienced by the particle to induce orientation, while still maintaining the same time-averaged field strength as a standard DMA experiment. The instrument is validated with polystyrene latex (PSL) spheres with accurately known size, and gold rods with dimensions accurately determined by transmission electron microscopy (TEM). We demonstrate how the instrument can be used for particle separation and extraction of shape information. In particular, we show how one can extract both length and diameter information for rod-like particles. This generic approach can be used to obtain dynamic shape factors or other multivariate dimensional information (e.g., length and diameter).