Size-resolved aerosol at a Coastal Great Lakes Site: Impacts of new particle formation and lake spray.

The quantification of aerosol size distributions is crucial for understanding the climate and health impacts of aerosols, validating models, and identifying aerosol sources. This work provides one of the first continuous measurements of aerosol size distribution from 1.02 to 8671 nm near the shore of Lake Michigan. The data were collected during the Lake Michigan Ozone Study (LMOS 2017), a comprehensive air quality measurement campaign in May and June 2017. The time-resolved (2-min) size distribution are reported herein alongside meteorology, remotely sensed data, gravimetric filters, and gas-phase variables. Mean concentrations of key aerosol parameters include PM2.5 (6.4 µg m-3), number from 1 to 3 nm (1.80x104 cm-3) and number greater than 3 nm (8x103 cm-3). During the field campaign, approximately half of days showed daytime ultrafine burst events, characterized by particle growth from sub 10 nm to 25-100 nm. A specific investigation of ultrafine lake spray aerosol was conducted due to enhanced ultrafine particles in onshore flows coupled with sustained wave breaking conditions during the campaign. Upon closer examination, the relationships between the size distribution, wind direction, wind speed, and wave height did not qualitatively support ultrafine particle production from lake spray aerosol; statistical analysis of particle number and wind speed also failed to show a relationship. The alternative hypothesis of enhanced ultrafine particles in onshore flow originating mainly from new particle formation activity is supported by multiple lines of evidence.

Quantitative analysis of dendron-conjugated cisplatin-complexed gold nanoparticles using scanning particle mobility mass spectrometry.

We report a high-resolution and traceable method to quantify the drug loading on nanoparticle-based cancer therapeutics, and demonstrate this method using a model cisplatin functionalized dendron-gold nanoparticle (AuNP) conjugate. Electrospray differential mobility analysis (ES-DMA) provides upstream size classification based on the electrical mobility of AuNP conjugates in aerosol form following electrospray conversion from the aqueous suspension. A condensation particle counter (CPC) and inductively coupled plasma mass spectrometer (ICP-MS) provide the principal downstream quantification. CPC and ICP-MS yield complementary number-based and elemental mass-based particle size distributions, respectively. Conjugation using three different dendron formulations was differentiated based on changes in the mean mobility particle size. The subsequent cisplatin complexation to the dendron conjugates was quantified by coupling ES-DMA with ICP-MS. Discrete AuNP clusters (e.g., dimers, trimers) could be resolved from the relative quantity of atoms (i.e., Au and Pt) per particle after separation by ES-DMA. Surface density of cisplatin on Au was shown to be proportional to the density of carboxylic groups present and was independent of the state of AuNP clustering. Additionally, we found that colloidal stability of the conjugate is inversely proportional to the surface loading of cisplatin. This study demonstrates a prototype methodology to provide traceable quantification and to determine other important formulation factors relevant to therapeutic performance.

Real-time size discrimination and elemental analysis of gold nanoparticles using ES-DMA coupled to ICP-MS.

We report the development of a hyphenated instrument with the capacity to quantitatively characterize aqueous suspended gold nanoparticles (AuNPs) based on a combination of gas-phase size separation, particle counting, and elemental analysis. A customized electrospray-differential mobility analyzer (ES-DMA) was used to achieve real-time upstream size discrimination. A condensation particle counter and inductively coupled plasma mass spectrometer (ICP-MS) were employed as downstream detectors, providing information on number density and elemental composition, respectively, of aerosolized AuNPs versus the upstream size selected by ES-DMA. A gas-exchange device was designed and optimized to improve the conversion of air flow (from the electrospray) to argon flow required to sustain the ICP-MS plasma, the key compatibility issue for instrumental hyphenation. Our work provides the proof of concept and a working prototype for utilizing this construct to successfully measure (1) number- and mass-based distributions; (2) elemental compositions of nanoparticles classified by size, where the size classification and elemental analysis are performed within a single experiment; (3) particle concentrations in both solution (before size discrimination) and aerosol (after size discrimination) phases; and (4) the number of atoms per nanoparticle or the nanoparticle density.

Quantifying dithiothreitol displacement of functional ligands from gold nanoparticles.

Dithiothreitol (DTT)-based displacement is widely utilized for separating ligands from their gold nanoparticle (AuNP) conjugates, a critical step for differentiating and quantifying surface-bound functional ligands and therefore the effective surface density of these species on nanoparticle-based therapeutics and other functional constructs. The underlying assumption is that DTT is smaller and much more reactive toward gold compared with most ligands of interest, and as a result will reactively displace the ligands from surface sites thereby enabling their quantification. In this study, we use complementary dimensional and spectroscopic methods to characterize the efficiency of DTT displacement. Thiolated methoxypolyethylene glycol (SH-PEG) and bovine serum albumin (BSA) were chosen as representative ligands. Results clearly show that (1) DTT does not completely displace bound SH-PEG or BSA from AuNPs, and (2) the displacement efficiency is dependent on the binding affinity between the ligands and the AuNP surface. Additionally, the displacement efficiency for conjugated SH-PEG is moderately dependent on the molecular mass (yielding efficiencies ranging from 60 to 80% measured by ATR-FTIR and ≈90% by ES-DMA), indicating that the displacement efficiency for SH-PEG is predominantly determined by the S-Au bond. BSA is particularly difficult to displace with DTT (i.e., the displacement efficiency is nearly zero) when it is in the so-called normal form. The displacement efficiency for BSA improves to 80% when it undergoes a conformational change to the expanded form through a process of pH change or treatment with a surfactant. An analysis of the three-component system (SH-PEG + BSA + AuNP) indicates that the presence of SH-PEG decreases the displacement efficiency for BSA, whereas the displacement efficiency for SH-PEG is less impacted by the presence of BSA.

Tumor necrosis factor interaction with gold nanoparticles.

We report on a systematic investigation of molecular conjugation of tumor necrosis factor-α (TNF) protein onto gold nanoparticles (AuNPs) and the subsequent binding behavior to its antibody (anti-TNF). We employ a combination of physical and spectroscopic characterization methods, including electrospray-differential mobility analysis, dynamic light scattering, polyacrylamide gel electrophoresis, attenuated total reflectance-Fourier transform infrared spectroscopy, fluorescence assay, and enzyme-linked immunosorbent assay. The native TNF used in this study exists in the active homotrimer configuration prior to conjugation. After binding to AuNPs, the maximum surface density of TNF is (0.09 ± 0.02) nm(-2) with a binding constant of 3 × 10(6) (mol L(-1))(-1). Dodecyl sulfate ions induce desorption of monomeric TNF from the AuNP surface, indicating a relatively weak intermolecular binding within the AuNP-bound TNF trimers. Anti-TNF binds to both TNF-conjugated and citrate-stabilized AuNPs, showing that non-specific binding is significant. Based on the number of anti-TNF molecules adsorbed, a substantially higher binding affinity was observed for the TNF-conjugated surface. The inclusion of thiolated polyethylene glycol (SH-PEG) on the AuNPs inhibits the binding of anti-TNF, and the amount of inhibition is related to the number ratio of surface bound SH-PEG to TNF and the way in which the ligands are introduced. This study highlights the challenges in quantitatively characterizing complex hybrid nanoscale conjugates, and provides insight on TNF-AuNP formation and activity.

Quantification of ligand packing density on gold nanoparticles using ICP-OES.

In this study, a prototypical thiolated organic ligand, 3-mercaptopropionic acid (MPA), was conjugated on gold nanoparticles (AuNPs), and packing density was measured on an ensemble-averaged basis using inductively coupled plasma optical emission spectrometry. The effects of sample preparation, including centrifugation and digestion, as well as AuNP size and concentration, on recovery were investigated. For AuNPs with diameters of 5, 10, 30, 60, and 100 nm, calculated packing density is independent of size, averaging 7.8 nm(-2) and ranging from 6.7 to 9.0 nm(-2), and is comparable to reported values for MPA and similar short-chain ligands on AuNPs. These preliminary data provide fundamental information on the advantages and limitations of ICP-based analyses of conjugated AuNP systems. Moreover, they provide necessary information for the development of more broadly applicable methods for quantifying nanoparticle-ligand conjugates of critical importance to nanomedicine applications.

Nanoparticle dissolution from the particle perspective: insights from particle sizing measurements.

In this study, the dissolution of copper nanoparticles in aqueous low-pH suspensions is examined. The dissolution phenomenon is examined using both bulk measurements of copper ion production, as detected by inductively coupled plasma-optical emission spectroscopy (ICP/OES), and a decrease in nanoparticle size using particle-sizing instruments. For size measurements, an electrospray atomizer coupled to a scanning mobility particle sizer (ES-SMPS) was used to monitor changes in the particle size distribution (PSD) of the copper nanoparticles as they dissolved in hydrochloric acid solution in real time. Measured PSDs show interesting changes during the dissolution process, including a change in modality (mono to multi) with time. Although there may be several causes for the observed modality changes upon dissolution, it is clear that only through direct measurements of nanoparticles and nanoparticle PSDs can these dynamic details be captured as these particles change size, thus providing important insights into nanoscale processes.

Airborne monitoring to distinguish engineered nanomaterials from incidental particles for environmental health and safety.

Two methods were used to distinguish airborne engineered nanomaterials from other airborne particles in a facility that produces nano-structured lithium titanate metal oxide powder. The first method involved off-line analysis of filter samples collected with conventional respirable samplers at each of seven locations (six near production processes and one outdoors). Throughout most of the facility and outdoors, respirable mass concentrations were low (<0.050 mg/m(3)) and were attributed to particles other than the nanomaterial (<10% by mass titanium determined with inductively coupled plasma atomic emission spectrometry). In contrast, in a single area with extensive material handling, mass concentrations were greatest (0.118 mg m(-3)) and contained up to 39% +/- 11% lithium titanium, indicating the presence of airborne nanomaterial. Analysis of the filter samples collected in this area by transmission electron microscope and scanning electron microscope revealed that the airborne nanomaterial was associated only with spherical aggregates (clusters of fused 10-80 nm nanoparticles) that were larger than 200 nm. This analysis also showed that nanoparticles in this area were the smallest particles of a larger distribution of submicrometer chain agglomerates likely from welding in an adjacent area of the facility. The second method used two, hand-held, direct-reading, battery-operated instruments to obtain a time series of very fine particle number (<300 nm), respirable mass, and total mass concentration, which were then related to activities within the area of extensive material handling. This activity-based monitoring showed that very fine particle number concentrations (<300 nm) had no apparent correlation to worker activities, but that sharp peaks in the respirable and total mass concentration coincided with loading a hopper and replacing nanomaterial collection bags. These findings were consistent with those from the filter-based method in that they demonstrate that airborne nanoparticles in this facility are dominated by "incidental" sources (e.g., welding or grinding), and that the airborne "engineered" product is predominately composed of particles larger than several hundred nanometers. The methods presented here are applicable to any occupational or environmental setting in which one needs to distinguish incidental sources from engineered product.

Pentazole-based energetic ionic liquids: a computational study.

The structures of protonated pentazole cations (RN5H+), oxygen-containing anions such as N(NO2)2-, NO3-, and ClO4- and the corresponding ion pairs are investigated by ab initio quantum chemistry calculations. The stability of the pentazole cation is explored by examining the decomposition pathways of several monosubstituted cations (RN5H+) to yield N2 and the corresponding azidinium cation. The heats of formation of these cations, which are based on isodesmic (bond-type conserving) reactions, are calculated. The proton-transfer reaction from the cation to the anion is investigated.