Automated identification and quantification of tire wear particles (TWP) in airborne dust: SEM/EDX single particle analysis coupled to a machine learning classifier.

The share of non-exhaust particles, including tire wear particles (TWP), within the airborne dust and particularly within PM10 has increased in recent years due to a significant reduction of other particles including exhaust road traffic emissions. However, the quantification of TWP is a demanding task due to the non-specificity of tracers, and the fact that they are commonly contained in analytically challenging low concentrations (e.g. Zn, styrene, 1,3-butadiene, vinylcyclohexene). This difficulty is amplified by the chemical and morpho-textural heterogeneity of TWP resulting from the interaction between the tires and the road surface. In contrast to bulk techniques, automated single particle SEM/EDX analysis can benefit from the ubiquitous heterogeneity of environmental TWP as a diagnostic criterion for their identification and quantification. For this purpose, we follow a machine-learning (ML) approach that makes use of an extensive number (67) of morphological, textural (backscatter-signal based) and chemical descriptors to differentiate environmental particles into the following classes: TWP, metals, minerals and biogenic/organic. We present a ML-based model developed to classify airborne samples (trained by >100,000 environmental particles including 6841 TWP), and its application within a one-year monitoring campaign at two Swiss sites. In this study, the mass concentrations of TWP in the airborne fractions PM80-10, PM10-2.5 and PM2.5-1 were determined. Furthermore, the particle size distribution and shape characteristics of 5621 TWP were evaluated. A cut through a TWP by means of FIB-SEM evidences that the mineral and metal particles typically found in TWP are not only present on the particle surface but also throughout the complete TWP volume. At the urban background site, the annual average mass fraction of TWP and micro-rubber in PM10 was 1.8% (0.28 µg/m3) and 0.9%, respectively. At the urban kerbside site, the corresponding values were 6 times higher amounting to 10.5% (2.24 µg/m3) for TWP, and 5.0% for micro-rubber.

Evaluation of polyvinylpyrrolidone and block copolymer micelle encapsulation of serine chlorin e6 and chlorin e4 on their reactivity towards albumin and transferrin and their cell uptake.

Encapsulation of porphyrinic photosensitizers (PSs) into polymeric carriers plays an important role in enhancing their efficiency as drugs in photodynamic therapy (PDT). Porphyrin aggregation and low solubility as well as the preservation of the advantageous photophysical properties pose a challenge on the design of efficient PS-carrier systems. Block copolymer micelles (BCMs) and polyvinylpyrrolidone (PVP) are promising drug delivery vehicles for physical entrapment of PSs. BCMs exhibit enhanced dynamics as compared to the less flexible PVP network. In the current work the question is addressed how these different dynamics affect PS encapsulation, release from the carrier, reaction with serum proteins, and cellular uptake. The porphyrinic compounds serine-amide of chlorin e6 (SerCE) and chlorin e4 (CE4) were used as model PSs with different lipophilicity and aggregation properties. 1H NMR and fluorescence spectroscopy were applied to study their interactions with PVP and BCMs consisting of Kolliphor P188 (KP). Both chlorins were well encapsulated by the carriers and had improved photophysical properties. Compared to SerCE, the more lipophilic CE4 exhibited stronger hydrophobic interactions with the BCM core, stabilizing the system and preventing exchange with the surrounding medium as was shown by NMR NOESY and DOSY experiments. PVP and BCMs protected the encapsulated chlorins against interaction with human transferrin (Tf). However, SerCE and CE4 were released from BCMs in favor of binding to human serum albumin (HSA) while PVP prevented interaction with HSA. Fluorescence spectroscopic studies revealed that HSA binds to the surface of PVP forming a protein corona. PVP and BCMs reduced cellular uptake of the chlorins. However, encapsulation into BCMs resulted in more efficient cell internalization for CE4 than for SerCE. HSA significantly lowered both, free and carrier-mediated cell uptake for CE4 and SerCE. In conclusion, PVP appears as the more universal delivery system covering a broad range of host molecules with respect to polarity, whereas BCMs require a higher drug-carrier compatibility. Poorly soluble hydrophobic PSs benefit stronger from BCM-type carriers due to enhanced bioavailability through disaggregation and solubilization allowing for more efficient cell uptake. In addition, increased PS-carrier hydrophobic interactions have a stabilizing effect. For more hydrophilic PSs, the main advantage of polymeric carriers like PVP or poloxamer micelles lies in their protection during the transport through the bloodstream. HSA binding plays an important role for drug release and cell uptake in carrier-mediated delivery to the target tissue.