The impact of water and hydrocarbon concentration on the sensitivity of a polymer-based quartz crystal microbalance sensor for organic compounds

Long-term environmental monitoring of organic compounds in natural waters requires sensors that respond reproducibly and linearly over a wide concentration range, and do not degrade with time. Although polymer coated piezoelectric based sensors have been widely used to detect hydrocarbons in aqueous solution, very little information exists regarding their stability and suitability over extended periods in water. In this investigation, the influence of water aging on the response of various polymer membranes [polybutadiene (PB), polyisobutylene (PIB), polystyrene (PS), polystyrene-co-butadiene (PSB)] was studied using the quartz crystal microbalance (QCM). QCM measurements revealed a modest increase in sensitivity towards toluene for PB and PIB membranes at concentrations above 90 ppm after aging in water for 4 days. In contrast, the sensitivity of PS and PSB coated QCM sensors depended significantly on the toluene concentration and increased considerably at concentrations above 90 ppm after aging in water for 4 days. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR–FTIR) showed that there is a change in the sorption mechanism at higher toluene levels for PS and PSB. Positron annihilation lifetime spectroscopy (PALS) studies were performed to investigate the free volume properties of all polymers and to monitor any changes in the free volume size and distribution due to water and toluene exposure. The PALS did not detect any considerable variation in the free volume properties of the polymer films as a function of solution composition and soaking time, implying that viscoelastic and/or interfacial processes (i.e. surface area changes) are probably responsible for variations in the QCM sensitivity at high hydrocarbon concentrations. The results suggest that polymer membrane conditioning in water is an issue that needs to be considered when performing QCM measurements in the aqueous phase. In addition, the study shows that the hydrocarbon response is concentration dependant for polymers with a high glass transition temperature, and this feature is often neglected when comparing sensor sensitivity in the literature.     

Protonated Porphyrins: Bifunctional Catalysts for the Metal-Free Synthesis of N-Alkyl-Oxazolidinones

The protonation of commercially available porphyrin ligands yields a class of bifunctional catalysts able to promote the synthesis of N-alkyl oxazolidinones by CO₂ cycloaddition to corresponding aziridines. The catalytic system does not require the presence of any Lewis base or additive, and shows interesting features both in terms of cost effectiveness and eco-compatibility. The metal-free methodology is active even with a low catalytic loading of 1 % mol, and the chemical stability of the protonated porphyrin allowed it to be recycled three times without any decrease in performance. In addition, a DFT study was performed in order to suggest how a simple protonated porphyrin can mediate CO₂ cycloaddition to aziridines to yield oxazolidinones.     

Donor-Acceptor Aminocyclobutane Monoesters: Synthesis and Silylium-Catalyzed (4+2) Annulation with Indoles

A convenient one-step synthesis of β-aminocyclobutane monoesters starting from commercially available reagents is reported. The obtained strained rings undergo (4+2) dearomative annulation with indole partners using silylium catalysis. This organocatalyzed annulation provided tricyclic indolines with four new stereocenters in up to quantitative yield and >95 : 5 diastereoselectivity and can proceed both intra- and intermolecularly. When performed intramolecularly, the tetracyclic structure of either akuamma or malagasy alkaloids was obtained selectively depending on the temperature of the reaction. This divergent outcome could be rationalized based on DFT calculations.     

Synthesis of soluble,all-trans poly(2,5-diheptyl-p-phenylenevinylene) via metathesis polycondensation

The synthesis of substituted poly(p-phenylenenvinylene) (PPV) was carried out via metathesis polycondensation of 2,5-diheptyl-1,4-divinylbenzene (DHepDVB). A stable molybdenumcarbene complex served as catalyst. The preparation of the educt employed (DHepDPV, 3a ) is described. The obtained poly(2,5-diheptyl-1,4-phenylenevinylene) (DHepPPV, 5 ), an intensely yellow product, has an all-trans-configuration and, with a degree of polymerization of ≈ 10 is soluble in conventional organic solvents.     

Blended Conjugated Host and Unconjugated Dopant Polymers Towards N-type All-Polymer Conductors and High-ZT Thermoelectrics

N-Type thermoelectrics typically consist of small molecule dopant+polymer host. Only a few polymer dopant+polymer host systems have been reported, and these have lower thermoelectric parameters. N-type polymers with high crystallinity and order are generally used for high-conductivity ( ) organic conductors. Few n-type polymers with only short-range lamellar stacking for high-conductivity materials have been reported. Here, we describe an n-type short-range lamellar-stacked all-polymer thermoelectric system with highest of 78 S⁻¹, power factor (PF) of 163 μW m⁻¹ K⁻², and maximum Figure of merit (ZT) of 0.53 at room temperature with a dopant/host ratio of 75 wt%. The minor effect of polymer dopant on the molecular arrangement of conjugated polymer PDPIN at high ratios, high doping capability, high Seebeck coefficient (S) absolute values relative to , and atypical decreased thermal conductivity ( ) with increased doping ratio contribute to the promising performance.