CMOS-MEMS VOC sensors functionalized via inkjet polymer deposition for high-sensitivity acetone detection.

CMOS-MEMS microresonators have become excellent candidates for developing portable chemical VOC sensing systems thanks to their extremely large mass sensitivity, extraordinary miniaturization capabilities, and on-chip integration with CMOS circuitry to operate as a self-sustained oscillator. This paper presents two 4-anchored MEMS plate resonators, with a resonance frequency of 2.2 MHz and 380 kHz, fabricated together with the required circuitry using a commercial 0.35 µm CMOS technology and then coated with poly-4-vinylheduorocumyl alcohol (P4V) via inkjet deposition. Such P4V constitutes a functionalization layer for specific acetone detection as a key step in the development of an integrated device for non-invasive diabetes diagnosis through exhaled human breath. The coated sensor system has been proven to increase the acetone injection response by 6-times compared to the uncoated platform and shows a cross-sensitivity to butane of 1 : 11. Experimental data show an acetone sensitivity of -0.012 ppm Hz-1 in the best case that, together with a measured frequency Allan deviation of 0.32 ppm, provides an expected limit of detection as low as 20 ppb of acetone. Additionally, this work presents an alternative resonator design with folded flexure anchors that provide a drastic reduction of the sensor temperature sensitivity and mitigate the impact of a fluid flow inherent to the calibration system.

Janus-like squaramide-based hosts: dual mode of binding and conformational transitions driven by ion-pair recognition.

New tripodal squaramide-based hosts have been synthesised and structurally characterised by spectroscopic methods. In 2.5 % (v/v) [D(6)]DMSO in CDCl(3), compound 4 formed dimeric assemblies [log K(dim)=3.68(8)] as demonstrated by (1)H NMR spectroscopy and UV dilution experiments. AFM and SEM analyses revealed the formation of a network of bundled fibres, which indicates a preferential mechanism for aggregation. These C(3)-symmetric tripodal hosts exhibited two different and mutually exclusive modes of binding, each one easily accessible by simultaneous reorientation of the squaramide groups. In the first, a convergent disposition of the NH squaramide protons allowed the formation of an array of N-H⋅⋅⋅X(-) hydrogen bonds with anions. In the second mode, reorientation of carbonyl squaramide groups allowed multiple C=O⋅⋅⋅H interactions with ammonium cations. The titration of 4 with different tetraalkylammonium iodides persistently showed the formation of 1:1 complexes, as well as 1:2 and 1:3 complexes. The corresponding stoichiometries and binding affinities of the complexes were evaluated by multi-regression analysis. The formation of high-order complexes, supported by ROESY, NOESY and mass spectrometry experiments, has been attributed to the insertion of NR(4)I ion pairs between the carbonyl and NH protons of the squaramide groups located in adjacent arms of 4. The observed effects reflect the induction of significant conformational changes in the hosts, mainly in relation to the relative orientation of the squaramide groups adapting their geometries to incoming ion-pair complementary substrates. The results presented herein identify and fully describe two different modes of ion-pair recognition aimed at directing conformational transitions in the host, therefore establishing a base for controlling more elaborate movements of molecular devices through ion-pair recognition.

Evidence of anion-induced dimerization of a squaramide-based host in protic solvents.

The combination of squaramide units with tetraalkylammonium groups leads two hosts that bind distinctively dianions in water-ethanol mixtures. The formation of complexes of 2:1 stoichiometry with host was supported by ITC, fluorescence, and (1)H NMR data.