Correction of 2π Phase Jumps for Silicon Photonic Sensors Based on Mach Zehnder Interferometers with Application in Gas and Biosensing.

Silicon photonic sensors based on Mach Zehnder Interferometers (MZIs) have applications spanning from biological and olfactory sensors to temperature and ultrasound sensors. Although a coherent detection scheme can solve the issues of sensitivity fading and ambiguity in phase direction, the measured phase remains 2π periodic. This implies that the acquisition frequency should ensure a phase shift lower than π between each measurement point to prevent 2π phase jumps. Here, we describe and experimentally characterize two methods based on reference MZIs with lower sensitivities to alleviate this drawback. These solutions improve the measurement robustness and allow the lowering of the acquisition frequency. The first method is based on the phase derivative sign comparison. When a discrepancy is detected, the reference MZI is used to choose whether 2π should be added or removed from the nominal MZI. It can correct 2π phase jumps regardless of the sensitivity ratio, so that a single reference MZI can be used to correct multiple nominal MZIs. This first method relaxes the acquisition frequency requirement by a factor of almost two. However, it cannot correct phase jumps of 4π, 6π or higher between two measurement points. The second method is based on the comparison between the measured phase from the nominal MZI and the phase expected from the reference MZI. It can correct multiple 2π phase jumps but requires at least one reference MZI per biofunctionalization. It will also constrain the corrected phase to lie in a limited interval of [-π, +π] around the expected value, and might fail to correct phase shifts above a few tens of radians depending on the disparity of the nominal sensors responses. Nonetheless, for phase shift lower than typically 20 radians, this method allows the lowering of the acquisition frequency almost arbitrarily.

Silicon photonic olfactory sensor based on an array of 64 biofunctionalized Mach-Zehnder interferometers.

Silicon photonics can address a variety of applications, from datacom and biosensing to lidars. Recently, this technology has been explored for gas sensing. Detection and identification of odors remains a critical challenge in diverse areas such as air quality, food spoilage, or personal well-being. In this work, we present an olfactory sensor based on an array of 64 biofunctionalized Mach-Zehnder interferometers integrated on a silicon nitride platform. The ability to analyze odors at ppm level is demonstrated for several volatile organic compounds.

Surfactant-like Peptide Self-Assembled into Hybrid Nanostructures for Electronic Nose Applications.

An electronic nose (e-nose) utilizes a multisensor array, which relies on the vector contrast of combinatorial responses, to effectively discriminate between volatile organic compounds (VOCs). In recent years, hierarchical structures made of nonbiological materials have been used to achieve the required sensor diversity. With the advent of self-assembling peptides, the ability to tune nanostructuration, surprisingly, has not been exploited for sensor array diversification. In this work, a designer surfactant-like peptide sequence, CG7-NH2, is used to fabricate morphologically and physicochemically heterogeneous "biohybrid" surfaces on Au-covered chips. These multistructural sensing surfaces, containing immobilized hierarchical nanostructures surrounded by self-assembled monolayers, are used for the detection and discrimination of VOCs. Through a simple and judicious design process, involving changes in pH and water content of peptide solutions, a five-element biohybrid sensor array coupled with a gas-phase surface plasmon resonance imaging system is shown to achieve sufficient discriminatory capabilities for four VOCs. Moreover, the limit of detection of the multiarray system is bench-marked at <1 and 6 ppbv for hexanoic acid and phenol (esophago-gastric biomarkers), respectively. Finally, the humidity effects are characterized, identifying the dissociation rate constant as a robust descriptor for classification, further exemplifying their efficacy as biomaterials in the field of artificial olfaction.

Reliable chiral recognition with an optoelectronic nose.

Chiral discrimination is a key problem in analytical chemistry. It is generally performed using expensive instruments or highly-specific miniaturized sensors. An electronic nose is a bio-inspired instrument capable after training of discriminating a wide variety of analytes. However, generality is achieved at the cost of specificity which makes chiral recognition a challenging task for this kind of device. Recently, a peptide-based optoelectronic nose which can board up to hundreds of different sensing materials has shown promising results, especially in terms of specificity. In line with these results, we describe here its use for chiral recognition. This challenging task requires care, especially in terms of statistical reliability and experimental confounds. For these reasons, we set up an automatic gas sampling system and recorded data over two long sessions, taking care to exclude possible confounds. Two couples of chiral molecules, namely (R) and (S) Limonene and (R) and (S) Carvone, were tested and several statistical analyses indicate the almost perfect discrimination of their two enantiomers. A method to highlight discriminative sensing materials is also proposed and shows that successful discrimination is likely achieved using just a few peptides.

Improvement of sensitivity of surface plasmon resonance imaging for the gas-phase detection of volatile organic compounds.

The analysis of volatile organic compounds (VOCs) is an important issue in various domains. For this, electronic noses (eN) are very promising as novel analytical tools that are portable, inexpensive, and efficient for reliable and rapid analyses. Recently, we have demonstrated that surface plasmon resonance imaging (SPRI) is especially interesting for the development of eNs dedicated for gas-phase analysis of VOCs. To further improve the performance of the eN based on SPRI, in this study, we investigated the influence of the LED wavelength on the sensitivity of the system. For this, a complete theoretical study together with a related experimental investigation for the validation were carried out. We have shown that the wavelength of the light source has an impact on the surface sensitivity of SPRI for the detection of VOCs. Indeed, in the studied wavelength range from 530 nm to 740 nm, both bulk sensitivity and surface sensitivity increase as the wavelength increases with good coherence between theoretical and experimental results. With the optimal LED wavelength, the detection limits of our eN reach low ppb range for VOC such as 1-butanol.

Highly-Selective Optoelectronic Nose Based on Surface Plasmon Resonance Imaging for Sensing Volatile Organic Compounds.

Monitoring volatile organic compounds (VOCs) is an important issue, but difficult to achieve on a large scale and on the field using conventional analytical methods. Electronic noses (eNs), as promising alternatives, are still compromised by their performances due to the fact that most of them rely on a very limited number of sensors and use databases devoid of kinetic information. To narrow the performance gap between human and electronic noses, we developed a novel optoelectronic nose, which features a large sensor microarray that enables multiplexed monitoring of binding events in real-time with a temporal response. For the first time, surface plasmon resonance imaging is demonstrated as a promising novel analytical tool for VOC detection in the gas phase. By combining it with cross-reactive sensor microarrays, the obtained optoelectronic nose shows a remarkably high selectivity, capable of discriminating between homologous VOCs differing by only a single carbon atom. In addition, the optoelectronic nose has good repeatability and stability. Finally, the preliminary assays using VOC binary and ternary mixtures show that it is also very efficient for the analysis of more complex samples, opening up the exciting perspective of applying it to "real-world" samples in diverse domains.

Covalent assembly and micropatterning of functionalized multiwalled carbon nanotubes to monolayer-modified Si(111) surfaces.

Multiwalled carbon nanotubes (MWNTs) covalently bound to monocrystalline p-type Si(111) surfaces have been prepared by attaching soluble amine-functionalized MWNTs onto a preassembled undecanoic acid monolayer using carbodiimide coupling. SEM analysis of these functionalized surfaces shows that the bound MWNTs are parallel to the surface rather than perpendicular. The voltammetric and electrochemical impedance spectroscopy measurements reveal that the electron transfer at the MWNT-modified surface is faster than that observed at a MWNT-free alkyl monolayer. We have also demonstrated that it is possible to prepare MWNT micropatterns using this surface amidation reaction and a "reagentless" UV photolithography technique. Following this approach, MWNT patterns surrounded by n-dodecyl areas have been produced and the local electrochemical properties of these micropatterned surfaces have been examined by scanning electrochemical microscopy. In particular, it is demonstrated that the MWNT patterns allow a faster charge transfer which is consistent with the results obtained for the uniformly modified surfaces.