The apparent increase in hormone-induced cancers and disorders of the reproductive tract has led to a growing demand for new technologies capable of detecting endocrine disruptors. However, a long-lasting challenge unaddressed is how to achieve ultrahigh sensitive, continuous, and in situ measurement with a portable device for in-field and remote environmental monitoring. Here we demonstrate a simple-to-implement plasmonic optical fiber biosensing platform to achieve an improved light–matter interaction and advanced surface chemistry for ultrasensitive detection of endocrine disruptors. Our platform is based on a gold-coated highly tilted fiber Bragg grating that excites high-density narrow cladding mode spectral combs that overlap with the broad absorption of the surface plasmon for high accuracy interrogation, hence enabling the ultrasensitive monitoring of refractive index changes at the fiber surface. Through the use of estrogen receptors as the model, we design an estradiol–streptavidin conjugate with the assistance of molecular dynamics, converting the specific recognition of environmental estrogens (EEs) by estrogen receptor into surface-based affinity bioassay for protein. The ultrasensitive platform with conjugate-induced amplification biosensing approach enables the subsequent detection for EEs down to 1.5 × 10⁻³ ng ml⁻¹ estradiol equivalent concentration level, which is one order lower than the defined maximal E₂ level in drinking water set by the Japanese government. The capability to detect EEs down to nanogram per liter level is the lowest limit of detection for any estrogen receptor-based detection reported thus far. Its compact size, flexible shape, and remote operation capability open the way for detecting other endocrine disruptors with ultrahigh sensitivity and in various hard-to-reach spaces, thereby having the potential to revolutionize environment and health monitoring.

A method to enable surface plasmon resonance (SPR) sensors to discriminate between bulk and surface-localized refractive index changes is demonstrated with modified gold-coated tilted fiber Bragg grating SPR sensors (TFBG-SPR). Without this capability, all high-resolution SPR sensors should be using reference channels and strict temperature control to prevent the contamination of the desired detection of surface-localized chemical or binding events by drift of the refractive index of the medium, in which the experiment is carried out. The very fine comb of high-quality-factor resonances of a TFBG-SPR device coupled to the large differential sensitivity of some of the resonances to various perturbations is used to measure unambiguously the refractive index changes within a surface layer thinner than 25 nm from those of the bulk surrounding. The enabling modification of the conventional TFBG-SPR is a reduction of the gold coating from its optimum value near 50–30 nm: at this lower thickness, a surface plasmon wave can still be excited by a limited number of cladding mode resonances, but at the same time, the metal is thin enough to allow modes away from the SPR to tunnel across the metal and probe the bulk RI value. Measurements and simulations of the deposition of a self-assembled monolayer of 1-dodecanethiol in ethanol show that the bulk refractive index changes as small as 0.0004 can be distinguished from the formation of a 1 nm thick coating on the surface of the fiber.

Real-time and high-sensitivity monitoring of heavy metal ions in solution is of great significance in environmental monitoring. Traditional electrochemical methods suffer from electrochemical noise and environmental interferences for heavy metal trace detection. To address these issues, we propose a novel electrochemical surface plasmon resonance (EC-SPR) optical fiber sensor. The sensor comprises a tilted fiber Bragg grating imprinted in a commercial single-mode fiber and coated with a nanoscale gold film for high-efficiency SPR excitation. The gold coated optical fiber serves as working electrode, performing the dual functions of anodic stripping voltammetry and SPR optical sensing. We demonstrate detection of Pb2+ as an example of a typical heavy metal ion. We show a stable and reproducible correlation between the real-time ion deposition-stripping cycles and the optical transmission of the optical fiber, with a limit of detection of 10-10 M and a dynamic range of nearly five orders of magnitude. Moreover, by taking derivative of the SPR amplitude change, we can clearly identify the peak stripping potential of the detected ions and therefore realize specific ion identification. The method proposed is inherently immune to temperature cross-talk because the core mode is temperature-dependent but insensitive to surrounding media. The proposed EC-SPR fiber-optic sensor has the advantages of compact size, flexible shape and remote operation capability, thereby opening the way for other opportunities for electrochemical monitoring in various hard-to-reach locations and remote environments.

Formation of transplantable reproducible hiPSC organoids can be aided with real-time label-free intracellular spectroscopy.

The reduction potential of cytochrome b₅ is modulated ia the formation of a complex with polylysine at the electrode surface (Rivera et al., Biochemistry, 1998, 37, 1485). This modulation is thought to originate from the neutralization of a solvent exposed heme propionate and from dehydration of the complex interface. Although direct evidence demonstrating that neutralization of the charge on the heme propionate contributes to the modulation of the redox potential of cytochrome b₅ has been obtained, evidence demonstrating that water exclusion from the complex interface plays a similar role has not been conclusive. Herein we report the preparation of the V45I/V61I double mutant of rat liver outer mitochondrial membrane (OM) cytochrome b₅. This mutant has been engineered with the aim of restricting water accessibility to the exposed heme edge of cytochrome b₅. The X-ray crystal structure of the V45I/V61I mutant revealed that the side chain of Ile at positions 45 and 61 restricts water accessibility to the interior of the heme cavity and protects a large section of the heme edge from the aqueous environment. Electrochemical studies performed with the V45I/V61I mutant of cytochrome b₅ , and with a derivative in which the heme propionates have been converted into the corresponding dimethyl ester groups, clearly demonstrate that dehydration of the heme edge contributes to the modulation of the reduction potential of cytochrome b₅. In fact, these studies showed that exclusion of water from the complex interface exerts an effect (∽40 mV shift) that is comparable, if not larger, than the one originating from neutralization of the charge on the solvent exposed heme propionate (∽30 mV shift).

Microwave photonic interrogation of a high-speed and high-resolution refractive index (RI) sensor based on a tilted fiber Bragg grating with surface plasmon resonance (TFBG-SPR) is proposed and experimentally demonstrated. Instead of demodulating the wavelength shift or intensity change of a TFBG-SPR spectrum in the optical domain, we convert the TFBG-SPR spectrum to the time domain based on spectral shaping (SS) and wavelength-to-time (WTT) mapping and use a digital signal processor (DSP) to extract the RI information at a high speed and high resolution. In the experiment, when an Au-coated TFBG is immersed in a solution, the TFBG-SPR spectrum will produce a dip. When the RI changes, the location of the dip in the TFBG-SPR spectrum will shift, which is a function of the RI. By passing a broadband frequency-chirped optical pulse generated by a frequency swept laser source to the TFBG-SPR and detecting the optical pulse at the output of the TFBG-SPR at a photodetector (PD), due to SS-WTT mapping, a temporal waveform with its shape identical to the optical spectrum is produced. A DSP is then used to extract the SPR envelope information from the temporal waveform. By monitoring the changes of the SPR envelope, the RI information is interrogated with a high resolution of 1.123 × 10 ^-6 RIU at a high speed over 20 kHz.