We demonstrate electrochemical control of the nitrogenase MoFe protein, in the absence of Fe protein or ATP, using europium(III/II) polyaminocarboxylate complexes as electron transfer mediators. This allows the potential dependence of proton reduction and inhibitor (CO) binding to the active site FeMo-cofactor to be established. Reduction of protons to H₂ is catalyzed by the wild type MoFe protein and β-98^Tyr→His and β-99^Phe→His variants of the MoFe protein at potentials more negative than −800 mV (vs. SHE), with greater electrocatalytic proton reduction rates observed for the variants compared to the wild type protein. Electrocatalytic proton reduction is strongly attenuated by carbon monoxide (CO), and the potential-dependence of CO binding to the FeMo-cofactor is determined by in situ infrared (IR) spectroelectrochemistry. The vibrational wavenumbers for CO coordinated to the FeMo-cofactor are consistent with earlier IR studies on the MoFe protein with Fe protein/ATP as reductant showing that electrochemically generated states of the protein are closely related to states generated with the native Fe protein as electron donor.

Silicon photonic devices with either silicon or silicon nitride waveguides have increasingly been used in many applications besides communications, especially as sensors in label-free biosensing, where guided light signals are affected by biorecognition molecules immobilized on the surface. The coating of protein (i.e., bioreceptors) by biochemical process on the waveguide surface is a crucial step in creating a functionalized device that can be used for biosensing. As a conventional method that uses 3-aminopropryltriethoxysilane (APTES) and glutaraldehyde (GA), the APTES-GA method has the limitation of using a GA crosslink, of which the two functional groups can bind to nonspecific proteins, causing irregular binding. In this study, we proposed a new coating technique to avoid such problem by applying APTES silanization with 1-ethyl-3-(3-dimethyl aminopropyl)-carbodiimide (EDC)-N-hydroxysuccinimide (NHS) protein crosslink, denoted by the APTES-(EDC/NHS) method. The EDC/NHS reaction was shown to be able to immobilize protein in ordered orientation due to consistent arrangement between a carboxylic group of protein molecules and an amine group of covalent-linked APTES on surface. By applying APTES silanization, we circumvented the use of hazardous cleaning agent in the conventional EDC/NHS technique. Several surface characterization techniques were carried out to assess and compare the two biocoating techniques, including scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), spectroscopic ellipsometry (SE), and atomic force microscopy (AFM). On silicon, the results of antihuman TNF-alpha antibody coating showed that the proposed APTES-(EDC/NHS) technique has better repeatability in terms of less roughness of the coated protein at 1.5 nm compared with 6.3 nm, due to the ordered arrangement of coated antibody molecules. On a silicon nitride waveguide device, the proposed APTES-(EDC/NHS) technique exhibits dense antibody immobilization on a waveguide in SEM images due to stable amide bond formation via EDC/NHS crosslink mechanism. The specificity of the immobilized antibodies was confirmed by enzyme-linked immunosorbent assays (ELISA), with an average optical density at 450 nm of 0.175 ± 0.01 compared with 0.064 ± 0.009 of negative control. The proposed technique also reduced the overall process time since proteins are crosslinked to the silanized waveguide surface in a single step.

The COVID-19 pandemic has forced analytical chemistry educators in Thailand to change methods of teaching and learning to new normal ones. Higher education has faced additional challenges because of a lack of hands-on experiments and an increasing number of students in foundation chemistry courses being hindered from practicing skills. This work aimed to develop a Lab-at-Home (LAH) for new normal, analytical chemistry experimentation. The LAH implemented a hands-on green chemistry experiment, i.e., colorimetric determination of iron using non-hazardous reagents (supporting Sustainable Development Goal (SDG) 12-responsible consumption and production). The LAH was sent to students at their location before the synchronous class, where the instructors were prompt to supervise. Thus, this supports SDG4-quality education and SDG10-reduced inequalities. The learning outcome achievements, i.e., the analytical characteristics and colorimetry principles comprehension, as well as the ability to perform data analysis, were evaluated by a quiz and laboratory report. LAH satisfaction was assessed by questionnaire and focus group discussion. The learning outcomes were successfully achieved, although students who performed the experiment individually received higher scores than those who did in groups. Students were very satisfied with the LAH as a tool for new normal experimentation, yet some students faced a poor Internet connection during the synchronous online class.

To minimize chemical waste and protect the environment, our team has used green analysis with natural reagents. In this work, we designed a natural-reagent assay kit for iron determination and implemented it in chemistry education in Thailand. The iron assay method was adapted from Thai local wisdom of testing water quality using guava leaves. The guava leaf powder served as a natural reagent in the assay. The kit included equipment, standard and buffer solutions and a manual. A smart device with a built-in camera was used as a detector. Educators in six universities in Thailand implemented the kit in laboratories with modifications depending on their learning outcomes. The kit implementation was evaluated using a survey with questions in four aspects: usability, learning achievement, green chemistry and portability. The high average scores for all questions (> 4.00 of 5.00 points), with the average overall score of 4.53 ± 0.60, indicated satisfaction regarding in all aspects. Using a locally available bio-resource as a natural reagent for green analysis in chemistry education supported sustainable education in Thailand, in terms of quality education (SDG 4) and reduced inequalities (SDG 10) and environmental sustainability (SDG 6—Clean water and sanitation, 12—Responsible consumption and production and 14—Life be-low water).