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Abstract From a comparison of the known molecular stoichiometry and x-ray photoemission spectroscopy, it is evident that the Fe(III) spin crossover salt [Fe(qsal)₂Ni(dmit)₂] has a preferential surface termination with the Ni(dmit)₂moiety, where qsal = N(8quinolyl)salicylaldimine, and dmit²⁻= 1,3-dithiol-2-thione-4,5-dithiolato. This preferential surface termination leads to a significant surface to bulk core level shift for the Ni 2p x-ray photoemission core level, not seen in the corresponding Fe 2p core level spectra. A similar surface to bulk core level shift is seen in Pd 3d in the related [Fe(qsal)₂]₂Pd(dmit)₂. Inverse photoemission spectroscopy, compared with the x-ray absorption spectra at the Ni-L3,2 edge provides some indication of the density of states resulting from the dmit²⁻= 1,3-dithiol-2-thione-4,5-dithiolato ligand unoccupied molecular orbitals and thus supports the evidence regarding surface termination in the Ni(dmit)₂moiety. 

Hemoglobin (Hb) is a multifaceted protein, classified as a metalloprotein, chromoprotein, and globulin. It incorporates iron, which plays a crucial role in transporting oxygen within red blood cells. Hb functions by carrying oxygen from the respiratory organs to diverse tissues in the body, where it releases oxygen to fuel aerobic respiration, thus supporting the organism's metabolic processes. Hb can exist in several forms, primarily distinguished by the oxidation state of the iron in the heme group, including methemoglobin (MetHb). Measuring the concentration of MetHb is crucial because it cannot transport oxygen; hence, higher concentrations of MetHb in the blood causes methemoglobinemia. Here, we use optically detected magnetic relaxometry of paramagnetic iron spins in MetHb drop-cast onto a nanostructured diamond doped with shallow high-density nitrogen-vacancy (NV) spin qubits. We vary the concentration of MetHb in the range of 6 × 106–1.8 × 107 adsorbed Fe+3 spins per micrometer squared and observe an increase in the NV relaxation rate Γ1 (=1/T1, where T1 is the NV spin lattice relaxation time) up to 2 × 103 s−1. NV magnetic relaxometry of MetHb in phosphate-buffered saline solution shows a similar effect with an increase in Γ1 to 6.7 × 103 s−1 upon increasing the MetHb concentration to 100 μM. The increase in NV Γ1 is explained by the increased spin noise coming from the Fe+3 spins present in MetHb proteins. This study presents an additional usage of NV quantum sensors to detect paramagnetic centers of biomolecules at volumes below 100 picoliter. 

Abstract In this study, the structure and transport properties of two polymorphs, nanoparticles and nanorods, of the iron(II) triazole [Fe(Htrz)₂(trz)](BF₄) spin crossover complex were compared. Conductive atomic force microscopy was used to map the electrical conductivity of individual nanoparticles and nanorods. The [Fe(Htrz)₂(trz)](BF₄) nanorods showed significantly higher conductivity compared to nanoparticles. This difference in electrical conductivity is partially associated to the different Fe–N bond lengths in each of the polymorphs, with an inverse relationship between Fe–N bond length and conductivity. Transport measurements were done on the nanorods for both high spin (at 380 K) and low spin (at 320 K) states under dark and illuminated conditions. The conductance is highest for the low spin state under dark conditions. In illumination, the conductance change is much diminished. 

The spin crossover complex Fe(phen)2(NCS)2 and its composite, Fe(phen)2(NCS)2, combined with the conducting polymer polyaniline (PANI) plus varying concentrations of iron magnetite (Fe3O4) nanoparticles were studied. A cooperative effect is evident from the hysteresis width in the plot of magnetic susceptibility multiplied by temperature versus temperature (χmT versus T) for Fe(phen)2(NCS)2 with PANI plus varying concentrations of Fe3O4 nanoparticles. The hysteresis width in the composites vary no more than 2 K with respect to the pristine Fe(phen)2(NCS)2 spin crossover crystallites despite the fact that there exists a high degree of miscibility of the Fe(phen)2(NCS)2 spin crossover complex with the PANI. The Fe3O4 nanoparticles in the Fe(phen)2(NCS)2 plus PANI composite tend to agglomerate at higher concentrations regardless of the spin state of Fe(phen)2(NCS)2. Of note is that the Fe3O4 nanoparticles are shown to be antiferromagnetically coupled with the Fe(phen)2(NCS)2 when Fe(phen)2(NCS)2 is in the high spin state. 

Abstract In an effort to reconcile the various interpretations for the cation components of the 2p_3/2observed in x-ray photoelectron spectroscopy (XPS) of several spinel oxide materials, the XPS spectra of both spinel alloy nanoparticles and crystalline thin films are compared. We observed that different components of the 2p_3/2core level XPS spectra, of these inverse spinel thin films, are distinctly surface and bulk weighted, indicating surface-to-bulk core level shifts in the binding energies. Surface-to-bulk core level shifts in binding energies of Ni and Fe 2p_3/2core levels of NiFe₂O₄thin film are observed in angle-resolved XPS. The ratio between surface-weighted components and bulk-weighted components of the Ni and Fe core levels shows appreciable dependency on photoemission angle, with respect to surface normal. XPS showed that the ferrite nanoparticles Ni_xCo_1−xFe₂O₄(x= 0.2, 0.5, 0.8, 1) resemble the surface of the NiFe₂O₄thin film. Surface-to-bulk core level shifts are also observed in CoFe₂O₄and NiCo₂O₄thin films but not as significantly as in NiFe₂O₄thin film. Estimates of surface stoichiometry of some spinel oxide nanoparticles and thin films suggested that the apportionment between cationic species present could be farther from expectations for thin films as compared to what is seen with nanoparticles. 

Rapid and ultrasensitive point-of-care RNA detection plays a critical role in the diagnosis and management of various infectious diseases. The gold-standard detection method of reverse transcription-quantitative polymerase chain reaction (RT-qPCR) is ultrasensitive and accurate yet limited by the lengthy turnaround time (1-2 days). On the other hand, antigen test offers rapid at-home detection (15-20 min) but suffers from low sensitivity and high false-negative rates. An ideal point-of-care diagnostic device would combine the merits of PCR-level sensitivity and rapid sample-to-result workflow comparable to antigen testing. However, the existing RNA detection platform typically possesses superior sensitivity or rapid sample-to-result time, but not both. This paper reports a point-of-care microfluidic device that offers ultrasensitive yet rapid detection of viral RNA from clinical samples. The device consists of a microfluidic chip for precisely manipulating small volumes of samples, a miniaturized heater for viral lysis and ribonuclease (RNase) inactivation, a CRISPR Cas13a- electrochemical sensor for target preamplification-free and ultrasensitive RNA detection, and a smartphone-compatible potentiostat for data acquisition. As demonstrations, the devices achieve the detection of heat-inactivated SARS-CoV-2 samples with a limit of detection (LOD) down to 10 aM within 25 minutes, which is comparable to the sensitivity of RT-PCR and rapidness of antigen test. The platform also successfully distinguishes all nine positive unprocessed clinical SARS-CoV-2 nasopharyngeal swab samples from four negative samples within 25 minutes of sample-to-result time. Together, this device provides a point-of-care solution that can be deployed in diverse settings beyond laboratory environments for rapid and accurate detection of RNA from clinical samples. The device can potentially be expandable to detect other viral targets, such as human immunodeficiency virus (HIV) self-testing and Zika virus, where rapid and ultrasensitive point-of-care detection is required. 

The coordination chemistry of uranyl ions with surface immobilized peptides was studied using X-ray photoemission spectroscopy (XPS). All the peptides in the study were modified using a six-carbon alkanethiol as a linker on a gold substrate with methylene blue as the redox label. The X-ray photoemission spectra reveal that each modified peptide interacts differently with the uranyl ion. For all the modified peptides, the XPS spectra were taken in both the absence and presence of the uranium, and their comparison reveals that the interaction depends on the chemical group present in the peptides. The XPS results show that, among all the modified peptides in the current study, the (arginine)9 (R9) modified peptide showed the largest response to uranium. In the order of response to uranium, the second largest response was shown by the modified (arginine)6 (R6) peptide followed by the modified (lysine)6 (K6) peptide. Other modified peptides, (alanine)6 (A6), (glutamic acid)6 (E6) and (serine)6 (S6), did not show any response to uranium. 

Abstract Adding Fe₃O₄nanoparticles to composites of [Fe(Htrz)₂(trz)](BF₄) spin-crossover polymer and polyaniline (PANI) drives a phase separation of both and restores the molecular structure and cooperative effects of the spin-crossover polymer without compromising the increased conductivity gained through the addition of PANI. We observe an increased on-off ratio for the DC conductivity owing to an enlarged off state resistivity and a 20 times larger AC conductivity of the on state compared with DC values. The Fe₃O₄nanoparticles, primarily confined to the [Fe(Htrz)₂(trz)](BF₄) phase, are ferromagnetically coupled to the local moment of the spin-crossover molecule suggesting the existence of an exchange interaction between both components.