Nitrogen vacancy defects in single-particle nanodiamonds sense paramagnetic transition metal spin noise from nanoparticles on a transmission electron microscopy grid.

Spin-active nanomaterials play a vital role in current and upcoming quantum technologies, such as spintronics, data storage and computing. To advance the design and application of these materials, methods to link size, shape, structure, and chemical composition with functional magnetic properties at the nanoscale level are needed. In this work, we combine the power of two local probes, namely, Nitrogen Vacancy (NV) spin-active defects in diamond and an electron beam, within experimental platforms used in electron microscopy. Negatively charged NVs within fluorescent nanodiamond (FND) particles are used to sense the local paramagnetic environment of Rb0.5Co1.3[Fe(CN)6]·3.7H2O nanoparticles (NPs), a Prussian blue analogue (PBA), as a function of FND-PBA distance (order of 10 nm) and local PBA concentration. We demonstrate perturbation of NV spins by proximal electron spins of transition metals within NPs, as detected by changes in the photoluminescence (PL) of NVs. Workflows are reported and demonstrated that employ a Transmission Electron Microscope (TEM) finder grid to spatially correlate functional and structural features of the same unique NP studied using NV sensing, based on a combination of Optically Detected Magnetic Resonance (ODMR) and Magnetic Modulation (MM) of NV PL, within TEM imaging modalities. Significantly, spin-spin dipole interactions were detected between NVs in a single FND and paramagnetic metal centre spin fluctuations in NPs through a carbon film barrier of 13 nm thickness, evidenced by TEM tilt series imaging and Electron Energy-Loss Spectroscopy (EELS), opening new avenues to sense magnetic materials encapsulated in or between thin-layered nanostructures. The measurement strategies reported herein provide a pathway towards solid-state quantitative NV sensing with atomic-scale theoretical spatial resolution, critical to the development of quantum technologies, such as memory storage and molecular switching nanodevices.

Unravelling the resilience of the KGK VI population from the Gumelnița site (Romania) through stable isotopes.

The Gumelnița site belongs to the Kodjadermen-Gumelnița-Karanovo VI (KGK VI) communities (c. 4700-3900 cal BC) and comprises the tell-type settlement and its corresponding cemetery. This paper reconstructs the diet and lifeways of the Chalcolithic people in the northeastern Balkans using archaeological remains found at the Gumelnița site (Romania). A multi-bioarchaeological investigation (archaeobotany, zooarchaeology, anthropology) was conducted on vegetal, animal, and human remains, alongside radiocarbon dating and stable isotope analyses (δ13C, δ15N) of humans (n = 33), mammals (n = 38), reptiles (n = 3), fishes (n = 8), freshwater mussels shells (n = 18), and plants (n = 24). According to the results of δ13C and δ15N values and FRUITS, the inhabitants of Gumelnița had a diet based on crops and using natural resources, such as fish, freshwater molluscs and game. Although domestic fauna was occasionally exploited for meat, it had a role in providing secondary products. Crops were heavily manured, and chaff and other crop waste may have been necessary fodder for cattle and sheep. Dogs and pigs fed on human waste, although the diet of the latter is more similar to that of wild boars. Foxes had a diet close to dogs, which may indicate synanthropic behaviour. Radiocarbon dates were calibrated with the percentage of freshwater resources obtained by FRUITS. As a result, the corrected dates for the freshwater reservoir effect (FRE) have a delay of an average of 147 years. According to our data, this agrarian community developed a subsistence strategy under the pressure of some climatic changes that started after 4300 cal BC, corresponding to KGK VI rapid collapse/decline episode tracked recently (that begins around 4350 cal BC). This matching of our data in the two models (climatic and chrono-demographic) allowed us to capture the economic strategies that led to the resilience of those people more than other contemporary KGK VI communities.

Unexpected morphological diversity in ancient dogs compared to modern relatives.

Dogs are among the most variable species today, but little is known about the morphological variability in the early phases of their history. The Neolithic transition to farming may have resulted in an early morphological diversification as a result of changes in the anthropic environment or intentional selection on specific morphologies. Here, we describe the variability and modularity in mandible form by comparing 525 dog mandibles from European archaeological sites ranging from 8100 to 3000 cal. BC to a reference sample of modern dogs, wolves, and dingoes. We use three-dimensional geometric morphometrics to quantify the form of complete and fragmented mandibles. We demonstrate that an important morphological variability already existed before the Bronze Age in Europe, yet the largest, smallest, most brachycephalic or dolichocephalic extant dogs have no equivalent in the archaeological sample, resulting in a lower variation compared to modern relatives. The covariation between the anterior and posterior parts of the mandible is lower in archaeological dogs, suggesting a low degree of intentional human selection in early periods. The mandible of modern and ancient dogs differs in functionally important areas, possibly reflecting differences in diet, competition, or the implication of ancient dogs in hunting or defence.

A research of service quality perceptions and patient satisfaction: Case study of public hospitals in Romania.

The quality of medical services provided by public hospitals has become a crucial principle in health. Awareness and satisfaction of patients are increasing in pace with technological processes and therapeutic procedures. Therefore, Romania's public hospitals must provide quality to patients and assure medical staff's efficiency and professionalism, a high level of satisfaction, and patient safety. This paper aimed to evaluate patient satisfaction measures used in Romania's Healthcare System. Between January and February 2019, an exploratory study was conducted. Data were collected through face-to-face interviews based on a questionnaire only with patients who used the health system last year. The results showed that only 39.71% of Romanians are satisfied with the quality of medical services, which means that 61.29% of respondents are disappointed by the health system. Because it is free of charge, the public sector is the only option available for a wide range of patients. The study's results may be an essential basis in developing and successfully improving marketing research on the quality of medical services provided through public hospitals especially considering that Romania must improve the health care system perception. Findings suggest that traditional patient satisfaction measures fail, and new ways must be taken into consideration.

Sensor-Fusion for Smartphone Location Tracking Using Hybrid Multimodal Deep Neural Networks.

Many engineered approaches have been proposed over the years for solving the hard problem of performing indoor localization using smartphone sensors. However, specialising these solutions for difficult edge cases remains challenging. Here we propose an end-to-end hybrid multimodal deep neural network localization system, MM-Loc, relying on zero hand-engineered features, but learning automatically from data instead. This is achieved by using modality-specific neural networks to extract preliminary features from each sensing modality, which are then combined by cross-modality neural structures. We show that our choice of modality-specific neural architectures can estimate the location independently. But for better accuracy, a multimodal neural network that fuses the features of early modality-specific representations is a better proposition. Our proposed MM-Loc system is tested on cross-modality samples characterised by different sampling rate and data representation (inertial sensors, magnetic and WiFi signals), outperforming traditional approaches for location estimation. MM-Loc elegantly trains directly from data unlike conventional indoor positioning systems, which rely on human intuition.

Dynamic Quantum Sensing of Paramagnetic Species Using Nitrogen-Vacancy Centers in Diamond.

Naturally occurring paramagnetic species (PS), such as free radicals and paramagnetic metalloproteins, play an essential role in a multitude of critical physiological processes including metabolism, cell signaling, and immune response. These highly dynamic species can also act as intrinsic biomarkers for a variety of disease states, while synthetic paramagnetic probes targeted to specific sites on biomolecules enable the study of functional information such as tissue oxygenation and redox status in living systems. The work presented herein describes a new sensing method that exploits the spin-dependent emission of photoluminescence (PL) from an ensemble of nitrogen-vacancy centers in diamond for rapid, nondestructive detection of PS in living systems. Uniquely this approach involves simple measurement protocols that assess PL contrast with and without the application of microwaves. The method is demonstrated to detect concentrations of paramagnetic salts in solution and the widely used magnetic resonance imaging contrast agent gadobutrol with a limit of detection of less than 10 attomol over a 100 µm × 100 µm field of view. Real-time monitoring of changes in the concentration of paramagnetic salts is demonstrated with image exposure times of 20 ms. Further, dynamic tracking of chemical reactions is demonstrated via the conversion of low-spin cyanide-coordinated Fe3+ to hexaaqua Fe3+ under acidic conditions. Finally, the capability to map paramagnetic species in model cells with subcellular resolution is demonstrated using lipid membranes containing gadolinium-labeled phospholipids under ambient conditions in the order of minutes. Overall, this work introduces a new sensing approach for the realization of fast, sensitive imaging of PS in a widefield format that is readily deployable in biomedical settings. Ultimately, this new approach to nitrogen vacancy-based quantum sensing paves the way toward minimally invasive real-time mapping and observation of free radicals in in vitro cellular environments.

Quantum Sensing in a Physiological-Like Cell Niche Using Fluorescent Nanodiamonds Embedded in Electrospun Polymer Nanofibers.

Fluorescent nanodiamonds (fNDs) containing nitrogen vacancy (NV) centers are promising candidates for quantum sensing in biological environments. This work describes the fabrication and implementation of electrospun poly lactic-co-glycolic acid (PLGA) nanofibers embedded with fNDs for optical quantum sensing in an environment, which recapitulates the nanoscale architecture and topography of the cell niche. A protocol that produces uniformly dispersed fNDs within electrospun nanofibers is demonstrated and the resulting fibers are characterized using fluorescent microscopy and scanning electron microscopy (SEM). Optically detected magnetic resonance (ODMR) and longitudinal spin relaxometry results for fNDs and embedded fNDs are compared. A new approach for fast detection of time varying magnetic fields external to the fND embedded nanofibers is demonstrated. ODMR spectra are successfully acquired from a culture of live differentiated neural stem cells functioning as a connected neural network grown on fND embedded nanofibers. This work advances the current state of the art in quantum sensing by providing a versatile sensing platform that can be tailored to produce physiological-like cell niches to replicate biologically relevant growth environments and fast measurement protocols for the detection of co-ordinated endogenous signals from clinically relevant populations of electrically active neuronal circuits.

Reactivation from the Ni-B state in [NiFe] hydrogenase of Ralstonia eutropha is controlled by reduction of the superoxidised proximal cluster.

The tolerance towards oxic conditions of O2-tolerant [NiFe] hydrogenases has been attributed to an unusual [4Fe-3S] cluster that lies proximal to the [NiFe] active site. Upon exposure to oxygen, this cluster converts to a superoxidised (5+) state, which is believed to secure the formation of the so-called Ni-B state that is rapidly reactivated under reducing conditions. Here, the reductive reactivation of the membrane-bound [NiFe]-hydrogenase (MBH) from Ralstonia eutropha in a native-like lipid membrane was characterised and compared to a variant that instead carries a typical [4Fe-4S] proximal cluster. Reactivation from the Ni-B state was faster in the [4Fe-4S] variant, suggesting that the reactivation rate in MBH is limited by the reduction of the superoxidised [4Fe-3S] cluster. We propose that the [4Fe-3S] cluster plays a major role in protecting MBH by blocking the reversal of electron transfer to the [NiFe] active site, which would produce damaging radical oxygen species.

A Decaheme Cytochrome as a Molecular Electron Conduit in Dye-Sensitized Photoanodes.

In nature, charge recombination in light-harvesting reaction centers is minimized by efficient charge separation. Here, it is aimed to mimic this by coupling dye-sensitized TiO2 nanocrystals to a decaheme protein, MtrC from Shewanella oneidensis MR-1, where the 10 hemes of MtrC form a ≈7-nm-long molecular wire between the TiO2 and the underlying electrode. The system is assembled by forming a densely packed MtrC film on an ultra-flat gold electrode, followed by the adsorption of approximately 7 nm TiO2 nanocrystals that are modified with a phosphonated bipyridine Ru(II) dye (RuP). The step-by-step construction of the MtrC/TiO2 system is monitored with (photo)electrochemistry, quartz-crystal microbalance with dissipation (QCM-D), and atomic force microscopy (AFM). Photocurrents are dependent on the redox state of the MtrC, confirming that electrons are transferred from the TiO2 nanocrystals to the surface via the MtrC conduit. In other words, in these TiO2/MtrC hybrid photodiodes, MtrC traps the conduction-band electrons from TiO2 before transferring them to the electrode, creating a photobioelectrochemical system in which a redox protein is used to mimic the efficient charge separation found in biological photosystems.

Enhanced oxygen-tolerance of the full heterotrimeric membrane-bound [NiFe]-hydrogenase of Ralstonia eutropha.

Hydrogenases are oxygen-sensitive enzymes that catalyze the conversion between protons and hydrogen. Water-soluble subcomplexes of membrane-bound [NiFe]-hydrogenases (MBH) have been extensively studied for applications in hydrogen-oxygen fuel cells as they are relatively tolerant to oxygen, although even these catalysts are still inactivated in oxidative conditions. Here, the full heterotrimeric MBH of Ralstonia eutropha, including the membrane-integral cytochrome b subunit, was investigated electrochemically using electrodes modified with planar tethered bilayer lipid membranes (tBLM). Cyclic voltammetry and chronoamperometry experiments show that MBH, in equilibrium with the quinone pool in the tBLM, does not anaerobically inactivate under oxidative redox conditions. In aerobic environments, the MBH is reversibly inactivated by O2, but reactivation was found to be fast even under oxidative redox conditions. This enhanced resistance to inactivation is ascribed to the oligomeric state of MBH in the lipid membrane.