Detection of human serum albumin using a rare-earth nanosheet fluorescent probe based on intensity and lifetime signals.

Human serum albumin (HSA) is an important biomarker for early disease diagnosis. Therefore, the detection of HSA in biological samples is important. In this study, for the sensitive detection of HSA, a fluorescent probe based on Eu(III)-doped yttrium hydroxide nanosheets was designed and sensitized by α-thiophenformyl acetone trifluoride as an antenna. The morphology and structure of the as-prepared nanosheet fluorescent probe were studied by transmission electron microscopy and atomic force microscopy. A detailed investigation of the fluorescence properties of the as-obtained nanosheet probe revealed that the Eu(III) emission intensity was linearly and selectively enhanced by the consecutive addition of HSA. Furthermore, the lifetime signal of this probe was enhanced with increasing concentration. The sensitivity of the nanosheet probe to HSA is discussed based on the results of ultraviolet-visible, fluorescence, and infrared spectral analyses, the findings demonstrate that the nanosheet fluorescent probe we prepared is a highly sensitive and selective tool for detecting HSA concentration with a high intensity and a large lifetime change.

Preparation and characterization of two novel osteoinductive fishbone-derived biphasic calcium phosphate bone graft substitutes.

Many studies have reported on the conversion of natural resources into xenografts with hydroxyapatite (HA) as major component, but the extraction of biphasic calcium phosphate (HA/ß-TCP) from animal bones and transformation into bone graft substitutes are rarely reported. In this research, two kinds of fish bones were made into granular porous biphasic calcium phosphate bone graft substitutes with particle sizes between 500 to 1000 µm through a series of preparation procedures (Salmo salar calcined at 900°C named Sa900 and Anoplopoma fimbria calcined at 800°C named An800). The chemical composition was characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The morphology and porous structure of the scaffolds were comparatively analyzed by scanning electron microscopy (SEM) and mercury porosimeter. The specific surface area of materials was measured by the nitrogen adsorption technique based on BET theory. Cytotoxicity and ectopic osteogenesis were also carried out to investigate the biocompatibility and osteoinductive potential of these materials. The results showed that both fishbone-derived scaffolds were composed of HA and ß-TCP with different proportions, and numerous interconnected pores with different sizes were observed at the surface of materials. An800 had higher total porosity reaching 74.8% with higher interconnectivity and micropores mostly distributed at 0.27 µm and 0.12 µm, while Sa900 had a higher specific surface area and higher intraparticle porosity with nanopores mostly distributed at 0.07 µm. CCK-8 assays and Live/dead staining demonstrated excellent biocompatibility. Material-induced osteoid formation were observed on the interface of both internal pores and periphery of materials after implantation in muscle pouch of Wistar rats for 8 weeks which indicated some extent of osteoinductive potential of materials. The possible mechanism of material-induced osteogenesis and the effects of chemical composition, surface topography, and spatial structure on osteogenesis were also discussed in this paper.

Gd/Y Hydroxide Nanosheets as Highly Efficient T1/T2 MRI Contrast Agents.

To develop highly efficient T1/T2 magnetic resonance imaging (MRI) contrast agents (CAs), Gd/Y hydroxide nanosheets were synthesized by a simple exfoliation method from layer compounds using sodium polyacrylate (PAA) as a dispersant and stabilizer. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) results revealed the excellent performance of monolayer nanosheets with thicknesses of up to 1.5 nm. The MRI results of the T1 and T2 relaxation times showed that all of the Gd/Y hydroxide nanosheets have high longitudinal and transverse relaxivities (r1 and r2). In particular, the 10% Gd-LRH nanosheets exhibited excellent MRI performance (r1 = 103 mM-1 s-1, r2 = 372 mM-1 s-1), which is rarely reported. Based on the relationship between the structure of 10% Gd-LRH nanosheets and their MRI performances, and the highly efficient MRI of spaced Gd atoms in the nanosheets, a special model to explain the outstanding MRI performance of the 10% Gd-LRH nanosheets is suggested. The cytotoxicity assessment of the 10% Gd-LRH nanosheets, evaluated by CCK-8 assays on HeLa cells, indicated no significant cytotoxicity. This study presents a significant advancement in 2D nanomaterial MRI CA research, with Gd-doped nanosheets positioned as highly efficient T1/T2 MRI CA candidates.

A selective and sensitive fluorescent probe for bilirubin in human serum based on europium(III) post-functionalized Zr(IV)-Based MOFs.

In the present study, a kind of Eu(III) post-functionalized Zr(IV)-based metal-organic framework (UiO-66(COOH)2, Zr-MOF: Eu3+) was synthesized and utilized as an independently luminescent probe for sensing bilirubin (BR) in human serum, a biomarker of jaundice hepatitis. It can be served as a turn-off fluorescent switch for BR because its red emission from Eu3+ can be easily quenched by BR through a fluorescent resonant energy transfer (FRET) process between BR and its ligands, and as a result, BR is recognized successfully. Particularly, Zr-MOF: Eu3+ has shown many appealing properties, such as high sensitivity, quick response (less than 1 min), broad response window (0-15 µM), and excellent selectivity. Most importantly, a kind of portable test paper based on Zr-MOF: Eu3+ probe has been developed for directly assessing the level of BR in real human serum and further diagnosing bilirubin-related diseases via visually observing the luminescent color variation.

Tb(iii)-doped nanosheets as a fluorescent probe for the detection of dipicolinic acid.

A new fluorescent probe based on terbium(iii)-doped nanosheets was designed for detecting low-levels of dipicolinic acid (DPA), a biomarker of bacterial spores. The ability to detect ultra-low concentrations of DPA is therefore of great significance. First, Tb(iii)-doped ytterbium hydroxide nanosheets were obtained by mechanical exfoliation from layered rare-earth hydroxide (LRH) materials. The morphology of the as-synthesized nanosheets was studied by transmission electron microscopy and atomic force microscopy. The Tb(iii)-doped nanosheets are demonstrated to be highly sensitive to DPA, which remarkably enhances Tb(iii) luminescence intensities at a wavelength of 544 nm. Furthermore, Tb(iii) emission increases linearly with DPA concentration. Selectivity studies were conducted by adding different competing aromatic ligands to the sensing solution; however, their fluorescence responses were observed to be negligibly small in comparison with that of DPA. Our findings provide a basis for the application of Tb(iii)-doped nanosheets for accurate, sensitive, and selective monitoring of DPA as a biomarker of anthrax.

Selective non-enzymatic total bilirubin detection in serum using europium complexes with different ß-diketone-derived ligands as luminescence probes.

Three europium(III) complexes, Eu(ectfd)3 (Hectfd = 1-(9-ethyl-9H-carbazol-7-yl)-4,4,4-trifluorobutane-1,3-dione), Eu(tta)3 (Htta = 4,4,4-trifluoro-1-(thiophen-2-yl)-butane-1,3-dione), and Eu(dbt)3 (Hdbt = 2-(4',4',4'-trifluoro-1',3'-dioxobutyl)dibenzothiophene), were synthesized and employed to detect total bilirubin (BR) in blood-serum samples. UV-visible absorption and fluorescence (FL) spectroscopies were used to evaluate the selectivity of each europium (III) fluorescence probe to BR, which was shown to remarkably reduce the luminescence intensities of the europium(III) complexes at a wavelength of 612 nm. The luminescence intensity of each complex is linearly related to BR concentration. Eu(tta)3 was shown to be the more-appropriate fluorescence probe for the sensitive and reliable detection of total BR in blood serum samples than either Eu(ectfd)3 or Eu(dbt)3. This observation can be ascribed to special σ-hole bonding between Htta and BR. In addition, the optimal pH test conditions for the detection of BR in human serum by the Eu(tta)3 probe were determined. Sensitivity was shown to be dramatically affected by the pH of the medium. The experimental results reveal that pH 7.5 is optimal for this probe, which coincides with the pH of human serum. Furthermore, BR detection using the Eu(tta)3 luminescence probe is simple, practical, and relatively free of interference from coexisting substances; it has a minimum detection limit (DL) of 68 nM and is a potential candidate for the routine assessment of total BR in serum samples. Graphical Abstract ᅟ.

Development of a New Robotic Ankle Rehabilitation Platform for Hemiplegic Patients after Stroke.

A large amount of hemiplegic survivors are suffering from motor impairment. Ankle rehabilitation exercises act an important role in recovering patients' walking ability after stroke. Currently, patients mainly perform ankle exercise to reobtain range of motion (ROM) and strength of the ankle joint under a therapist's assistance by manual operation. However, therapists suffer from high work intensity, and most of the existed rehabilitation devices focus on ankle functional training and ignore the importance of neurological rehabilitation in the early hemiplegic stage. In this paper, a new robotic ankle rehabilitation platform (RARP) is proposed to assist patients in executing ankle exercise. The robotic platform consists of two three-DOF symmetric layer-stacking mechanisms, which can execute ankle internal/external rotation, dorsiflexion/plantarflexion, and inversion/eversion exercise while the rotation center of the distal zone of the robotic platform always coincides with patients' ankle pivot center. Three exercise modes including constant-speed exercise, constant torque-impedance exercise, and awareness exercise are developed to execute ankle training corresponding to different rehabilitation stages. Experiments corresponding to these three ankle exercise modes are performed, the result demonstrated that the RARP is capable of executing ankle rehabilitation, and the novel awareness exercise mode motivates patients to proactively participate in ankle training.

Sensitive detection of free bilirubin in blood serum using ß-diketone modified europium-doped yttrium oxide nanosheets as a luminescent sensor.

Free bilirubin, when present in excess in the human body, can cause a multitude of diseases and disorders and even be fatal; hence, detecting it is of paramount importance. Herein, we report a luminescence quenching-based non-enzymatic method for the convenient, reliable, and rapid detection of free bilirubin in blood serum samples using sensing films (nanosheets/PS, nanosheets-tta/PS, and nanosheets-dbt/PS) as luminescent sensors. The luminescence intensity of the sensing films is linearly related to the free bilirubin concentration. Nanosheets-tta/PS demonstrated excellent sensing properties for the sensitive and reliable detection of free bilirubin in the range of 0.0-60.0 µM with a correlation coefficient of 0.9915, as compared to nanosheets/PS or nanosheets-dbt/PS. The limit of detection for the determination of free bilirubin was 41 nM. This method can be used to design a sensor-based test spot as a medical detection device for the visual detection of free bilirubin.

Controlled synthesis of ZnS quantum dots and ZnS quantum flakes with graphene as a template.

Novel ZnS quantum dots (QDs) and ZnS quantum flakes (QFs) were successfully prepared with graphene nanosheets (GNs) as a special template, and two unique heterostructures of ZnS/GNs were also obtained. Due to the structure-directing template effect of GNs, the as-synthesized ZnS with different morphologies, dots or flakes, were uniformly distributed on the surface of GNs by controlling nucleation and growth. The two different heterostructures of ZnS/GNs exhibited obvious photovoltaic response, and ZnS/GN QFs-on-sheet heterostructures show higher photovoltage than that of ZnS/GN QDs-on-sheet.

Luminescence properties of cubic HfO2-Sc2O3:Eu3+ nano-powders.

The cubic nano-structured HfO2-Sc2O3:Eu3+ were successfully synthesized via a combustion process. Phase evolution of the synthesized powders was determined by X-ray diffraction measurements. Pure cubic phase of HfO2-Sc2O3 solid solution was obtained after being calcined at 800 degrees C for 2 h.The particle size and morphology were analyzed by TEM. The luminescence properties were also investigated. Photoluminescence spectra of Eu3+ doped HfO2-Sc2O3 nano-powders showed red emission at 613 nm which corresponds to the 5D0-7F2 transition of Eu3+ ion.