Sensitive detection of cyanide using bovine serum albumin-stabilized cerium/gold nanoclusters.

A simple, sensitive, and selective fluorescence assay for the detection of CN(-) has been demonstrated using bovine serum albumin-stabilized cerium/gold nanoclusters (BSA-Ce/Au NCs). When excited at 325 nm, BSA-Ce/Au NCs have two fluorescence bands centered at 410 and 658 nm, which are assigned to BSA-Ce/Au complexes and Au NCs, respectively. Each BSA-Ce/Au NC contains 22 Au atoms and 8 Ce ions. Through etching of the Au core in BSA-Ce/Au NCs by CN(-), the fluorescence at 658 nm is quenched, while that at 410 nm enhances during the formation of complexes among BSA, Ce(4+), and [Au(CN)2](-). The circular dichroism spectra reveal that relative to BSA-Au NCs, BSA-Ce/Au NCs have looser structures of the BSA templates. As a result, it is easier for CN(-) to access the Au cores in BSA-Ce/Au NCs, allowing faster (within 15 min) etching of the Au cores by CN(-). At pH 12.0, this assay allows the detection of CN(-) down to 50 nM, with linearity over 0.1-15 µM. This assay has been applied to the determination of the concentrations of CN(-) in spiked drinking water and pond water samples.

MCQ-construction improves Quality of Essay Assessment among undergraduate dental students.

A well-constructed essay is indicative of deep strategic understanding and is considered a valid assessment tool in many dental schools. It has been suggested that constructing MCQs could be an effective learning tool for students while at the same time contribute towards a pool of well-constructed MCQs that could stand up to scrutiny at high-stakes examinations. This study aimed to compare the quality of essays written by students trained and untrained in MCQ construction. The null hypothesis was that construction of MCQs did not result in higher grades achieved in "closed-book" time-limited assessment conditions. A Test cohort (n=48) of undergraduate dental students were taught and constructed MCQs during their preclinical prosthodontics course. The Control cohort (n=48) consisted of students who underwent the same course 1 year prior. The same question was administered to both cohorts without the students׳ knowledge. Answers were de-identified and randomized for grading by a blinded expert prosthodontic examiner not involved in the teaching of the students. Based on a passing grade of 50 and a maximum grade of 100, the Test cohort exhibited significantly improved essay quality, scoring a mean grade of 73.0±8.0, compared to a mean grade of 63.6±11.8 achieved by the control cohort (p<0.001). The null hypothesis was rejected. Under the conditions of this double-blind study, MCQ-construction resulted in better essays written by students under examination conditions.

Selective Colorimetric Detection of Hydrogen Sulfide Based on Primary Amine-Active Ester Cross-Linking of Gold Nanoparticles.

Hydrogen sulfide (H2S) is a highly toxic environmental pollutant and also an important gaseous transmitter. Therefore, selective detection of H2S is very important, and visual detection of it with the naked eye is preferred in practical applications. In this study, thiolated azido derivates and active esters functionalized gold nanoparticles (AE-AuNPs)-based nanosensors have been successfully prepared for H2S perception. The sensing principle consists of two steps: first, H2S reduces the azide group to a primary amine; second, a cross-linking reaction between the primary amine and active ester induces the aggregation of AuNPs. The AE-AuNPs-based nanosensors show high selectivity toward H2S over other anions and thiols due to the specific azide-H2S chemistry. Under optimal conditions, 0.2 µM H2S is detectable using a UV-vis spectrophotometer, and 4 µM H2S can be easily detected by the naked eye. In addition, the practical application of the designed nanosensors was evaluated with lake water samples.

Anodic composite deposition of RuO2/reduced graphene oxide/carbon nanotube for advanced supercapacitors.

Anodic composite deposition is demonstrated to be a unique method for fabricating a ternary ruthenium dioxide/reduced graphene oxide/carbon nanotube (RuO2 xH2O/rGO/CNT, denoted as RGC) nanocomposite onto Ti as an advanced electrode material for supercapacitors. The rGO/CNT composite in RGCs acts as a conductive backbone to facilitate the electron transport between current collector and RuO2 xH2O nanoparticles (NPs), revealed by the high total specific capacitance (C(S,T) = 808 F g(-1)) of RGC without annealing. The contact resistance among RuO2 xH2O NPs is improved by low-temperature annealing at 150 °C (RGC-150), which renders slight sintering and enhances the specific capacitance of RuO2 xH2O to achieve 1200 F g(-1). The desirable nanocomposite microstructure of RGC-150 builds up the smooth pathways of both protons and electrons to access the active oxy-ruthenium species. This nanocomposite exhibits an extremely high C(S,T) of 973 F g(-1) at 25 mV s(-1) (much higher than 435 F g(-1) of an annealed RuO2 xH2O deposit) and good capacitance retention (60.5% with scan rate varying from 5 to 500 mV s(-1)), revealing an advanced electrode material for high-performance supercapacitors.

An Arduino-Based Resonant Cradle Design with Infant Cries Recognition.

This paper proposes a resonant electric cradle design with infant cries recognition, employing an Arduino UNO as the core processor. For most commercially available electric cradles, the drive motor is closely combined with the bearing on the top, resulting in a lot of energy consumption. In this proposal, a ball bearing design was adopted and the driving force is under the cradle to increase the distance from the object to fulcrum and torque. The sensors are designed to detect the oscillation state, and then the force is driven at the critical time to achieve the maximum output response while saving energy according to the principle of resonance. As for the driving forces, the winding power and motors are carefully placed under the cradle. The sensors, including the three-axis accelerometer and infrared sensor, are tested and applied under swinging amplitude control. In addition, infant cry recognition technology was incorporated in the design to further develop its functionality, which is a rare feature in this kind of hardware. The proposed nonlinear operator of fundamental frequency (f0) analysis is able to identify different types of infant cries. In conclusion, this paper proposes an energy-saving electric cradle with infant cries recognition and the experimental results demonstrate the effectiveness of this approach.

Sensitive detection of platelet-derived growth factor through surface-enhanced Raman scattering.

A surface-enhanced Raman scattering (SERS) assay using two different nanomaterials has been demonstrated for highly sensitive and selective detection of platelet-derived growth factor (PDGF). Gold nanoparticles (Au NPs; 13 nm) are conjugated with aptamer (Apt) and 4-mercaptobenzoic acid (MBA) as the recognition element and reporter, respectively, while Au pearl necklace nanomaterials (Au PNNs) are used for generating reproducible and enhanced SERS signal of 4-MBA. The Apt/MBA-Au NPs bind PDGF through a specific interaction between Apt and PDGF in a fashion of 2:1, leading to concentration of the analyte and removal of the sample matrix. Through electrostatic interaction, the PDGF-Apt/MBA-Au NPs complexes form aggregates with Au PNNs, leading to an enhanced Raman signal of 4-MBA. Au PNNs allow enhancement factors up to 1.3 × 10(7) and relative standard deviations of Raman signals for 4-MBA down to 15% (five measurements). The assay allows detection of PDGF BB down to 0.5 pM, with linearity of the Raman signal of 4-MBA against the concentration of PDGF over 1-50 pM. Having advantages of sensitivity and reproducibility, this assay has been further applied for the determination of the concentration of PDGF in urine samples, showing its great potential for ultrasensitive analysis of target proteins in biological samples.

Detection of mercury(II) ions using colorimetric gold nanoparticles on paper-based analytical devices.

An on-field colorimetric sensing strategy employing gold nanoparticles (AuNPs) and a paper-based analytical platform was investigated for mercury ion (Hg(2+)) detection at water sources. By utilizing thymine-Hg(2+)-thymine (T-Hg(2+)-T) coordination chemistry, label-free detection oligonucleotide sequences were attached to unmodified gold nanoparticles to provide rapid mercury ion sensing without complicated and time-consuming thiolated or other costly labeled probe preparation processes. Not only is this strategy's sensing mechanism specific toward Hg(2+), rather than other metal ions, but also the conformational change in the detection oligonucleotide sequences introduces different degrees of AuNP aggregation that causes the color of AuNPs to exhibit a mixture variance. To eliminate the use of sophisticated equipment and minimize the power requirement for data analysis and transmission, the color variance of multiple detection results were transferred and concentrated on cellulose-based paper analytical devices, and the data were subsequently transmitted for the readout and storage of results using cloud computing via a smartphone. As a result, a detection limit of 50 nM for Hg(2+) spiked pond and river water could be achieved. Furthermore, multiple tests could be performed simultaneously with a 40 min turnaround time. These results suggest that the proposed platform possesses the capability for sensitive and high-throughput on-site mercury pollution monitoring in resource-constrained settings.

Multivalent antiviral XTEN-peptide conjugates with long in vivo half-life and enhanced solubility.

XTENs are unstructured, nonrepetitive protein polymers designed to prolong the in vivo half-life of pharmaceuticals by introducing a bulking effect similar to that of poly(ethylene glycol). While XTEN can be expressed as a recombinant fusion protein with bioactive proteins and peptides, therapeutic molecules of interest can also be chemically conjugated to XTEN. Such an approach permits precise control over the positioning, spacing, and valency of bioactive moieties along the length of XTEN. We have demonstrated the attachment of T-20, an anti-retroviral peptide indicated for the treatment of HIV-1 patients with multidrug resistance, to XTEN. By reacting maleimide-functionalized T-20 with cysteine-containing XTENs and varying the number and positioning of cysteines in the XTENs, a library of different peptide-polymer combinations were produced. The T-20-XTEN conjugates were tested using an in vitro antiviral assay and were found to be effective in inhibiting HIV-1 entry and preventing cell death, with the copy number and spacing of the T-20 peptides influencing antiviral activity. The peptide-XTEN conjugates were also discovered to have enhanced solubilities in comparison with the native T-20 peptide. The pharmacokinetic profile of the most active T-20-XTEN conjugate was measured in rats, and it was found to exhibit an elimination half-life of 55.7 ± 17.7 h, almost 20 times longer than the reported half-life for T-20 dosed in rats. As the conjugation of T-20 to XTEN greatly improved the in vivo half-life and solubility of the peptide, the XTEN platform has been demonstrated to be a versatile tool for improving the properties of drugs and enabling the development of a class of next-generation therapeutics.

Gold nanosponges: green synthesis, characterization, and cytotoxicity.

A simply approach for the synthesis of Au nanostructures in tea infusions at room temperature is developed. By controlling the concentrations of tea infusions, Au nanostructures in various shapes and sizes have been prepared. From 1 x (original concentration) and 0.01 x (100 times diluted) tea infusions, 52.2 +/- 8.1 nm Au nanosponges (T-Au NSs) and 23 +/- 2 nm spherical Au nanoparticles (T-Au NPs) were prepared. The phytochemicals present on the surface of T-Au NSs were proved by surface-assisted laser desorption/ionization mass spectrometry, Fourier transform infrared spectrometry and capillary electrophoresis coupled with UV detection. The energy-dispersive X-ray spectroscopy and powder X-ray diffraction data reveal pure crystalline structures of the T-Au NSs. The dark field scattering images observe that the T-Au NSs have significant affinity toward HeLa cells. The cytotoxicity of T-Au NSs on HeLa cells is through caspase-3 activation.

Functionalized polymer spheres via one-step photoinduced synthesis for antimicrobial activity and gene delivery.

Despite the fact that polystyrene (PS) spheres have been developed as polymeric carriers or matrices for various biomedical applications, the synthesis of PS spheres is time-consuming. This work describes the fabrication of a uniform PS sphere, coated with silver nanoparticles (Ag-PS), by simultaneous photoinduced polymerization and reduction fabricated using x-rays in aqueous solution without any initiator. The solution contains only styrene, silver ions (Ag(+)), and poly(vinyl pyrrolidone) (PVP) as a stabilizer. The proposed mechanism of the formation of the Ag-PS nanocomposite spheres involves the generation of radicals in the aqueous solution to induce PS polymerization and the reduction of Ag. The distribution of the sizes of the core PS spheres in the Ag-PS nanocomposite spheres was systematically examined as a function of irradiation time, concentration of styrene, and amount of PVP. Ag-PS nanocomposite spheres exhibit antimicrobial activity against bacteria (Escherichia coli and Staphylococcus aureus). Additionally, the cationic (vinylbenzyl)trimethylammonium (TMA) monomer was photopolymerized to form positively charged TMA-PS spheres as gene carriers with uniquely low cytotoxicity. Given these design advantages, the method proposed herein is simpler than typical approaches for synthesizing PS spheres with functionalized groups and PS spheres coated with Ag nanoparticles.

Synthesis of Ring-Locked Tetracyclic Dithienocyclopentapyrans and Dibenzocyclopentapyran via 1,5-Hydride Shift and Copper-Catalyzed C-O Bond Formation for Nonfullerene Acceptors.

We discovered a unique synthetic route to construct 2H-pyran-containing tetracyclic dithienocyclopentapyran (DTCP) and dibenzocyclopentapyran (DBCP) architectures. The synthesis involves an acid-induced dehydration cyclization followed by a [1,5] hydride-shift isomerization to form a cyclopentanone moiety which was converted to the pyran-embedded tetracyclic products by a CuI-catalyzed intramolecular C-O bond formation in good yield. DTCP was used as a building block to prepare an acceptor-donor-acceptor (A-D-A) type n-type material DTCP-BC leading to a solar cell efficiency of 9.32%.

Cell-free synthesis and maturation of [FeFe] hydrogenases.

[FeFe] hydrogenases catalyze the reversible reduction of protons to molecular hydrogen (Adams (1990); Biochim Biophys Acta 1020(2): 115-145) and are of significant interest for the biological production of hydrogen fuel. They are complex proteins with active sites containing iron, sulfur, and carbon monoxide and cyanide ligands (Peters et al. (1998); Science 282(5395): 1853-1858). Maturation enzymes for [FeFe] hydrogenases have been identified (Posewitz et al. (2004); J Biol Chem 279(24): 25711-25720), but complete mechanisms have not yet been elucidated. The study of [FeFe] hydrogenases has been impeded by the lack of an easily manipulated expression/activation system capable of producing these complex and extremely oxygen-sensitive enzymes. Here we show the first expression of functional [FeFe] hydrogenases in an Escherichia coli-based cell-free transcription/translation system. We have produced and matured both algal and bacterial hydrogenases using E. coli cell extracts containing the HydG, HydE, and HydF proteins from Shewanella oneidensis. The current system produces approximately 22 microg/mL of active protein, constituting approximately 44% of the total protein produced. Active protein yield is greatly enhanced by pre-incubation of the maturation enzyme-containing extract with inorganic iron and sulfur for reconstitution of the [Fe-S] clusters in HydG, HydE, and HydF. The absence of cell walls permits direct addition of cofactors and substrates, enabling rapid production of active protein and providing control over the maturation conditions. These new capabilities will enhance the investigation of complex proteins requiring helper proteins for maturation and move us closer to the development of improved hydrogenases for biological production of hydrogen as a clean, renewable alternative fuel.

Accelerated Arterial Stiffening Change in Early Years of Spinal Cord Injury.

Patients with spinal cord injury (SCI) possess higher arterial stiffness index (SI) than the healthy population. This study aimed to clarify the effect of post-morbid duration on arterial stiffening change among SCI sufferers. Seventy-one SCI patients were recruited. The demographic data including age, gender, level of injury, body mass index, American Spinal Cord Injury Association Impairment Scale, and post-morbid duration were collected. The age was 36.4 ± 11.7 years and the duration was 87.5 ± 106.4 months. SI was assessed with digital volume pulse analysis. Correlation matrix demonstrated that age is the most significant determinant of SI (R = 0.503). The scatter plot of duration versus SI showed that they were correlated significantly, but in a logarithmic rather than linear trend. Partial correlation showed that the natural log of duration (Lnduration) has higher adjusted correlation coefficient (0.357) than duration when the effect of age and other factors were eliminated. Multiple linear regression modeling also exhibited that Lnduration is the only factor that significantly increases the explanation of SI by age. In conclusion, Lnduration is an independent determinant of SI. SCI accelerates vascular aging especially in the early several years. Therefore, there should be emphasis on primary prevention of cardiovascular disorders during early years of SCI.

A propeller-shaped µ4-carbonate hexanuclear dysprosium complex with a high energetic barrier to magnetisation relaxation.

A Dy6 complex composed of two Dy3 triangular units, [Dy6(µ3-OH)(CO3)3(bsc)3(MeOH)14(H2O)](Cl)5·(H2O)·(MeOH)2 (1), was isolated and found to exhibit slow relaxation of the magnetisation under zero applied dc field, resulting in a high energetic barrier to relaxation.

Immobilization of aptamer-modified gold nanoparticles on BiOCl nanosheets: Tunable peroxidase-like activity by protein recognition.

A self-assembled nanocomposite is prepared from an aqueous mixture of aptamer-modified gold nanoparticles (Apt-Au NPs), bismuth ions and chloride ions. The Apt-Au NPs are immobilized on bismuth oxychloride (BiOCl) nanosheets in situ to form Apt-Au NPs/BiOCl nanocomposites. The as-prepared nanocomposites exhibit high peroxidase-like activity for the catalytic conversion of Amplex Red (AR) to fluorescent resorufin in the presence of H2O2. The catalytic activity of Apt-Au NPs/BiOCl nanocomposites is at least 90-fold higher than that of Apt-Au NPs or BiOCl nanosheets, revealing synergistic effects on their activity. The catalytic activity of Apt-Au NPs/BiOCl nanocomposites is suppressed by vascular endothelial growth factor-A165 (VEGF-A165) molecules that specifically interact with the aptamer units (Del-5-1 and v7t-1) on the nanocomposite surface. The AR/H2O2-Apt-Au NPs/BiOCl nanocomposites probe shows high selectivity (>1000-fold over other proteins) and sensitivity (detection limit ~0.5nM) for the detection of VEGF-A165. Furthermore, the probe is employed for the detection of VEGF isoforms and for the study of interactions between VEGF and VEGF receptors. The practicality of this simple, rapid, cost-effective probe is validated by the analysis of VEGF-A165 in cell culture media, showing its great potential for the analysis of VEGF in biological samples.

Comparison of Standing Posture Bioelectrical Impedance Analysis with DXA for Body Composition in a Large, Healthy Chinese Population.

Bioelectrical impedance analysis (BIA) is a common method for assessing body composition in research and clinical trials. BIA is convenient but when compared with other reference methods, the results have been inconclusive. The level of obesity degree in subjects is considered to be an important factor affecting the accuracy of the measurements. A total of 711 participants were recruited in Taiwan and were sub-grouped by gender and levels of adiposity. Regression analysis and Bland-Altman analysis were used to evaluate the agreement of the measured body fat percentage (BF%) between BIA and DXA. The BF% measured by the DXA and BIA methods (Tanita BC-418) were expressed as BF%DXA and BF%BIA8, respectively. A one-way ANOVA was used to test the differences in BF% measurements by gender and levels of adiposity. The estimated BF%BIA8 and BF%DXA in the all subjects, male and female groups were all highly correlated (r = 0.934, 0.901, 0.916, all P< 0.001). The average estimated BF%BIA8 (22.54 ± 9.48%) was significantly lower than the average BF%DXA (26.26 ± 11.18%). The BF%BIA8 was overestimated in the male subgroup (BF%DXA< 15%), compared to BF%DXA by 0.45%, respectively. In the other subgroups, the BF%BIA8 values were all underestimated. Standing BIA estimating body fat percentage in Chinese participants have a high correlation, but underestimated on normal and high obesity degree in both male and female subjects.

Optical and electrochemical applications of silicon-carbon dots/silicon dioxide nanocomposites.

Various colors of photoluminescent SiC-dots/SiO2 prepared through a simple heating process have been employed for optical and electrochemical applications. Blue (B)-, green (G)-, and tan (T)-SiC-dots/SiO2 powders have been prepared from SiC-dots that had been prepared from 3-aminopropyl trimethoxysilane through a hydrothermal route by simply controlling heating at 60 °C for 60 min and 300 °C for 10 and 20 min, respectively. The B-, G-, and T-SiC-dots/SiO2 nanocomposites emit at 455, 534, and 574 nm, respectively, under excitation at 360 nm. B-, G-, and T-SiC-dots/SiO2 glass films show at least seven colors when excited at 360, 460, and 520 nm. Through a heat-induced photoluminescence (PL) change, a representative lithographic pattern of B-SiC-dots/SiO2 films has been fabricated using a near-infrared laser. The B-, G-, and T-SiC-dots/SiO2 also possess high electrocatalytic activity for the oxygen reduction reaction. Having such interesting PL and electrical properties, the stable, low-toxic, and cost-effective B-, G-, and T-SiC-dots/SiO2 nanocomposites show great economic potential in many applications such as light-emitting diodes, photoluminescent windows, and fuel cells.

Unibody core-shell smart polymer as a theranostic nanoparticle for drug delivery and MR imaging.

Developing novel multifunctional nanoparticles (NPs) with robust preparation, low cost, high stability, and flexible functionalizability is highly desirable. This study provides an innovative platform, termed unibody core-shell (UCS), for this purpose. UCS is comprised of two covalent-bonded polymers differed only by the functional groups at the core and the shell. By conjugating Gd(3+) at the stable core and encapsulating doxorubicin (Dox) at the shell in a pH-sensitive manner, we developed a theranostic NPs (UCS-Gd-Dox) that achieved a selective drug release (75% difference between pH 7.4 and 5.5) and MR imaging (r1 = 0.9 and 14.5 mm(-1) s(-1) at pH 7.4 and 5.5, respectively). The anti-cancer effect of UCS-Gd-Dox is significantly better than free Dox in tumor-bearing mouse models, presumably due to enhanced permeability and retention effect and pH-triggered release. To the best of our knowledge, this is the simplest approach to obtain the theranostic NPs with Gd-conjugation and Dox doping.

In situ imaging of mitochondrial outer-membrane pores using atomic force microscopy.

Here we describe a technique for imaging of the outer contours of the mitochondrial membrane using atomic force microscopy, subsequent to or during a toxic or metabolic challenge. Pore formation in both glucose-challenged and 1,3-dinitrobenzene (DNB)-challenged mitochondria was observed using this technique. Our approach enables quantification of individual mitochondrial membrane pore formations. With this work, we have produced some of the highest resolution images of the outer contours of the in situ mitochondrial membrane published to date. These are potentially the first images of the component protein clusters at the time of formation of the mitochondrial membrane transition pore in situ. With the current work, we have extended the application of atomic force microscopy of mitochondrial membranes to fluid imaging. We have also begun to correlate 3-D surface features of mitochondria dotted with open membrane pores with features previously viewed with electron microscopy (EM) of fixed sections.