Combining cooperativity with sequestration: a novel strategy for discrimination of single nucleotide variants.

We present a novel strategy for the discrimination of single nucleotide variants (SNVs) by combining cooperativity with sequestration, which displays remarkably high specificity (discrimination factors ranging from 67 to 618 with a median of 194) against 12 model SNVs and can be easily integrated with PCR amplification to detect KRAS G12D mutation.

DNA Dendrimer-Streptavidin Nanocomplex: an Efficient Signal Amplifier for Construction of Biosensing Platforms.

We develop a DNA dendrimer-streptavidin (SA) nanocomplex as a novel signal amplifier to create biosensing platforms for disease-related species. The DNA dendrimer-SA nanocomplex is fabricated by cross-linking the nonlinear hybridization chain reaction based DNA dendrimer with the SA-coupled linker DNA and possesses multiple sticky ends, a high molecular weight, and a hyperbranched nanostructure with large numbers of DNA duplexes. Taking advantage of the DNA dendrimer-SA nanocomplex and a label-free quartz crystal microbalance (QCM) technology, we first construct a mass-sensitive QCM biosensing platform for nucleic acids, which displays high selectivity and sensitivity, with a detection limit of 0.062 nM KRAS gene fragment. Then we present a fluorescent sensing strategy toward HeLa cells by functionalizing the DNA dendrimer-SA nanocomplex using the sgc8 aptamer and the SYBR Green I intercalating dye. The spiked recoveries of targets in physiological media are greater than 90%, demonstrating potential application of created biosensing platforms in clinical diagnosis. This work expands the rule set of designing DNA nanomaterials for development of biosensing strategies, and provides universal platforms for detecting disease-related species through simply altering the related capture and reporter DNA sequences.

Ultra-specific discrimination of single-nucleotide mutations using sequestration-assisted molecular beacons.

Reliably distinguishing single-nucleotide mutations (SNMs) at low abundance is of great significance in clinical diagnosis. However, the specificity of most current SNM discrimination methods based on the Watson-Crick hybridization is seriously limited by the cross-reactivity of the probe with closely related unintended sequences. Herein, we propose a sequestration-assisted molecular beacon (MB) strategy for highly specific SNM discrimination. The new SNM discrimination system consists of a target-specific MB and a series of hairpin sequestering agents (SEQs). The rationally designed hairpin SEQs can effectively sequester the corresponding unintended sequences and thus dramatically improve the hybridization specificity of the MB in recognizing SNMs. The developed SNM discrimination method shows remarkably high specificity (discrimination factors ranging from 12 to 1144 with a median of 117) against 20 model SNMs, and can work rapidly and robustly over a wide range of conditions. Notably, our SNM discrimination method can be easily combined with PCR amplification for the detection of KRAS G12D (c.35G>A) and G12V (c.35G>T) mutations at abundance as low as 0.5%. This work expands the rule set of designing hybridization-based SNM discrimination strategies and shows promising potential application in clinical diagnosis.

A local representation of the head-related transfer function.

Spatial descriptions of the head-related transfer function (HRTF) using spherical harmonics, which is commonly used for the purpose, consider all directions simultaneously. However, in perceptual studies, it is necessary to model HRTFs with different angular resolutions at different directions. To this end, an alternative spatial representation of the HRTF, based on local analysis functions, is introduced. The proposal is shown to have the potential to describe the local features of the HRTF. This is verified by comparing the reconstruction error achieved by the proposal to that of the spherical harmonic decomposition when reconstructing the HRTF inside a spherical cap.

Synthesis, crystal structure and magnetic properties of a new copper oxo-antimony sulphate CuSb6O8(SO4)2.

The new copper oxo-antimony sulphate CuSb6O8(SO4)2 crystallizes in the triclinic space group P1[combining macron] with the unit cell parameters a = 5.5342(4) Å, b = 7.6706(6) Å, c = 9.2374(7) Å, α = 96.505(5)°, ß = 93.818(4)°, γ = 109.733(4)° and Z = 1. The crystal structure is made up of layers stacking along [001]. The layers are charge neutral and are connected to each other by only weak interactions. The copper atoms adopt a square planar [CuO4] coordination and such units are well separated from each other by corner and edge sharing to [SbO4] building blocks. The latter polymerize to form sheets with the formula [Sb3O8]∞. Sulphate groups connect to the antimony oxide sheets by corner sharing and are located at the interface of the layers. Above ∼10 K the magnetic susceptibility follows very well a Curie-Weiss law whereas below 10 K increasing deviations indicate the onset of antiferromagnetic correlations. Fitting the data in the range 10-50 K yields a Curie-Weiss temperature θ of -2.25(5) K. A sharp anomaly centered at TC = 0.67 K in the heat capacity data indicates long-range magnetic ordering. Short range antiferromagnetic correlations well above TC are seen in the magnetic contribution to the heat capacity and the magnetic susceptibility. These can be well described by the magnetism of a spin S = 1/2 Heisenberg chain with the nearest neighbor antiferromagnetic spin exchange interaction of Jintra = ∼2.8 K.

An Oxofluoride Catalyst Comprised of Transition Metals and a Metalloid for Application in Water Oxidation.

The application of the recently discovered oxofluoride solid solution (Cox Ni1-x )3 Sb4 O6 F6 as a catalyst for water oxidation is demonstrated. The phase exhibits a cubic arrangement of the active metal that forms oxo bridges to the metalloid with possible catalytic participation. The Co3 Sb4 O6 F6 compound proved to be capable of catalyzing 2H2 O→O2 +4H(+) +4e(-) at 0.33 V electrochemical and ≤0.39 V chemical overpotential with a TOF of 4.4⋅10(-3) , whereas Ni3 Sb4 O6 F6 needs a higher overpotential. Relatively large crystal cubes (0.3-0.5 mm) are easily synthesized and readily handled as they demonstrate both chemical resistance to wear after repeated in situ tests under experimental conditions, and have a mechanical hardness of 270 V0.1 using Vickers indentation. The combined properties of this compound offer a potential technical advantage for incorporation to a catalytic interface in future sustainable fuel production.

An in situ assembly of a DNA-streptavidin dendrimer nanostructure: a new amplified quartz crystal microbalance platform for nucleic acid sensing.

We developed a target-triggered in situ layer-by-layer assembled DNA-streptavidin dendrimer nanostructure as an efficient mass amplifier to create a facile quartz crystal microbalance platform for highly sensitive and selective nucleic acid sensing.

Integrating dye-intercalated DNA dendrimers with electrospun nanofibers: a new fluorescent sensing platform for nucleic acids, proteins, and cells.

We integrated for the first time a novel dye-intercalated DNA dendrimer probe (G3SG) with the electrospun nanofibers (NFs) to create an amplified fluorescent sensing platform for the detection of nucleic acids, proteins, and cancer cells. The sensing platform is constructed based on the formation of the NF-capture/target/reporter-G3SG sandwich-type nanocomplex on the NF membrane surface, leading to large fluorescence signal amplification. Taking advantage of the dual-amplification of both the strong emission intensity of G3SG and the large surface area-to-volume ratio of NFs, this platform enables highly sensitive detection of 20 pM of a ß-thalassemia gene fragment. Furthermore, by easily altering the correlative capture and reporter sequences, the proposed sensing platform can also be applied to detect various targets including thrombin and HeLa cells with high sensitivity and selectivity. This work would provide a simple and versatile strategy for detecting disease-related species in biological samples.

A universal molecular translator for non-nucleic acid targets that enables dynamic DNA assemblies and logic operations.

A universal molecular translator based on the target-triggered DNA strand displacement was developed, which was able to convert various kinds of non-nucleic acid targets into a unique output DNA. This translation strategy was successfully applied in directing dynamic DNA assemblies and in realizing three-input logic gate operations.

Crystal structure and magnetic properties of the S = 1/2 quantum spin system Cu7(TeO3)6F2 with mixed dimensionality.

The new oxofluoride Cu7(TeO3)6F2 has been synthesized by hydrothermal synthesis. It crystallizes in the triclinic system, space group P1. The crystal structure constitutes a Cu-O framework with channels extending along [001] where the F(-) ions and the stereochemically active lone-pairs on Te(4+) are located. From magnetic susceptibility, specific heat, and Raman scattering measurements we find evidence that the magnetic degrees of freedom of the Cu-O-Cu segments in Cu7(TeO3)6F2 lead to a mixed dimensionality with single Cu S = (1)/2 moments weakly coupled to spin-chain fragments. Due to the weaker coupling of the single moments, strong fluctuations exist at elevated temperatures, and long-range magnetic ordering evolves at comparably low temperatures (TN = 15 K).

Crystal structure and magnetic properties of FeSeO(3)F--alternating antiferromagnetic S = 5/2 chains.

The new oxofluoride FeSeO3F, which is isostructural with FeTeO3F and GaTeO3F, was prepared by hydrothermal synthesis, and its structure was determined by X-ray diffraction. The magnetic properties of FeSeO3F were characterized by magnetic susceptibility and specific heat measurements, by evaluating its spin exchanges on the basis of density functional theory (DFT) calculations, and by performing a quantum Monte Carlo simulation of the magnetic susceptibility. FeSeO3F crystallizes in the monoclinic space group P21/n and has one unique Se(4+) ion and one unique Fe(3+) ion. The building blocks of FeSeO3F are [SeO3] trigonal pyramids and cis-[FeO4F2] distorted octahedra. The cis-[FeO4F2] octahedra are condensed by sharing the O-O and F-F edges alternatingly to form [FeO3F]∞ chains, which are interconnected via the [SeO3] pyramids by corner-sharing. The magnetic susceptibility of FeSeO3F is characterized by a broad maximum at 75(2) K and a long-range antiferromagnetic order below ∼45 K. The latter is observed by magnetic susceptibility and specific heat measurements. DFT calculations show that the Fe-F-Fe spin exchange is stronger than the Fe-O-Fe exchange, so each [FeO3F]∞ chain is a Heisenberg antiferromagnetic chain with alternating antiferromagnetic spin exchanges. The temperature dependence of the magnetic susceptibility is well-reproduced by a quantum-Monte Carlo simulation.

Cobalt selenium oxohalides: catalysts for water oxidation.

Two new oxohalides Co4Se3O9Cl2 and Co3Se4O10Cl2 have been synthesized by solid state reactions. They crystallize in the orthorhombic space group Pnma and the monoclinic space group C2/m respectively. The crystal structure of the two compounds are made up of similar building blocks; Co4Se3O9Cl2 is made up of [CoO4Cl2], [CoO5Cl] and [SeO3] polyhedra and Co3Se4O10Cl2 is made up of [CoO4Cl2] and [SeO3] polyhedra. As several Co-containing compounds have proved to be good catalysts for water oxidation, the activities of the two new compounds were compared with the previously found oxohalide Co5Se4O12Cl2 in reference to CoO and CoCl2. The one electron oxidant Ru(bpy)3(3+) was used as oxidizing species in a phosphate buffer and it was found that the activities of the oxohalide species were in between CoO and CoCl2. The roles of Cl(-) and PO4(3-) ions are discussed.

Synthesis and crystal structure of Fe6Ca2(SeO3)9Cl4--a porous oxohalide.

A porous oxohalide, Fe6Ca2(SeO3)9Cl4, has been synthesized by solid state reactions using concentrated HCl as the Cl-source. It crystallizes in the hexagonal space group P63/m with unit cell parameters a = 12.118(2) Å, c = 12.703(4) Å, Z = 2. The crystal structure is an open framework having one-dimensional channels extending along [001] that the chlorine atoms and lone pairs on Se(4+) are facing. The channels in this framework structure are unusually large compared to other oxohalide compounds and also accessible to guest molecules. Water vapor sorption measurements show an uptake of 9 wt% at 293 K.

Synthesis and crystal structure of two synthetic oxofluoride framework compounds--Co2TeO3F2 and Co2SeO3F2.

Two new isostructural Co(2+) containing tellurium and selenium oxofluoride compounds Co(2)TeO(3)F(2) and Co(2)SeO(3)F(2) are synthesized and their structures determined by single crystal X-ray diffraction. They crystallize in the orthorhombic space group Pnma with the unit cell parameters a = 7.3810(5) Å, b = 10.1936(7) Å, c = 5.3013(3) Å and a = 7.2655(8) Å, b = 10.0013(13) Å, c = 5.3564(6) Å, respectively. The Co(II) ion has octahedral coordination [CoO(3)F(3)] and builds up a 3D framework by corner- and edge sharing. The Se(IV) and the Te(IV) ions have the coordinations [SeO(3)E] and [TeO(3)E] respectively where E is the lone-pair electrons. The Se(IV) and Te(IV) ions are isolated from each other and bond only to the [CoO(3)F(3)] polyhedra. The electronegative element fluorine takes the role of a network builder like oxygen and helps to form the 3D framework structure. This is a difference compared to many oxohalide compounds containing Cl and Br where the halide ions are terminating ions preventing a 3D network from being formed. Long range antiferromagnetic interactions dominate at temperatures < 20 K. The magnetic susceptibility follows the Curie-Weiss law above 25 K with the Curie constant C = 5.62 emu K mol(-1), the Weiss temperature θ = -56 K and the effective magnetic moment µ(eff) = 4.74 µ(B) per cobalt atom.