Production and certification of BOTS-1: bovine muscle-certified reference material for incurred veterinary drug residues.

A freeze-dried bovine muscle-certified reference material (CRM), known as BOTS-1 (DOI: https://doi.org/10.4224/crm.

Quantification and Stability Determination of Surface Amine Groups on Silica Nanoparticles Using Solution NMR.

Surface chemistry is a critical factor for determining the behavior of a nanomaterial after incorporation in composites, devices, and biomedical products, and is also important for nanotoxicology studies. We have developed an optimized protocol for dissolution of aminated silicas and determination of functional-group contents by quantitative H NMR (qNMR) analysis of the released amines. A number of variables were optimized for the dissolution protocol, including the base concentration, mass of silica, time, temperature, and method of sample agitation, in order to achieve adequate NMR signals for quantification.

Purity assignment for peptide certified reference materials by combining qNMR and LC-MS/MS amino acid analysis results: application to angiotensin II.

The purity value assignment of metrologically traceable peptide reference standards requires specialized primary methods. Conventionally, amino acid analysis by isotope dilution tandem mass spectrometry (LC-MS/MS) following peptide hydrolysis is employed as a reference method. By contrast, quantitative nuclear magnetic resonance (qNMR) spectroscopy allows for quantitation of intact peptides, thus eliminating potential bias due to hydrolysis.

Determination of cyanocobalamin by isotope dilution LC-MS/MS.

Cyanocobalamin (CNCbl) is an active form of vitamin B12, commonly employed for the preparation of multivitamin supplements and fortified food. In this study, we present a novel analytical method for its determination based on stable isotope dilution liquid chromatography electrospray tandem mass spectrometry (ID LC-MS/MS). Isotopically enriched CNCbl was synthesized in-house and used as internal standard.

Determination of chemical purity and isotopic composition of natural and carbon-13-labeled arsenobetaine bromide standards by quantitative(1)H-NMR.

In this study, we report the characterization of three arsenobetaine-certified reference materials by quantitative NMR. We have synthesized an arsenobetaine bromide high-purity standard of natural isotopic composition (ABET-1) and two carbon-13-labeled isotopic standards (BBET-1 and CBET-1). Assignments of the chemical purity and isotopic composition are not trivial in the case of arsenobetaine, and in this study we utilized quantitative(1)H-NMR techniques for the determination of the mass fractions (chemical purity).

Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies.

One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.

Low-temperature approach to highly emissive copper indium sulfide colloidal nanocrystals and their bioimaging applications.

We report our newly developed low-temperature synthesis of colloidal photoluminescent (PL) CuInS2 nanocrystals (NCs) and their in vitro and in vivo imaging applications. With diphenylphosphine sulphide (SDPP) as a S precursor made from elemental S and diphenylphosphine, this is a noninjection based approach in 1-dodecanethiol (DDT) with excellent synthetic reproducibility and large-scale capability. For a typical synthesis with copper iodide (CuI) as a Cu source and indium acetate (In(OAc)3) as an In source, the growth temperature was as low as 160 °C and the feed molar ratios were 1Cu-to-1In-to-4S.

Ultraviolet ZnSe₁-xSx gradient-alloyed nanocrystals via a noninjection approach.

Highly emissive ultraviolet ZnSeS nanocrystals (NCs), with a core-shell-like structure, were designed and synthesized via a one-step noninjection approach in 1-octadecene (ODE). These ultraviolet ZnSeS NCs exhibit bright bandgap emission with high color purity and little trap emission. With full width at half-maximum (fwhm) of ∼21 nm only, photoluminescent (PL) quantum yield (QY) of ∼60% was estimated for one ensemble dispersed in toluene exhibiting bandgap absorption peaking at ∼380 nm and bandgap emission at ∼389 nm.

Effect of clathrate hydrate formation and decomposition on NMR parameters in THF-D2O solution.

The NMR spin-lattice relaxation time (T(1)), spin-spin relaxation time (T(2)) and the diffusion coefficient D were measured for (1)H in a 1:17 mol % solution of tetrahydrofuran (THF) in D(2)O. The aim of the work was to clarify some earlier points raised regarding the utility of these measurements to convey structural information on hydrate formation and reformation. A number of irregularities in T(1) and T(2) measurements during hydrate processes reported earlier are explained in terms of the presence of interfaces and possible temperature gradients.

Size reduction of CdSe/ZnS quantum dots by a peptidic amyloid supergelator.

Anchoring of a self-assembling dipeptide on the surface of core/shell CdSe/ZnS quantum dots resulted in a competition between coordination of the surface atoms of the QDs and the strong tendency for the dipeptide to self-assemble in toluene. This resulted in a mild QD etching and in a corresponding increase in the band gap of the nanocrystals whose photoluminescent emission gradually turns blue with time. The FmocLeuLeuOH dipeptide supergelator self-assembles in fibrils in which the Fmoc groups are surrounded by the pendant isobutyl side chains of the leucine residues with vibrational circular dichroism (VCD) and liquid- and solid-state NMR attributes of twist anti-parallel β-sheets.

Highly-photoluminescent ZnSe nanocrystals via a non-injection-based approach with precursor reactivity elevated by a secondary phosphine.

Highly-photoluminescent ZnSe quantum dots with 72% quantum yield and 22 nm full width at half maximum were synthesized with more reactive precursors via a non-injection approach with high synthetic reproducibility; (31)P NMR provided insight into the formation mechanisms of ZnSe monomers.

In-situ observation of nucleation and growth of PbSe magic-sized nanoclusters and regular nanocrystals.

In-situ observation of the temporal evolution of the absorption of PbSe nanocrystals (NCs) via a low-temperature noninjection approach is presented. Based on a model reaction of lead oleate (Pb(OA)(2) ) and n-trioctylphosphine selenide (TOPSe) in 1-octadecene at 35-80 °C, the use of commercially available TOP (90 or 97%) in affecting the formation of the NCs is explored. TOPSe solutions made from TOP 90% exhibited higher reactivity than those made from TOP 97%.

Low-temperature noninjection approach to homogeneously-alloyed PbSe(x)S(1-x) colloidal nanocrystals for photovoltaic applications.

Homogeneously alloyed PbSe(x)S(1-x) nanocrystals (NCs) with their excitonic absorption peaks in wavelength shorter than 1200 nm were developed for photovoltaic (PV) applications. Schottky-type solar cells fabricated with our PbSe₀.₃S₀.

Clusters of superparamagnetic iron oxide nanoparticles encapsulated in a hydrogel: a particle architecture generating a synergistic enhancement of the T2 relaxation.

Clusters of iron oxide nanoparticles encapsulated in a pH-responsive hydrogel are synthesized and studied for their ability to alter the T(2)-relaxivity of protons. Encapsulation of the clusters with the hydrophilic coating is shown to enhance the transverse relaxation rate by up to 85% compared to clusters with no coating. With the use of pH-sensitive hydrogel, difficulties inherent in comparing particle samples are eliminated and a clear increase in relaxivity as the coating swells is demonstrated.

Low-temperature approach to high-yield and reproducible syntheses of high-quality small-sized PbSe colloidal nanocrystals for photovoltaic applications.

Small-sized PbSe nanocrystals (NCs) were synthesized at low temperature such as 50-80 °C with high reaction yield (up to 100%), high quality, and high synthetic reproducibility, via a noninjection-based one-pot approach. These small-sized PbSe NCs with their first excitonic absorption in wavelength shorter than 1200 nm (corresponding to size < ∼3.7 nm) were developed for photovoltaic applications requiring a large quantity of materials.

CdS magic-sized nanocrystals exhibiting bright band gap photoemission via thermodynamically driven formation.

CdS magic-sized nanocrystals (MSNs) exhibiting both band gap absorption and emission at 378 nm with a narrow bandwidth of approximately 9 nm and quantum yield (QY) of approximately 10% (total QY approximately 28%, in hexane) were synthesized via a one-pot noninjection approach. This CdS MSN ensemble is termed as Family 378. It has been acknowledged that magic-sized quantum dots (MSQDs) are single-sized, and only homogeneous broadening contributes to their bandwidth.

Photoluminescent quantum dot?cucurbituril nanocomposites.

The preparation of entrapped CdSe?ZnS fluorescent quantum dots (QDs) in cucurbituril (CB) polymer capsules is reported.

The effect of aminoglycoside antibiotics on the thermodynamic properties of liposomal vesicles.

Liposomes are ideal drug-delivery systems because they can alter the pharmacokinetic characteristics and biodistribution profile of the incorporated bioactive molecule. The effect of the aminoglycoside antibiotics, gentamicin (GN), tobramycin (TOB), and amikacin (AMI), on the thermodynamic properties of multilamellar vesicles composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) was studied by using differential scanning calorimetry (DSC), electron paramagnetic resonance (EPR), and (31)P nuclear magnetic resonance (NMR) spectroscopy. The relationship between the structure of aminoglycoside antibiotics and their effect on the physical properties of the liposomal bilayers was investigated.

Inclusion complexes of coumarin in cucurbiturils.

Coumarin was found to form stable inclusion complexes with cucurbiturils. In the presence of cucurbit[7]uril (CB[7]), 1 : 1 inclusion complexes were observed in aqueous solution, as monitored by (1)H NMR and UV-visible absorption spectroscopies, and further supported by ab initio calculations, whereas with cucurbit[8]uril (CB[8]) a solid phase 1 : 2 host : guest complex was found in a single crystal X-ray diffraction structure determination.

Discovery of indoline-based, natural-product-like compounds as probes of focal adhesion kinase signaling pathways.

With the goal of identifying small molecule modulators of protein-protein interactions, we developed a solid-phase synthesis method, which was then successfully utilized in a library generation of 164 aminoindoline-derived, natural-product-like compounds. This library and several other related intermediates synthesized during this project were then subjected to different biological assays in search of small molecule modulators of focal adhesion kinase (FAK)-mediated signaling pathways. This study included (i) an in vitro, full length FAK inhibition assay, (ii) a cell proliferation assay, and (iii) a wound healing assay.

Single-crystal to single-crystal phase transition of cucurbit[5]uril hydrochloride hydrates: large water-filled channels transforming to layers of unusual stability.

Cucurbit[5]uril hydrochloride hydrate crystals with large water-filled channels transform to a highly stable layer structure via a single-crystal to single-crystal mechanism; (129)Xe NMR showed that porosity in CB[5] samples depends critically on the method of preparation.

Building skeletally diverse architectures on the Indoline Scaffold: the discovery of a chemical probe of focal adhesion kinase signaling networks.

Inspired by bioactive indoline alkaloid natural products, here, we report a divergent synthesis approach that led to skeletally diverse indoline alkaloid-inspired compounds. The natural product-inspired compounds obtained were then subjected to a series of in vitro and cellular assays to examine their properties as modulators of focal adhesion kinase (FAK) activity. This study resulted in the identification of a promising lead inhibitor of FAK (42), which also showed activity in a wound healing and cell invasion assay.