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53.
Qu Y Porter R Shan F Carter JD Guo T 《Langmuir : the ACS journal of surfaces and colloids》2006,22(14):6367-6374
We report the synthesis of tubular gold and silver nanoshells on silica nanowire core templates in solution. Silica nanowires were synthesized and characterized with optical and NMR methods. Gold nanoparticle seeds (2 to 3 nm) with weak repulsive surfactants such as tetrakis-hydroxymethyl-phosphonium chloride (THPC) were conjugated to the surface of these nanowires. A regrowth process was initiated from these nanoparticles on the surface of the silica nanowires dispersed in gold or silver stock solutions in the presence of reducing agents. Micrometers-long gold and silver tubular nanoshells (80-150 nm o.d.) were made, fully covering the silica nanowires. 相似文献
54.
In Part I of this work, we developed a method for the detection of drugs of abuse in biological samples based on fast gradient elution liquid-chromatography coupled with diode array spectroscopic detection (LC-DAD). In this part of the work, we apply the chemometric method of target factor analysis (TFA) to the chromatograms. This algorithm identifies the target compounds present in chromatograms based on a spectral library, resolves nearly co-eluting components, and differentiates between drugs with similar spectra. The ability to resolve highly overlapped peaks using the spectral data afforded by the DAD is what distinguishes the present method from conventional library searching methods. Our library has a mean list length (MLL) of 1.255 and a discriminating power of 0.997 when both retention index and spectral factors are considered. The algorithm compares a library of 47 different compounds of toxicological relevance to unknown samples and identifies which compounds are present based on spectral and retention index matching. The application of a corrected retention index for identification rather than raw retention times compensates for long-term and column-to-column retention time shifts and allows for the use of a single library of spectral and retention data. Training data sets were used to establish the search and identification parameters of the method. A validation data set of 70 chromatograms was used to calculate the sensitivity (correct identification of positives) and specificity (correct identification of negatives) of the method, which were found to be 92% and 94%, respectively. 相似文献
55.
John R. Kucklick Michele M. Schantz Rebecca S. Pugh Barbara J. Porter Dianne L. Poster Paul R. Becker Teri K. Rowles Stefan Leigh Stephen A. Wise 《Analytical and bioanalytical chemistry》2010,397(2):423-432
The National Institute of Standards and Technology (NIST) has a diverse collection of control materials derived from marine
mammal blubber, fat, and serum. Standard Reference Material (SRM) 1945 Organics in Whale Blubber was recertified for polychlorinated
biphenyl (PCB) congeners, organochlorine pesticides, and polybrominated diphenyl ether (PBDE) congeners. SRM 1945 has also
been assigned mass fraction values for compounds not frequently determined in marine samples including toxaphene congeners,
coplanar PCBs, and methoxylated PBDE congeners which are natural products. NIST also has assigned mass fraction values, as
a result of interlaboratory comparison exercises, for PCB congeners, organochlorine pesticides, PBDE congeners, and fatty
acids in six homogenate materials produced from marine mammal blubber or serum. The materials are available from NIST upon
request; however, the supply is very limited for some of the materials. The materials include those obtained from pilot whale
blubber (Homogenates III and IV), Blainville’s beaked whale blubber (Homogenate VII), polar bear fat (Homogenate VI), and
California sea lion serum (Marine Mammal Control Material-1 Serum) and blubber (Homogenate V). 相似文献
56.
A series of planar beta-linked oligothiophenes based on thieno[3,2-b]thiophene and dithieno[3,2-b:2',3'-d]thiophene fused units were synthesized. The optical data indicate a blue shift of the absorption maximum in comparison to the alpha-linked analogues due to cross-conjugation between fused rings. The crystal structures of 3,3'-bi(thieno[3,2-b]thiophene) and 3,3';6',3"-ter(thieno-[3,2-b]thiophene) reveal edge-to-face pi-stacked dimer motifs, whereas the crystal structure of 3,3'-bis(dithieno[3,2-b:2',3'-d]thiophene) consists of face-to-face pi-stacked molecules. [structure: see text] 相似文献
57.
Point D Davis WC Christopher SJ Ellisor MB Pugh RS Becker PR Donard OF Porter BJ Wise SA 《Analytical and bioanalytical chemistry》2007,387(7):2343-2355
An accurate, ultra-sensitive and robust method for speciation of mono, di, and tributyltin (MBT, DBT, and TBT) by speciated isotope-dilution gas chromatography-inductively coupled plasma-mass spectrometry (SID-GC-ICPMS) has been developed for quantification of butyltin concentrations in cryogenic biological materials maintained in an uninterrupted cryo-chain from storage conditions through homogenization and bottling. The method significantly reduces the detection limits, to the low pg g(-1) level (as Sn), and was validated by using the European reference material (ERM) CE477, mussel tissue, produced by the Institute for Reference Materials and Measurements. It was applied to three different cryogenic biological materials-a fresh-frozen mussel tissue (SRM 1974b) together with complex materials, a protein-rich material (whale liver control material, QC03LH03), and a lipid-rich material (whale blubber, SRM 1945) containing up to 72% lipids. The commutability between frozen and freeze-dried materials with regard to spike equilibration/interaction, extraction efficiency, and the absence of detectable transformations was carefully investigated by applying complementary methods and by varying extraction conditions and spiking strategies. The inter-method results enabled assignment of reference concentrations of butyltins in cryogenic SRMs and control materials for the first time. The reference concentrations of MBT, DBT, and TBT in SRM 1974b were 0.92 +/- 0.06, 2.7 +/- 0.4, and 6.58 +/- 0.19 ng g(-1) as Sn (wet-mass), respectively; in SRM 1945 they were 0.38 +/- 0.06, 1.19 +/- 0.26, and 3.55 +/- 0.44 ng g(-1), respectively, as Sn (wet-mass). In QC03LH03, DBT and TBT concentrations were 30.0 +/- 2.7 and 2.26 +/- 0.38 ng g(-1) as Sn (wet-mass). The concentration range of butyltins in these materials is one to three orders of magnitude lower than in ERM CE477. This study demonstrated that cryogenically processed and stored biological materials are a promising alternative to conventional freeze-dried materials for organotin speciation analysis, because these are, at present, the best conditions for minimizing degradation of thermolabile species and for long-term archival. Finally, the potential of the analytical method was illustrated by analysis of polar bear (Ursus maritimus) and beluga whale (Delphinapterus leuca) liver samples that had been collected in the Arctic and archived at the Marine Environmental Specimen Bank. Significant concentrations of butyltin compounds were found in the samples and provide the first evidence of the presence of this class of contaminant in the Arctic marine ecosystem. Figure Eye catch image. 相似文献
58.
Luojuan Hu Tim Quach Sifei Han Shea F. Lim Preeti Yadav Danielle Senyschyn Natalie L. Trevaskis Jamie S. Simpson Christopher J. H. Porter 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(44):13904-13909
First‐pass hepatic metabolism can significantly limit oral drug bioavailability. Drug transport from the intestine through the lymphatic system, rather than the portal vein, circumvents first‐pass metabolism. However, the majority of drugs do not have the requisite physicochemical properties to facilitate lymphatic access. Herein, we describe a prodrug strategy that promotes selective transport through the intestinal lymph vessels and subsequent release of drug in the systemic circulation, thereby enhancing oral bioavailability. Using testosterone (TST) as a model high first‐pass drug, glyceride‐mimetic prodrugs incorporating self‐immolative (SI) spacers, resulted in remarkable increases (up to 90‐fold) in TST plasma exposure when compared to the current commercial product testosterone undecanoate (TU). This approach opens new opportunities for the effective development of drugs where oral delivery is limited by first‐pass metabolism and provides a new avenue to enhance drug targeting to intestinal lymphoid tissue. 相似文献
59.
Davis WC Christopher SJ Pugh RS Donard OF Krupp EA Point D Horvat M Gibicar D Kljakovic-Gaspic Z Porter BJ Schantz MM 《Analytical and bioanalytical chemistry》2007,387(7):2335-2341
This paper describes the development of two independent analytical methods for the extraction and quantification of methylmercury
from marine biota. The procedures involve microwave extraction, followed by derivatization and either headspace solid-phase
microextraction (SPME) with a polydimethylsiloxane (PDMS)-coated silica fiber or back-extraction into iso-octane. The identification
and quantification of the extracted compounds is carried out by capillary gas chromatography/mass spectrometric (GC/MS) and
inductively coupled plasma mass spectrometric (GC/ICP-MS) detection. Both methods were validated for the determination of
methylmercury (MeHg) concentrations in a variety of biological standard reference materials (SRMs) including fresh-frozen
tissue homogenates of SRM 1946 Lake Superior fish tissue and SRM 1974a organics in mussel tissue (Mytilus edulis) and then applied to the certification effort of SRM 1947 Lake Michigan fish tissue and SRM 1974b organics in mussel tissue
(Mytilus edulis). While past certifications of methylmercury in tissue SRMs have been based on two independent methods from the National
Institute of Standards and Technology (NIST) and participating laboratories, the methods described within provide improved
protocols and will allow future certification efforts to be based on at least two independent analytical methods within NIST. 相似文献
60.
Aminonaphthols are easily transformed into a variety of 1- and 2-naphthyl piperazines using a sequence of diazotization, iodide substitution and Pd(0) catalyzed coupling reactions. 相似文献