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In vitro and in vivo investigation of matrix metalloproteinase
expression in metastatic tumor models
Larissa Gribat
The spread of cancer may occur through the lymph nodes causing early death. During malignancy, an overexpression of matrix metalloproteinases(MMPs) occurs through which early detection could lead to more accurate prognosis. A peptide, CCT (CTTHWGFTLC) is a possible inhibitor of MMP-2 and MMP-9 to determine the location of cancer growth. CCT is conjugated with DOTA (1,4,7,10-tetraazacyclotetradecane-N’,N’’,N’’’,N’’’’-tetraacetic acid) and 64Cu. Both in vivo and in vitro inhibition is measured. Positron emission tomography (PET) can identify Cu(2)-DOTA-CCT for imaging with tumor gelatinase targeting while in vitro affinity is determined with a fluorogenic substrate assay. Cu(2)-DOTA-CCT inhibited hMMP-2 and mMMP-9 in vitro. For both B16F10 and MDA-MB-435 tumors in vivo, Cu(2)-DOTA-CCT was taken up inconsistently with microPET and zymography. Thus, Cu(2)-DOTA-CCT is not selective enough for inhibition of MMP-2 and MMP-9 for cancer spread diagnosis. The unspecific uptake of Cu(2)-DOTA-CCT is due to instability in blood for protein-bound radioactivity. (Anderson, C.J. In vitro and in vivo investigation of matrix metalloproteinase expression in metastatic tumor models. Nucl Med Biol. 2006, 33, 227-237).
Polystyrene Aerogels with β, γ, and ε Crystalline Phases
Joe Siegel
The effects
of thermal treatment and supercritical carbon dioxide extraction procedures on the
crystal structure of sPS gels are observed by wide-angle X-ray diffraction and
electron microscopy. Supercritical carbon dioxide extraction
treatment is used to create the δ, β, and γ crystalline
phases. These phases are found to have a high porosity with a fibrillar morphology. Also the ε crystalline
phase was obtained by treating the γ-form with liquid chloroform followed
by chloroform removal by volatile guests of sPS aerogels. Measurements of
the sorption of organic molecules from diluted aqueous solutions, with
different crystalline phases, indicate that the ε-form is best suited for
the detection and removal of long organic pollutants.
Food-Miles and the Relative
Climate Impacts of Food Choices in the United States
Philip Denight
In the world today carbon
emissions and greenhouse gases play an enormous role in how we interact with
the environment. In the United States, very few studies have compared the
life-cycle of greenhouse gas to the food production cycle. Through the
input-output life cycle assessment these figures can be determined and utilized
to figure out how to decrease the carbon-footprint. Several variety of food
sources (red meat, dairy products, cereals, etc) and methods of transportation
(water, truck, rail) were recorded for carbon output.
It was found that trucking is responsible for a majority (71%) of transport
related greenhouse gases and red meat and cereals equally share the
carbon-footprint (2300 ton-km/household-yr) for food sources. It is recommended
that dietary shift can be an effective means of lowering greenhouse gases by
switching to chicken, eggs, fish or vegetables and away from red meats and
cereals.
Article:
http://pubs.acs.org/doi/abs/10.1021/es702969f?prevSearch=Food-miles%2Band%2Bthe%2Brelative%2Bclimate%2Bimpacts%2Bof%2Bfood%2Bchoices&searchHistoryKey=
Medicinal
Applications of Animal Toxins
Avash Shrestha
Animal toxin is one of the most
useful biochemical substances that exist in nature, consisting of specific peptides,
proteins, and organic and inorganic molecules/ions. These chemicals have the
potential to deliver their contents to specific locations within an animal’s
body for specific functions, usually very lethal. The ability of animal toxins
to be location specific in its actions makes it fascinating for the study of
its medicinal characteristics based on its potency and effects on the human
body. Specific animal toxins such as bees, snakes and scorpions venom have
shown that they can be used in treating diseases like Alzheimer’s disease,
cardiovascular diseases muscular disorders .
Armugam, A.,
and K. Jeyaseelan. "Snake venom components and their applications in
biomedicine." Cellular and Molecular Life Sciences
13 Nov. 2006
Time-Resolved pH/pO2 Mapping
with Luminescent Hybrid Sensors
Laura Tvedte
A method for simultaneous detection of two or more parameters (in this case, pH and pO2) using absorbent or luminescent dyes as indicators is described. This method involves detection of the pH signal as a hybrid signal (dependent on pH and pO2) along with detection of the pO2 signal as a pure (non-hybrid) signal. This method affords an advantage in determining parameters in systems where changes are based on two or more parameters. The hybrid pH sensor successfully measures a range of pH 7.6-pH 8.7 with a maximum deviation of pH 0.03. The pO2 sensor measures a range of 0-200 hPa pO2 with a maximum deviation of 6.5 hPa pO2. PH/pO2 example images obtained in marine sediment are taken using this method and presented.
Chemical Mechanisms for Skin
Sensitization by Aromatic Compounds with Hydroxy and Amino Groups
Jeff Boschen
Skin sensitization is observed in aromatic diamino-, dihydroxy-, and amino-hydroxy compounds. As a result of a recent animal testing ban on chemicals used for cosmetics in the European Union, new methods are needed for predicting skin sensitization potency. One potential method is analysis of reaction methods. In this study, the potency and cross-reactivity data from published animal tests is used to make mechanistic predictions. For para and ortho substituted compounds, two reaction mechanisms are suggested: oxidation to electrophilic quinones or quinone imines, or formation of free radicals such as the Wurster salt. For meta compounds neither of these mechanisms are favored, instead a different molecular mechanism is proposed. Using quantum mechanics calculations, this mechanism can be used to explain potency data for meta substituted structures.
Bibliography
Aptula, A. O., Enoch, S.J., Roberts, D. W. Chem. Res. Toxicol. 2009 22 (9), 1541-1547
Roberts,
D. W. and Aptula, A. O. J. Appl. Toxicol. 2007 28, 377–
387
Aptula, A. O. and Roberts, D. W. Chem. Res. Toxicol. 2006 19, 1097– 1105
Primary and
Secondary Phosphine Complexes of Iron Porphyrins and Ruthenium Phthalocyanine:
Synthesis, Structure, and P-H Bond Functionalization
Jeff Hon
Interactions of hemoproteins are widely studied for their implications in
humans and medicine. Specifically, the binding mechanism of hemoproteins
and various drugs are of concern and provide insight into new drug synthesis. Phthalocyanine complexes serve as a useful analog to
hemoglobin and are used to study binding interactions, specifically phosphine substrates. The reduction of ruthenium(II)
phthalocyanine have generated several primary and
secondary phosphines of interest. Furthermore, the
P-H bond has been functionalized and provide
further interest into phosphine complexes.
Bibliography
1. Huang,
J et al. Inorg. Chem., 2008, 47 (20), pp 9166–9181
2. Dahlen, M.A. Ind. Eng. Chem., 1939, 31 (7), pp 839–847
3. Wink, D and Ford, P.C. Excited States and Reactive
Intermediates, Chapter 14, 1986, pp 197-211 ACS Symposium Series,
Volume 307.
Analysis of Ecologically
Relevant Pharmaceuticals in Wastewater and Surface Water Using Selective
Solid-Phase Extraction and UPLC—MS/MS
Kevin Schmitt
CHEM 345: Junior Chemistry Seminar
Increasing production and variety of
active pharmaceutical ingredients (APIs) and metabolites used in human and
veterinary medicine leads to the release of greater quantities of these
materials into the environment. The presence of these compounds or their
derivatives in increasing concentrations in wastewater and surface water
provides opportunities for undesirable ecological effects to occur. A new
method for the analysis of 6 metabolites and 48 API’s in water samples is
presented. The target analytes are selected with regard to their
predicted environmental impact, and the method utilizes the techniques of
selective solid-phase extraction and ultraperformance liquid chromatography
with triple quadrupole mass spectrometry. Four separate chromatographic
runs are used to determine the presence and concentration of analytes in the
following groups: basic APIs 1 (antidepressants, antibiotics), basic APIs
2 (cardiovascular drugs, pain medications), neutral APIs, and acidic
APIs. The total time required for analysis of all 54 compounds is 48
minutes, and the method limits of detection range from 1.0 to
51 ng/L. Analysis of wastewater and surface water samples resulted
in the detection of 38 and the quantitation of 36 of the 54 total analytes.
Bibliography
(1) Kostich,
M.S.; Lazorchak, J.M.; Batt, A.L. Anal. Chem. 2008, 80,
5021-5030.
(2) Swartz, M.E. Separation
Science Redefined [Online] 2005, May, 8-14.
http://chromatographyonline.findanalytichem.com/lcgc/data/articlestandard//lcgc/242005/164646/article.pdf
(accessed Oct 7, 2005).
(3) Richardson, S.D. Anal. Chem. 2008, 80, 4379-4384.
Kinetic Study
of the Phthalimide N-Oxyl (PINO) Radical in Acetic Acid
Adam Kell
A common method of alcohol oxidation
is to use a nitroxyl-radical-catalyzed reaction.
These are not complete oxidations however, since nitroxyl
radicals are selective oxidants. The discovery of the catalytic reactivity of N-hydroxyphthalimide
(NHPI) has shown the phthalimide N-oxyl (PINO) radical to be a good
candidate for oxidizing hydrocarbons. Reactions of PINO with hydrocarbons are
slightly exothermic or thermoneutral. The bond
dissociation energy (BDE) of the O-H of NHPI gives the same conclusion. A
difference in the kinetic isotope effect (KIE) between PINO and the dimbromide readical can be
explained by the difference in their enthalpies for reactions with the same
hydrocarbons.
Bibliography
Ishii, Y.; Sakaguchi, S.; Iwahama, T. Adv.
Synth.
Catal.
2001, 343, 393-427.
Ueda, C.; Noyama,
M.; Ohmori, H.; Masui, M. Chem. Pharm. Bull.1987,
35, 1372-1377.
(−)-Mutisianthol:
First Total Synthesis, Absolute Configuration, and Antitumor Activity
Chris Jeffrey
Understanding the makeup of the
natural world is a major part of chemistry, and one aspect of that is being
able to understand the molecular structure of the naturally occurring products.
Alongside that is being able to reproduce the product synthetically. One of
those products is mutisianthol, found in the Mutisa genus of flowers. In previous works,
synthesis of mutisianthol had successfully produced a
stereo-isomer, however, the route for total synthesis
was recently discovered. Furthermore, the new process has fewer steps and is
more efficient. Additionally, the product was shown to have moderate anti-tumor
properties with a few cells.
-Bianco, G.G.; et. al., J.
Org. Chem. 2009, 74, 2561-2566
Trace Analysis of Peroxide-Based Explosives
Michael Hogard
In recent
years, peroxide-based explosives have been commonly been involved in drug
crimes and terrorism incidents, mainly due to their relatively simple and cheap
synthesis. The study develops the first method for trace analysis of two
peroxide-based explosives, triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD). A reversed-phase high-performance liquid
chromatography method with postcolumn UV irradiation
and fluorescence detection is used for the analysis after the analytes have been degraded to hydrogen peroxide, which
allowed for the explosives to be identified with a high degree of selectivity.
The limits of detection for both TATP and HMTD were 2 × 10-6 mol/L.
This method has been used and proven effective on not only samples prepared in
the laboratory, but in the analysis of real samples.
Bibliography
(1) Schulte-Ladbeck,
R.; Karst, U.; Kolla, P. Trace
analysis of peroxide-based explosives. Anal.
Chem. 2003, 75 (4),
731-735.
(2) Schaefer, W.P.; Fourkas, J.T.; Tiemann, B.G.
Structure of hexamethylene triperoxide
diamine. J. Am. Chem. Soc. 1985, 107 (8), 2461-2463.
(3) Groth,
P. Crystal structure of
3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexa-oxacyclononane ("trimeric acetone peroxide"). Acta
Chem. Scand. 1969, 23 (4), 1311−1329.
Quantitative
and Real-Time Detection of Secretion of Chemical Messengers from Individual
Platelets
Ivan Lenov
Serotonin release is essential for
normal body functions and can be measured using radiometric assays and
chromatographic separations. However, those methods have very poor temporal
resolution and can’t focus on a single cell. In this study, a carbon-fiber
microelectrode is used to measure individual cell release of serotonin and
histamine from rabbit cells with amperometry. The quantal release of serotonin was measured to be a
concentration of 0.6 M with a release time of 7 ms.
In addition, it was found that quantal size increased
under hypotonic conditions in the cell’s environment, but no change was
observed when the conditions were both hypertonic and isotonic. This approach
can be implemented in future studies in fields such as pharmacology
Crystallization
from Water-in-Oil Emulsions As a Route to Spherical
Particulates: Glycine and the Hydrochloride Salts of Glutamic Acid and Ephedrine
Patrick Barney
Emulsion crystallization is a method
of controlling particle properties, and is part of technique that is used to
form spherical particles. In pharmaceutical industries, spherical particles are
known to have advantages in terms of flow and compression properties. This study was carried out to define possible
working space for the development of emulsion crystallization of materials that
could mimic pharmaceutically active compounds.
In this study three water-soluble materials, glycine,
L-glutamic acid hydrochloride, and ephedrine
hydrochloride from water-in-oil emulsion were explored. In particular, work on these compounds show
the significance of stirring, surfactant, and templating
additive choice. It is evident that these are important in developing a
practical route to utilizing this technology.
It is also seen that the relative solubility of the solute in the two
liquid phases may prevent the use of the drops as crystallisation
environments. This leads to unwanted
growth of large crystals in the continuous phase.
Bibliography
(1)
Chadwick,
K.; Davey,R.J.; Mughal R. Crystallisation from
water-in-oil emulsions as a route to spherical particulates: glycine and the hydrochloride salts of glutamic
acid and ephedrine. Org. Process Res. Dev. 2009.
(2)
Chen, B.D.; Cilliers, J. J. L.; Daver, R. J.; Garside, J; Woodburn, E.T. J. Am. Chem. Soc. 1998, 120, 1625-1626
(3)
Berge, N. D.; Ramsburg, A.
C. Oil-in-Water emulsions for
encapsulated delivery of reactive iron particles. Environ.
Sci. Technol., 2009, 43 (13),
pp 5060–5066
Ethanol-Drug
Absorption Interaction: Potential for a Significant Effect on the Plasma
Pharmacokinetics of Ethanol Vulnerable Formulations
Brent Dresser
Gastric delivery of controlled
release formulations of opiate drugs is controlled by a wide variety of
factors. Ethanol can compromise the time-release formulation, resulting in dose
dumping. This process is aggravated by formulations that are soluble in
ethanol. This can be a serious health concern considering plasma increases of
16 times in vivo studies. In this
study Hydromorphone was studied, in addition to other
time release opiates, and it was that hydromorphone
was most affected by ethanol concentrations of 20-40%. The other
characteristics of the ethanol ingested have a variety of effects on the dose
dumping phenomenon. Weighing the variety of factors is almost impossible in
determining the individual effects of dose dumping, and thus the safety of the
product is compromised.
Lennemas,H.,
Mol. Pharmaceutics, 2009, 6 (5), pp
1429–1440
A NIST Standard
Reference Material (SRM) to Support the Detection of Trace Explosives
Chelsea Stockwell
Determination of trace explosives
residues is a component of anticipatory detection of terrorist threats as well
as forensic evaluations. A reference material was created in order to simulate
residues produced from explosive handling. Nine potential materials were tested
by coating with Composition C-4, TNT (2,4,6-trinitrotoluene), or HMX
(octahydro-1,3,5,7-tetranitro-1,3,5,7-Tetrazocine) and the best material was
deduced based on characteristics including coating efficiency, extractability
with organic solvents, thermal storage stability, consistency of particle size,
and calibration potential. The reference choice was determined to be oxtadecylsilane-modified silica (C18) with a
particle size of 20-30 μm size. The SRM
(Standard Reference Material) was then concentration certified and tested by
liquid chromatography with ultraviolet absorbance detection (LC/UV), and liquid
chromatography with mass spectrometric methods (LC/MS).
Bibliography
MacCrehan, W. A.; A NIST standard reference
material (SRM) to support the detection of trace explosives. J. Anal. Chem. 2009,
81, 7189-7196.
Schulte-Ladbeck, R.; Karst, U.; Kolla, P. Trace analysis of peroxide-based explosives. Anal. Chem. 2003,
75 (4), 731-735.
Verkouteren, J. R.; J. Forensic Sci. 2007, 52 (2), 335-340.
Structural
Phase Transformations of Mg3N2 at High Pressure:
Experimental and Theoretical Studies
Margaret A. Mudd
Magnesium nitride, Mg3N2,
has been used as a nitriding agent and as a catalyst.
The crystal structure under ambient conditions is cubic antibixbyite
(anti-C-type), similar to sesquioxides. The cubic antibixbyite structure is known to undergo structural
changes with respect to temperature and pressure. For sesquioxides,
transitions occur from C- to B- (monocyclic) to A-type (hexagonal) with
increasing pressure. By X-ray diffraction analysis at room temperate, a
reversible transformation from anti-C- to anti-B-type (monocyclic) was observed
beginning at 20.6 GPa and
complete at 32.5 GPa. First-principle calculations
were found to be in agreement with the experimental findings. A further
transformation to anti-A-type at higher pressures was not experimentally found
but was predicted theoretically by use of enthalpy calculations to occur at
approximately 67 GPa.
Biboliography
Hao, J.; Li, Y.; Zhou, Q.; Iiu, D.;
Li, M.; Li, F.; Lei, W.; Chen, X.; Ma, Y.; cui, Q.; Zou,
G.; Liu, J.; li, X. Inorg. Chem. 2009, 48, 9737-9741.
Guo, Q.;
Zhao, Y.; Jiang, C.; Mao, W. L.; Wang, A.; Zhang, A.; Wang, Z. Inorg. Chem., 2007, 46, 6164–6169.
Walsh,
A.; Catlow, C. R.; Sokol,
A. A.; Woodley, S. M. Chem. Mat., 2009, 21, pp 49624969
The Chemical
Imagination at Work in Very Tight Places
Therese Gerbich
When subjected to extreme pressures
(hundreds of GPa’s), the
typical models for structure and bonding offer an incomplete understanding of
the nature of matter. Such high pressures produce a variety of responses in
molecules, including the exclusion of Van der Waals
space, increasing coordination numbers, shrinking bond length, and even
reexamining what closest packing really means.
Bibliography:
Grochala, W.; Hoffman, R.; Feng, J.; Ashcroft, N. W. Angew. Chem. Int. Ed. 2007, 46, 3620 – 3642
Uptake of Aromatic Arsenicals from Soil Contaminated with Diphenylarsinic Acid by Rice
Annie Froeschner, CHEM 345
Many chemical warfare agents used in
the 20th century contained aromatic arsenicals (AAs), which are
known to leak into the environment. The
uptake of AAs in agricultural soil by rice was studied to determine which part
of the plant contained the arsenicals, which metabolic pathway AAs in soil and
rice follow, and which conditions rice should be grown under to reduce the
uptake of AAs. Methylphenylarsinic
acid (MPAA) was detected in rice grown in contaminated soil. Dimethlyphenylarsine oxide (DMPAO) and methyldiphenylarsine
oxide (MDPAO) were detected in the straw but not in the grains grown in the
contaminated soil. Phenylarsinic
acid (PAA) and MPAA concentrations decreased and DMPAO concentration increased
under flooded conditions, but their concentrations were found to be unchanged
under upland conditions. MPAA and diphenylarsinic acid (DPAA) were methylated
in the soil, not in the plants, and dephenylated
products were detected in the straw.
DMPAO and MDPAO absorbed by the shoots were retained, and MPAA and DPAA
absorbed by the shoots were translocated to the
grains more easily than other AAs.
Rapid Screening of Anabolic Steroids in Urine by Reactive
Desorption Electrospray Ionization
Drew Garwood
The use of anabolic steroids in professional
and collegiate sports has increased at an exponential rate. The accepted method
in testing for these substances has been gas chromatography and mass
spectrometry based on the great detail produced. Steps in the procedure make
this a long process, for which a faster one is sought after. A faster more
efficient method combines reactive desorption electrospray
ionization (reactive DESI) and tandem mass spectrometry. The seven steroids
being tested include a carbonyl group, which reacted with the hydroxylamine
contained in the spray during the ionization process. The dehydration of the
adduct and the oxime formed was observed by reactive
DESI and the protonated and sodiated
forms of the ionized steroid were observed with reactive DESI and DESI that didn’t
include the hydroxylamine. Analysis times were only a few seconds, limits of
detection for pure compounds were less than 1 ng, and
dynamic ranges were typically 2 orders of magnitude. Considerable improvements
in the time efficiency needed to test for steroids were displayed by using
reactive DESI rather than conventional DESI.
The tandem mass spectrometry was used as conformation identification for
the rapid screening process.
High Precision Quantitative Proteomics Using iTRAQ on an LTQ Orbitrap: A New Mass Spectrometric Method Combining the Benefits of
All
Matt July
Mass spectrometry
has a plethora of applications in areas other than chemistry, especially in the
field of proteomics. Various types of
mass spectrometric analyzers are able to quantify and identify specific proteins
in tissue samples, but the degree of accuracy and efficiency varies among the
analyzers. Since proteomics has promising applications in finding treatments
for diseases, determining the method of analysis that best optimizes these
parameters is important. Three methods
of mass spectrometric analysis were tested: pulsed Q dissociation (PQD), higher
energy C-trap dissociation (HCP), and a hybrid collisional
induced dissociation (CID) – HCP.
CID-HCP identified over twice as many proteins in a complex peptide
mixture. In addition, CID-HCP was better
suited in measuring small amounts of proteins than HCP alone. Finally, the hybrid analyzer showed practical
utility in the determination of protein changes in an in vivo mouse model of cardiac hypertrophy.
Bibliography
Kösher, T.; et al. J. Proteome Res. 2009, 8, 4743-4752.
Karp, G. Cell and Molecular Biology :
Concepts and Experiments; John Wiley & Sons, Inc.: Danvers, MA, 2008;
pp 49-74.
Robinson, J.W.; et al. Undergraduate Instrumental Analysis; Marcel Dekker: New York, 2005; pp 620-647.