Abstract: Objectives/Hypotheses: The adverse health effect potential of dietary lipid oxidation products (LOPs) has evoked much clinical interest. Therefore, we employed a 1H NMR-linked Principal Component Regression (PCR) chemometrics modelling strategy to explore relationships between data matrices comprising (1) aldehydic LOP concentrations generated in culinary oils/fats when exposed to laboratory-simulated shallow frying practices, and (2) the prior saturated (SFA), monounsaturated (MUFA) and polyunsaturated fatty acid (PUFA) contents of such frying media (FM), together with their heating time-points at a standard frying temperature (180 oC). Methods: Corn, sunflower, extra virgin olive, rapeseed, linseed, canola, coconut and MUFA-rich algae frying oils, together with butter and lard, were heated according to laboratory-simulated shallow-frying episodes at 180 oC, and FM samples were collected at time-points of 0, 5, 10, 20, 30, 60, and 90 min. (n = 6 replicates per sample). Aldehydes were determined by 1H NMR analysis (Bruker AV 400 MHz spectrometer). The first (dependent output variable) PCR data matrix comprised aldehyde concentration scores vectors (PC1* and PC2*), whilst the second (predictor) one incorporated those from the fatty acid content/heating time variables (PC1-PC4) and their first-order interactions. Results: Structurally complex trans,trans- and cis,trans-alka-2,4-dienals, 4,5-epxy-trans-2-alkenals and 4-hydroxy-/4-hydroperoxy-trans-2-alkenals (group I aldehydes predominantly arising from PUFA peroxidation) strongly and positively loaded on PC1*, whereas n-alkanals and trans-2-alkenals (group II aldehydes derived from both MUFA and PUFA hydroperoxides) strongly and positively loaded on PC2*. PCR analysis of these scores vectors (SVs) demonstrated that PCs 1 (positively-loaded linoleoylglycerols and [linoleoylglycerol]:[SFA] content ratio), 2 (positively-loaded oleoylglycerols and negatively-loaded SFAs), 3 (positively-loaded linolenoylglycerols and [PUFA]:[SFA] content ratios), and 4 (exclusively orthogonal sampling time-points) all powerfully contributed to aldehydic PC1* SVs (p 10-3 to < 10-9), as did all PC1-3 x PC4 interaction ones (p 10-5 to < 10-9). PC2* was also markedly dependent on all the above PC SVs (PC2 > PC1 and PC3), and the interactions of PC1 and PC2 with PC4 (p < 10-9 in each case), but not the PC3 x PC4 contribution. Conclusions: NMR-linked PCR analysis is a valuable strategy for (1) modelling the generation of aldehydic LOPs in heated cooking oils and other FM, and (2) tracking their unsaturated fatty acid (UFA) triacylglycerol sources therein.
Abstract: According to IR, 13C and 1H NMR, APT, 1D NOE,
2D heteronuclear 1H/13C HSQC and 2D DOSY experiments the main
chemical constituent of high-molecular preparations from Symphytum
asperum, S. caucasicum, S. officinale and Anchusa italica
(Boraginaceae) was found to be caffeic acid-derived polyether,
namely poly[3-(3,4-dihydroxyphenyl)glyceric acid] (PDPGA) or
poly[oxy-1-carboxy-2-(3,4-dihydroxyphenyl)ethylene]. Most
carboxylic groups of this polymer of A. italica are methylated.
Abstract: Honeys are produced by Apis mellifera and stingless
bees (Meliponini) in Ecuador. We studied honey produced in
beeswax combs by Apis mellifera, and honey produced in pots by
Geotrigona and Scaptotrigona bees. Chloroform extracts of honey
were obtained for fast NMR spectra. The 1D spectra were acquired at
298 K, with a 600 MHz NMR Bruker instrument, using a modified
double pulsed field gradient spin echoes (DPFGSE) sequence.
Signals of 1H NMR spectra were integrated and used as inputs for
PCA, PLS-DA analysis, and labelled sets of classes were successfully
identified, enhancing the separation between the three groups of
honey according to the entomological origin: A. mellifera,
Geotrigona and Scaptotrigona. This procedure is therefore
recommended for authenticity test of honey in Ecuador.
Abstract: Control of honey frauds is needed in Ecuador to
protect bee keepers and consumers because simple syrups and new
syrups with eucalyptus are sold as genuine honeys. Authenticity of
Ecuadorian commercial honeys was tested with a vortex emulsion
consisting on one volume of honey:water (1:1) dilution, and two
volumes of diethyl ether. This method allows a separation of phases
in one minute to discriminate genuine honeys that form three phase
and fake honeys that form two phases; 34 of the 42 honeys analyzed
from five provinces of Ecuador were genuine. This was confirmed
with 1H NMR spectra of honey dilutions in deuterated water with an
enhanced amino acid region with signals for proline, phenylalanine
and tyrosine. Classic quality indicators were also tested with this
method (sugars, HMF), indicators of fermentation (ethanol, acetic
acid), and residues of citric acid used in the syrup manufacture. One
of the honeys gave a false positive for genuine, being an admixture of
genuine honey with added syrup, evident for the high sucrose.
Sensory analysis was the final confirmation to recognize the honey
groups studied here, namely honey produced in combs by Apis
mellifera, fake honey, and honey produced in cerumen pots by
Geotrigona, Melipona, and Scaptotrigona. Chloroform extractions of
honey were also done to search lipophilic additives in NMR spectra.
This is a valuable contribution to protect honey consumers, and to
develop the beekeeping industry in Ecuador.
Abstract: Epidermal Growth Factor (EGF, Mw=6,045) has been
reported to have high efficiency of wound repair and anti-wrinkle
effect. However, the half-life of EGF in the body is too short to exert
the biological activity effectively when applied in free form. Growth
Factors can be stabilized by immobilization with carbohydrates from
thermal and proteolytic degradation. Low molecular weight chitosan
(LMCS) and its derivate prepared by hydrogen peroxide has high
solubility. LM6A6DC was successfully prepared as a reactive
carbohydrate for the stabilization of EGF by the reactions of LMCS
with alkalization, tosylation, azidation and reduction. The structure of
LM6A6DC was confirmed by FT-IR, 1H NMR and elementary
analysis. For enhancing the stability of free EGF, EGF was attached
with LM6A6DC by using water-soluble carbodiimide.
EGF-LM6A6DC conjugates did not show any cytotoxicity on the
Normal Human Dermal Fibroblast (NHDF) 3T3 proliferation at least
under 100 μg/ml. In the result, it was considered that LM6A6DC is
suitable to immobilize of growth factor.
Abstract: Doxorubicin, also known as Adriamycin, is an
anthracycline class of drug used in cancer chemotherapy. It is used in
the treatment of non-Hodgkin’s lymphoma, multiple myeloma, acute
leukemia, breast cancer, lung cancer, endometrium cancer and ovary
cancers. It functions via intercalating DNA and ultimately killing
cancer cells. The major side effects of doxorubicin are hair loss,
myelosuppression, nausea & vomiting, oesophagitis, diarrhea, heart
damage and liver dysfunction. The minor modifications in the
structure of compound exhibit large variation in the biological
activity, has prompted us to carry out the synthesis of sulfonamide
derivatives. Sulfonamide is an important feature with broad spectrum
of biological activity such as antiviral, antifungal, diuretics, antiinflammatory,
antibacterial and anticancer activities. Structure of the
synthesized compound N-(1-methyl-2-oxo-2-N-methyl anilinoethyl)
benzene sulfonamide confirmed by proton nuclear magnetic
resonance (1H NMR),13C NMR, Mass and FTIR spectroscopic tools
to assure the position of all protons and hence stereochemistry of the
molecule. Further we have reported the binding potential of
synthesized sulfonamide analogues in comparison to doxorubicin
drug using Auto Dock 4.2 software. Computational binding energy
(B.E.) and inhibitory constant (Ki) has been evaluated for the
synthesized compound in comparison of doxorubicin against Poly
(dA-dT).Poly (dA-dT) and Poly (dG-dC).Poly (dG-dC) sequences.
The in vitro cytotoxic study against human breast cancer cell lines
confirms the better anticancer activity of the synthesized compound
over currently in use anticancer drug doxorubicin. The IC50 value of
the synthesized compound is 7.12 μM whereas for doxorubicin is 7.2
μM.
Abstract: Polylactic acid-g-polyvinyl acetate (PLLA-g-PVAc)
was used as a compatibilizer for 50/50 starch/PLLA blend. PLLA-g-
PVAc with different mol% of PVAc contents were prepared by
grafting PVAc onto PLLA backbone via free radical polymerization
in solution process. Various conditions such as type and the amount
of initiator, monomer concentration, polymerization time and
temperature were studied. Results showed that the highest mol% of
PVAc grafting (16 mol%) was achieved by conducting graft
copolymerization in toluene at 110°C for 10 h using DCP as an
initiator. Chemical structure of the PVAc grafted PLLA was
confirmed by 1H NMR. Blending of modified starch and PLLA in the
presence compatibilizer with different amounts and mol% PVAc was
acquired using internal mixer at 160°C for 15 min. Effects of PVAc
content and the amount of compatibilizer on mechanical properties of
polymer blend were studied. Results revealed that tensile strength and
tensile modulus of polymer blend with higher PVAc grafting content
compatibilizer showed better properties than that of lower PVAc
grafting content compatibilizer. The amount of compatibilizer was
found optimized in the range of 0.5-1.0 Wt% depending on the mol%
PVAc.
Abstract: Since hyaluronic acid (HA) receptor such as CD44 is
over-expressed at sites of cancer cells, HA can be used as a targeting
vehicles for anti-cancer drugs. The aim of this study is to synthesize
block copolymer composed of hyaluronic acid and
poly(ε-caprolactone) (HAPCL) and to fabricate polymeric micelles for
anticancer drug targeting against CD44 receptor of tumor cells.
Chemical composition of HAPCL was confirmed using 1H NMR
spectroscopy. Doxorubicin (DOX) was incorporated into polymeric
micelles of HAPCL. The diameters of HAPHS polymeric micelles
were changed around 80nm and have spherical shapes. Targeting
potential was investigated using CD44-overexpressing. When
DOX-incorporated polymeric micelles was added to KB cells, they
revealed strong red fluorescence color while blocking of CD44
receptor by pretreatment of free HA resulted in reduced intensity,
indicating that HAPCL polymeric micelles have targetability against
CD44 receptor.
Abstract: Optimization study of the diesters biolubricant oleyl 9(12)-hydroxy-10(13)-oleioxy-12(9)-octadecanoate (OLHYOOT) was synthesized in the presence of sulfuric acid (SA) as catalyst has been done. Optimum conditions of the experiment to obtain high yield% of OLHYOOT were predicted at ratio of OL/HYOOA of 1:1 g/g, ratio of SA/HYOOA of 0.20:1 g/g, reaction temperature 110 °C and 4.5 h of reaction time. At this condition, the Yield% of OLHYOOT was 88.7. Disappearance of carboxylic acid (C=O) peak has observed by FTIR with appearance ester (C=O) at 1738 cm-1. 1H NMR spectra analyses confirmed the result of OLHYOOT with appearance ester (-CHOCOR) at 4.05ppm and also the 13C-NMR confirmed the result with appearance ester (C=O) peak at 173.93ppm.