Abstract: This project concerns with the detection efficiency of the portable Triple-to-Double Coincidence Ratio (TDCR) at the National Institute of Metrology of Ionizing Radiation (INMRI-ENEA) which allows direct activity measurement and radionuclide standardization for pure-beta emitter or pure electron capture radionuclides. The dependency of the simulated detection efficiency of the TDCR, by using Monte Carlo simulation Geant4 code, on the Birks factor (kB) and defocusing parameter has been examined especially for low energy beta-emitter radionuclides such as 3H and 14C, for which this dependency is relevant. The results achieved in this analysis can be used for selecting the best kB factor and the defocusing parameter for computing theoretical TDCR parameter value. The theoretical results were compared with the available ones, measured by the ENEA TDCR portable detector, for some pure-beta emitter radionuclides. This analysis allowed to improve the knowledge of the characteristics of the ENEA TDCR detector that can be used as a traveling instrument for in-situ measurements with particular benefits in many applications in the field of nuclear medicine and in the nuclear energy industry.
Abstract: Here, we report a simple method for the direct conversion of 6-Nitro-1H-indole into N-substituted indoles via electrochemical dehydrogenative reaction with halogenated reagents under strongly basic conditions through N–R bond formation. The N-protected indoles have been prepared under moderate and scalable electrolytic conditions. The conduct of the reactions was performed in a simple divided cell under constant current without oxidizing reagents or transition-metal catalysts. The synthesized products have been characterized via UV/Vis spectrophotometry, 1H-NMR, and FTIR spectroscopy. A possible reaction mechanism is discussed based on the N-protective products. This methodology could be applied to the synthesis of various biologically active N-substituted indole derivatives.
Abstract: Surface wettability is a crucial factor in oil recovery. In oil industry, the rock wettability involves the interplay between water, oil, and solid surface. Therefore, studying the interplay between adsorptions of water and hydrocarbon molecules on solid surface would be very informative for understanding rock wettability. Here we use the in-situ Nuclear Magnetic Resonance (NMR) gas isotherm technique to study competitive adsorptions of water and isopropanol, an intermediate step from hydrocarbons. This in-situ NMR technique obtains information on thermodynamic properties such as the isotherm, molecular dynamics via spin relaxation measurements, and adsorption kinetics such as how fast the system can reach thermal equilibrium after changes of vapor pressures. Using surfaces of silica glass beads, which can be modified from hydrophilic to hydrophobic, we obtained information on the influence of surface hydrophilicity on the state of surface water via obtained thermodynamic and dynamic properties.
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: This study presents the synthesis of a series of methoxybenzoylthiourea amino acid derivatives. The compounds were obtained from the reactions between 2/3/4-methoxybenzoyl isothiocyanate with threonine. All of the compounds were characterized via mass spectrometry, 1H and 13C NMR spectrometry, UV-Vis spectrophotometer and FT-IR spectroscopy. Mass spectra for all of the compounds showed the presence of molecular ion [M]+ peaks at m/z 312, which are in agreement to the calculated molecular weight. For 1H NMR spectra, the presence of OCH3, C=S-NH and C=O-NH protons were observed within range of δH 3.8-4.0 ppm, 11.1-11.5 ppm and 10.0-11.5 ppm, respectively. 13C NMR spectra in all compounds displayed the presence of OCH3, C=O-NH, C=O-OH and C=S carbon resonances within range of δC 55.0-57.0 ppm, 165.0-168.0 ppm, 170.0-171.0 ppm and 180.0-182.0 ppm, respectively. In UV spectra, two absorption bands have been observed and both were assigned to the n-π* and π-π* transitions. Six vibrational modes of v(N-H), v(O-H), v(C=O-OH), v(C=O-NH), v(C=C) aromatic and v(C=S) appeared in the FT-IR spectra within the range of 3241-3467 cm-1, 2976-3302 cm-1, 1720-1768 cm-1, 1655-1672 cm-1, 1519-1525 cm-1 and 754-763 cm-1, respectively. The antibacterial activity for all of the compounds was screened against Staphylococcus aureus, Staphylococcus epidermidis, Salmonella typhimurium and Escherichia coli. However, no activity was observed.
Abstract: Two organic dyes comprising carbazole as the electron donors and cyanoacetic acid moieties as the electron acceptors were synthesized. The organic dye was prepared by standard reaction from carbazole as the starting material. To this end, carbazole was reacted with bromobenzene and further oxidation and reacted with cyanoacetic acid. The obtained organic dye was purified and characterized using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (1HNMR), carbon nuclear magnetic resonance (13CNMR) and elemental analysis. The influence of heteroatom on carbazole donors and cyno substitution on the acid acceptor is evidenced by spectral and electrochemical photovoltaic experiments. Finally, light fastness properties for organic dye were investigated.
Abstract: Cellulose acetate (CA) is a natural biodegradable polymer. It forms transparent films by the casting technique. CA suffers from high degree of water permeability as well as the low thermal stability at high temperatures. To adjust the CA polymeric films to the manufacture of food packaging, its thermal and mechanical properties should be improved. The modification of CA by grafting it with N-Amino phenyl maleimide (N-APhM) led to the construction of hydrophobic branches throughout the polymeric matrix which reduced its wettability as compared to the parent CA. The branches built onto the polymeric chains had been characterized by UV/Vis, 13C-NMR and ESEM. The improvement of the thermal properties was investigated and compared to the parent CA using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), differential thermal analysis (DTA), contact angle and mechanical testing measurements. The results revealed that the water-uptake was reduced by increasing the graft percentage. The thermal and mechanical properties were also improved.
Abstract: Ecological pollution is of great concern for human health and the environment. Numerous organic and inorganic pollutants usually discharged into the water caused carcinogenic or toxic effect for human and different life form. In this respect, this work aims to treat water contaminated by organic and inorganic waste using sorbent based on polystyrene. Therefore, two different series of adsorbent material were prepared; the first one included the preparation of polymeric sorbent from the reaction of styrene acrylate ester and alkyl acrylate. The second series involved syntheses of composite ion exchange resins of waste polystyrene and amorphous carbon thin film (WPS/ACTF) by solvent evaporation using micro emulsion polymerization. The produced ACTF/WPS nanocomposite was sulfonated to produce cation exchange resins ACTF/WPSS nanocomposite. The sorbents of the first series were characterized using FTIR, 1H NMR, and gel permeation chromatography. The thermal properties of the cross-linked sorbents were investigated using thermogravimetric analysis, and the morphology was characterized by scanning electron microscope (SEM). The removal of organic pollutant was determined through absorption tests in a various organic solvent. The chemical and crystalline structure of nanocomposite of second series has been proven by studies of FTIR spectrum, X-rays, thermal analysis, SEM and TEM analysis to study morphology of resins and ACTF that assembled with polystyrene chain. It is found that the composite resins ACTF/WPSS are thermally stable and show higher chemical stability than ion exchange WPSS resins. The composite resin was evaluated for calcium hardness removal. The result is evident that the ACTF/WPSS composite has more prominent inorganic pollutant removal than WPSS resin. So, we recommend the using of nanocomposite resin as new potential applications for water treatment process.
Abstract: Nuclear Magnetic Resonance (NMR) spectroscopy is an indispensable technique used in structure determination of small and macromolecules to study their physical properties, elucidation of characteristic interactions, dynamics and thermodynamic processes. Quantum mechanics defines the theoretical description of NMR spectroscopy and treatment of the dynamics of nuclear spin systems. The phenomenon of residual dipolar coupling (RDCs) has become a routine tool for accurate structure determination by providing global orientation information of magnetic dipole-dipole interaction vectors within a common reference frame. This offers accessibility of distance-independent angular information and insights to local relaxation. The measurement of RDCs requires an anisotropic orientation medium for the molecules to partially align along the magnetic field. This can be achieved by introduction of liquid crystals or attaching a paramagnetic center. Although anisotropic paramagnetic tags continue to mark achievements in the biomolecular NMR of large proteins, its application in small organic molecules remains unspread. Here, we propose a strategy for the synthesis of a lanthanide tag and the measurement of RDCs in organic molecules using paramagnetic lanthanide complexes.
Abstract: The main objective of this research was to study the differences of aluminum hydrolytic products between two PACl preparation methods. These two methods were the acidification process of freshly formed amorphous Al(OH)3 and the conventional alkalization process of aluminum chloride solution. According to Ferron test and 27Al NMR analysis of those two PACl preparation procedures, the reaction rate constant (k) values and Al13 percentage of acid addition process at high basicity value were both lower than those values of the alkaline addition process. The results showed that the molecular structure and size distribution of the aluminum species in both preparing methods were suspected to be significantly different at high basicity value.
Abstract: The processes of complexation of the Zn-tetraarylporphyrins with eight 4-(4-(3,6-bis(t-butyl)carbazol-9-yl-phenyl)-1,2,3-triazole (ZnP1) and eight 4-(4-(3,6-di-tert-butyl-9-H-carbazol-9-yl)phenoxy)methyl)-2,4,6-trimethylphenyl (ZnP2)with the 1,10-diaza-4,7,13,18tetraoxabicyclo[8.5.5]eicosane (L1),1,10-diaza-4,7,13,16,21,24-hexaoxabicyclo[8.8.8]hexacosane (L2)and 1,10-diaza-5,6,14,15-dibenzo-4,7,13,16,21,24 hexaoxabicyclo[8.8.8] hexacosane (L3) were investigated by the method of spectrophotometric titration and 1H NMR-spectroscopy. We determined the structures of the host-guest complexes, and their stability constants in toluene were calculated. It was found out that the ZnP1 interacts with the guest molecules L1, L2 with the formation of stable "nest" type complexes and does not form similar complexes with the L3 (presumably due to the fact that the L3 does not match the size of the porphyrin ZnP(1) cavity). On the other hand, the porphyrin ZnP2 binds all of the ligands L1-L3, however complexes thus formed are less stable than complexes ZnP1-L1, ZnP1-L2. In the report, we will also discuss the influence of the alkali cations additives on the stability of the complexes between the porphyrin ZnP1, ZnP2 hosts and guest molecules of the ligands L1-L3.
Abstract: This study was initiated to evaluate and optimize the conversion of animal fat from tannery wastes into methyl ester. In the pre-treatment stage, animal fats feedstock was hydrolysed and esterified through solid state fermentation (SSF) using Microbacterium species immobilized onto sand silica matrix. After 72 hours of fermentation, predominant esters in the animal fats were found to be with 83.9% conversion rate. Later, esterified animal fats were transesterified at 3 hour reaction time with 1% NaOH (w/v %), 6% methanol to oil ratio (w/v %) to produce 89% conversion rate. C13 NMR revealed long carbon chain in fatty acid methyl esters at 22.2817-31.9727 ppm. Methyl esters of palmitic, stearic, oleic represented the major components in biodiesel.
Abstract: Cytotoxic platinum compounds play a major role in the chemotherapy of a large number of human cancers. However, due to the severe side effects for the patient and other problems associated with their use, there is a need for the development of more efficient drugs and new methods for their selective delivery to the tumours. One way to achieve the latter could be in the use of nanoparticular substrates that can adsorb or chemically bind the drug. In the cell, the drug is supposed to be slowly released, either by physical desorption or by dissolution of the particle framework. Ideally, the cytotoxic properties of the platinum drug unfold only then, in the cancer cell and over a longer period of time due to the gradual release. In this paper, we report on our first steps in this direction. The binding properties of a series of cytotoxic Pt(II) oxadiazoline compounds to mesoporous silica particles has been studied by NMR and UV/vis spectroscopy. High loadings were achieved when the Pt(II) compound was relatively polar, and has been dissolved in a relatively nonpolar solvent before the silica was added. Typically, 6-10 hours were required for complete equilibration, suggesting the adsorption did not only occur to the outer surface but also to the interior of the pores. The untreated and Pt(II) loaded particles were characterised by C, H, N combustion analysis, BET/BJH nitrogen sorption, electron microscopy (REM and TEM) and EDX. With the latter methods we were able to demonstrate the homogenous distribution of the Pt(II) compound on and in the silica particles, and no Pt(II) bulk precipitate had formed. The in vitro cytotoxicity in a human cancer cell line (HeLa) has been determined for one of the new platinum compounds adsorbed to mesoporous silica particles of different size, and compared with the corresponding compound in solution. The IC50 data are similar in all cases, suggesting that the release of the Pt(II) compound was relatively fast and possibly occurred before the particles reached the cells. Overall, the platinum drug is chemically stable on silica and retained its activity upon prolonged storage.
Abstract: The study explores the hybrid combination of Hydrodynamic Cavitation (HC) and Subcritical Wet Air Oxidation-based pretreatment of complex industrial effluent to enhance the biodegradability selectively (without major COD destruction) to facilitate subsequent enhanced downstream processing via anaerobic or aerobic biological treatment. Advanced oxidation based techniques can be less efficient as standalone options and a hybrid approach by combining Hydrodynamic Cavitation (HC), and Wet Air Oxidation (WAO) can lead to a synergistic effect since both the options are based on common free radical mechanism. The HC can be used for initial turbulence and generation of hotspots which can begin the free radical attack and this agitating mixture then can be subjected to less intense WAO since initial heat (to raise the activation energy) can be taken care by HC alone. Lab-scale venturi-based hydrodynamic cavitation and wet air oxidation reactor with biomethanated distillery wastewater (BMDWW) as a model effluent was examined for establishing the proof-of-concept. The results indicated that for a desirable biodegradability index (BOD: COD - BI) enhancement (up to 0.4), the Cavitation (standalone) pretreatment condition was: 5 bar and 88 min reaction time with a COD reduction of 36 % and BI enhancement of up to 0.27 (initial BI - 0.17). The optimum WAO condition (standalone) was: 150oC, 6 bar and 30 minutes with 31% COD reduction and 0.33 BI. The hybrid pretreatment (combined Cavitation + WAO) worked out to be 23.18 min HC (at 5 bar) followed by 30 min WAO at 150oC, 6 bar, at which around 50% COD was retained yielding a BI of 0.55. FTIR & NMR analysis of pretreated effluent indicated dissociation and/or reorientation of complex organic compounds in untreated effluent to simpler organic compounds post-pretreatment.
Abstract: Highly stable and homogeneously dispersed amino
acid coated silver nanoparticles (ANP) of ≈ 10 nm diameter, ranging
from 420 to 430 nm are prepared on AgNO3 solution addition to gum
of Azadirachta indica solution at 373.15 K. The amino acids were
selected based on their polarity. The synthesized nanoparticles were
characterized by UV-Vis, FTIR spectroscopy, HR-TEM, XRD, SEM
and 1H-NMR. The coated nanoparticles were used as catalyst for the
reduction of methylene blue dye in presence of Sn(II) in aqueous,
anionic and cationic micellar media. The rate of reduction of dye was
determined by measuring the absorbance at 660 nm,
spectrophotometrically and followed the order: Kcationic > Kanionic >
Kwater. After 12 min and in absence of the ANP, only 2%, 3% and 6%
of the dye reduction was completed in aqueous, anionic and cationic
micellar media respectively while, in presence of ANP coated by
polar neutral amino acid with non-polar -R group, the reduction
completed to 84%, 95% and 98% respectively. The ANP coated with
polar neutral amino acid having non-polar -R group, increased the
rate of reduction of the dye by 94, 3205 and 6370 folds in aqueous,
anionic and cationic micellar media respectively. Also, the rate of
reduction of the dye increased by three folds when the micellar media
was changed from anionic to cationic when the ANP is coated by a
polar neutral amino acid having a non-polar -R group.
Abstract: The 1:1 cocrystal of 2-amino-4-chloro-6-
methylpyrimidine (2A4C6MP) with 4-methylbenzoic acid (4MBA)
(I) has been prepared by slow evaporation method in methanol,
which was crystallized in monoclinic C2/c space group, Z = 8, and a
= 28.431 (2) Å, b = 7.3098 (5) Å, c = 14.2622 (10) Å and β =
109.618 (3)°. The presence of unionized –COOH functional group in
cocrystal I was identified both by spectral methods (1H and 13C
NMR, FTIR) and X-ray diffraction structural analysis. The
2A4C6MP molecule interact with the carboxylic group of the
respective 4MBA molecule through N—H⋯O and O—H⋯N
hydrogen bonds, forming a cyclic hydrogen–bonded motif R2
2(8).
The crystal structure was stabilized by Npyrimidine—H⋯O=C and
C=O—H⋯Npyrimidine types hydrogen bonding interactions.
Theoretical investigations have been computed by HF and density
function (B3LYP) method with 6–311+G (d,p)basis set. The
vibrational frequencies together with 1H and 13C NMR chemical
shifts have been calculated on the fully optimized geometry of
cocrystal I. Theoretical calculations are in good agreement with the
experimental results. Solvent–free formation of this cocrystal I is
confirmed by powder X-ray diffraction analysis.
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: The objective of this study was to synthesize and
characterize the poly(alkenoic acid)s with different molecular
structures, use these polymers to formulate a dental cement
restorative, and study the effect of molecular structures on reaction
kinetics, viscosity, and mechanical strengths of the formed polymers
and cement restoratives. In this study, poly(alkenoic acid)s with
different molecular structures were synthesized. The purified
polymers were formulated with commercial Fuji II LC glass fillers to
form the experimental cement restoratives. The reaction kinetics was
studied via 1HNMR spectroscopy. The formed restoratives were
evaluated using compressive strength, diametral tensile strength,
flexural strength, hardness and wear-resistance tests. Specimens were
conditioned in distilled water at 37oC for 24 h prior to testing. Fuji II
LC restorative was used as control. The results show that the higher
the arm number and initiator concentration, the faster the reaction
was. It was also found that the higher the arm number and branching
that the polymer had, the lower the viscosity of the polymer in water
and the lower the mechanical strengths of the formed restorative. The
experimental restoratives were 31-53% in compressive strength, 37-
55% in compressive modulus, 80-126% in diametral tensile strength,
76-94% in flexural strength, 4-21% in fracture toughness and 53-96%
in hardness higher than Fuji II LC. For wear test, the experimental
restoratives were only 5.4-13% of abrasive and 6.4-12% of attritional
wear depths of Fuji II LC in each wear cycle. The aging study also
showed that all the experimental restoratives increased their strength
continuously during 30 days, unlike Fuji II LC. It is concluded that
polymer molecular structures have significant and positive impact on
mechanical properties of dental cement restoratives.
Abstract: The high-molecular water-soluble preparations from
several species of two genera (Symphytum and Anchusa) of
Boraginaceae family Symphytum asperum, S. caucasicum, S.officinale
and Anchusa italica were isolated. According to IR, 13C and 1H
NMR, APT, 1D NOE, 2D heteronuclear 1H/13C HSQC and 2D
DOSY experiments, the main chemical constituent of these
preparations 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 caffeic acid-derived polymer of A. italica are methylated.
Abstract: In this study, nuclear magnetic resonance
spectroscopy and nuclear quadrupole resonance spectroscopy
parameters of 14N (Nitrogen in imidazole ring) in N–H…O hydrogen
bonding for Histidine hydrochloride monohydrate were calculated via
density functional theory. We considered a five-molecule model
system of Histidine hydrochloride monohydrate. Also we examined
the trends of environmental effect on hydrogen bonds as well as
cooperativity. The functional used in this research is M06-2X which
is a good functional and the obtained results has shown good
agreement with experimental data. This functional was applied to
calculate the NMR and NQR parameters. Some correlations among
NBO parameters, NMR and NQR parameters have been studied
which have shown the existence of strong correlations among them.
Furthermore, the geometry optimization has been performed using
M062X/6-31++G(d,p) method. In addition, in order to study
cooperativity and changes in structural parameters, along with
increase in cluster size, natural bond orbitals have been employed.