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American Journal of Physical Chemistry 2015 44: 30-37 Published online October 15 2015 http://www.sciencepublishinggroup.com/j/ajpc doi: 10.11648/j.ajpc.20150404.11 ISSN: 2327-2430 Print ISSN: 2327-2449 Online Characterization of Physico-Chemical and Spectroscopic Properties of Biofield Energy Treated 4-Bromoacetophenone Mahendra Kumar Trivedi 1 Alice Branton 1 Dahryn Trivedi 1 Gopal Nayak 1 Gunin Saikia 2 Snehasis Jana 2 1 Trivedi Global Inc. Henderson USA 2 Trivedi Science Research Laboratory Pvt. Ltd. Hall-A Chinar Mega Mall Chinar Fortune City Hoshangabad Rd. Bhopal Madhya Pradesh India Email address publicationtrivedisrl.com S. Jana To cite this article: Mahendra Kumar Trivedi Alice Branton Dahryn Trivedi Gopal Nayak Gunin Saikia Snehasis Jana. Characterization of Physico-Chemical and Spectroscopic Properties of Biofield Energy Treated 4-bromoacetophenone. American Journal of Physical Chemistry. Vol. 4 No. 4 2015 pp. 30-37. doi: 10.11648/j.ajpc.20150404.11 Abstract: 4-Bromoacetophenone is an acetophenone derivative known for its usefulness in organic coupling reactions and various biological applications. The aim of the study was to evaluate the impact of biofield energy treatment on 4- bromoacetophenone using various analytical methods. The material is divided into two groups for this study i.e. control and treated. The control group remained as untreated and the treated group was subjected to Mr. Trivedi’s biofield energy treatment. Then both the samples were characterized using X-ray diffraction XRD differential scanning calorimetry DSC thermogravimetric analysis TGA Fourier transform infrared FT-IR gas chromatography-mass spectrometry GC-MS and UV-visible spectrometry UV-vis. The XRD study revealed that the crystallite size of treated 4-bromoacetophenone was decreased significantly to 16.69 with decreased intensity as compared to the control. The thermal studies revealed that the slight change was observed in the melting point and latent heat of fusion ∆H of biofield energy treated sample as compared to the control. Maximum degradation temperature T max of treated 4-bromoacetophenone was decreased by 7.26 as compared to the control 169.89°C→157.54°C. The FT-IR spectra showed that the CO stretching frequency at 1670 cm -1 was shifted to higher frequency region 1672 in T1 and 1685 cm -1 in T2 in two treated samples for FT-IR after biofield energy treatment. Moreover the GC-MS data revealed that the isotopic abundance ratio of either 13 C/ 12 C or 2 H/ 1 H PM+1/PM was decreased up to 9.12 in T2 sample whereas increased slightly up to 3.83 in T3 sample. However the isotopic abundance ratio of either 81 Br/ 79 Br or 18 O/ 16 O PM+2/PM of treated 4-bromoacetophenone was decreased from 0.10 to 1.62 where PM-primary mass of the molecule PM+1 and PM+2 are isotopic mass of the molecule. The UV spectra showed the similar electronic behavior like absorption maximum in control and treated samples. Overall the experimental results suggest that Mr. Trivedi’s biofield energy treatment has significant effect on the physical thermal and spectral properties of 4-bromoacetophenone. Keywords: 4-Bromoacetophenone Biofield Energy Treatment Fourier Transform Infrared Differential Scanning Calorimetry Thermogravimetric Analysis X-ray Diffraction Gas Chromatography-Mass Spectrometry 1. Introduction 4-Bromoacetophenone is basically a natural product and found in the environment as degradation products of industrial chemicals. It is used as a basic starting material in most of the metal catalyzed coupling reactions due to the presence of both electron-rich and electron-withdrawing functionalities within the same molecule 1. In biological systems halogen bonding has its importance due to their high directionality and specificity. Therefore they can be used effectively in drug design to direct the binding of ligands to the target sites 2. The bromoacetophenone derivatives upon excitation with ultraviolet radiation can generate phenyl

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31 Mahendra Kumar Trivedi et al.: Characterization of Physico-Chemical and Spectroscopic Properties of Biofield Energy Treated 4-Bromoacetophenone radicals. The utility of haloarenes were studied by Paul et al. as radical progenitors for DNA cleavage. It is reported that haloarenes are readily available compounds upon UV excitation and halo acetophenones are effective DNA cleaving agents 3 4. 4-Bromoacetophenone has been used as basic starting material in coupling reactions such as Heck coupling Suzuki coupling and Stille reactions 5. Furthermore guaiacyl syringyl and p-hydroxyphenyl-type bromoacetophenone derivatives were synthesized as the starting materials for β-O-4 type artificial lignin polymers 6. Apart from that the acetophenones were screened for activity against positive phototaxis of Chlamydomonas cells a process that requires coordinated flagellar motility. Several acetophenones including 3 4-dimethylacetophenone and 4- ethylacetophenone showed inhibitory effects on phototaxis in Chlamydomonas in a concentration-dependent manner indicating that these compounds nonspecifically interfere with phototaxis by disrupting overall cell viability 7. Due to their wide range of applications in biology and synthetic organic chemistry the objective of the current study was to evaluate the impact of biofield energy treatment on the physical and chemical properties of 4- bromoacetophenone. The biofield is defined as the complex dynamic electromagnetic EM field. The field resulting from the EM fields contributed by each individual oscillator or electrically charged ensemble of particles of the body ion molecule cell tissue etc. 8 9. The term “biofield” has been accepted by the U.S. National Library of Medicine as a medical subject heading 10. The biofield which surrounds the human body can be harnessed from the Universe. It has been applied on materials or living things by experts in a controlled way to make the changes 11. Mr. Trivedi’s unique biofield energy treatment is known as The Trivedi Effect ® 12. The Trivedi Effect has been applied in various research fields including microbiology research 13 agriculture research 14 15 and biotechnology research 16. Thus by observing the various transformations happened due to the unique biofield treatment of Mr. Trivedi this study aimed to evaluate the impact of biofield energy treatment on 4-bromoacetophenone with respect to their physical thermal and spectral properties. 2. Materials and Methods 2.1. Study Design 4-Bromoacetophenone was procured from Loba Chemie Pvt. Ltd. India. The compound was divided into two parts i.e. control and treated. The control sample was remained as untreated and the treated sample in sealed pack was given to Mr. Trivedi for biofield energy treatment. Mr. Trivedi provided the treatment through his energy transmission process to the treated group. The control and treated samples were evaluated using various physical thermal and spectroscopic techniques. Percent change in various parameters in treated sample with respect to control was calculated using the following equation: change Treated − Control Control × 100 2.2. X-ray Diffraction XRD Study The X-ray powder diffraction studies were carried out to characterize the crystallinity of 4-bromoacetophenone using Phillips Holland PW 1710 X-ray diffractometer system with radiation of wavelength 1.54056 Å in the 2θ range 10°- 99.99°. The crystallite size G was calculated by using the formula: G kλ/bCosθ. Here λ is the wavelength of radiation θ is the corresponding Bragg angle b is full-width half maximum FWHM of the peaks and k is the equipment constant 0.94. 2.3. Differential Scanning Calorimetry DSC Study The DSC thermogram of 4-bromoacetophenone was acquired using Perkin Elmer/Pyris-1 USA at the flow rate of 5 mL/min using closed aluminum pan to determine the melting temperature and latent heat of fusion. 2.4. Thermogravimetric Analysis TGA/ Derivative Thermogravimetry DTG TGA/DTG results were obtained using Mettler Toledo simultaneous thermogravimetric analyzer at a heating rate of 5ºC/min from room temperature to 400ºC under air atmosphere. 2.5. FT-IR Spectroscopic Analysis FT-IR FT-IR characterization was done with Shimadzu Fourier transform infrared spectrometer Japan with the frequency range of 500-4000 cm -1 . 4-bromoacetophenone was run as pressed disks using KBr as the diluent. 2.6. GC-MS Spectrometry Analysis The gas chromatography-mass spectrometry GC-MS analysis was performed on Perkin Elmer/auto system XL with Turbo Mass USA having detection limit up to 1 picogram. The GC-MS spectrum was obtained as abundance vs. mass to charge ratio m/z. The isotopic ratio of PM+1/PM and PM+2/PM was expressed by its deviation in treated samples as compared to the control. 2.7. UV-Vis Spectroscopic Analysis UV-Vis spectra of control and treated samples were obtained from Shimadzu UV spectrophotometer 2400 PC with quartz cell of 1 cm and a slit width of 2.0 nm. The analysis was done at the wavelength range of 200-400 nm. 3. Results and Discussion 3.1. XRD Studies The XRD study was conducted on both control and treated samples of 4-bromoacetophenone and diffractograms are

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American Journal of Physical Chemistry 2015 44: 30-37 32 shown in Figure 1. Both control and treated 4- bromoacetophenone samples exhibited very sharp and intense peaks of intensity 1350 a.u. and 630 a.u. respectively in their X-ray diffractogram. The control 4- bromoacetophenone exhibited the XRD peaks at 2θ equal to 19.05° 28.71° 38.57° and 49.04° Table 1. However the XRD diffractogram of treated 4-bromoacetophenone showed the XRD peaks at 2θ equal to 18.91° 20.45° 23.28° 28.57° 38.46° and 48.62 ° with decreased intensity as compared to the control. The crystallite size was calculated using Scherrer formula and found decreased after biofield treatment by 16.69 in the treated 4-bromoacetophenone. It was reported that the strain produced by energy milling had reduced the crystallite size in the crystal 17. Thus it is assumed that biofield energy treatment might induce the energy that causes milling in the treated 4-bromoacetophenone which is responsible for a decrease in crystallite size. Table 1. XRD analysis of control and treated 4-bromoacetophenone. 2θ FWHM of peak intensity 100 Crystallite size ‘G’ x 10 -9 m Percent change in ‘G’ wrt control Control 19.05 28.71 38.57 49.04 0.12 85.43 Treated 18.91 20.45 23.28 28.57 38.46 48.62 0.14 71.17 -16.69 FWHM: full width half maximum wrt: with respect to. Fig. 1. X-ray diffractograms of control and treated samples of 4-bromoacetophenone. 3.2. DSC Analysis Measurement of melting point and latent heat of fusion ∆H was done using DSC analysis. The melting point and ∆H of control and treated samples of 4-bromoacetophenone are presented in Table 2. The latent heat of fusion ∆H was decreased in the treated 4-bromoacetophenone from 230.55 J/g to 228.38 J/g. A lower melting point was observed in the treated 4-bromoacetophenone 54.44°C as compared to the control sample 55.22°C Table 2. This result showed that

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33 Mahendra Kumar Trivedi et al.: Characterization of Physico-Chemical and Spectroscopic Properties of Biofield Energy Treated 4-Bromoacetophenone treated 4-bromoacetophenone sample needed less energy in the form of ∆H to undergo the process of melting at a lower temperature after biofield energy treatment. It is hypothesized that the biofield energy might reduce the intermolecular force in the treated 4-bromoacetophenone molecules which possibly decrease the melting point and latent heat of fusion. Table 2. DSC analysis of control and treated 4-bromoacetophenone. Parameter Control Treated Percent change Latent heat of fusion ∆H J/G 230.35 228.38 -0.85 Melting point °C 55.22 54.44 -1.41 3.3. TGA/DTG Analysis The TGA/DTG thermograms of both control and treated samples of 4-bromoacetophenone are shown in Figure 2. TGA curve showed that the control and treated samples were degraded in one step. In control 4-bromoacetophenone the onset temperature was at 128.69°C and endset at 199.86°C. However in treated sample onset temperature was observed at 124.95°C and endset at 186.66°C. In this process the control sample lost 59.24 of its initial weight whereas treated sample lost 57.44 of its initial weight. The DTG thermogram showed the T max at 169.89°C and 157.54°C respectively in the control and treated sample. Thus the decrease in maximum degradation temperature of treated 4- bromoacetophenone can be related to decreasing in thermal stability. The overall decreases in thermal stability of treated sample might be advantageous to be used as a reaction intermediate in coupling and photo excitation reactions. Fig. 2. TGA-DTG thermogram of control and treated samples of 4-bromoacetophenone. 3.4. FT-IR Analysis The treated sample of 4-bromoacetophenone was divided into two parts as T1 and T2. The FT-IR spectra of control and treated samples of 4-bromoacetophenone are presented in Figure 3. The FT-IR spectra showed the aromatic C-H stretching frequency at 3010 cm -1 for control and treated samples of 4-bromoacetophenone. The IR spectra of control 4-bromoacetophenone sample showed CO stretching at 1670 cm -1 however in treated samples the CO stretching frequency shifted to higher energy region T11672 cm -1 T21685 cm -1 . The carbon-halogen bond is stronger covalent bond and it can be easily identifiable and appeared at 609 cm -1 for the C−Br bending vibration in both control and treated samples. The absorption at 1587 cm -1 and 1359 cm -1 in control sample are due to the CC stretching in

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American Journal of Physical Chemistry 2015 44: 30-37 34 aromatic ring 1359 cm -1 was first reduced to 1354 cm -1 and then increased to 1361 cm -1 in the treated T1 and T2 samples respectively. Furthermore the C-H deformation bends were assigned to the peaks at 1269 cm -1 in both control and treated samples of 4-bromoacetophenone. The FT-IR spectra indicated that there was a slight alteration in the CO and CC stretching frequencies in the treated 4- bromoacetophenone which increased after biofield energy treatment. The FT-IR results did not show any major changes in vibrational frequencies for the aromatic C-H stretching frequencies. The FT-IR spectral data is well matched with the literature data 18. Fig. 3. FT-IR spectra of control and treated samples of 4-bromoacetophenone. 3.5. GC-MS Analysis The treated sample of 4-bromoacetophenone was divided into four parts as T1 T2 T3 and T4. The mass spectra of control and treated samples of 4-bromoacetophenone are shown in Figure 4a and 4b respectively. The mass spectra showed the PM primary molecule peak at m/z 198 in the control and treated samples of 4-bromoacetophenone. The m/z peak intensity intensity ratio and isotopic abundance ratio of PM+1/PM and PM+2/PM peaks are presented in Table 3. There were six major peaks observed in both control and treated samples of 4-bromoacetophenone. The peaks are at m/z 198 183 155 76 50 and 43 due to 4- bromoacetophenone and its degraded products. The degradation of 4-bromoacetophenone corresponded to the following ions: C 8 H 9 Br + p-bromoehtylbenzene C 6 H 5 Br + bromobenzene C 6 H 5 + benzene C 4 H 2 + 1 3-butadyine and C 2 H 4 O + acetaldehyde respectively were well matched with the reported GC-MS data 19. The treated 4- bromoacetophenone samples T1-T4 were fragmented in a similar way with varied intensities as the control sample. Isotopic abundance ratio of PM+1/PM and PM+2/PM in 4-bromoacetophenone was calculated and presented in Figure 5. It is seen from the Figure 5 that the isotopic abundance ratio of PM+1/PM in 4-bromoacetophenone was increased by 3.83 in T3 sample while it was decreased by 9.12 in treated T2 sample as compared to the control. However the isotopic abundance ratio of PM+2/PM in 4- bromoacetophenone was decreased from 0.1 to 1.62 in T1 to T4 samples as compared to the control. The biofield treatment may have altered the isotopic abundance ratio of PM+1/PM and PM+2/PM of treated 4- bromoacetophenone from the control sample. Furthermore it is assumed that the lower isotopic ratio of PM+1/PM and

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35 Mahendra Kumar Trivedi et al.: Characterization of Physico-Chemical and Spectroscopic Properties of Biofield Energy Treated 4-Bromoacetophenone PM+2/PM might have decreased the stability of the compound due to the decreased µ reduced mass and binding energy in molecules with lighter isotopic bonds. This lower binding energy may lead to decrease the bond strength for treated 4-bromoacetophenone however the reverse might happen in treated T3 sample 20. It is reported that the isotope fractionation for bromine and oxygen is slower than chlorine carbon hydrogen and nitrogen which is much dependent on the reaction path kinetic of organohalogen compounds 21 and we have observed a slow depletion of PM+2/PM ratio 1.62. Thus GC-MS data suggested that biofield treatment has significantly altered the isotopic ratio of in treated 4-bromoacetophenone molecule. Fig. 4a. GC-Mass spectra of control sample of 4-bromoacetophenone. Fig. 4b. GC-MS spectra of treated T1 T2 T3 and T4 samples of 4-bromoacetophenone.

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American Journal of Physical Chemistry 2015 44: 30-37 36 Fig. 5. Percent change in isotopic abundance ratio of PM+1/PM and PM+2/PM in treated samples of 4-bromoacetophenone. Table 3. GC-MS isotopic abundance analysis result of 4- bromoacetophenone. Parameter Control Treated T1 T2 T3 T4 Peak intensity at m/z PM 21.93 20.47 66.46 23.00 22.74 Peak intensity at m/z PM+1 1.91 1.72 5.26 2.08 1.96 Peak intensity at m/z PM+2 21.38 19.77 64.04 22.04 21.82 Percent change of isotopic abundance in PM+1/PM -3.52 -9.12 3.83 -4.06 Percent change of isotopic abundance in PM+2/PM -0.93 -1.16 -0.1 -1.62 Fig. 6. UV-Vis spectra of control and treated 4-bromoacetophenone sample. 3.6. UV-Vis Analysis The UV spectra of control and treated 4- bromoacetophenone are shown in Figure 6. The UV spectrum of control sample showed the absorbance maxima λ max at 205 and 254 nm. Similarly the spectra of treated sample showed the λ max at 203 and 254 nm. The peak at 254 nm absorption maximum in control sample did not show any shift of wavelength after biofield energy treatment. However the peak at higher energy region showed a minor blueshift from 205 nm control to 203 nm treated. The result showed that similar pattern but a minor shift of absorbance maxima was exibited by the treated sample as compared to the control. Therefore it is suggested that the biofield treatment did not disturb the HOMO-LUMO energy gap in the treated sample as compared to the control. 4. Conclusion In summary the crystallite size was significantly decreased by 16.69 with decreased intensity of the diffractogram in treated 4-bromoacetophenone as compared to the control. The melting point latent heat of fusion and T max were decreased slightly by 1.42 0.85 and 7.26 respectively in the treated sample as compared to the control indicated the reduced thermal stability of the biofield treated 4-bromoacetophenone. The isotopic abundance ratio of PM+1/PM of treated 4-bromoacetophenone was significantly decreased to 9.12 in T2 and slight increased up to 3.83 in T3 sample as compared to the control. However the isotopic abundance ratio of PM+2/PM in treated 4-bromoacetophenone was decreased by 1.62. It is assumed that due to the lowering of isotopic abundance ratio of PM+1/PM and PM+2/PM of treated 4- bromoacetophenone with lower binding energy may lead to lowering of chemical stability than the control sample. The lowering of isotopic abundance is well corroborated with the shifting of CO and CC peak to higher wavenumber region in FT-IR spectra. It is assumed that the lowering of thermal stability in treated 4-bromoacetophenone could make it useful as a reaction intermediate in various coupling reactions and in the synthesis of polymers. Abbreviations XRD: X-ray diffraction FT-IR: Fourier transform infrared GC-MS: Gas chromatography-mass spectrometry DSC: Differential scanning calorimetry TGA: Thermogravimetric analysis PM: Primary mass m/z 198 for 4-bromoacetophenone PM+1: represents isotopic molecule m/z 199 PM+2: represents isotopic molecule m/z 200 Acknowledgments The authors would like to acknowledge the whole team of MGV Pharmacy College Nashik for providing the instrumental facility. We would also like to thank Trivedi Science TM Trivedi Master Wellness TM and Trivedi Testimonials for their support during the work.

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37 Mahendra Kumar Trivedi et al.: Characterization of Physico-Chemical and Spectroscopic Properties of Biofield Energy Treated 4-Bromoacetophenone References 1 Gulcemal S Cetinkaya B 2013 Palladium-EDTA and palladium-EdteH 4 catalyzed Heck coupling reactions in pure water. Turk J Chem 37: 840-847. 2 Lu Y Shi T Wang Y Yang H Yan X et al. 2009 Halogen bonding- A novel interaction for rational drug design. J Med Chem 52: 2854-2862. 3 Wender PA Jeon R 1999 Bromoacetophenone-based photonucleases: Photoinduced cleavage of DNA by 4- bromoacetophenone-pyrrolecarboxamide conjugates. Org Lett 1: 2117-2120. 4 Laronze M Boisbrun M Leonce S Pfeiffer B Renard P et al. 2005 Synthesis and anticancer activity of new pyrrolo4- bromoacetophenones and pyrrolo-beta-carbolines. Bioorg Med Chem 13: 2263-2283. 5 Weskamp T Bohm VPW Herrmann WA 1999 Combining N-heterocyclic carbenes and phosphines: Improved palladium II catalysts for aryl coupling reactions. J Organomet Chem 585: 348-352. 6 Kishimoto T Uraki Y Ubukata M 2008 Synthesis of bromoacetophenone derivatives as starting monomers for β-O- 4 type artificial lignin polymers. J Wood Chem Technol 28: 97-105. 7 Evans SK Pearce AA Ibezim PK Primm TP Gaillard AR 2010 Select acetophenones modulate flagellar motility in Chlamydomonas. Chem Biol Drug Des 75: 333-337. 8 Welch GR 1992 An analogical “field” construct in cellular biophysics history and present status. Prog Biophys Mol Biol 57: 71-128. 9 Yates FE 1994 Order and complexity in dynamical systems: Homeodynamics as a generalized mechanics for biology. Math Comput Model 19: 49-74. 10 Rubik B Pavek R Ward R Greene E Upledger J 1994 Manual healing methods. NIH Publication No. 94–066 Alternative Medicine: Expanding Medical Horizons. Washington D. C. US Government Printing Office 1994a: 134-157. 11 Rubik B 2002 The biofield hypothesis: Its biophysical basis and role in medicine. J Altern Complement Med 8: 703-717. 12 Trivedi MK Patil S Tallapragada RMR 2015 Effect of biofield treatment on the physical and thermal characteristics of aluminium powders. Ind Eng Manage 4: 151. 13 Trivedi MK Patil S Shettigar H Bairwa K Jana S 2015 Phenotypic and biotypic characterization of Klebsiella oxytoca: An impact of biofield treatment. J Microb Biochem Technol 7: 203-206. 14 Shinde V Sances F Patil S Spence A 2012 Impact of biofield treatment on growth and yield of lettuce and tomato. Aust J Basic Appl Sci 6: 100-105. 15 Sances F Flora E Patil S Spence A Shinde V 2013 Impact of biofield treatment on ginseng and organic blueberry yield. Agrivita J Agric Sci 35: 22-29. 16 Patil SA Nayak GB Barve SS Tembe RP Khan RR 2012 Impact of biofield treatment on growth and anatomical characteristics of Pogostemon cablin Benth.. Biotechnology 11: 154-162. 17 Fuse M Shirakawa Y Shimosaka A Hidaka J 2003 Mechanically strain-induced modification of selenium powders in the amorphization process. J Nanopart Res 5: 97- 102. 18 http://webbook.nist.gov/cgi/cbook.cgiIDC99901UnitsC ALTypeIR-SPEC. 19 http://webbook.nist.gov/cgi/cbook.cgiIDC99901Mask20 0. 20 Rieley G 1994 Derivatization of organic-compounds prior to gas-chromatographic combustion-isotope ratio mass- spectrometric analysis: Identification of isotope fractionation processes. Analyst 119: 915-919. 21 Eggenkamp H 2014 The geochemistry of stable chlorine and bromine isotopes. In series: Advances in Isotope Geochemistry Springer-Verlag Heidelberg.

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