
ABSTRACT
Background and Objective: The crystal structure of title compound (4-Carboxyanilinium Dihydrogen Phosphate) was already reported. But in the best of the knowledge, there is no report on spectroscopy and antimicrobial activity studies of this compound. So objective of study was to grow the 4-carboxyanilinium dihydrogen phosphate complex crystal from slow evaporation technique and characterized by single crystal XRD, powder XRD, FTIR, FT-Raman, UV-Visible spectroscopy, SEM with EDX and antimicrobial activity studies. Materials and Methods: The title crystal (4-Carboxyanilinium Dihydrogen Phosphate Semi-Organic Complex Crystal) was obtained by slow evaporation technique from the aqueous ethanol solution of 4-aminobenzoic acid and orthophosphoric acid in 1:1 stoichiometric ratio. In this crystal growth process, 4-aminobenzoic acid, orthophosphoric acid, ethanol and deionized water were used as the raw materials which were purchased from Sigma Aldrich Company, India. Results: The crystal lattice parameters and space group was obtained from the single crystal XRD study. The powder X-ray diffraction peaks were indexed using the INDX software. The FTIR and FT-Raman spectra of 4-carboxyanilinium dihydrogen phosphate crystal have been recorded at room temperature. The spectra were interpreted in terms of these wavenumber assignments. The optical band gap was determined from the UV-Visible spectroscopy analysis. Also, the morphology and antimicrobial activity studies were performed on the title crystal. Conclusion: The title crystal has monoclinic crystal system with the space group P21/n. The average crystalline size is found to be as 54 nm. Further, the presence of functional groups and elements were verified using FTIR and FT-Raman spectroscopy and energy dispersive X-ray studies. The SEM analysis shows that the complex crystal has smooth surface and flower like morphology. The optical band gap is determined as 3.8 eV. The antimicrobial activity study shows that the complex crystal screened the bacteria than that of the parent crystal. This modified chemical structure may improve the solubility and reduce the toxicity of drug compound.
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DOI: 10.3923/ajaps.2017.159.169
URL: https://scialert.net/abstract/?doi=ajaps.2017.159.169
INTRODUCTION
A cyclic amino acid compound of p-aminobenzoic acid is also known as B10 which cannot be synthesized by human1. It is present in foods naturally and it is produced by essential symbiotic bacteria to metabolize constantly in the human body2-4. P-carboxyaniline (4-aminobenzoic acid) is an important biological molecule which has an anticoagulant and antioxidant properties. The active sites of several biological systems have kind of hydrogen bonding in hybrid compounds5. Due to the interest in the field of new materials and medicine, the crystal structures of organic-inorganic hybrid materials have been extensively investigated6. The crystal structures of 4-carboxyanilinium dihydrogen phosphate and 4-carboxyanilinium hydrogen sulfate have been already reported by Benali-Cherif et al.7,8 in which the organic bases and phosphoric acid occur in its crystalline form. In these structures, the transfer of a proton from the inorganic acid leads to protonation on the NH2 site of the bacterial vitamin 4-aminobenzoic acid and forms the 4-carboxyanilinium cation. The crystal structures of 4-carboxyanilinium nitrate, perchlorate monohydrate and bis (4-carboxy phenyl ammonium) sulfate were reported by Athimoolam and Natarajan9. Susindran et al.10, reported the spectroscopy study of 4-carboxyanilinium chlorate, bromate crystals. Also Muthuselvi et al.11, reported recently the vibrational and antimicrobial activity studies of 4-carboxyanilinium perchlorate monohydrate. But there is no report on the spectroscopy and antimicrobial studies of 4-carboxyanilinium dihydrogen phosphate crystal with our knowledge. So in the present investigation, an attempt has been made on the growth of 4-carboxyanilinium dihydrogen phosphate crystal by slow evaporation technique. The characterization was performed using single crystal XRD, powder XRD, FTIR, FT-Raman, UV-Visible spectroscopy, SEM with EDX and antimicrobial activity studies for the title crystal and these results are summarized in the present study.
MATERIALS AND METHODS
The 4-aminobenzoic acid, orthophosphoric acid, ethanol and deionized water were used in the crystal growth process of title compound and they were purchased from Sigma Aldrich Company, India. The single crystal of 4-carboxyanilinium dihydrogen phosphate was obtained by slow evaporation technique at room temperature from the aqueous ethanol solution of 4-aminobenzoic acid mixed with aqueous solution of orthophosphoric acid in 1:1 stoichiometric ratio.
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Fig. 1: | Grown crystal of 4-carboxyanilinium dihydrogen phosphate |
This solution was stirred well for 1 h and after filtering process it was poured into the petri disc. After a period of 15 days, rod like crystals of title compound was harvested and which is shown in Fig. 1. The single crystal Bruker SMART APEX CCD X-ray diffractometer with Mo Kα radiation (λ = 0.71073 Å) was used to carry out the unit cell dimension and space group. This data was taken from SAIF, IIT Madras, Chennai, Tamil Nadu, India. The XPERTPRO Xray diffractometer with Cu Kα (λ = 1.54060 Å) radiation was used to record the powder diffraction pattern in CSIR-CECRI, Karaikudi, Tamil Nadu, India. The FTIR vibrational spectrum was recorded using SHIMADZU FTIR spectrometer in the range 4000-400 cm1. Also, the FT-Raman spectrum was recorded in SAIF, IIT Madras, Chennai using the BRUKER: RFS 27 Raman spectrometer in the wavenumber range 4000-400 cm1. The optical absorption spectrum of 4-carboxyanilinium dihydrogen phosphate crystal has been recorded with SHIMADZU-UV1800 double beam spectrometer in the wavelength range 200-1100 nm in steps of 1 nm at V.H.N.S.N. College, Virudhunagar, Tamil Nadu, India.
The surface morphology and elemental analysis has been carried out by CARLZEISS EVO18 scanning electron microscope at CSIR-CECRI, Karaikudi, Tamil Nadu, India. Using the disc diffusion method, the antimicrobial activity of parent and its complex crystals were tested against 4 different kinds of microorganisms in Sri Kaliswari College, Sivakasi, Tamil Nadu, India.
RESULTS AND DISCUSSION
Single crystal XRD: The unit cell parameter and space group of 4-carboxyanilinium dihydrogen phosphate crystal was obtained using the SMART APEX CCD area detector diffractometer. Initially, these are checked with the Cambridge Structural Database (CSD) for confirmation. The report shows that the title crystal was exactly matched with already reported values7. The crystallographic data of 4-carboxyanilinium dihydrogen phosphate crystal is shown in Table 1 and was compared with already reported values7. The molecular structure of title crystal is illustrated in Fig. 2.
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Fig. 2: | Molecular structure of 4-carboxyanilinium dihydrogen phosphate |
The single crystal XRD study revealed that the grown crystal was a complex one, since the one proton of phosphoric acid was liberated and joined with 4-carboxyaniline NH2 group, then it becomes as 4-carboxyaniline cation and dihydrogen phosphate anion. Also this study confirmed the grown crystal crystallizes in the monoclinic system with space group P21/n.
Powder XRD analysis: The powder X-ray diffraction patterns of 4-carboxyanilinium dihydrogen phosphate crystal is shown in Fig. 3 which was recorded using XPERT-PRO X-ray diffractometer with Cu Kα (λ = 1.54060 Å) radiation from 10 80̊ at 10̊/sec scan step time. The diffracted peaks are indexed using INDX software. The good crystalline nature and purity of the grown crystal was observed from the sharp intensity PXRD pattern.
Table 1: | Crystallographic data of 4-carboxyanilinium dihydrogen phosphate crystal |
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Fig. 3: | Diffraction patterns for 4-carboxyanilinium dihydrogen phosphate crystal |
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Fig. 4: | FTIR spectrum for 4-carboxyanilinium dihydrogen phosphate crystal |
The Debye-Scherrer equation was used to determine the average crystalline size of 4-carboxyanilinium dihydrogen phosphate crystal, which can be written as:
D | = | Average crystallite size |
K | = | Dimensionless shape factor (0.94) |
λ | = | Wavelength of X-ray radiation (Cu Kα=1.54060Ε) |
θ | = | Diffraction angle |
β | = | Full width at half maximum intensity |
The dislocation density can be calculated from, following formula:
δ | = | Dislocation density, |
D | = | Crystallite size |
For the 4-carboxyanilinium dihydrogen phosphate crystal, the average crystalline size is found to be as 54 nm. The dislocation density of this crystal is determined as 3.43×1014 m2.
Vibrational analysis: The FTIR and FT-Raman spectra of 4-carboxyanilinium dihydrogen phosphate complex crystal are shown in Fig. 4 and 5, respectively and their corresponding IR and Raman assignments are listed in Table 2. The title compound has [NH3]+, -COOH, para substituted benzene ring and H2PO4‾ functional groups.
-[NH3]+cation vibration: Normally, -[NH3]+ group has C3v symmetry in the free state with a pyramidal structure. The normal modes of vibrations of this group occurs as ν1 (A1), ν2 (A1), ν3 (E) and ν4 (E)12. Among these vibrations, the symmetry stretching and bending modes (ν1 and ν2) are non-degenerative whereas the antisymmetric stretching and bending modes (ν3 and ν4) are doubly degenerated. All these modes are both IR and Raman active12. The antisymmetric and symmetric stretching modes of -[NH3]+ group are expected in the region of 3200 and 2800 cm1, respectively12,13. Also, the antisymmetric and symmetric deformation modes are expected to appear in the region of 1660-1610 and 1550-1480 cm1, respectively13. The -[NH3]+antisymmetric stretching wavenumber of title crystal was observed as strong band at 3233 cm1 in IR and as a weak band at 3226 cm1 in Raman spectra and the stretching wavenumber of this group was identified at 2810 cm1 (IR), 2831 cm1 (Raman), respectively.
The antisymmetric bending mode was identified at 1655 cm1, 1612 cm1 in IR and at 1649 cm-1, 1616 cm1 in Raman spectra for the title compound, respectively. Also, symmetric bending mode was attributed at 1580 cm1, 1541 cm1 in IR and at 1525 cm1 in Raman spectra, respectively.
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Fig. 5: | FT-Raman spectrum for 4-carboxyanilinium dihydrogen phosphate crystal |
Table 2: | Wavenumber assignments for 4-carboxyanilinium dihydrogen phosphate crystal in FTIR and FT-Raman spectra |
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w: Weak, s: Strong, br: Broad, m: Medium, υ: Stretching, υs: Symmetric stretching, υas: Anti symmetric stretching, δs: Symmetric bending, δas: Antisymmetric bending, γ: Out-of-plane bending, ß: In-plane bending, ρ: Rocking, t: Torsional, ω: Wagging |
In the present study, the strong bands observed at 1138 cm1 in IR and at 1134 cm1 in Raman spectra was assigned to the rocking mode of [NH3]+group. The [NH3]+ wagging mode was observed as a strong band at 961 cm1 in the FTIR spectrum only. The torsional mode of [NH3]+ group was also identified in the range of 760-750 cm1 14,15. In present case, the torsional mode vibration was observed at 758 cm1 as a medium band in the IR spectrum only. The broad band centered at 3000 cm1 in IR spectrum was attributed to the presence of extensive 3 dimensional hydrogen bonding network that exists in the crystal.
Carboxylic group vibration: The antisymmetric and symmetric stretching vibrational mode of C=O group in carboxylic acid have wavenumbers in the region 1720-1680 cm1 and 1680-1640 cm1, respectively13. In the present study, νas (C=O) mode occurs at 1655 cm1 in IR and at 1649 cm1 Raman spectra. Also, bands observed at 1612 cm1, 1616 cm1 in both spectra was assigned to the νs (C=O) mode for the title crystal. The ν (C-O) mode of carboxylic group normally occurs in the vibrational region of 1320-1210 cm116. The title compound has wavenumbers at 1325, 1215 cm1 in IR and at 1324 cm1, 1214 cm1 in Raman spectra was attributed to ν (C-O) mode. The O-H stretch from CO-OH group was identified at 3065-2826 cm1 15,17. It was attributed at 3071, 2810 cm1 in IR and at 3095, 3065, 3018, 2831 cm1 in Raman spectra, respectively for title compound.
Table 3: | Vibrational distribution of [PO4]3- ion to [H2PO4]‾ ion |
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The in-plane and out-of plane bending wave numbers of O-H group appears in the region between 1440-1395 cm1 and 960-875 cm1, respectively15,17. In the present study, β(OH) mode was identified as medium intensity bands at 1454 cm1, 1425 cm1 in IR and at 1445 cm1 in Raman spectra. Also γ (O-H) mode was attributed only at 961 cm1, 891 cm1 in IR spectrum and at 893 cm1 in Raman spectrum, respectively for title compound.
Para substituted benzene ring vibration: The C-H stretching mode for para substituted benzene ring was expected in the region 3115-3005 cm-1 12,15. In this case, the bands observed at 3071cm-1 in IR and at 3095, 3065, 3018 cm1 in Raman spectra was assigned to ν (C-H) mode. The C-H in-plane and out-of-plane bending vibrations are seen in the range 1250-1000 and 900-690 cm1, respectively15. For the title compound, the β(C-H) mode was identified at 1215, 1138, 1067 cm1 in FTIR and at 1214, 1182, 1134, 1007 cm1 in FT-Raman spectra, respectively. The γ (C-H) mode was identified at 891, 758, 687 cm1 in IR spectrum and at 893 cm1 in Raman spectrum for the title compound. The C = C and C-C ring stretching modes occur in the region 1650-1430 and 1400-1300 cm1, respectively13. For the title compound ν (C = C) mode was assigned at 1612, 1580, 1541, 1512 cm1 in IR and 1616, 1525 cm1 in Raman spectra. Also ν (C-C) mode was observed at 1325 cm1, 1302 cm1 in IR spectrum. The C-N stretching mode was identified at 1325 cm1 in spectrum for this title compound. The ring breathing mode was identified at 853 cm1 in IR and 836 cm1 in Raman spectra for the title compound.
Dihydrogen phosphate anion vibration: The phosphate ion has Td symmetry in the free state which has symmetric stretching ν1(A1), antisymmetric stretching ν3(F2), symmetric bending ν2(E) and antisymmetric bending ν4(F2) internal vibrational modes. These wavenumbers occur at 936 cm1 (νsym), 420 cm1 (δsym), 1004 cm1 (νasym) and 573 cm1 (δasym)18,19. Due to the presence of two P-OH bonds, the molecular symmetry of [H2PO4]-ion reduces to C2v symmetry. As a result, the degeneracy of the modes ν2, ν3 and ν4 was fully lifted: ν2 splits into two components (A1+A2) and ν3 and ν4 split into three components (A1+B1+B2) each18. The symmetric stretching mode (A1) normally occurs at 880 cm1 and the symmetric bending mode E splits into two, appearing at 385 (A1) and 373 (A2) cm1. The antisymmetric stretching mode (F2) splits into three occurring at 1090 (A1), 1123 (B1) and 940 (B2) cm1. The antisymmetric bending mode (F2) has also lost its degeneracy and was expected to occur at 525 (A1), 510 (B1) and 503 (B2) cm1. All the species are both infrared and Raman active except for A2 species, which was only Raman active19.
In the present study, the antisymmetric stretching mode of [H2PO4]‾ ion was identified at 1067(A1), 1138(B1), 961(B2) cm1 and the symmetric stretching mode was observed in IR and Raman spectra at 891(A1), 893(A1) cm1, respectively. Also, the symmetric bending mode of this group was attributed at 387, 374 cm1 in Raman spectrum only and antisymmetric bending mode was identified at 544(A1), 434(B1) and 488(B2) cm1 in IR spectrum only. All these assignments confirm the existence of dihydrogen phosphate anion in the C2v symmetry and it is clearly depicted in Table 3. The P-OH group has a strong band in the region 1040-810 cm1 which was due to the stretching of P-OH bands20. The medium bands occur at 891, 853 cm1 in IR sand at 893 cm1 in Raman spectra was assigned to P-OH stretching vibration of title crystal. The in-plane and out-of-plane bending vibrations occur in the region 1350-1200 and 950-750 cm1, respectively19,20. For the title compound these modes are identified in IR spectrum at 1215, 891 cm1 and in Raman spectrum at 1214, 893 cm1, respectively. The stretching vibrations of P=O generally give rise to strong band in the region 1300-1140 cm1 for dihydrogen phosphate. The absorption bands at 1185, 1182 cm1 in both spectra is assigned to P=O stretching mode of 4-carboxyanilinium dihydrogen phosphate crystal.
Optical analysis: 4-carboxyanilinium dihydrogen phosphate single crystal absorbance spectrum is obtained using SHIMADZU-UV1800 double beam spectrometer in the wavelength range 200-1100 nm. The absorbance spectrum of title crystal is shown in Fig. 6. The lower cut-off wavelength was found to be at 248 nm and at 337 nm. The title crystal has 100% transmittance in the entire visible region which makes usefulness of this material in optical application. The energy gap Eg is determined by using the Taucs relation (αhν)2 = A(hν- Eg) by plotting the (αhν)2Vs photon energy and extrapolate the linear portion of (αhν)2 to the photon energy axis and obtained value is 3.8 eV from the Fig. 7.
SEM with EDX analysis: The morphology and elemental analysis of title compound were performed by SEM with EDX analysis. The microphotograph of title crystal with 4 different magnifications is depicted in Fig. 8. This image reveals that the grown crystal has a smooth surface and flower like morphology. The EDX spectrum for 4-carboxyanilinium dihydrogen phosphate crystal is shown in Fig. 9. The elemental composition of title crystal is shown in Table 4. The EDX analysis reveals that C, N, O and P elements are present in the 4-carboxyanilinium dihydrogen phosphate crystal.
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Fig. 6: | Absorbance spectrum for 4-carboxyanilinium dihydrogen phosphate crystal |
Antimicrobial activity study: Staphylococcus epidermidis (S. epidermidis), Serratia marcescens (S. marcescens), Methicillin-resistant Staphylococcus aureus (MRSA) and Polyphosphate-accumulating organisms (PAO-1) was used to analyze the antimicrobial activity of 4-carboxyaniline parent and 4-carboxyanilinium dihydrogen phosphate complex crystals by disc diffusion method. The photographic view of bacterial screening for parent and its complex crystals are shown in Fig. 10a and b, respectively. The above mentioned bacterial species were prepared at 50 μg mL1 and 100 μg L1 concentrations. The measured diameter zone of inhibition of these micro-organisms is shown in Table 5. Both parent and complex crystals show an effective zone of microorganism inhibition if the concentration was increased.
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Fig. 7: | Optical band gap for 4-carboxyanilinium dihydrogen phosphate crystal |
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Fig. 8(a-d): | SEM photograph for 4-carboxyanilinium dihydrogen phosphate crystal, (a) 6000x, (b) 12,000x, (c) 20,000x and (d) 24,000x |
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Fig. 9: | EDX spectrum for4-carboxyanilinium dihydrogen phosphate crystal |
Moreover, the zone of inhibition for the complex crystal was increased due to the presence of phosphoric acid. Especially, it was very dominant against the S. marcescens bacteria. From the Table 5, it is clear that 4-carboxyanilinium dihydrogen phosphate complex crystal was very active against all the organisms except MRSA and PAO-I.
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Fig. 10(a-b): | Photographic view showing inhibition region of 4 different micro-organisms (a) 50 μg mL1 and 100 μg L1 concentrations against the 4-carboxyaniline parent crystal and (b) 50 μg mL1 and 100 μg L1 concentrations against the 4-carboxyanilinium dihydrogen phosphate complex crystal |
Table 4: | Elemental composition for 4-carboxyanilinium dihydrogen phosphate crystal |
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This chemically altered complex molecule may be used to reduce toxicity and increase solubility of drug. It was also given to the human beings in their natural form with the desirable characteristic.
Table 5: | Effective values of inhibited zone for 4-carboxyaniline and 4-carboxyanilinium dihydrogen phosphate crystals |
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S. epi: Staphylococcus epidermidis, S. mar: Serratia marcescens, MRSA: Methicillin-resistant Staphylococcus aureus, PAO: 1Polyphosphate-accumulating organisms |
CONCLUSION
The 4-carboxyanilinium dihydrogen phosphate complex crystal was grown by the slow evaporation technique at room temperature in this study. It has monoclinic crystal system with the space group P21/n as suggested by single-crystal X-ray diffraction technique. The average crystalline size of grown crystal is found to be as 54 nm and its PXRD peaks are indexed using the INDX software. Further, the presence of functional groups and elements were verified using FTIR and FT-Raman spectroscopy and energy dispersive X-ray studies. The SEM analyzes shows that the complex crystal has smooth surface and flower like morphology. The optical property of this crystal was analyzed by UV-Visible spectroscopy technique. Also, the optical band gap of title crystal is determined as 3.8 eV. The grown crystals were involved in an antibacterial activity against certain potentially threatening microbes such as Staphylococcus epidermidis, Serratia marcescens, Methicillin resistant Staphylococcus aureus and Polyphosphate accumulating organisms by disc diffusion method which shows that the complex crystal screened the bacteria than that of the parent crystal especially for Staphylococcus epidermidis, Serratia marcescens microorganisms.
SIGNIFICANCE STATEMENT
This study discovers the drug complex crystal that can be beneficial for people in the medicinal field. This study help the researchers to uncover the critical areas of crystal growth in organic-inorganic hybrid that many researchers were not able to explore. Thus a new theory on this complex crystal may be arrived at.
ACKNOWLEDGMENT
The authors sincerely acknowledge their thanks to the Management and Principal of Devanga Arts College, Aruppukottai for their permission and encouragement during their research work.
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