Comparative Study of Properties of L-Histidine and L-Histidine Nickel Nitrate Hexahydrate Crystals Grown by Slow Evaporation

R Vinayagamoorthy, A Albert Irudayaraj, A Dhayal Raj, S Karthick, G Jayakumar

<figure><img src="image_1.png" /></figure>

► To cite this version:

R Vinayagamoorthy, A Albert Irudayaraj, A Dhayal Raj, S Karthick, G Jayakumar. Comparative Study of Properties of L-Histidine and L-Histidine Nickel Nitrate Hexahydrate Crystals Grown by Slow Evaporation. Mechanics, Materials Science & Engineering Journal, 2017, 9, 10.2412/mmse.83.74.689. hal-01503639

HAL Id: hal-01503639

https://hal.science/hal-01503639

Submitted on 7 Apr 2017

HAL is a multi-disciplinary open access
archive for the deposit and dissemination of sci-
entific research documents, whether they are pub-
lished or not. The documents may come from
teaching and research institutions in France or
abroad, or from public or private research centers.

L'archive ouverte pluridisciplinaire HAL, est
destinée au dépôt et à la diffusion de documents
scientifiques de niveau recherche, publiés ou non,
émanant des établissements d'enseignement et de
recherche français ou étrangers, des laboratoires
publics ou privés.

<figure><img src="image_2.png" /></figure>

Distributed under a Creative Commons Attribution 4.0 International License
# Comparative Study of Properties of L-Histidine and L-Histidine Nickel Nitrate Hexahydrate Crystals Grown by Slow Evaporation

R. Vinayagamoorthy¹, a, A. Albert Irudayaraj¹, A. Dhayal Raj¹, S. Karthick¹, G. Jayakumar¹

1. PG and Research Department of Physics, Sacred Heart College, Tirupattur, Vellore, India

a. vinayaga76@gmail.com

<figure><img src="image_3.png" /></figure>

DOI 10.2412/mmse.83.74.689 provided by [Seo4U.link](https://link.springer.com/10.2412/mmse.83.74.689)

**Keywords:** Semi organic, Amino acid, Phase transition, SHG efficiency.

**ABSTRACT.** L-Histidine (LH) is an amino acid. It is an organic material. L-Histidine Nickel Nitrate Hexahydrate (LHNNH) is a semi organic material. It is a complex of bivalent nickel ion with L-Histidine amino acid. Complexes of bivalent metal ions with amino acids are generally good NLO materials. Crystals of L-Histidine and L-Histidine Nickel Nitrate Hexahydrate (LHNNH) have been successfully grown by slow evaporation method using water as solvent. The crystal structure and lattice parameters of LH and LHNNH are determined by Single crystal X-ray diffraction analysis. The functional groups in LH and LHNNH are confirmed by FTIR analysis. With the help of UV-Vis spectroscopy the optical band gap and optical transparency are studied. The chemical composition of LH and LHNNH are studied by CHN and EDAX analysis. Thermally stability and thermal phase transitions of LH and LHNNH are analyzed by TGA/DTA. The Second Harmonic Generation (SHG) efficiency of LH and LHNNH have been experimentally estimated.

**Introduction:** L-Histidine is an optically active α-amino acid and is a tridentate ligand that has an imidazole ring, amino and carboxylate groups. Amino acids are the potential candidates for optical second harmonic generation because they contain chiral carbon atom and crystallize in non-centro symmetric space groups and it is an essential criterion for nonlinear application [1]. Amino acids are interesting materials for NLO applications. Complexes of amino acids with inorganic salts are promising materials for optical Second Harmonic Generation. In recent years semi organic crystals have emerged as extremely promising building blocks for NLO materials. They share the properties of both organic and inorganic materials. Amino acids are interesting materials for NLO applications, as they exhibit molecular chirality, absence of strongly conjugated bonds and zwitterionic nature of the molecule [2].

Hence L-Glutamine, L-Serine, L-Histidine, L-Alanine and L-Valine have been subjected for the formation of salts with different inorganic acids. As a result very good semiorganic nonlinear optical materials such as L-Glutamine sodium nitrate [3], L-Serine sodium nitrate [4], L-Alanine cadmium chloride [5], L-Histidine cadmium chloride monohydrate [6], L-Histidine barium chloride dihydrate [7] and L-Valine cadmium chloride [8] are some of the good examples which proved very suitable materials for NLO applications.

In the present investigation an attempt has been made to grow L-Histidine and L-Histidine Nickel Nitrate Hexahydrate by slow evaporation method at room temperature. The grown crystals have been subjected to Single crystal, FTIR, UV-Visible, CHN, EDAX, TG/DTA and NLO studies.

## Experimental procedure

**Preparation of LH and LHNNH:** The saturated solution of LH was prepared from the commercially available LH and the prepared solution was filtered using wattmann filter paper. The solution was
transferred into a petri dish and covered with the polythene paper. Holes were made on the cover and the solution was allowed for the evaporation. After a period of few months, L-Histidine crystals were collected.

L-Histidine Nickel Nitrate Hexahydrate (LHNNH) was synthesized from L-Histidine and Nickel Nitrate Hexahydrate according to the following reaction.

$$2[C_6H_9N_3O_2] + Ni (No_3)_2. \rightarrow 6H_2O [C_6H_9N_3O_2]_2$$

L-Histidine and Nickel Nitrate Hexahydrate were taken in the molar ratio (2:1). The calculated amount of L-Histidine was first dissolved in 100ml de-ionized water. Followed by Nickel Nitrate Hexahydrate was added to the solution slowly by continuous stirring to get a homogeneous mixture. Then the solution was left undisturbed. After few months, L-Histidine Nickel Nitrate Hexahydrate raw material was collected. The Crystals of LH and LHNNH were recrystallized thrice to improve the purity of the crystal. Good quality crystals of LH and LHNNH were obtained. Photograph of the grown LH and LHNNH crystals are shown in Figure 1.

<figure><img src="image_4.png" /><figcaption>Fig. 1. As grown (a) LH (b) LHNNH.</figcaption></figure>

**Single crystal X-ray diffraction analysis:** The single crystal X-ray analysis of LH and LHNNH crystal was carried out using an X-ray diffractometer (ENRAF NONIUS CAD4-MV31 BRUKER KAPPA APEX II). It was observed that both the crystals possess orthorhombic system and space group P212121. The lattice parameter values of LH and LHNNH are a=5.14(Å), b=7.32(Å), c=18.76(Å), V=705.84(Å³)[9] and a=15.74(Å), b=13.17(Å), c=7.31(Å), V=1515.33(Å³) respectively.

**Fourier Transform Infrared (FTIR) Spectral analysis:** To analyze the presence of functional groups in LH and LHNNH crystals, the infrared was recorded in the range from 400 cm⁻¹ to 4000 cm⁻¹ with the help of PERKIN ELMER FTIR spectrometer using KBr pellet. The recorded FTIR spectrum of LH and LHNNH were shown in Figure 2. In the higher wave number region the CH₂ asymmetric stretching peak at 2714 cm⁻¹. The peak at 1635 cm⁻¹ is due to C=O stretching. The peak at 1563 cm⁻¹ is due to C=C stretching. The peak at 1468 cm⁻¹ is due to NH₂ bending. The peak at 1156 cm⁻¹ is due to C-H in plane bending. The peak at 1073 cm⁻¹ is due to C-O stretching of carboxyl group. The peak at 904 cm⁻¹ is due to ring symmetric stretching. The peak at 845 cm⁻¹ is due to C-N out of plane bending. The peak at 779 cm⁻¹ is due to C-N deformation. The peak at 701 cm⁻¹ is due to out of plane bending of NH₂.
<figure><img src="image_5.png" /><figcaption>Fig. 2. FTIR Spectrum of (a) LH (b) LHNNH.</figcaption></figure>

The peak at 632 cm⁻¹ is due to C-H deformation. The peak at 527 cm⁻¹ is due to torsion oscillation of NH₃⁺. On the other hand, in the case of L-Histidine crystal sample almost all the important vibration modes corresponding to respective functional groups have been observed [10]. The assignments confirm the presence of various functional groups of LH and LHNNH.

**UV-Visible spectral analysis:** UV-Vis transmission spectrum of LHNNH crystal was recorded using Perkin Elmer make Lambda 35 UV-Visible Spectrometer in the range 200nm to 800nm and the observed spectrum of LHNNH crystal is shown in Figure 3. The LH and LHNNH crystal are transparent in the entire UV-Visible region. It has a transparency of about 85% with a lower cut-off wavelength at 228nm and 254nm. The wide range transmission is an important requirement for a crystal exhibiting NLO behavior. The optical band gap as calculated from UV-Vis analysis was found to be 5.44 eV and 4.89 eV respectively.

<figure><img src="image_6.png" /><figcaption>Fig. 3. UV-Visible Spectrum of (a) LH (b) LHNNH.</figcaption></figure>

**CHN Analysis:** The percentage composition of the C, H, and N elements in the synthesized LH and LHNNH was examined by CHN analysis using Elemental vario micro CHN Analyzer. The
percentage composition LH of carbon, hydrogen and nitrogen are C=46.44 % (46.75), H=5.84% (6.05) and N=27.08% (27.38). The percentage composition LHNNH of carbon, hydrogen and nitrogen are C=21.32 % (21.79), H=2.68% (3.91) and N=20.73% (19.23).

## EDAX Analysis

<figure><img src="image_7.png" /><figcaption>Fig. 4. EDAX Spectrum of LHNNH.</figcaption></figure>

<table><caption>Table 2. EDAX quantification of LHNNH</caption><thead><tr><td>Element</td><td>Wt (%)</td><td>At (%)</td></tr></thead><tbody><tr><td>C</td><td>31.82</td><td>64.18</td></tr><tr><td>O</td><td>06.93</td><td>10.50</td></tr><tr><td>Fe</td><td>02.70</td><td>01.17</td></tr><tr><td>Ni</td><td>58.55</td><td>24.16</td></tr></tbody></table>

Energy dispersive X-ray analysis (EDAX) was an analytical technique. It was used to obtain useful information regarding the chemical composition of the grown crystal. The grown crystal was subjected to EDAX analysis using the instrument FEI QUANTA FEG 250 scanning electron microscope. A fine beam of X-rays was made to fall into the LHNNH sample. The number and energy of the X-rays emitted by the sample was measured of the X-rays emitted from the sample was attributed to the energy difference between the two shells and of the atomic structure of the compound, the elemental composition of the specimen can be measured. The EDAX spectrum of LHNNH is shown in Figure 4.

<figure><img src="image_8.png" /><figcaption>Fig. 5. TGA and DTA curves of (a) LH (b) LHNNH.</figcaption></figure>

**Thermal analysis:** The thermo gravimetric analysis (TGA) and differential thermal Analyses (DTA) for LH and LHNNH have been carried out in the temperature range of 20 - 400°C using a CNST
thermal analyzer. Alumina pan was used for heating and the analysis was performed in an atmosphere of nitrogen at a heating rate of 20°C/min. The results were presented in Figure.5. In TGA, it was found that LH and LHNNH crystal were stable up to 268°C and 78°C. The melting point of LH is 288°C [10]. The DTA, LHNNH indicates the exothermic covering the temperature range 152°C to 210°C.

**NLO studies.** The nonlinear optical conversion efficiency test was carried out for the grown crystals using Kurtz-Perry Powder technique. KDP was used as reference for the present measurement. The emission of green light confirmed generation of second harmonic radiation. The second harmonic generation efficiency of LH and LHNNH are found to be 0.72 and 0.39 times to that of KDP.

**Summary.** Single crystals of L-histidine and L-histidine nickel nitrate hexahydrate have been grown by slow evaporation method using water as solvent. The structure of LH and LHNNH are Orthorhombic with the space group P2₁2₁2₁. The functional groups in LH and LHNNH are confirmed by FTIR analysis. The LH and LHNNH are transparent in the entire UV-Visible region. The transparency of the crystal is above 85%. The UV lower cut off wavelength of LH and LHNNH crystals occurs at 228nm and 254nm. The optical band gap is found to be 5.44 eV and 4.89 eV. The chemical composition of LH and LHNNH are studied by CHN and EDAX analysis. The LH and LHNNH are thermally stable up to 268°C and 78°C. The melting point of LH is 288°C. The second harmonic generation efficiency of LH and LHNNH were found to be 0.72 and 0.39 times to that of KDP.

**References**

[1] P. Praveen Kumar, V. Manivannan, S. Tamilselvan, S. Senthil, Victor Antony Raj, P. Sagayaraj, J. Madhavan, Growth and characterization of a pure and doped nonlinear optical L-Histidine acetate single crystal, Optics Communications 2008, 281, 2989-2995. 10.1016/j.optcom.2008.01.058.

[2] C. Alosious Gonsago, Helen Merina Albert, J. Karthikeyan, P. Joseph Arul Pragasam, Crystal structure, optical and thermal studies of a new organic nonlinear optical material: L-histidinium maleate 1.5-hydrate, Materials Research Bulletin, 2012, 47, 1648-1652. 10.1016/j.materresbull.2012.03.061.

[3] Redrothu Hanumanthrao, S. Kalainathan, Studies on structural, thermal and optical properties of novel NLO crystal bis L-glutamine sodium nitrate, Materials Letters, 2012, 74, 74-77. 10.1016/j.matlet.2012.01.051.

[4] P. Koteeswari, S. Suresh, P. Mani, Synthesis, Theoretical, Mechanical and Dielectric Property of L-Serine sodium nitrate NLO single crystal, American Journal of Condensed Matter Physics, 2012, 2(5), 116-119. 10.5923/j.ajccmp.20120205.02.

[5] S. Dhanuskodi, K. Vasantha, P. A. Angeli Mary, Structural and thermal characterization of a semiorganic NLO material: L-Alanine cadmium chloride, Spectrochimica Acta Part A, 2007. 10.1016/j.saa.2005.06.052.

[6] J. Chandrasekaran, P. Ilayabarathi, P. Maadeswaran, P. Mohamed Kutty, S. Pari, Growth and characterization of L-histidine cadmium chloride monohydrate a semiorganic nonlinear optical materials, Optics Communications, 2012, 285, 2096-2100. 10.1016/j.optcom.2011.12.063.

[7] T. R. Beena T. Chithambarathanu, S.L. Rayar, Growth and characterization of a semiorganic NLO material: L-histidine barium chloride dihydrate, Green Chemistry & Technoloty Letters, 2016, V-2, No.1, 26-30. 10.18510/getl.2015.215.

[8] P. Maadeswaran, J. Chandrasekaran, Synthesis, growth and characterization of L-valine cadmium chloride monohydrate- A novel semiorganic nonlinear optical crystal, Optik, 2011, 122, 1128-1131.10.1016/j.ijleo.2010.07.006.

[9] P. Anandan, M. Arivanandan, Y. Hayakawa, D. Rajan Babu, R. Jayavel, G. Ravi, G. Bhagavannarayana, Investigations on the growth aspects and characterization of semiorganic
nonlinear optical single crystals of L-histidine and its hydrochloride derivative, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, 121, 508-513. 10.1016/j.saa.2013.11.021.

[10] Yun Zhang, Hua Li, Bin Xi, Yunxia Che, Jimin Zheng, Growth and characterization of L-histidine nitrate single crystal, a promising semiorganic NLO material, Materials Chemistry and Physics, 2008, 108, 192-195. 10.1016/j.matchemphy.2007.09.006.

Cite the paper

R. Vinayagamoorthy, A. Albert Irudayaraj, A. Dhayal Raj, S. Karthick, G. Jayakumar (2017). *Comparative Study of Properties of L-Histidine and L-Histidine Nickel Nitrate Hexahydrate Crystals Grown by Slow Evaporation*. Mechanics, Materials Science & Engineering, Vol 9. Doi 10.2412/mmse.83.74.689