Effect of metal and aminoacid dopants on the growth and properties of l-lysine monohydrochloride dihydrate single crystal

doi:10.1016/j.matchemphys.2010.07.033

Materials Chemistry and Physics

Volume 124, Issue 1, 1 November 2010, Pages 681-688

https://doi.org/10.1016/j.matchemphys.2010.07.033 Get rights and content

Abstract

In this paper, the effect of metal (Cu²⁺ and Mg²⁺) and aminoacid (glycine) dopants on the growth and properties of l-lysine monohydrochloride dihydrate single crystals is reported. The grown pure and doped l-LMHCl single crystals were confirmed by single crystal X-ray diffraction (XRD) and FT-IR spectral analysis. High-resolution X-ray diffraction (HRXRD) and etching studies were carried out in order to analyze the crystalline perfection and surface morphology of the grown pure and doped crystals, respectively. The mechanical properties, dielectric behaviour, optical transmittance and second harmonic generation efficiency have been studied for pure and doped l-LMHCl single crystals.

Introduction

The presence of small amount of impurities in a crystallization system can modify the properties, growth kinetics and morphology of the crystal [1], [2], [3], [4]. Recent reports reveal that the second harmonic generation (SHG) efficiency and mechanical strength of single crystals enhanced by substituting the metal ions and aminoacid dopants as minor impurities during the crystal growth [5], [6], [7], [8], [9]. These reports prompted the present investigation on the effect of metal and aminoacid dopants on l-LMHCl single crystal. l-Lysine monohydrochloride dihydrate (C₆H₁₅N₂O₂·Cl·2H₂O) is one of the aminoacid complexes, crystallizes in monoclinic crystal system with the non-centrosymmetric P2₁ space group and the crystal structure were determined [10]. Synthesis of metal chelates and physico-chemical studies of l-LMHCl complexes were reported [11]. Recently, the nonlinear optical, dielectric properties of these crystals were reported [12], [13], [14]. The SHG efficiency of l-LMHCl was found to be 2.5 times more than that of urea [15] and the laser damage threshold was 52.25 MW cm⁻² at 1064 nm which is better than that of several other semi-organic crystals [16]. The aim of the present communication is to study the effect of Cu²⁺, Mg²⁺ and glycine dopants on the growth and properties of l-LMHCl single crystals. We have grown pure, Cu²⁺, Mg²⁺ and glycine doped l-LMHCl single crystals by slow evaporation solution growth technique (SEST). The structural, optical, spectral and mechanical properties of the grown crystals have been studied.

Section snippets

Solubility test and crystal growth

The solubility of pure, Cu²⁺, Mg²⁺ and glycine doped l-LMHCl in deionized water was determined as a function of temperature. The raw material of l-LMHCl was dissolved in deionized water in a glass beaker at constant temperature with stirring. After obtaining the saturation, the equilibrium concentration was analyzed gravimetrically. The solubility of pure and doped l-LMHCl at different temperatures was determined using the same process. Fig. 1 shows the solubility curves of pure and doped l

Growth habit of doped crystals

Pure, Cu²⁺, Mg²⁺ and glycine doped l-LMHCl single crystals grown by SEST are shown in Fig. 2. The morphology of Cu²⁺ and glycine are similar to pure crystal but the morphology of Mg²⁺ doped l-LMHCl is different and as shown in Fig. 2c. It is due to the adsorption of dopants (Mg²⁺) at kinks, and at surface terrace decrease the value of surface free energy [17], which consequently increases the growth rate along 〈0 1 1〉 orientation. Also 〈0 1 −1〉 orientation of Mg²⁺ (1 M%) doped l-LMHCl single

Conclusion

The pure and Cu²⁺, Mg²⁺ and glycine doped l-LMHCl single crystals were successfully grown by slow evaporation solution growth technique (SEST). The slight variation in the lattice parameter values reveals the contribution of metals dopants in the interstitial sites of l-LMHCl crystal lattice. Also, the slight shift in absorption bands may be due to addition of dopants in the crystal lattice and the covalent bond formation between the dopants and carboxylic and amino group was confirmed from the

Acknowledgements

The authors (V.V. and R.R.) would like to gratefully acknowledge the Council of Scientific and Industrial Research (CSIR), Government of India for financial support (Grant No. 03/(1105)/08/EMR/II) of this work. Also the author (V.V.) grateful to Council of Scientific and Industrial Research, Government of India for providing Senior Research Fellowship.

References (23)

B. Simon et al.
J. Cryst. Growth
(1981)
G. Clydesdale et al.
J. Cryst. Growth
(1994)
K. Sangwal et al.
J. Cryst. Growth
(2002)
S. Dhanuskodi et al.
Spectrochim. Acta, Part A
(2003)
A. Joseph Arul Pragasam et al.
J. Cryst. Growth
(2005)
P. Praveen Kumar et al.
Opt. Commun.
(2008)
A.S. Haja Hameed et al.
J. Cryst. Growth
(1999)
N.R. Dhumane et al.
Opt. Mater.
(2008)
U. Sharma
Thermochim. Acta
(1983)
A. Senthil et al.
J. Cryst. Growth
(2009)

V. Krishnakumar et al.

Spectrochim. Acta Part A: Mol. Biomol. Spectrosc.

(2008)

Cited by (16)

Influence of most reactive inorganic cation in the optical and biological activities of L-Lysine monohydrochloride crystal
2020, Saudi Journal of Biological Sciences
Citation Excerpt :
This range is the most remarkable range in the study of organic, inorganic and semi organic compound (Pasupathi and Philominathan, 2008; Balasubramanian et al., 2010; Ushasree et al., 1999). The FTIR vibrational spectra and its assignments of gown crystals agree well with the literature values (Vasudevan et al., 2010) (see Table 1). The band observed at 3443 cm−1 is assigned as NH3+ asymmetric stretching vibrations.
Slow evaporation method was used to grow the pure and K⁺ ion doped L-Lysine monohydrochloride (L-LMHCL) crystals which has optical and antibiotic applications. The space group, structure and slight shifting of peaks are confirmed using single crystal XRD and the powder XRD. The FTIR analysis also shows that the K⁺ doped L-LMHCL has a slight shifting in the spectrum which indicates the functional group of L-LMHCL and the interaction between the K⁺ ions. The existence of K⁺ ion in the doped crystal is assured by the presence of potassium in the EDAX spectrum. The wide optical band gap was found for pure and K⁺ doped crystal using UV spectra and these are utilized in optoelectronic and nonlinear applications. The Kurtz Perry technique specified the NLO property of grown crystals. The dielectric property crystals was studied by varying the temperature. As a result, the highest dielectric constant is observed in doped crystal. An antibacterial activity against certain bacteria like E-coli, pseudomonas aeruginosa and staphylococcus aureus are provided by mm range for the grown crystals.
Studies on optical, electrical, mechanical and theoretical investigation of 4-nitro-benzoic acid (3-ethoxy-2-hydroxy-benzylidene)-hydrazide: A novel Schiff base organic NLO material
2019, Journal of Molecular Structure
New organic non-centrosymmetric Schiff base material 4-Nitro-benzoic acid (3-ethoxy-2-hydroxy-benzylidene)-hydrazide was synthesized and grown as single crystal by slow evaporation solution growth technique. Single crystal X-ray diffraction reveals the noncentrosymmetric nature of the grown crystal with space group Pna2_1. The nonlinear efficiency of the grown material was studied by Kurtz-Perry powder technique and found to be 0.7 times that of KDP. The photoluminescence emission of the grown crystal shows emission at 360 nm. The mechanical stability of the crystal was examined by Vicker's microhardness study and the yield strength of the material was calculated. Low dielectric constant at higher frequencies was observed from dielectric measurements. Reduction in charge carriers when the sample was illuminated by halogen lamp proves the negative photoconductivity of the sample. In addition, quantum chemical calculations were carried out using density functional theory for the NEH molecule optimized at B3LYP/6-31 + G (d, p) basis set to calculate its frontier molecular orbital, electrostatic potential and Mulliken charge analysis.
Systematic investigation and applications of an efficient NLO crystal: Glycine lithium sulphate
2019, Materials Today: Proceedings
Glycine Lithium Sulphate (GLS), a non-centrosymmetric semi organic NLO single crystals were grown from aqueous solution with dimension of 10 x 11 x 12 mm³ by slow evaporation technique at room temperature using water as the suitable solvent. Crystalline phase and information on unit cell measurements of the grown Glycine Lithium Sulphate single crystal have been identified by using X-ray powder diffraction (PXRD) study with CuKα radiation. FT-IR spectra of the nonlinear optical material Glycine Lithium Sulphate crystal have been recorded and analyzed. The crystalline perfection has been examined by using High Resolution X-ray diffractometer (HRXRD) technique and found that the specimen quality is good. Optimization of the title compound is done using the Gaussian 09 software with B3LYP using 6-31 G (d, p) as basis set. From the HOMO-LUMO and hyperpolarizability analysis, the stability and the occurrence of strong intermolecular hydrogen bonding in the molecule is confirmed. Nonlinear optical absorption of the title compound has been studied at 633 nm using single laser pulses, using Z-scan technique. It is found that the GLS molecule is a potential candidate for optical limiting applications and optoelectronic device fabrications.
Synthesis, growth, optical, band gap energy and mechanical properties of semiorganic nonlinear optical material: 2-Aminopyridine potassium dihydrogen orthophosphate lithium chloride (2APKDPL) crystal
2018, Materials Science for Energy Technologies
2APKDPL salt was synthesized by taking equimolar ratio (1:1:1) of 2-aminopyridine, potassium dihydrogen orthophosphate and lithium chloride by slow evaporation technique. Optimum level of purity is achieved by successive recrystallization process. Solubility curve was drawn gravimetrically for different temperature with time interval 5 °C from 30 °C to 55 °C. Optically good quality 2APKDPL crystal of moderate size 9 mm × 4 mm × 2 mm was harvested over the period of 75 days. The functional groups presences in the crystallized 2APKDPL sample were identified by Fourier Transform Infrared (FTIR) spectroscopy. A well defined sharp Bragg’s peak in powder X-ray diffraction analysis identifies the crystalline nature of the grown sample. Single crystal X-ray diffraction study reveals that the 2APKDPL crystal belongs to tetragonal crystal system with noncentrosymmetric space group I4. UV–vis-NIR spectrophotometer study shows the cut-off wavelength of the grown samples as 262 nm and the optical band gap (Eg = 4.62 eV) was calculated for 2APKDPL crystal. SHG efficiency of 2APKDPL is 1.14 times than that of standard potassium dihydrogen phosphate (KDP). The work hardening coefficient (n = 0.5) of 2APKDPL crystal confirming that the grown 2APKDPL crystal belongs to hard category. The mechanical properties, Stiffness constant (C₁₁), Yield Strength (σ_y), Fracture toughness (K_c), Brittleness index (B_i), Tensile Strength (T) and Yield Point (Y) are calculated and the corresponding graphs were plotted. The dielectric constant and dielectric loss of grown 2APKDPL crystal have been studied. EDAX study was carried out to identify the presence of metal ion in 2APKDPL crystal. The growth mechanism of 2APKDPL crystal was analysed by chemical etching process.
Synthesis, growth, structure and characterization of 1-Ethyl-2-(2-p-tolyl-vinyl)-pyridinium iodide (TASI) – An efficient material for third-order nonlinear optical applications
2017, Materials Chemistry and Physics
A new organic stilbazolium derivative, 1-Ethyl-2-(2-p-tolyl-vinyl)-pyridinium iodide (TASI), was grown from methanol:acetonitrile (1:3) mixed solvent by slow evaporation technique. Single crystal X-ray diffraction analysis revealed that TASI crystallizes in triclinic system with a centrosymmetric space group P-1. The molecular structure and the presence of expected functional groups of TASI were confirmed by ¹H NMR and FT-IR spectroscopic studies. The HOMO and LUMO energies influence the charge transfer takes place within the molecule. The grown crystal was thermally stable up to 210 °C as determined by TG/DTA analysis. UV-Vis-NIR spectral study showed that the grown crystal was transparent in the wavelength range of 438–1100 nm. Mechanical behaviour and surface laser damage threshold were studied to find the suitability of the grown crystal for device fabrication. Studies of its third-order nonlinear optical properties using a Z-scan technique demonstrates that TASI crystal is capable of exhibiting reverse saturable absorption and self-focusing performance with the second-order molecular hyperpolarizability (γ) 4.983 × 10⁻³⁴ esu. The third-order nonlinear susceptibility of TASI was found to be 8.931 × 10⁻⁶ esu, which is higher than a few other stilbazolium derivative crystals.
Crystal growth and DFT insight on sodium para-nitrophenolate para-nitrophenol dihydrate single crystal for NLO applications
2016, Journal of Molecular Structure
Single crystals of sodium para-nitrophenolate para-nitrophenol dihydrate (SPPD) were grown by slow evaporation technique and its structure has been studied by FT-IR, FT-Raman and single crystal X-ray diffraction techniques. The optical and electrical properties were characterized by UV-Vis spectrum, and dielectric studies respectively. SPPD was thermally stable up to 128 °C as determined by TG-DTA curves. Using the Kurtz-Perry powder method, the second-harmonic generation efficiency was found to be five times to that of KDP. Third-order nonlinear response was studied using Z-scan technique with a He-Ne laser (632.8 nm) and NLO parameters such as intensity dependent refractive index, nonlinear absorption coefficient and third-order susceptibility were also estimated. The molecular geometry from X-ray experiment in the ground state has been compared using density functional theory (DFT) with appropriate basis set. The first-order hyperpolarizability also calculated using DFT approaches. Stability of the molecule arising from hyperconjugative interactions leading to its nonlinear optical activity and charge delocalization were analyzed using natural bond orbital technique. HOMO-LUMO energy gap value suggests the possibility of charge transfer within the molecule. Based on optimized ground state geometries, Natural bond orbital (NBO) analysis was performed to study donor-acceptor interactions.

View all citing articles on Scopus

View full text

Effect of metal and aminoacid dopants on the growth and properties of l-lysine monohydrochloride dihydrate single crystal

Abstract

Introduction

Section snippets

Solubility test and crystal growth

Growth habit of doped crystals

Conclusion

Acknowledgements

J. Cryst. Growth

J. Cryst. Growth

J. Cryst. Growth

Spectrochim. Acta, Part A

J. Cryst. Growth

Opt. Commun.

J. Cryst. Growth

Opt. Mater.

Thermochim. Acta

J. Cryst. Growth

Spectrochim. Acta Part A: Mol. Biomol. Spectrosc.