FT Raman and IR spectra of the crystallized biologically active molecule, 5-Amino-3-methyl-1-phenyl-
1H-pyrazole-4-carbaldehyde (5-APHC, C11H11N3O) have been recorded and analyzed. The equilibrium
geometry, bonding features and harmonic vibrational frequencies of 5-APHC have been investigated with
the help of B3LYP density functional theory (DFT) method with 6-31G(d) and 6-311+G(d,p) as basis set.
The calculated molecular geometry has been compared with the experimental data. The assignments of
the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following
the scaled quantum mechanical force field (SQM) technique. The optimized geometry shows the
co-planarity of the aldehyde group with pyrazole ring. Potential energy surface (PES) scan studies has
also been carried out by ab initio calculations with B3LYP/6-311+G(d,p) basis set. The red shifting of
NH2 stretching wavenumber indicates the formation of N–H  O hydrogen bonding. 1H and 13C NMR
spectra were recorded and 1H and 13C nuclear magnetic resonance chemical shifts of the molecule were
calculated using the gauge independent atomic orbital (GIAO) method. UV–Vis spectrum of the
compound was recorded in the region 200–400 nm and the electronic properties HOMO and LUMO
energies were calculated by time-dependent TD-DFT approach. Mulliken charges of the 5-APHC molecule
was also calculated and interpreted.

Prostate cancer (PCa) is the most commonly diagnosed cancer in men. The progression and invasion of PCa are normally mediated by the overexpression of chemokine receptors (CKRs) and the interaction between CKRs and their cognate ligands. We recently demonstrated that venom extracted from Walterinnesia aegyptia (WEV) either alone or in combination with silica nanoparticles (WEV+NP) mediated the growth arrest and apoptosis of breast cancer cells. In the present study, we evaluated the impact of WEV alone and WEV+NP on the migration, invasion, proliferation and apoptosis of prostate cancer cells. We found that WEV alone and WEV+NP decreased the viability of all cell types tested (PCa cells isolated from patient samples, PC3 cells and LNCaP cells) using an MTT assay. The IC(50) values were determined to be 10 and 5 μg/mL for WEV alone and WEV+NP, respectively. WEV+NP decreased the surface expression of the CKRs CXCR3, CXCR4, CXCR5 and CXCR6 to a greater extent than WEV alone and subsequently reduced migration and the invasion response of the cells to the cognate ligands of the CKRs (CXCL10, CXCL12, CXCL13 and CXCL16, respectively). Using a CFSE proliferation assay, we found that WEV+NP strongly inhibited epidermal growth factor-mediated PCa cell proliferation. Furthermore, analysis of the cell cycle indicated that WEV+NP strongly altered the cell cycle of PCa cells and enhanced the induction of apoptosis. Finally, we demonstrated that WEV+NP robustly decreased the expression of anti-apoptotic effectors, such as B cell Lymphoma-2 (Bcl-2), B cell Lymphoma-extra large (Bcl-(XL) and myeloid cell leukemia sequence-1 (Mcl-1), and increased the expression of pro-apoptotic effectors, such as Bcl-2 homologous antagonist/killer (Bak), Bcl-2-associated X protein (Bax) and Bcl-2-interacting mediator of cell death (Bim). WEV+NP also altered the membrane potential of mitochondria in the PCa cells. Our data reveal the potential of nanoparticle-sustained delivery of snake venom as effective treatments for prostate cancer.

Optical transmittance measurements near the absorption edge of [Kx(NH4)1x]2ZnCl4 mixed crystals, where x ¼ 0.00, 0.232, 0.522,
0.644, 0.859 and 1.00, are reported over 276–350K range. Analysis reveals that the type of transition is the indirect allowed one. The
absorption edge shifted towards lower energy with increasing temperature. It is shown that [Kx(NH4)1x]2ZnCl4 mixed crystals with
xp0.644 reveal a phase transition at 319 K, this phase disappeared at high concentrations of K+ ions. The steepness parameter is given,
its value is used to estimate the temperature dependence of the indirect energy gap. In the region of the absorption edge, the absorption
coefficient obeys Urbach’s rule. Urbach parameters are investigated as a function of temperature.
r 2007 Elsevier Ltd. All rights reserved.

Optical transmittance measurements near the absorption edge of [Kx(NH4)1x]2ZnCl4 mixed crystals, where x ¼ 0.00, 0.232, 0.522,
0.644, 0.859 and 1.00, are reported over 276–350K range. Analysis reveals that the type of transition is the indirect allowed one. The
absorption edge shifted towards lower energy with increasing temperature. It is shown that [Kx(NH4)1x]2ZnCl4 mixed crystals with
xp0.644 reveal a phase transition at 319 K, this phase disappeared at high concentrations of K+ ions. The steepness parameter is given,
its value is used to estimate the temperature dependence of the indirect energy gap. In the region of the absorption edge, the absorption
coefficient obeys Urbach’s rule. Urbach parameters are investigated as a function of temperature.
r 2007 Elsevier Ltd. All rights reserved.

Optical transmittance measurements near the absorption edge of [Kx(NH4)1x]2ZnCl4 mixed crystals, where x ¼ 0.00, 0.232, 0.522,
0.644, 0.859 and 1.00, are reported over 276–350K range. Analysis reveals that the type of transition is the indirect allowed one. The
absorption edge shifted towards lower energy with increasing temperature. It is shown that [Kx(NH4)1x]2ZnCl4 mixed crystals with
xp0.644 reveal a phase transition at 319 K, this phase disappeared at high concentrations of K+ ions. The steepness parameter is given,
its value is used to estimate the temperature dependence of the indirect energy gap. In the region of the absorption edge, the absorption
coefficient obeys Urbach’s rule. Urbach parameters are investigated as a function of temperature.
r 2007 Elsevier Ltd. All rights reserved.

The effects of x-beam irradiation with different doses on microhardness and its related physical constants on
[Ky(NH4)1-y]2ZnCl4 mixed crystals with concentrations, y equals 0.000, 0.232, 0.644, 0.859 or 1.000 has been
studied. The tests were performed for x-doses from 0.2 kGy up to 1.6 kGy for loads from 20 to 160 g. The
variation of hardness on (010) faces of orthorhombic [Ky(NH4)1-y]2ZnCl4 mixed crystals with load were
studied. The experimental results showed that, the hardness decreased as the x-doses increased. Variation of
the microhardness follows the normal ISE trend for low x-doses and un-irradiated crystals, then follows the
reverse ISE trend for high x-doses. Analysis of the experimental results revealed that: the radial cracks length,
indentation size and applied indentation load are mutually related, and these dependences related with fracture
mechanics are the basis of Meyer's empirical law. Indentation size effect (ISE) can be explained satisfactory
by Hays-Kendall's approach and proportional specimen resistance model. Brittleness of two cracks system are
applicable for characterizing cracks around indentation impression (i.e. radial cracks) and another is (lateral
cracks) for [Ky(NH4)1-y]2ZnCl4 mixed crystals, crystals in the load range 60 – 160 g. It is shown that
indentation induced microhardness decreases, whereas the length of radial cracks induced on indentation
increases with the increase of x-doses.

The effects of x-beam irradiation with different doses on microhardness and its related physical constants on
[Ky(NH4)1-y]2ZnCl4 mixed crystals with concentrations, y equals 0.000, 0.232, 0.644, 0.859 or 1.000 has been
studied. The tests were performed for x-doses from 0.2 kGy up to 1.6 kGy for loads from 20 to 160 g. The
variation of hardness on (010) faces of orthorhombic [Ky(NH4)1-y]2ZnCl4 mixed crystals with load were
studied. The experimental results showed that, the hardness decreased as the x-doses increased. Variation of
the microhardness follows the normal ISE trend for low x-doses and un-irradiated crystals, then follows the
reverse ISE trend for high x-doses. Analysis of the experimental results revealed that: the radial cracks length,
indentation size and applied indentation load are mutually related, and these dependences related with fracture
mechanics are the basis of Meyer's empirical law. Indentation size effect (ISE) can be explained satisfactory
by Hays-Kendall's approach and proportional specimen resistance model. Brittleness of two cracks system are
applicable for characterizing cracks around indentation impression (i.e. radial cracks) and another is (lateral
cracks) for [Ky(NH4)1-y]2ZnCl4 mixed crystals, crystals in the load range 60 – 160 g. It is shown that
indentation induced microhardness decreases, whereas the length of radial cracks induced on indentation
increases with the increase of x-doses.

The effects of x-beam irradiation with different doses on microhardness and its related physical constants on
[Ky(NH4)1-y]2ZnCl4 mixed crystals with concentrations, y equals 0.000, 0.232, 0.644, 0.859 or 1.000 has been
studied. The tests were performed for x-doses from 0.2 kGy up to 1.6 kGy for loads from 20 to 160 g. The
variation of hardness on (010) faces of orthorhombic [Ky(NH4)1-y]2ZnCl4 mixed crystals with load were
studied. The experimental results showed that, the hardness decreased as the x-doses increased. Variation of
the microhardness follows the normal ISE trend for low x-doses and un-irradiated crystals, then follows the
reverse ISE trend for high x-doses. Analysis of the experimental results revealed that: the radial cracks length,
indentation size and applied indentation load are mutually related, and these dependences related with fracture
mechanics are the basis of Meyer's empirical law. Indentation size effect (ISE) can be explained satisfactory
by Hays-Kendall's approach and proportional specimen resistance model. Brittleness of two cracks system are
applicable for characterizing cracks around indentation impression (i.e. radial cracks) and another is (lateral
cracks) for [Ky(NH4)1-y]2ZnCl4 mixed crystals, crystals in the load range 60 – 160 g. It is shown that
indentation induced microhardness decreases, whereas the length of radial cracks induced on indentation
increases with the increase of x-doses.

Mixed crystals of potassium-ammonium zinc chloride in different concentrations were grown from aqueous
solution employing the techniques of slow cooling and controlled evaporation. Powder x-ray diffraction
studies were carried out on the grown crystals. The comparison between lattice parameters a, b and c are
experimentally determined and calculated by Vegad's law. The concentration of K+ ions in the crystals was
measured by the atomic absorption technique. The crystal morphology changed considerably by increasing
K+ concentration. The optical absorption coefficient (α) indicated strong influence changing concentration.
The optical energy gap was found to decrease with increasing K+ concentration.