Mirosław Szybowicz

Determination of composition and structure of spongy bone tissue in human head of femur by Raman spectral mapping

Biomechanical properties of bone depend on the composition and organization of collagen fibers. In this study, Raman microspectroscopy was employed to determine the content of mineral and organic constituents and orientation of collagen fibers in spongy bone in the human head of femur at the microstructural level. Changes in composition and structure of trabecula were illustrated using Raman spectral mapping. The polarized Raman spectra permit separate analysis of local variations in orientation and composition. The ratios of ν2PO43−/Amide III, ν4PO43−/Amide III and ν1CO32−/ν2PO43− are used to describe relative amounts of spongy bone components. The ν1PO43−/Amide I ratio is quite susceptible to orientation effect and brings information on collagen fibers orientation. The results presented illustrate the versatility of the Raman method in the study of bone tissue. The study permits better understanding of bone physiology and evaluation of the biomechanical properties of bone.

The increase of apatite layer formation by the poly(3-hydroxybutyrate) surface modification of hydroxyapatite and β-tricalcium phosphate

The aim of this study was the surface modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) grafting and characterization of modificates. The bioactivity examination was carried out by the determination to grow an apatite layer on modified materials during incubation in simulated body fluid at 37°C. The additional issue taken up in this paper was to investigate the influence of fluid replacement. The process of the surface modification of biomaterials was evaluated by means of infrared and Raman spectroscopy. Formation of the apatite layer was assessed by means of scanning electron microscopy and confirmed by energy dispersive, Raman and Fourier transformed infrared spectroscopy. During exposure in simulated body fluid, the variation of the zeta potential, pH measurement and relative weight was monitored. Examination of scanning electron microscopy micrographs suggests that modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) significantly increases apatite layer formation. Raman spectroscopy evaluation revealed that the formation of the apatite layer was more significant in the case of hydroxyapatite modificate, when compared to the β-tricalcium phosphate modificate. Both modificates were characterized by stable pH, close to the natural pH of human body fluids. Furthermore, we have shown that a weekly changed, simulated body fluid solution increases apatite layer formation.

Determination of Collagen Fibers Arrangement in Bone Tissue by Using Transformations of Raman Spectra Maps

The goal of this work was to evaluate the ability of Raman spectroscopy to identify molecular organization and chemical composition of extracellular matrix such as the collagen fibers arrangement, the level of mineralization, and the carbonate accumulation in mineral phase in spongy bone of the human head of the femur. Changes in composition and structure of the spongy bone tissue were illustrated using maps of polarized Raman spectra. In particular, the purpose of the present study was determination of arrangement of mineralized collagen on surface of trabecula by using transformations of Raman spectra maps. Transformations of Raman spectra maps were needed in order to remove impact of chemical composition on images of Raman spectra map, which display the collagen fibers orientation. These transformations allow to obtain simultaneously the distribution of constituents of bone and arrangement of collagen fibers on tissue surface. A method to indicate the collagen orientations is developed to understand the molecular organization in healthy and unhealthy bone at the microstructural level.

Temperature study of lattice constants and Raman scattering of SrLaGaO4 single crystal

The lattice parameters of SrLaGaO4 (SLG) single crystal were measured in the temperature range from 300 to 700 K using X-ray spectroscopy. The measurements revealed that (i) the thermal coefficient along a and c axes is different and (ii) thermal expansion coefficient in a direction depends on temperature, showing the transition temperature at about 460 K. To verify this result we have also studied the Raman intensity IR and full width at half maximum (FWHM) of the Raman band at 218 cm−1 ascribed to the librational lattice mode. The above temperature dependences display a characteristic discontinuity at about 460 K which coincides with the previous data obtained from X-ray measurements. The obtained results are discussed in terms of the nature of defects which might arise in the ABCO4 lattice during the crystal growth process.

The method of purifying bioengineered spider silk determines the silk sphere properties.

Bioengineered spider silks are a biomaterial with great potential for applications in biomedicine. They are biocompatible,biodegradable and can self-assemble into films, hydrogels, scaffolds, fibers, capsules and spheres. A novel, tag-free, bioengineered spider silk named MS2(9x) was constructed. It is a 9-mer of the consensus motif derived from MaSp2–the spidroin of Nephila clavipes dragline silk. Thermal and acidic extraction methods were used to purify MS2(9x). Both purification protocols gave a similar quantity and quality of soluble silk; however, they differed in the secondary structure and zeta potential value. Spheres made of these purified variants differed with regard to critical features such as particle size, morphology, zeta potential and drug loading. Independent of the purification method, neither variant of the MS2(9x) spheres was cytotoxic, which confirmed that both methods can be used for biomedical applications. However, this study highlights the impact that the applied purification method has on the further biomaterial properties.

Band Structure of SrLaGaO3+δ and SrLaAlO3+δ

The influence of oxygen on the electronic structure of strontium lanthanum gallate SrLaGaO 3 δ (SLG) and strontium lanthanum alluminate SrLaAlO 3+δ (SLA) crystals is presented. The band structures of SLA and SLG crystals were calculated by ab-initio tight-binding linear muffin tin orbital (TB LMTO) method within an atomic sphere approximation. The self-consistent band calculations indicate that SrLaGaO 4 , SrLaAlO 4 and SrLaAlO 3 are semiconductors, while SrLaGaO 3 , SrLaGaO 3+δ and SrLaAlO 3+δ for δ = 2 and 3 have the metallic character.

Study of the A1‐xBxC Mixed Crystals by Raman Scattering

Observations of Raman scattering associated with vibrational modes in Zn 1-x Mg x Se and Zn 1-x Be x Se semiconducting mixed crystals are reported. Measurements were made at room temperature for Zn 1-x Mg x Se crystals with Mg content in the range 0 < x < 0.43 and Zn 1-x Be x Se crystals with Be content in the range 0 < x < 0.41. From the polarized Raman spectra the longitudinal optical (LO) and transverse optical (TO) modes which corresponding to ZnSe-, MgSe- and BeSe-like single crystals are distinguished. Theoretical calculations of the frequencies of the ZnSe- and BeSe-like modes were also performed using modified random element isodisplacement (MREI) model. The optical modes of Zn 1-x Be x Se are compared with those of Zn 1-x Mg x Se.

Study of CVD diamond layers with amorphous carbon admixture by Raman scattering spectroscopy

Abstract Raman spectroscopy is a most often used standard technique for characterization of different carbon materials. In this work we present the Raman spectra of polycrystalline diamond layers of different quality, synthesized by Hot Filament Chemical Vapor Deposition method (HF CVD). We show how to use Raman spectroscopy for the analysis of the Raman bands to determine the structure of diamond films as well as the structure of amorphous carbon admixture. Raman spectroscopy has become an important technique for the analysis of CVD diamond films. The first-order diamond Raman peak at ca. 1332 cm−1 is an unambiguous evidence for the presence of diamond phase in the deposited layer. However, the existence of non-diamond carbon components in a CVD diamond layer produces several overlapping peaks in the same wavenumber region as the first order diamond peak. The intensities, wavenumber, full width at half maximum (FWHM) of these bands are dependent on quality of diamond layer which is dependent on the deposition conditions. The aim of the present work is to relate the features of diamond Raman spectra to the features of Raman spectra of non-diamond phase admixture and occurrence of other carbon structures in the obtained diamond thin films.

Indium–chlorine and gallium–chlorine tetrasubstituted phthalocyanines in a bulk system, Langmuir monolayers and Langmuir–Blodgett nanolayers – Spectroscopic investigations

The paper deals with spectroscopic characterization of metallic phthalocyanines (Pcs) (indium and gallium) complexed with chlorine and substituted with four benzyloxyphenoxy peripheral groups in bulk systems, 2D Langmuir monolayers and Langmuir-Blodgett nanolayers. An influence of the molecular structure of dyes (the presence of metal and of substitutes attached to the phthalocyanine macroring) on the in situ measurements of light absorption is reported. Molecular arrangement of the phthalocyanine molecular skeleton in the Langmuir monolayers on water substrate and in the Langmuir-Blodgett nanolayers is evaluated. A comparison of the light absorption spectra of the phthalocyanine monolayers with the spectra of the dyes in solution supports the existence of dye aggregates in the monolayer. It was shown that the type of dye aggregates (oblique and H types) depends markedly on the dye molecular structures. The NIR-IR, IR reflection-absorption and Raman spectra are also monitored for Langmuir-Blodgett nanolayers in non-polarized and polarized light. It was shown that the dye molecules in the Langmuir-Blodgett layers are oriented nearly vertically with respect to a gold substrate.

Synthesis of carbon nanotubes and nanotube forests on copper catalyst

The growth of carbon nanotubes on bulk copper is studied. We show for the first time, that super growth chemical vapor deposition method can be successfully applied for preparation of nanotubes on copper catalyst, and the presence of hydrogen is necessary. Next, different methods of copper surface activation are studied, to improve catalyst efficiency. Among them, applied for the first time for copper catalyst in nanotubes synthesis, sulfuric acid activation is the most promising. Among tested samples the surface modified for 10 min is the most active, causing the growth of vertically aligned carbon nanotube forests. Obtained results have potential importance in application of nanotubes and copper in electronic chips and nanodevices.