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Adeno-associated virus (AAV) is one of the most promising viral gene delivery vectors with long-term gene expression and disease correction, featuring high efficiency and excellent safety in human clinical trials. During the production of AAV vectors, there are several quality control (QC) parameters that should be rigorously monitored to comply with clinical safety and efficacy. This review gives a short summary of the most frequently used AVV production and purification methods, focusing on the analytical techniques applied to determine the full/empty capsid ratio and the integrity of the encapsidated therapeutic DNA of the products.

Lung adenocarcinoma is one of the leading causes of mortality among cancer patients worldwide and Chronic Obstructive Pulmonary Disease (COPD) is also high in death statistics. In addition, patients with Chronic Obstructive Pulmonary Disease (COPD) have a high risk of developing primary lung cancer. Prevention, risk estimation and a non-invasive diagnostics are essential to decrease COPD and lung cancer mortality. Therefore, better and more accurate molecular diagnostic markers (biomarkers) are needed for the early differential diagnosis of these lung diseases to help clinicians make better therapeutic decisions. This review focuses on recently discovered adenocarcinoma and COPD biomarkers at the proteome and glycome level. In the first part, the protein markers are summarized, while the second part is focused on glycan markers. Their use to differentiate between chronic inflammation (COPD) and malignant (adenocarcinoma) diseases is discussed in detail.

Absztrakt: A krónikus obstruktív tüdőbetegség (COPD) világszerte előkelő helyet foglal el a morbiditási és mortalitási statisztikákban. A COPD megelőzhető és kezelhető betegség, kialakulásáért döntően a dohányzás tehető felelőssé. A prevenció kulcsfontosságú, de korlátozottan kivitelezhető, így a rizikó meghatározása és a korai noninvazív diagnosztika révén lehetne tovább csökkenteni a COPD miatti halálozást. A fejlődő diagnosztikus technikák ellenére az optimális szűrővizsgálat felfedezése még várat magára. Kellően szenzitív és specifikus biomarkerek felfedezése megfelelő eszközt adhat a klinikus kezébe a betegség korai diagnosztizálásához, a differenciáldiagnosztikához, a fenotipizáláshoz és a prognózis becsléséhez. Közleményünkben a COPD vonatkozásában a közelmúltban felfedezett potenciális fehérje és glikán biomarkereket foglaljuk össze. Orv Hetil. 2020; 161(4): 123–128.

The market segment of new biological drugs (monoclonal antibodies, fusion proteins, antibody-drug conjugates, and new modality protein therapeutics) is rapidly growing, especially after the patent expiration of the original biologics, initiating the emergence of biosimilars. N-glycosylation of therapeutic proteins has high importance on their stability, safety, immunogenicity, efficacy, and serum half-life. Therefore, Nglycosylation is considered to be one of the critical quality attributes. Consequently, it should be rigorously monitored during the development, manufacturing, and release of glycoprotein biologicals. In this review, first, the regulatory considerations for biosimilars are shortly summarized, followed by conferring the analytical techniques needed for monitoring and characterization of the N-glycosylation of biological drugs. Particular respect is paid to liquid phase separation techniques with high sensitivity and highresolution detection methods, including laser-induced fluorescence and mass spectrometry.

New complexes of Pd(II) with cationic phthalimido-functionalized N-heterocyclic carbene (NHC), the cis-Diacetonitrile(chloro)[1-(2′-phthalamidoethyl)-3-methylimidazolin-ylidene]palladium(II) Hexafluorophosphate (and its CD3CN derivative) had been successfully used as catalyst in the Suzuki–Miyaura cross-coupling reaction. This complex have been studied by structural (XRD), spectroscopic (infrared, far-infrared and Raman) and theoretical (DFT and normal coordinate calculations) methods. Palladium is bound to two acetonitrile ligands and one-one chloride ion and phthalimido-functionalized imidazolium salt, [3-methyl-1-(2′-phthalimidoethyl) imidazolium] (L = ligand) in a square–planar cis arrangement. The molecular structure of the [PdCl(NCCH3)2L]+ was obtained by XRD and DFT geometry optimization. The two acetonitrile ligands exhibited two different Pd-N bonds a shorter one 2.080 A (opposite to Cl ion) and a longer one 2.120 A (trans to heterocyclic ligand). The cationic [PdCl(NCCH3)2L+] complex has as much as 132 fundamental modes and practically all of them have been assigned. The complex has no symmetry elements, but interpretation has been performed on the basis of local symmetries of its fragments. Tans-conformation of the bridging –CH2-CH2– group has been established from vibrational spectra, and this local structure avoided interaction of phthalimido moiety with the palladium center. Special attention has been paid for understanding and interpretation of the characteristic imidazolium ring vibrations connected to the strong electron donor phthalimido ring at 1553, 1397, 1347, 1218, 1149, 1118, 845, 748, 666, 629, 471, 245, 212, 124 and 104 cm−1 which bands are up shifted comparing to those of 2,3-dialkyl substituted ring modes. Clear differences were established between the fundamentals and force constants of the two differently coordinated acetonitrile. The more strongly coordinated CH3CN(1) has Raman bands at 2336, 958 and 279 cm−1 while the other CH3CN(2) has at 2321, 936 and 266 cm−1 like antisymmetric CN, CC and Pd-N stretching modes, respectively. The Pd-N stretching modes were assigned with the help of spectral and calculated data of CD3CN complex. For acetonitrile (1) the light and heavy stretching modes were 279 and 275 cm−1, respectively exhibiting 4 cm−1 isotope shift whyle those for acetonitrile (2) were as 266 and 264 cm−1 with less isotope shift. Rather small but different 1.630 and 1.493 Ncm−1 Pd-N stretching force constants were fitted for stronger and weaker bonded acetonitrile as compared to those of 3.931 Ncm−1 for [Pd(NCCH3)2]2+, and 4.050 Ncm−1 for cis-PtCl2(NCCH3)2. In contrast, the strongly weakened Pd-N bonds the Pd-Cl bond is enhanced and exhibiting relative high 2.03 Ncm−1 force constants in comparison with 1.53 Ncm−1 of [PdCl4]2- anion. The enhanced Pd-Cl bond strength is escorted by strong weakening of Pd-acetonitrile coordination. Surprisingly, from DFT calculation and spectroscopic data higher Pd-N force constant was obtained for the Pd-N bond with longer bond length and opposite, lower force constant for shorter Pd-N bond. These unusual discrepancies between bond lengths and bond force constants can be explained with the presence of electron-rich σ-donating ligand opposite to acetonitrile (1) which lead to enhancement of Pd-N bond. These specific properties of coordination sphere of [PdCl(NCCH3)2L]+ complex providing possibilities for easily releasing acetonitrile ligands during catalytic processes and give reasonable structural explanation of its high catalytic activity.

Vibrational spectroscopic study of crystalline copper hexacyanoferrate complexes of composition K4CuII6 [FeII(CN)6]4·nH2O (1) and CuII6[FeIII(CN)6]4·nH2O (2) with -Cu-N≡C-Fe- bridging structures ha...

The effect of air plasma exposure time on the surface energies and acid-base characteristics of polydimethylsiloxane (PDMS) particles was studied. Polymerized PDMS powder was radio frequency induced air plasma irradiated for 2–10 s with the power of 500 W. The efficiency of the plasma treatments was investigated by a new generation inverse gas chromatograph, a surface energy analyzer. The dispersive component of surface energy was determined by the Dorris-Gray method describing the van der Waals interactions, while the specific component of surface energy expressed the surface ability for Lewis acid-base interactions. It was demonstrated that the air plasma treatment did not affect the dispersive and acidic parts of the surface energy and the change of surface hydrophilicity was caused by the raise of the electron-donor ability of the PDMS surface, characterized by van Oss-Good-Chaudhury’s base number. The optimal plasma treatment time was found to be 5 s. Analysis of the specific surface energy and acid-base characteristics with respect to exposure time showed that partial to complete hydrophobic recovery occurred within 38 h.

New composite materials based on clay minerals had been prepared by reductive calcination. These materials exhibit very strong infrared (IR) emission at quite low temperatures. The structural prope...

Continuous-flow processing in the manufacturing of modern biotherapeutics represents a great potential and could significantly improve productivity and product quality as well as reduce operating costs. Microfluidic perfusion systems are not only capable for producing therapeutic proteins but also suitable for organ-on-a-chip based drug testing and toxicology studies. Integrating modular unit operations for protein purification in the microfluidic cell culture device can lead to point-of-care therapeutic protein production. The multi-organ microfluidic platforms that integrate several organ-on-a-chip microfluidic units will help in preclinical testing of drug substances and toxicological studies by producing highly reliable preclinical pharmacokinetic data. In this perspective, the current state of the art and future trends of continuous flow systems are summarized for biopharmaceutical production and organ-on-a-chip drug testing.

Capillary coatings effectively improve the separation performance of proteins in capillary electrophoresis, mainly by reducing protein adsorption onto the inner capillary wall and by regulating the electroosmotic flow (EOF) to accommodate the separation problem in hand. In the first part of this review the newest trends in dynamic and permanent capillary coatings are summarized and discussed in detail. In the second part the application of nanomaterials as novel capillary coating materials is conversed. Nanomaterials have great potential in capillary coating preparations based on their advantageous properties such as large surface-to-volume ratios and a wide variety of chemistry options. Finally, some future prospective of capillary coatings in the emerging field of proteomics are given.

Capillary electrochromatography (CEC) is a powerful hybrid separation technique that combines capillary electrophoresis and capillary chromatography, capable to address the analytical challenges of proteomics and glycomics. The focus of this paper is to review the recent developments in capillary electrochromatography of proteins and carbohydrates. The different column types applied in capillary electrochromatography such as packed bed, open tubular and monoliths are conferred in detail with respective separation examples. A comprehensive comparison is also given listing the mostly utilized coating methods, stationary phase materials and column preparation methods. The choice of porogenic solvent combinations for monolithic column fabrication is thoroughly discussed, paying close attention to the fine tuning options for the separation driving electroosmotic flow. Application examples of CEC in process analytical technology for the biopharmaceutical and biomarker discovery in the biomedical fields are also given.

Chronic obstructive pulmonary disease (COPD) is worldwide a significant representative of morbidity and mortality statistics. COPD is a preventable and treatable disease and smoking is the main risk factor of disease development. Prevention is crucial, but it has its limitations, so risk estimation and early non-invasive diagnostics are essential to decrease COPD mortality. Although diagnostic techniques are evolving, the perfect screening tool is lacking. Discovery of properly sensitive and specific biomarkers is important. They could be effective diagnostic, differential diagnostic, phenotyping and prognostic tools to clinicians. The manuscript is focusing on recently discovered potential protein and glycan biomarkers for COPD. Orv Hetil. 2020; 161(4): 123-128.Absztrakt: A krónikus obstruktív tüdőbetegség (COPD) világszerte előkelő helyet foglal el a morbiditási és mortalitási statisztikákban. A COPD megelőzhető és kezelhető betegség, kialakulásáért döntően a dohányzás tehető felelőssé. A prevenció kulcsfontosságú, de korlátozottan kivitelezhető, így a rizikó meghatározása és a korai noninvazív diagnosztika révén lehetne tovább csökkenteni a COPD miatti halálozást. A fejlődő diagnosztikus technikák ellenére az optimális szűrővizsgálat felfedezése még várat magára. Kellően szenzitív és specifikus biomarkerek felfedezése megfelelő eszközt adhat a klinikus kezébe a betegség korai diagnosztizálásához, a differenciáldiagnosztikához, a fenotipizáláshoz és a prognózis becsléséhez. Közleményünkben a COPD vonatkozásában a közelmúltban felfedezett potenciális fehérje és glikán biomarkereket foglaljuk össze. Orv Hetil. 2020; 161(4): 123–128.

Magnetic nanoparticles are frequently used in a wide range of biomedical applications. In the first part of this review the most commonly used preparation and surface coating approaches of MNPs are briefly summarized including multifunctional hybrid particles. The second part gives a detailed overview of the use of MNPs in "traditional" biomedical applications related to cancer theranostics, like magnetic resonance imaging, drug delivery, hyperthermia and also their applicability in the next generation of point of care devices based on micro nuclear magnetic resonance and surface enhanced Raman spectroscopic detection technology that all can be routinely applied in everyday clinical practice.

The utilization of continuous-flow biochemical reactors, including biocatalysis, biotransformation, and biochemical interaction based flow-analytical systems, and enzyme reactors are recently the focus of attention to produce fine biochemicals and also show great potential in bioanalytical applications. Continuous-flow biochemical processes implemented in microstructured reactors enable short development time to production scale utilizing enzymatic processes to efficiently fulfill the current needs of the fine biochemical and pharmaceutical industry. Immobilization of the enzymes is preferable because it usually enhances their stability, and in some instances, immobilized enzymes can even be reused multiple times. In this review on the continuous-flow biochemical reactors, first the enzyme immobilization strategies will be briefly discussed followed by summarizing the recent developments in the field of immobilized enzyme microflow reactors for biocatalysis, bioconversion and bioanalytical purposes.

Design, fabrication, integration, and feasibility test results of a novel microfluidic cell capture device is presented, exploiting the advantages of proton beam writing to make lithographic irradiations under multiple target tilting angles and UV lithography to easily reproduce large area structures. A cell capture device is demonstrated with a unique doubly tilted micropillar array design for cell manipulation in microfluidic applications. Tilting the pillars increased their functional surface, therefore, enhanced fluidic interaction when special bioaffinity coating was used, and improved fluid dynamic behavior regarding cell culture injection. The proposed microstructures were capable to support adequate distribution of body fluids, such as blood, spinal fluid, etc., between the inlet and outlet of the microfluidic sample reservoirs, offering advanced cell capture capability on the functionalized surfaces. The hydrodynamic characteristics of the microfluidic systems were tested with yeast cells (similar size as red blood cells) for efficient capture.

The carbohydrate moieties on the polypeptide chains in most glycoprotein based biotherapeutics and their biosimilars play essential roles in such major mechanisms of actions as antibody-dependent cell-mediated cytotoxicity, complement-dependent cytotoxicity, anti-inflammatory functions and serum clearance. In addition, alteration in glycosylation may influence the safety and efficacy of the product. Glycosylation, therefore, is considered as one of the important critical quality attributes of glycoprotein biotherapeutics, and consequently for their biosimilar counterparts. Thus, the carbohydrate moieties of such biopharmaceuticals (both innovator and biosimilar products) should be closely scrutinized during all stages of the manufacturing process. In this paper we introduce a rapid, capillary gel electrophoresis based process to quantitatively assess the glycosylation aspect of biosimilarity (referred to as glycosimilarity) between the innovator and a biosimilar version of etanercept (Enbrel® and Benepali®, respectively), based on their N-linked carbohydrate profiles. Differences in sialylated, core fucosylated, galactosylated and high mannose glycans were all quantified. Since the mechanism of action of etanercept is TNFα binding, only mannosylation was deemed as critical quality attribute for glycosimilarity assessment due to its influence on serum half-life.

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The recent expiration of several protein therapeutics opened the door for biosimilar development. Biosimilars are biologic medical products that are similar but not identical copies of already-authorized protein therapeutics. Critical quality attributes (CQA), such as post-translational modifications of recombinant biotherapeutics, are important for the clinical efficacy and safety of both the innovative biologics and their biosimilar counterparts. Here, we summarize biosimilarity CQAs, considering the regulatory guidelines and the statistical aspects (e.g., biosimilarity index) and then discuss glycosylation as one of the important attributes of biosimilarity. Finally, we introduced the 'Glycosimilarity Index', which is based on the averaged biosimilarity criterion.

Determination of the oligosaccharide composition in different wort samples is important to monitor their change during the brewing process with different yeast types. In our work, the concentration of fermentable and non-fermentable sugars were monitored by capillary electrophoresis to observe the effect of two different types of yeasts, Saccharomyces pastorianus and Saccharomycodes ludwigii. The former first ferments the monosaccharides, then the higher sugar oligomers, such as maltose and maltotriose, to ethanol, while the latter fully ferments the monosaccharides, but ferments only very low percentages of the oligosaccharides. Therefore, breweries use Saccharomycodes ludwigii to produce beers with low alcohol content. The CE-LIF traces of the wort samples represented unique oligosaccharide signatures.

As a continuation of our previously published work, this paper presents a detailed evaluation of a microfabricated cell capture device utilizing a doubly tilted micropillar array. The device was fabricated using a novel hybrid technology based on the combination of proton beam writing and conventional lithography techniques. Tilted pillars offer unique flow characteristics and support enhanced fluidic interaction for improved immunoaffinity based cell capture. The performance of the microdevice was evaluated by an image sequence analysis based in-house developed single-cell tracking system. Individual cell tracking allowed in-depth analysis of the cell-chip surface interaction mechanism from hydrodynamic point of view. Simulation results were validated by using the hybrid device and the optimized surface functionalization procedure. Finally, the cell capture capability of this new generation microdevice was demonstrated by efficiently arresting cells from a HT29 cell-line suspension.

Circulating tumor cells (CTCs) in the bloodstream are considered good indicators of the presence of a primary tumor or even metastases. CTC capture has great importance in early detection of cancer, especially in identifying novel therapeutic routes for cancer patients by finding personalized druggable targets for the pharmaceutical industry. Recent developments in microfluidics and nanotechnology improved the capabilities of CTC detection and capture, including purity, selectivity and throughput. This article covers the recent technological improvements in microfluidics-based CTC-capture methods utilizing the physical and biochemical properties of CTCs. We critically review the most promising hydrodynamic, dielectrophoretic and magnetic force-based microfluidic CTC-capture devices.

The polarization layer can strongly affect the separation process by pervaporation. This paper defines the overall mass transfer rates, involving the effect of both the polarization and the membrane layers, in cases of constant diffusion coefficient, variable diffusion coefficient and application of the Flory–Huggins theory. These rate equations enable the user to take into account the exact effect of the polarization layer on the separation. Due to the low value of Peclet number, during pervaporation process the expressions of mass transfer rates, enrichment, and separation factor of binary mixtures can be essentially simplified. It has been stated that the Peclet number does not affect significantly the overall mass transfer rate, while it affects strongly the enrichment or the separation factor. It has been proved that the k/(kmH) value dominantly affects the separation efficiency during the pervaporation processes.

Novel organic–inorganic hybrid nanotubes containing silica and ethane (EtSNT), ethylene (ESNT) and acetylene (ASNT) units, as well as brominated ESNT (Br-ESNT) and glycine-modified Br-ESNT (Gly-ESNT) have been studied by IR and Raman spectroscopy. The results are compared with the spectral features for conventional silica nanotubes (SNT) and amorphous silica. Bands peculiar to organic moieties have been detected and assigned. Assignment of the silicate backbone vibrations was based on the results of normal coordinate calculations. Furthermore, characteristic silicate, so-called ‘nanotube’ vibrations have been identified and their band positions have been summarized to serve as a future reference for such compounds. SiOSi antisymmetric stretchings were observed in the range 1000–1110 cm−1, while the symmetric stretchings appeared between 760 and 960 cm−1 for EtSNT, ESNT and Br-ESNT. Force constants have been refined for models of the repeating structure units: O3SiOSi(OSi)3 for SNT and SiCHnCHnSi(OSi)3 for organosilica nanotubes (n = 2, EtSNT; n = 1, ESNT and n = 0, ASNT). The calculated SiO stretching force constants were increased from 4.79 to 4.88 and 5.11 N cm−1 for EtSNT, ESNT and ASNT, respectively. The force constants have been compared with those for several silicates and SiO bond length are predicted and discussed.

Surface modification of the inner capillary wall in CE of proteins is frequently required to alter EOF and to prevent protein adsorption. Manual protocols for such coating techniques are cumbersome. In this paper, an automated covalent linear polyacrylamide coating and regeneration process is described to support long-term stability of fused-silica capillaries for protein analysis. The stability of the resulting capillary coatings was evaluated by a large number of separations using a three-protein test mixture in pH 6 and 3 buffer systems. The results were compared to that obtained with the use of bare fused-silica capillaries. If necessary, the fully automated capillary coating process was easily applied to regenerate the capillary to extend its useful life-time.

The L-cysteine zwitterions in the orthorhombic crystal structure and in aqueous solution, including the deuterated isotopologues HSCD2CH(NH3 +)COO−, DSCH2CH(ND3 +)COO−, and DSCD2CH(ND3 +)COO−, have been studied by mid-infrared, far-infrared, and Raman spectroscopy. Density functional theory (DFT) calculations were performed for an equilibrium molecular geometry of the cysteine zwitterion to obtain vibrational frequencies of fundamental modes, infrared (IR) and Raman intensities, and the depolarization ratio of the Raman bands and combined with normal coordinate force field analyses. The force field obtained for dissolved (in H2O and D2O) cysteine, based on the 4 × 36 experimental fundamental modes of the four isotopologues, was successfully transferred to the two conformers in the solid state. The experimentally observed multiple bands (generally doublets) of L-cysteine and its deuterated isotopologues in the solid state were interpreted based on the coexistence of two conformers in the unit cell...

[Tetraamminecadmium(II)] bis(permanganate) (1) was prepared and its crystal structure was elucidated with XRD-Rietveld refinement and vibrational spectroscopic methods. Compound 1 has a cubic lattice consisting of a 3D hydrogen-bonded network built as four by four distorted tetrahedral blocks of [Cd(NH3)4]2+ cations and MnO4– anions, respectively. The other four permanganate ions are located in a crystallographically different environment, placed in the cavities formed by the attachment of the building blocks. A low-temperature (≈100 °C) solid phase quasi-intramolecular redox reaction producing ammonium nitrate and amorphous CdMn2O4 could be established. Neither solid phase nor aqueous solution phase thermal deammoniation of compound 1 can be used to prepare Cd(MnO4)2 and [Cd(NH3)2(MnO4)2]. During deammoniation of compound 1 in aqueous solution a precipitate consisting of Cd(OH)2 forms. Additionally, solid MnO2 and ammonium permanganate (NH4MnO4) forms. The solid phase deammoniation reaction (toluene used as heat convecting medium) with subsequent aqueous leaching of the ammonium nitrate formed has proved to be an easy and convenient technique for the synthesis of amorphous CdMn2O4+x type NOx and MeSH sensor precursors. The 1-D perdeuterated complex was also synthesized to distinguish the N–H(D) and O–H(D) fragment signals in the TG-MS spectra and to elucidate the vibrational characteristics of the overlapping Mn–O and Cd–N frequencies.

Mid-infrared, far-infrared and Raman vibrational spectroscopic studies were combined with DFT calculations and normal coordinate force field analyses for N,N’-dimethylurea (DMU), N,N,N’,N’-tetramet ...

Cerium(III) fluoride (CeF 3 ) nanoparticles were produced in aqueous solution by precipitation using cerium(III) excess and sulphate ions in order to assist the aggregation. This process was studied by dynamic light scattering in the solution. The nanonparticles (NPs) were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDX). The CeF 3 NPs have cylindrical shape and domain size of 8.1 nm estimated from the XRD analysis. The EDX spectrum shows sulphur content of the NPs, which indicates the sulphate adsorption on their surface. The spectrophotometric study confirms only an outer-sphere complex existing between the cerium fluoro species and the sulphate ion. Infrared (IR) and Raman spectroscopy was used in order to characterize the structure of the complex on the surface of the NPs. It can be concluded that also cerium hydroxo species adsorbed on the surface from the solution and formed a chelate complex with the sulphate ions.

IR, Raman measurements, and ab initio molecular dynamics simulations have been carried out to describe and understand the structural and dynamic behavior of hydrated Pt2+ ion in water. The experiments have revealed strong red-shifted O–H bond frequencies and blue-shifted ligand deformation bands. The simulations have showed that the presence of the doubly charged cation and the enhanced hydrogen bond formations between the first and second shells result in significant structural changes in the first solvation shell, which in turn yield the characteristic shifts in the vibrational spectra. The weakening of the ligand O–H bonds and the strengthened hydrogen-bonds around the cation can be accounted for as the result of the strong Coulombic field of the Pt(II)-ion. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009

Mid infrared, far-infrared and Raman spectroscopic studies, combined with force field analyses, were performed for the 1 hydrated platinum(II) and palladium(II) ions and cis-diammineplatinum(II) complex in acidic aqueous solutions. Simplified Density Functional Theory (DFT) calculations were made for the equatorial plane of the platinum complexes. Careful subtraction of solvent spectra allowed a number of 'internal' modes of coordinated H(2)O and NH(3) to be determined as weak residual bands. The [Pt(OH(2))(6)](2+) and [cis-Pt(NH(3))(2)(OH(2))(4)](2+) complexes were found to be six-coordinated with four ligands strongly bound in an equatorial plane. The assignments of the vibrational modes in the equatorial plane could be performed on the basis of the experimental observations and by comparison with metal-ligand vibrations of square-planar complexes, aided by normal coordinate calculations. For the weakly coordinated axial aqua ligands, the low wavenumber range and the polarizibility properties allowed the assignments of the bands at about 365 and 325 cm(-1) to the stretching modes of one short and one longer Pt - O* bound to axial aqua ligands, respectively. A similar picture with even less strongly bound axial water molecules emerges from Raman spectroscopy data for the hydrated palladium(II) ion, [Pd(OH(2))(6)](2+). The results are consistent with a description of the [Pt(OH(2))(6)](2+) and [Pd(OH(2))(6)](2+) aqua ions in C(4v) symmetry, and with the [cis-Pt(NH(3))(2)(OH(2))(4)](2+) complex in the Cs point group, and also in qualitative agreement with the structures devised from previous extended X-ray absorption fine structure (EXAFS) measurements.

Some seashells of the Philippine venus species and sea coral of Pontes sp. were studied by means of FT-Raman, Fourier transform infrared spectroscopy (FTIR) and Far-FTIR spectroscopic methods. The Raman spectra show that both Porites sp. and P. venus are of aragonite-structured CaCO3. Detailed spectral analysis, however, reveals some small differences, due to differences in the crystallite size or habit and to different minor element contents. IR spectra show that Porites sp. contains also some small quantities of calcite-structured carbonates. The I…2 band (shoulder) of calcite at 875.7 cm-1 is present in the IR spectrum. The separation of the two I…2 bands (856.4 cm-1 for aragonite and 875.7 cm-1 for calcite) suggests the absence of solid solution of the two polymorphic phases of CaCO3. Spectroscopic results were confirmed also by X-ray powder diffraction measurements.

Infrared, far-infrared and Raman spectra of Re2(O2CCH3)4X2 (X = Cl, Br) and Re2(O2CCD3)4Cl2 have been recorded. Assignments of the vibrational spectra of Os2(O2CCH3)4Cl2 and its deuterated derivative have been completed together with the Re complexes on the basis of normal-coordinate analysis. Force constant calculation was made for the acetate ion as well as for a four-atomic unit (with the CH3 and CD3 groups considered as point masses) using optimized masses of 16.7, 17.8, 20.5 and 21.6 for 12CH3, 13CH3, 12CD3 and 13CD3 groups, respectively. The force constants of the acetate ion have been adopted to the starting force field of the M2(O2CCH3)4X2 type complexes. The metal–halide (0.889, 0.997 and 1.286 N cm−1) and metal–metal stretching (3.32, 3.34 and 3.57 N cm−1) force constants were obtained for Re2(O2CCH3)4Cl2Re2(O2CCH3)4Br2 and Os2(O2CCH3)4Cl2 complexes, respectively. It was shown that the so-called diatomic approximation in most cases overestimates the M–M stretching force constants by 30–40%. Much better correlation has been obtained to fit these force constants, which produced values very close to those obtained by full normal-coordinate calculations. The Re–Re stretching force constants showed a reasonable correlation with the Re–Re bond distances for 18 rhenium complexes.

Vibrational spectra (IR, Raman, inelastic neutron scattering) were measured of natural wardite (ideal formula NaAl 3 (OH) 4 (PO 4 ) 2 ·2 H 2 O) from Trauira, Brazil, with the main impurities Fe and Ca. The spectra are discussed on the basis of a symmetry analysis restricted to one layer in the four-layer structure. The band pattern in the ν (OH) region is due to two different Al 2 OH groups and their correlation coupling; their deformations δ and γ are assigned based on IR and INS spectra. Contributions of the hydrogen-bonded H 2 O molecules are discussed, as are the vibrations of the AlO 6 octahedra dominating the Raman spectrum. From the fundamentals ν (OH) of the OH groups and their overtones anharmonicity constants have been estimated.

A microfluidic cell capture device was designed, fabricated, evaluated by numerical simulations and validated experimentally. The cell capture device was designed with a minimal footprint compartment comprising internal micropillars with the goal to obtain a compact, integrated bioanalytical system. The design of the device was accomplished by computational fluid dynamics (CFD) simulations. Various microdevice designs were rapidly prototyped in poly-dimethylsiloxane using conventional soft lithograpy technique applying micropatterned SU-8 epoxy based negative photoresist as moulding replica. The numerically modeled flow characteristics of the cell capture device were experimentally validated by tracing and microscopic recording the flow trajectories using yeast cells. Finally, we give some perspectives on how CFD modeling can be used in the early stage of microfluidics-based cell capture device development.

Both neutral and ionic platinum complexes of ( R )- N , N -bis(2-diphenylphosphinoethyl)-1-phenyl-ethylamine (PNP) were synthesised. In the reaction of PtCl 2 (PhCN) 2 and PNP cis -PtCl 2 (η 2 -P,P-PNP) ( 1 ) was formed coordinating PNP as a P,P-bidentate ligand. Diastereotopic phosphorus atoms were observed in 31 P NMR upon addition of SnCl 2 to the parent complex ( 1 ) due to the formation of [PtCl(PNP)][SnCl 3 ] ( 2a ). The formation of similar complex cations, [PtX(PNP)] + (where X=I ( 4 ), CN ( 5 )) containing PNP as a terdentate ligand was also observed when KI and KCN was added in the presence of SnCl 2 , which formed trichlorostannate counterion. The addition of PPh 3 to 1 resulted in the partial formation of [Pt(PPh 3 )(PNP)] 2+ ( 3 ), which could be accomplished upon addition of SnCl 2 . The catalytic activity of the platinum–PNP system in the hydroformylation of styrene is low.

Reaction of Re2{μ-O2CC(CH3)3}4Cl2 with [(CO)5M–CN]Na (M = Cr, Mo, W) leads to tetranuclear complexes of formula Re2{μ-O2CC(CH3)3}4[–NC–M(CO)5]2 (M = Cr, Mo, W). These complexes were characterized by 1H-, 13C-, and 95Mo-NMR, IR and Raman spectroscopy, elemental analysis and examined by cyclic voltammetry. The applied methods show the donor capabilities of the [(CO)5M–CN]− ligands which shift electron density towards the Re centers weakening the Re–Re quadruple bond. The Re–Re bond lengths and the ν(Re–Re) force constants are estimated based on the FT-IR and Raman examinations. Photochemical examinations and TG/MS experiments have also been conducted. The latter method shows that the product complexes decompose around 100 °C, by first loosing their carbonyl substituents; as do the Cr, Mo, W precursor compounds. The dirhenium tetrapivalate unit decomposes only at higher temperatures in a distinct second step.

A more general mass transport model of pressure retarded osmosis has been developed and will be presented in this lecture. Essential of this model is that it does not have any simplifications and/or neglects for description of the mass transport process. It takes into account the effect of the external boundary layers on both sides of the membrane, the dense and the sponge layers of an asymmetric membrane used, applying the diffusive-convective mass transport equation for every sub-layer except of the skin/dense layer of the membrane. A widely applied, “diffusive” transport equation was used for the dense layer, for the salt transport through it. Accordingly this model enables the user to calculate the membrane performance under all possible operating conditions. Thus, it can be used to optimize the operating conditions in order to get efficient energy generation unit. The energy density obtained by means of the presented and the literature model have been compared in the paper and showed the process performance under different conditions.