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The interaction of the phosphoric dendrimer with gold was performed by means of vibrational spectroscopy and quantum chemistry. Stable complexes are formed with a PN-PS linkage, whereas with an isolated PS bond this does not occur. The change in geometric parameters and delocalization of electric charge under the influence of gold was discovered. The classification of bands in the experimental vibrational spectra of the dendrimer and its complex was carried out. HOMO of molecule of the dendrimer is localized on the SPNP linkage, whereas the LUMO is located on the terminal group. In the SPNP linkage there is a noticeable delocalization of the charge which leads to a change in the reactivity of this group. Interaction energy was estimated as the difference between the energies of the complex and the energies of the molecules of the dendrimer G' 0 and two molecules AuCl and is equal to 25.2 eV. The ionization energy IE and electron affinity EA for AuCl are higher than for dendrimer, therefore, when the complex is formed, these quantities increases. Chemical potential and the electrophilicity index in the complex also increases., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Two generations of phosphoric dendrimers with piperidine functional groups were synthesized for use in biology and medicine. Neutral samples are soluble in organic solvents but after protonation these dendrimers become water soluble and can be used for biological experiments. The FTIR and FT Raman spectra of two generations of dendrimers G i constructed from the cyclotriphosphazene core, repeating units OC 6 H 4 CHNN(CH 3 )P(S)< and aminoethylpiperidine end groups NH(CH 2 ) 2 C 5 NH 11 were recorded. The study of the IR spectra shows that the NH groups form hydrogen bonds. The calculation of the molecular structure and vibrational spectra of the first generation dendrimer was performed by the method of DFT. This molecule has flat, repeating units and a plane of symmetry passing through the core. The calculation of the distribution of potential energy made it possible to classify the bands in the experimental spectra of dendrimers. Amine groups are manifested in the form of a band of NH stretching vibrations at 3389 cm -1 in the IR spectrum of G 1 . NH + stretching bands located at 2646 and 2540 cm -1 in the IR spectrum of G 2 . The stretching vibrations of NH + groups are noticeably shifted to low frequencies due to the formation of a hydrogen bond with the chlorine atom. The line at 1575 cm -1 in the Raman spectrum of G 1 is characteristic for repeating units., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Human natural killer (NK) cells play a key role in anti-cancer and anti-viral immunity, but their selective amplification in vitro is extremely tedious to achieve and remains one of the most challenging problems to solve for efficient NK cell-based immuno-therapeutic treatments against malignant diseases. Here we report that, when added to ex vivo culture of peripheral blood mononuclear cells from healthy volunteers or from cancer patients with multiple myeloma, poly (phosphorhydrazone) dendrimers capped with amino-bis(methylene phosphonate) end groups enable the efficient proliferation of NK cells with anti-cancer cytotoxicity in vivo. We also show that the amplification of the NK population relies on the preliminary activation of monocytes in the framework of a multistep cross-talk between monocytes and NK cells before the proliferation thereof. Thus poly(phosphorhydrazone) dendrimers represent a novel class of extremely promising drugs to develop NK-cell based anti-cancer therapies., (Copyright © 2016 Elsevier Inc. All rights reserved.)

The FTIR and FT Raman measurements of the phosphotrihydrazide (S)P[N(Me)-NH2]3 have been performed. This compound is a zero generation dendrimer G0 with terminal amine groups. Structural optimization and normal mode analysis were obtained for G0 by the density functional theory (DFT). Optimized geometric bond length and angles obtained by DFT show good agreement with experiment. The amine terminal groups are characterized by the well-defined bands at 3321, 3238, 1614cm(-1) in the experimental IR spectrum and by bands at 3327, 3241cm(-1) in the Raman spectrum of G0. The experimental frequencies of asymmetric and symmetric NH2 stretching vibrations of amine group are lower than theoretical values due to intramolecular NH⋯S hydrogen bond. This hydrogen bond is also responsible for higher experimental infrared intensity of these bands as compared with theoretical values. Relying on DFT calculations a complete vibrational assignment is proposed for the studied dendrimer., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The FTIR and FT Raman spectra of the second generation dendrimer G'2 built from thiophosphoryl core with terminal aldehyde groups have been recorded. The structural optimization and normal mode analysis were performed for model compound C, consisting of thiophosphoryl core, one branch with three repeated units, and four 4-oxybenzaldehyde terminal groups on the basis of the density functional theory (DFT) at the PBE/TZ2P level. The vibrational frequencies, infrared and Raman intensities for the t,g,g- and t,-g,g-conformers of the terminal groups were calculated. The t,g,g-conformer is 2.0 kcal/mol less stable compared to t,-g,g-conformer. A reliable assignment of the fundamental bands observed in the experimental IR and Raman spectra of dendrimer was achieved. For the low generations (G'1 to G'3) the disk form of studied dendrimer molecules is the most probable. For higher generations, the shape of dendrimer molecules will be that of a cauliflower., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The FT-Raman spectrum of the hexakis(4-N'(-di(4-oxyphenethylamino)-(thio)phosphonyl)-N'-methyl-diazobenzene)cyclotriphosphazene which is the first generation dendrimer G1 built from the cyclotriphosphazene core, six arms -O-C6H4-CH=N-N(CH3)-P(S)< and twelve 4-oxyphenethylamino terminal groups -O-C6H4-(CH2)2-NH2 G1 has been recorded. The structural optimization and normal mode analysis were performed for model compound C, consisting of cyclotriphosphazene core, one arm -O-C6H4-CH=N-N(CH3)-P(S)< and two 4-oxyphenethylamino terminal groups -O-C6H4-(CH2)2-NH2 on the basis of the density functional theory (DFT) at the PBE/TZ2P level. The calculated geometrical parameters and harmonic vibrational frequencies are predicted in good agreement with the experimental data. It was found that G1 has a concave lens structure with planar -O-C6H4-CH=N-N(CH3)-P(S)< fragments and slightly non-planar cyclotriphosphazene core. The 4-oxyphenethylamino groups attached to different arms show significant deviations from a symmetrical arrangement relative to the local planes of repeating units. The experimental Raman spectra of G1 dendron was interpreted by means of potential energy distribution. Relying on DFT calculations, as well as on experimental information, a spectral interpretation was proposed., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The FT Raman spectra of the zero (Gv0) and first generations (Gv1) of phosphorus-containing dendrons with terminal carbamate groups and one ester function and [2-(4-hydroxyphenyl)ethyl]-carbamic acid tert-butyl ester (C) have been recorded and analyzed. The lines of free ν(C=O) bonds are not observed in the experimental Raman spectrum of C and thus association of carbamate groups by hydrogen bonds occur. The frequencies of ν(C=O) lines in the experimental Raman spectrum reveal the presence of the different types of H-bonds in the amorphous state of Gv0. Density functional theory (DFT) calculations of C gave geometrical parameters for the t-g-, g-g-, tg-, gg-conformers. The most stable is the gg-conformer. The structural optimization and normal mode analysis were performed for dendrons on the basis of the DFT. The calculated geometrical parameters, harmonic vibrational frequencies and Raman intensities are predicted in a good agreement with the experimental data. The experimental Raman spectra of dendrons were interpreted by means of potential energy distribution. Relying on DFT calculations the lines of a core, repeating units and terminal groups of dendrons were assigned. The polarizabilities and lipophilicity of dendrons were estimated., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The FTIR and FT Raman spectra of the second generation phosphorus-viologen "molecular asterisk" G2 built from cyclotriphosphazene core with 12 viologen units and 6 terminal phosphonate groups have been recorded and analyzed. The experimental X-ray data of 1,1-bis(4-formylbenzyl)-4,4'-bipyridinium bis(hexaflurophosphate) was used in molecular modeling studies. The optimization of isolated 1,1-bis(4-formylbenzyl)-4,4'-bipyridinium (BFBP) molecule without counter ions PF6(-) does not lead to significant changes of dihedral angles, thus the molecular conformation does not depend on interactions with the counter ions. The structural optimization and normal mode analysis were performed for G2 on the basis of the density functional theory (DFT). The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that G2 has a kind of "egg timer" structure with planar OC6H4CHNN(CH3) fragments and slightly non-planar cyclotriphosphazene core. The experimental IR and Raman spectra of G2 were interpreted by means of potential energy distribution., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The inhibition of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) is the first step in checking whether new compounds can be considered as drugs for treating neurodegenerative diseases. The effect of viologen-phosphorus dendrimers on AChE and BChE activities was studied. The results show that the effects on the cholinesterase activities depend on dendrimer type and size. Viologen dendrimers can interact with the enzymes in two ways: they can bind either to a peripheral site of the enzyme or to amino acids located near the active site, inhibiting catalysis by both cholinesterases. All tested non-toxic viologen-phosphorus dendrimers inhibited the activities of both cholinesterases, showing their potential as new drugs for treating neurodegenerative diseases., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The FTIR and FT-Raman spectra of the first generation dendron built from the cyclotriphosphazene core, five arms -O-C(6)H(4)-CH=N-N(CH(3))-P(S) 2 bonds on the righthand side with ten carbamate terminal groups and one ester function G(v1) have been recorded. The IR and Raman spectra of the zero generation dendron G(v0) and first generation dendrimer G(1) with the same core and terminal groups were also examined. The structural optimization and normal mode analysis were performed for dendron G(v1) on the basis of the density functional theory (DFT). The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that G(v1) has a concave lens structure with planar -O-C(6)H(4)-CH=N-N(CH(3))-P(S) 2 bonds on the righhand side fragments and slightly non-planar cyclotriphosphazene core. The carbamate groups attached to different arms show significant deviations from a symmetrical arrangement relative to the local planes of repeating units. The experimental IR spectrum of G(v1) dendron was interpreted by means of potential energy distributions. The strong band 1604 cm(-1) shows marked changes of the optical density in dependence of the carbamate, ester or azomethyne substituents in the aromatic ring. The frequencies of ν(N-H) and ν(C=O) bands in the IR spectra reveal the presence of the different types of H-bonds in the studied dendrimers., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The aim of this work was to study the effect of phosphorus-containing dendrimers (generations G3 and G4) on the fibrillation of α-synuclein (ASN). The inhibition of fibril formation (filamentous and aggregates) is a potential therapeutic strategy for neurodegenerative disorders such as Parkinson's and other motor disorder neurodegenerative diseases. The interaction between phosphorus-containing dendrimers and ASN was studied by fluorescence spectroscopy. The decrease in the fluorescence intensity of intrisinic tyrosine was the most marked change in the fluorescence intensity observed upon addition of dendrimers. Furthermore, the effect of dendrimers on ASN fibril formation was studied using circular dichroism (CD) spectroscopy and CD studies were complemented by fluorescence assays using the dye thioflavin T (ThT). The results showed that phosphorus-containing dendrimers G3 and G4 inhibited fibril formation, when they were used in the ASN/dendrimer ratios 1:0.1 and 1:0.5. However, the higher concentrations of dendrimers did not show this effect., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The FTIR and FT Raman spectra of the "Janus"-type dendrimers, possessing five carbamate groups on one side and five fluorescent dansyl derivatives on the other side, with amide G(1) and hydrazone G(2) central linkages were studied. These surface-block dendrimers are obtained by the coupling of two different dendrons. The FTIR and FT-Raman spectra of the zero generation dendrons, built from the hexafunctional cyclotriphosphazene core, with five dansyl terminal groups and one carbamate G(0v) and one oxybenzaldehyde function G(0v)' have been recorded. The structural optimization and normal mode analysis were performed for dendron G(0v)' on the basis of the density functional theory (DFT). The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. It was found that dendron molecule G(0v)' has a concave lens structure with planar -O-C(6)H(4)-CHO fragments and slightly non-planar cyclotriphosphazene core. The experimental IR and Raman spectra of dendron G(0v)' were interpreted by means of potential energy distributions. Relying on DFT calculations a complete vibrational assignment is proposed. The strong band 1597 cm(-1) show marked changes of the optical density in dependence of substituents in the aromatic ring. The frequencies of ν(N-H) bands in the IR spectra reveal the presence of the different types of H-bonds in the dendrimers., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The FT-Raman spectra of 10 generations of phosphorus-containing dendrimers containing P=S and P=O bonds with terminal benzaldehyde and P-Cl groups have been recorded and analyzed. The Raman spectra of dendrimers are determined by the ratio T(n)/R(n) (T(n)--number of terminal groups, R(n)--number of repeating units). This ratio trends to r-1 (r--branching functionality of repeating unit), and becomes constant, when the generation number is higher than 3. The lines full width at half height in Raman spectra of 10 generations was measured. The possibility appears to separate the lines assigned to the core, repeating units and terminal groups of dendrimers by difference spectroscopy method. The influence of the encirclement on the line frequencies and intensities was studied and due to the predictable, controlled and reproducible structure of dendrimers the information, usually inaccessible is obtained. Some lines in the Raman difference spectra have characteristic EPR-like form. The strong line at 1600 cm(-1) show marked changes of intensity in dependence of aldehyde (-CH=O) or azomethyne (-CH=N) substituents in the aromatic ring., (Copyright 2010 Elsevier B.V. All rights reserved.)

The IR spectra of P(1) phosphorus dendrimer built from an octasubstituted metal-free phthalocyanine core have been recorded in the region 4000-400cm(-1). Besides the phthalocyanine core, P(1) possess also eight C(6)H(4)-CHN-N(CH(3))-P(S) arms and terminal P-Cl groups. The optimized molecular geometry, frequency and intensity of the IR bands have been calculated using density functional theory (DFT). The P(1) molecules exist in a stable conformation with planar C(6)H(4)-CHN-N(CH(3))- fragments and phthalocyanine core. The calculated geometrical parameters and harmonic vibrational frequencies are predicted in a good agreement with the experimental data. The experimental IR spectrum of P(1) dendrimer was interpreted by means of potential energy distributions. Relying on DFT calculations a complete vibrational assignment is proposed. The difference IR spectra of molecules built from the thiophosphoryl, cyclotriphosphazene, and phthalocyanine cores with the same repeated units and terminal groups were studied in order to undermine the role of the core functionality on the dendrimer architecture.

FTIR and FT-Raman spectra of four generations of phosphorus-containing dendrons with terminal aldehyde or PCl groups have been recorded and analyzed. Their spectral patterns are determined by the ratio T/R (T, the number of terminal groups; R, the number of repeated units). Bands assigned to the core, repeated units and terminal groups were separated by the difference spectroscopy method. The optimized geometry, frequencies and intensity of IR bands of G(1v) generation dendron with terminal aldehyde groups were obtained by the density functional theory (DFT). It was found that the internal skeleton of molecules exists in a single stable conformation with planar O-C(6)H(4)-CHN-N(CH(3))-P(S) fragments, but terminal groups may adopt the t,g,g- and t,-g,g-rotational isomers. The t,-g,g-conformer is 0.74 kcal/mol less stable compared to the t,g,g-conformer. The bond length and bond angles obtained by DFT show the best agreement with experimental data. Relying on DFT calculations a complete assignment of vibrations is proposed for different parts of the studied dendrons. The calculated frequencies and intensity of IR bands of the t,g,g- and t,-g,g-conformers of G(1v) are found to be in reasonable agreement with the experimental results. The most reactive site in dendron is the core function and vinyl group is preferred for nucleophilic attack. In dendrimer the most reactive are the terminal groups.

Inhibition of fibril assembly is a potential therapeutic strategy in prion diseases. The effect of cationic phosphorous dendrimers on the aggregation process of the prion peptide PrP 185-208 was studied using a spectrofluorometric assay with thioflavin T (ThT) and Fourier transformed infrared spectroscopy in order to monitor the kinetics of the process and the changes in the peptide secondary structure. The results show that phosphorous dendrimers are able to clearly interfere with PrP 185-208 aggregation process by both slowing down the formation of aggregates (by causing a decrease of the nucleation rate) and by lowering the final amount of amyloid fibrils, a common hallmark of conformational diseases. The dendrimers effect on the aggregation process would imply their interaction with peptide monomers and oligomers during the nucleation phase.

FT-IR spectra of phosphorus dendron G(1v) generation with terminal P-Cl groups have been recorded. Density functional theory is used for analyzing the properties of each structural part (core, branches, surface). It is found that the repeating branching units of G(1v) exist in a single stable conformation with planar -O-C(6)H(4)-CH=N-N(CH(3))-P fragments. DFT results for the structure of G(1v) are in good agreement with recent X-ray diffraction measurements. A complete vibrational assignment is proposed for different parts of G(1v). The global and local reactivity descriptors have been used to characterize the reactivity pattern of the core function and terminal group. Our study reveals that the most reactive site of G(1v) is the core function and =CH(2) side of vinyl group is preferred for nucleophilic attack. In the dendrimer G(1) the most reactive are the terminal groups. IR spectroscopy combined with ab initio DFT computation provides unique detailed information about the structure and reactivity of the technologically relevant materials, which could not be obtained before with any other technique.

FT-IR spectra of the phosphorus-containing dendron G'(0v) generation with terminal aldehyde groups have been recorded. The structural optimization and normal mode analysis are performed for the G'(0v) on the basis of the ab initio density functional theory. This calculations gave vibrational frequencies and infrared intensities for the t,g,g- and t,-g,g-conformers of the G'(0v). The t,-g,g-conformer is 0.71 kcal/mol less stable compared to t,g,g-conformer. Relying on DFT calculations a complete vibrational assignment is proposed for different parts of the dendron. The influence of encirclement on band frequencies and intensity is studied and the information usually inaccessible is obtained. The global and local reactivity descriptors have been used to characterize the reactivity pattern of the core function and terminal groups. Our study reveals that the most reactive site in the dendron is the core function and the CH(2) side of the vinyl group is preferred for nucleophilic attack. In the dendrimer the most reactive are the terminal groups.

FT IR and Raman spectra of 12 generations of the phosphorus-containing starburst dendrimers containing P=S and P=O bonds with terminal aldehyde and P-Cl groups were compared. The influence of the encirclement on the band frequencies and intensity is studied and due to the predictable, controlled and reproducible structure of the dendrimers the information usually inaccessible is obtained. Bands in the IR difference (G2'(P=O)-G2'(P=S)) spectra have characteristic EPR-like form. The strong band at 1600 cm(-1) show marked changes of the optical density in dependence of the aldehyde (-CH=O) or azomethyne (-CH=N-) substituents in the aromatic ring. The analysis of difference spectra enables one to assign the characteristic bands nu(P=S) and nu(P=O) for the bonds in the core, in the repeating unit and in the terminal groups of the dendrimers. This assignment is supported by the calculation of the absorption curves of the different fragments of dendrimer with the force constants and electro-optical parameters. The IR and Raman spectra of dendrimers are depended on the ratio of number terminal groups to a number of repeating units, which in its turn is strictly determined by the generation number. Thus, the marked differences in the vibrational spectra of the first successive generations aspire to zero for the higher ones. The rather rigid repeated units with little conformational flexibility define the perfect microstructure of the studied phosphorus-containing dendrimers up to the eleventh generation.

Various approximations to the analysis of the dendrimer vibrational spectra are introduced. The merits and demerits of the fragment method, calculation of the first generation and linear chains containing different number of the repeated units are discussed. The experimental spectra of two series of the phosphorus-containing starburst dendrimer generations are interpreted on the basis of the calculation of the frequencies of the normal vibrations and the band intensities in their IR spectra. The analysis of spectra enables one to assign the characteristic bands for the groups in the core, in the repeating unit and the terminal groups of the dendrimers. This assignment is supported by the calculation of the absorption curves with the force constants and electro-optical parameters (EOP). The vibrational spectra of studied starburst dendrimers (SD) (up to 11 generations) are in general identical to begin with four generation. The most marked changes of band position and their intensities are seen in spectra of the first generations, when all fragments of molecule contribute appreciably to the spectral pattern. The comparative study of vibrational spectra of SD and linear polymers reveal their main characteristic features, which are determined by their structural peculiarities.