Abstract
Fourier transform infrared spectroscopy and 2D correlation spectroscopy were used to study the microstructural changes occurring on heating of a new carbosilane dendrimer with peripheral ammonium groups. Temperature-dependent spectral variations in the 3,010–2,710, 1,530–1,170, and 1,170–625 cm−1 regions were monitored during the heating process. The dependence, on temperature, of integral absorptions and position of spectral bands was established and the spectral modifications associated with molecular conformation rearrangements, allowing molecular shape changes, were found. Before 180 °C, the studied carbosilane dendrimer proved to be stable, while at higher temperatures it oxidizes and Si–O groups appear. 2D IR correlation spectroscopy gives new information about the effect of temperature on the structure and dynamics of the system. Synchronous and asynchronous spectra indicate that, at low temperature, conformational changes of CH3 and CH3–N+ groups take place first. With increasing temperature, the intensity variation of the CH2, C–N, Si–C and C–C groups from the dendritic core is faster than that of the terminal units. This indicates that, with increasing temperature, the segments of the dendritic core obtain enough energy to change their conformation more easily as compared to the terminal units, due to their internal flexibility.
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Bobrovsky AY, Pakhomov AA, Zhu XM, Boiko NI, Shibaev VP, Stumpe J (2002) Photochemical and photoorientational behavior of liquid crystalline carbosilane dendrimer with azobenzene terminal groups. J Phys Chem B 106:540–546
Buhleier E, Wehner W, Vögtle F (1978) Cascade and nonskid-chain-like synthesis of molecular cavity topologies. Synthesis 2:155–158
Daniel M-C, Ruiz J, Nlate S, Blais J-C, Astruc D (2003) Nanoscopic assemblies between supramolecular redox active metallodendrons and gold nanoparticles: synthesis, characterization, and selective recognition of H2PO4-, HSO4-, and adenosine-5‘-triphosphate (ATP2-) anions. J Am Chem Soc 125:2617–2628
Dantlgraber G, Baumeister U, Diele S, Kresse H, Luehmann B, Lang H, Tschierske C (2002) Evidence for a new ferroelectric switching liquid crystalline phase formed by a carbosilane based dendrimer with banana-shaped mesogenic units. J Am Chem Soc 124:14852–14853
Fréchet JMJ, Tomalia DA (2001) Dendrimers and other dendritic polymers. Wiley, West Sussex
Furer VL, Vandukova II, Tatarinova EA, Muzafarov AM, Kovalenko VI (2008) FTIR spectroscopy and DFT studies of carbosilane dendrimers. Spectrochim Acta A Mol Biomol Spec 70:692–699
Gittins PJ, Twyman LJ (2003) Dendrimers and supramolecular chemistry. Supramol Chem 15:5–23
Gonzalo T, Clemente MI, Chonco L, Weber ND, Díaz L, Serramía MJ, Gras R, Ortega P, de la Mata FJ, Gómez R, López-Fernández LA, Muñoz-Fernández A, Jiménez JL (2010) Gene therapy in HIV-infected cells to decrease viral impact by using an alternative delivery method. Chem Med Chem 5:921–929
Hasegawa Y, Iimura M, Yajima S (1980) Synthesis of continuous silicon carbide fibre. J Mater Sci 15:720–728
Hawker CJ, Fréchet JMJ (1990) Preparation of polymers with controlled molecular architecture. A new convergent approach to dendritic macromolecules. J Am Chem Soc 112:7638–7647
Kauppinen JK, Moffatt DJ, Mantsch HH (1981) Fourier self-deconvolution—a method for resolving intrinsically overlapped bonds. Appl Spectrosc 35:271–276
Kleij AW, Klein Gebbink RJM, Lutz M, Spek AL, van Koten G (2001) Synthesis and characterization of platinum(II)-terminated dendritic carbosilanes: X-ray crystal structure of the model species (PtCl(C6H3(CH2NMe2)-2-SiMe3-5)(PPh3)). J Organomet Chem 621:190–196
Lebedev BV, Kulagina TG, Ryabkov MV, Ponomarenko SA, Makeev EA, Boikov NI, Shibaev VP, Rebrov EA, Muzafarov AM (2003) Carbosilane dendrimer of second generation with terminal methoxyundecylenate groups. J Therm Anal Calorim 71:481–492
Mazo MA, Zhilin PA, Gusarova EB, Sheiko SS, Balabaev NK (1998) Molecular dynamics simulation of dendrimer intramolecular mobility. Bull Russ Acad Sci (Phys Ser) 62:1098–1102
Muller M, Buchet R, Fringeli UP (1996) 2D-FTIR ATR spectroscopy of thermo-induced periodic secondary structural changes of Poly-(L)-lysine: a cross-correlation analysis of phase-resolved temperature modulation spectra. J Phys Chem 100:10810–10825
Murata H, Matsuura H, Ohno K, Sato T (1979) Vibrational spectra, normal vibrations and rotational isomerism of alkylsilanes: part I. Propylsilane, butylsilane and their Si-perdeuterium compounds. J Mol Struct 52:1–11
Nakano T, Shimada S, Saitoh R, Noda I (1993) Transit 2D IR correlation spectroscopy of the photopolymerization of acrylic and epoxy monomers. Appl Spectrosc 47:1337–1342
Newkome GR, Moorefield CN, Vögtle F (2001) Dendrimers and Dendrons. Wiley, Weinheim
Noda I (1990) Two-dimensional infrared (2D IR) spectroscopy: theory and applications. Appl Spectrosc 44:550–561
Noda I (1993) Generalized two-dimensional correlation method applicable to infrared, Raman, and other types of spectroscopy. Appl Spectrosc 47:1329–1336
Noda I, Liu Y, Ozaki Y (1996) Two-dimensional correlation spectroscopy study of temperature-dependent spectral variations of W-methylacetamide in the pure liquid state. 1. Two-dimensional infrared analysis. J Phys Chem 100:8665–8673
Ozaki Y, Liu Y, Noda I (1997) Two-dimensional infrared and near-infrared correlation spectroscopy: applications to studies of temperature-dependent spectral variations of self-associated molecules. Appl Spectrosc 51:526–535
Popescu M-C, Vasile C, Filip D, Macocinschi D, Singurel Gh (2004) Characterization by Fourier transform infrared spectroscopy of polyethylene adipate/cholesteryl palmitate blends. J Appl Polym Sci 94:1156
Popescu M-C, Filip D, Vasile C, Cruz C, Rueff JM, Marcos M, Serrano JL, Singurel G (2006) Characterization by Fourier transform infrared spectroscopy (FT-IR) and 2D IR correlation spectroscopy of PAMAM dendrimer. J Phys Chem B 110:14198–14211
Popescu M-C, Vasile C, Singurel Gh (2007) 2D IR correlation spectroscopy in polymer studies. In: Zaikov GE (ed) New trends in natural and synthetic polymer science. Nova Science Publishers, New York
Pugh VJ, Hu Q-S, Zuo X, Lewis FD, Pu L (2001) Optically active BINOL core-based phenyleneethynylene dendrimers for the enantioselective fluorescent recognition of amino alcohols. J Org Chem 66:6136–6140
Rasines B, Hernández-Ros JM, de las Cuevas N, Copa-Patiño JL, Soliveri J, Muñoz-Fernández MA, Gómez R, de la Mata FJ (2009) Water-stable ammonium-terminated carbosilane dendrimers as efficient antibacterial agents. Dalton Trans 40:8704–8713
Ren Y, Shimoyama M, Ninomiya T, Matsukawa K, Inoue H, Noda I, Ozaki Y (1999) Two-dimensional near-infrared correlation spectroscopy studies on composition-dependent spectral variations in ethylene/vinyl acetate copolymers: assignments of bands due to ethylene units in amorphous, disordered, and orthorhombic crystalline phases. Appl Spectrosc 53:919–926
Rossell O, Seco M, Angurell I (2003) Synthesis of transition metal-containing carbosilane dendrimers. Compet Rendus Chim 6:803–817
Sakthivel T, Florence AT (2003) Dendrimers and dendrons: facets of pharmaceutical nanotechnology. Drug Deliv Technol 3:73–78
Savitzky A, Golay JE (1964) Smoothing and differentiation of data by simplified least squares procedures. Anal Chem 36:1627–1639
Smeller L, Heremans K (1999) 2D FT-IR spectroscopy analysis of the pressure- induced changes in proteins. Vib Spectrosc 19:375–378
Sullivan EJ, Hunter DB, Bowman RS (1998) Fourier-transform Raman spectroscopy of sorbed HDTMA and the mechanism of chromate sorption to surfactant-modified clinoptilolite. Environ Sci Tech 32:1948–1955
Suwardie H, Kalyon DM, Kovenklioglu S (1991) Thermal behavior and curing kinetics of Poly(carbosilane). J Appl Polym Sci 42:1087–1095
Tomalia DA, Baker H, Dewald J, Hall M, Kallos G, Martin S, Roeck J, Ryder J, Smith P (1985) A new class of polymers: starburst-dendritic macromolecules. Polymer J 17:117–132
Tripathi PK, Khopade AJ, Dutta T, Umamaheshewari RB, Jain S, Saraf DK, Jain NK (2003) Dendrimer ploycation for delivery of gene. Indian J Pharm Sci 65:15–21
van der Made AW, Leeuwen PWNMJ (1992) Silane dendrimers. Chem Soc Chem Commun 19:1400–1401
Wang Y, Murayama K, Myojo Y, Tsenkova R, Hayashi N, Ozaki Y (1998) Two-dimensional Fourier transform near-infrared spectroscopy study of heat denaturation of ovalbumin in aqueous solutions. J Phys Chem B 102:6655–6662
Weber N, Ortega P, Clemente MI, Shcharbin D, Bryszewska M, de la Mata FJ, Gómez R, Muñoz-Fernández MA (2008) Characterization of carbosilane dendrimers as effective carriers of siRNA to HIV-infected lymphocytes. J Control Release 132:55–64
Yajima S, Hasegawa Y, Hayashi J, Iimura M (1978) Synthesis of continuous silicon carbide fibre with high tensile strength and high Young’s modulus. J Mater Sci 13:2569–2576
Acknowledgments
This study was performed in the framework of the COST action TD0802 “Dendrimers in Biomedical Applications”. M. C. Popescu acknowledges the financial support of European Social Fund—“Cristofor I. Simionescu” Postdoctoral Fellowship Programme (ID POSDRU/89/1.5/S/55216), Sectoral Operational Programme Human Resources Development 2007–2013. R.G. acknowledges the financial support of CTQ2011-23245 (MINECO) and Consortium NANODENDMED ref S2011/BMD-2351 (CAM) awarded to R. G. This study was also supported by CIBER-BBN financed by the Instituto de Salud Carlos III, with assistance from the European Regional Development Fund. E.F.-P. and M.G. acknowledge Ministerio de Educación y Ciencia (Spain).
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Popescu, MC., Gómez, R., de la Mata, F.J. et al. Characterization by Fourier transform infrared spectroscopy (FT-IR) and 2D IR correlation spectroscopy of a carbosilane dendrimer with peripheral ammonium groups. J Nanopart Res 15, 1713 (2013). https://doi.org/10.1007/s11051-013-1713-3
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DOI: https://doi.org/10.1007/s11051-013-1713-3