Sergey A. Ponomarenko

Photochemistry and photoorientational phenomena in carbosilane dendrimers with terminal azobenzene groups

Photo-optical properties of carbosilane dendrimers of the first, third, and fifth generations with terminal azobenzene groups are presented. The dendrimers synthesized display a crystalline phase, which melts into isotropic liquid at 81-91 °C (depending on the generation number). A comparative analysis of the photo-optical behavior of the dendrimers in dilute solutions and films was carried out. It was shown that under the action of UV irradiation (365 nm) an E/Z photoinduced isomerization of azobenzene groups takes place in the solutions and amorphous films. This process was found to be thermally reversible: annealing leads to a back Z/E isomerization. The processes of photoinduced orientation of terminal azobenzene groups of the dendrimers under the action of polarized UV light (365 nm) were studied.

Liquid Crystalline Carbosilane Dendrimers with Terminal Phenyl Benzoate Mesogenic Groups: Influence of Generation Number on Phase Behaviour

Abstract The thermal behaviour of two series of liquid crystalline carbosilane dendrimers of generations 1–5 containing 8, 16, 32, 64 and 128 terminal phenyl benzoate mesogenic groups, respectively, was investigated by means of polarising optical microscopy, DSC and X-ray methods. Mesogenic groups on the base of methoxybenzoic (anisic) acid (Anis) and methoxyphenol (MPhB) were linked to the carbosilane dendritic matrices through -OOC-(CH2)10-Si(CH3)2OSi(CH3)2- spacer. All LC dendrimers synthesised display smectic type mesophases and crystal phases over wide temperature region. LC dendrimers of fifth generation have more complex phase behaviour: heating the samples leads to transition from smectic to, most probably, columnar mesophases.

Nature-like solution for removal of direct brown 1 azo dye from aqueous phase using humics-modified silica gel

The objective was to estimate suitability of humics-modified silica gels for adsorptive removal of the Direct Brown 1 trisazo dye from aqueous phase. The major advantage of the proposed adsorbents is that of an ecologically sound procedure of immobilizing silanized humic derivatives onto silica gel in aquatic solutions. The silanized humic derivatives, in turn, are obtained without a use of organic solvent by reacting natural humic materials from peat and coal with 3-aminopropyltriethoxyorganosilane in water. These silanized derivatives are surface active and are capable of self assembling into humic adlayers at the water solid interface. A use of this approach allows for immobilization of up to 220 mg of humic materials per 1 g of SiO2. The adsorption capacity of humics-modified silica gels with respect to the Direct Brown 1 trisazo dye varied from 3.5 up to 8.8 mg per 1 g of SiO2. The maximum sorption obtained for the silanized derivative with 50% modification degree was comparable to adsorption capacity of activated coal to this dye (7.5 mg g(-1)). The results of this adsorption study, warrant further studies of azo dye removal from aqueous environments.

Self-assembly of alkoxysilanized humic substances into multidomain adlayers at the water–solid interface: linking surface morphology to the molecular structure of the adsorbate

Self assembly of natural organic materials (e.g., humic substances) on mineral surfaces leads to the formation of adlayers with physically different domains. However, direct evidence to explain the molecular interactions responsible for the formation of these domains is still missing. Here, we developed alkoxysilanized humic probes capable of self-assembling onto hydroxylated surfaces. Using modified humic substances from vastly differed sources (peat, water, coal) and DNA array glass slides as a flat surrogate for mineral surfaces, we create humic adlayers under aqueous conditions and show them to be homogeneous on the macroscale, but consisted of nanosize domains in coal and water humics and submicron-size domains in peat humics. The surface charge and hydrophilic–lipophilic balance of humic associates were proposed as major molecular drivers of the self-assembly with the former causing the formation of thin adlayers composed of separated nanosize domains (e.g., coal humics) and the latter enhancing the formation of thicker adlayers composed of interconnected domains linked in chains up to the submicron-size (e.g., peat humic materials). To the best of our knowledge, this is the first time alkoxysilanized humic probes were used to examine how humic adsorbates and their molecular structure influences the surface morphology of assembled adlayers. In this fashion, the humic adlayer with molecularly-defined functional elements can be assembled on any hydroxylated surface in situ, at the water–solid interface.

Nanostructured organosilicon luminophores as a new concept of nanomaterials for highly efficient down-conversion of light

Nanostructured organosilicon luminophores (NOLs) are branched molecular structures having two types of covalently bonded via silicon atoms organic luminophores with efficient Förster energy transfer between them. They combine the best properties of organic luminophores and inorganic quantum dots: high absorption cross-section, excellent photoluminescence quantum yield, fast luminescence decay time, good processability and low toxicity. A smart choice of organic luminophores allowed us to design and synthesize a library of NOLs, absorbing from VUV to visible region and emitting at the desired wavelengths from 390 to 650 nm. They can be used as unique wavelength shifters in plastic scintillators and other applications.

Thiophene-based monolayer OFETs prepared by Langmuir techniques

A novel fast, easily processible and highly reproducible approach to thiophene-based monolayer OFETs fabrication by Langmuir-Blodgett or Langmuir-Schaefer techniques was developed and successfully applied. It is based on selfassembly of organosilicon derivatives of oligothiophenes or benzothienobenzothiophene on the water-air interface. Influence of the conjugation length and the anchor group chemistry of the self-assembling molecules on the monolayer structure and electric performance of monolayer OFETs was systematically investigated. The efficient monolayer OFETs with the charge carrier mobilities up to 0.01 cm2/Vs and on/off ratio up to 106 were fabricated, and their functionality in integrated circuits under normal air conditions was demonstrated.

Design of low band gap small molecules with alkyldicyanovinyl acceptor and different donor groups for efficient bulk heterojunction organic solar cells

A library of low band gap small molecules with alkyldicyanovinyl acceptor and triphenylamine, tris(2- methoxyphenyl)amine or dithienosilole donor groups linked through (oligo)thiophene conjugated spacers was designed and successfully synthesized. Systematic variations of the alkyl chain length and the number of conjugated thiophene rings in the molecules allowed to elucidate the structure-properties relationships for their solubility, absorption spectra, phase behavior, morphology and structure in thin films, as well as photovoltaic properties. Bulk heterojunction organic solar cells prepared from these molecules as donors and PCBM[70] as acceptor by solution processing showed power conversion efficiency up to 5.4 - 6.4%.

Nonreversible Immobilization of Water-Borne Plutonium onto Self- Assembled Adlayers of Silanized Humic Materials

The objective was to study plutonium partitioning between immobile and mobile humic materials at the water-solid interfaces. Immobilization of the humic materials on solid supports was performed in situ using self-adhesive silanized humic derivatives. The presence of the humic adlayers on solid supports was shown to significantly enhance Pu sorption and its retention under both steady state and dynamic conditions. While plutonium may exist in multiple oxidations states plus colloidal forms, the major thrust in this work was to study the behavior of most mobile--the PuO2(+) form in dilute solutions. The values of the plutonium partition coefficients (Kd) between water and humics-coated silica gels after 10 days exposure reached 1.6 × 10(4) L · kg(-1) at pH 7.5 under anaerobic conditions with a total plutonium concentration of 1.2 × 10(-8) M exceeding those for the uncoated SiO2 (6.3 × 10(2) L · kg(-1)). Column tests showed substantial sequestration of water-borne plutonium (up to 73%) on the humics-coated silica gels. Remobilization experiments conducted under batch conditions at different pH values (3.5, 4.5, 7.5) showed that no more than 3% of the sequestered Pu was remobilized from the humics-coated silica gels by treatment with dissolved humic materials at environmentally relevant pH of 7.5. Consequently, silanized humic materialas can be seen as both molecular probes and as potent candidate materials for scavenging mobile Pu from an aqueous phase.

Organosilicon dimer of BTBT as a perspective semiconductor material for toxic gas detection with monolayer organic field-effect transistors

Monolayer organic field effect transistors (OFETs) provide opportunity for ultrahigh sensitivity gas sensor applications due to a strong dependence of OFET key parameters on the environment. However, an impressive combination of both high sensitivity and instantaneous response of such gas sensors can be achieved only on low-defect dense monolayers with high electrical performance. Herein, we investigated monolayer thin film formation of recently developed benzothieno[3,2-b][1]benzothiophene (BTBT) organosilicon dimer D2-Und-BTBT-Hex by Langmuir–Blodgett, Langmuir–Schaefer and spin-coating methods. For all these techniques, the conditions of uniform low-defect monolayer formation were found. These monolayers were used for preparation of OFET devices, which demonstrated excellent electrical performance with a hole mobility up to 7 × 10−2 cm2 V−1 s−1, a threshold voltage around 0 V and an on–off ratio of 105 as well as long-term stability of half-year storage under ambient conditions. Preliminary investigations demonstrated that the monolayer OFETs give an instantaneous response to ammonia at low concentrations (down to 400 ppb). These findings show a great potential of BTBT-based OFETs for large-area sensing device application.

Organosilicon derivatives of BTBT for monolayer organic field effect transistors

Synthesis of novel organosilicon derivatives of [1]benzothieno[3,2-b][1]-benzothiophene (BTBT) linked though flexible aliphatic spacers to a disiloxane anchor group is reported. They were successfully used in monolayer OFETs with the charge carrier mobilities up to 0.02 cm2 /Vs, threshold voltage close to 0 V and On/Off ratio up to 10,000. Influence of the chemical structure of the molecules synthesized on the morphology, molecular 2D ordering in the monolayers and their semiconducting properties is considered. The effect of different methods of the ultrathin semiconducting layer preparation, such as Langmuir-Blodgett, Langmuir-Schaefer, spin coating or doctor blade, on the OFET performance is discussed.