Ivan Jerman

As a promising organic semiconducting material, polymeric graphitic carbon nitride (g-C3N4) has attracted much attention due to its excellent optical and photoelectrochemical properties, thermal stability, chemical inertness, nontoxicity, abundance, and low cost. Its advantageous visible light-induced photocatalytic activity has already been beneficially used in the fields of environmental remediation, biological applications, healthcare, energy conversion and storage, and fuel production. Despite the recognized potential of g-C3N4, there is still a knowledge gap in the application of g-C3N4 in the field of textiles, with no published reviews on the g-C3N4-functionalization of textile materials. Therefore, this review article aims to provide a critical overview of recent advances in the surface and bulk modification of textile fibres by g-C3N4 and its composites to tailor photocatalytic self-cleaning, antibacterial, and flame retardant properties as well as to create a textile catal...

Polyiodides (Ix−, x=3 and 5) and 2I−…I2 adducts were established from the Raman spectra study of 1-methyl-3-propylimidazolium iodide (MPIm+Ix−; 1≤x≤5) ionic liquids containing various amounts of iodine (0mol≤I2≤2mol). The existence of I3− and 2I−…I2 was established for 1≤x≤2.5, symmetric I3− ions for x=3, while linear and discrete I5− was substantiated for 3≤x≤5. The presence of polyiodide species in MPIm+Ix− (1≤x≤5) was correlated with an enhanced ionic conductivity, attributed to the established relay-type Grotthus mechanism. Two-step conductivity increase was also reflected in decrease of the hydrogen bond interactions between the CH ring groups and polyiodides. While in the concentration range 1≤x≤3 (triiodides and tetraiodides) IR bands changed only slightly in intensity, in the concentration range x>3 the CH stretching bands (3040–3170cm−1) split and the new band at 1585cm−1 appeared in the IR spectra beside the already existing Im+ ring stretching mode at 1566cm−1.

Surfaces exhibiting antimicrobial activity were prepared for potential medical application. A polycationic lipopeptide polymyxin B was selected as the bioactive agent for covalent immobilization onto the surface. First, by using sol–gel technology the inert glass substrate was functionalized by a silane coating with epoxide rings to which the peptide was coupled by means of a catalyst. Preparation of the coating and presence of the peptide on the surface were followed by FTIR, XPS and AFM analyses. The obtained material showed antimicrobial effect indicating that in spite of immobilization the peptide has retained its bioactivity. The coated surface was able to reduce bacterial cell counts of the Gram-negative bacterium Escherichia coli by more than five orders of magnitude in 24 h of incubation. It can be concluded that bioactive coatings with covalently bound polycationic peptides have potential for application on medical devices where leakage into the surrounding is not allowed in order to prevent bacterial growth and biofilm formation.

A tri-functional polyhedral oligomeric silsesquioxane (POSS) based silane precursor R x R y R z (SiO 3/2 ) n (x + y + z = n = 6, 8, 10, ….) bearing 3-(N-(3-triethoxysilylpropyl)ureido)propyl , isooctyl and perfluoropropyl groups was synthesized and investigated as corrosion ...

Multifunctional, water and oil repellent and antimicrobial finishes for cotton fibres were prepared from a commercially available fluoroalkylfunctional water-born siloxane (FAS) (Degussa), nanosized silver (Ag) (CHT) and a reactive organic–inorganic binder (RB) (CHT). Two different application procedures were used: firstly, one stage treatment of cotton fabric samples by FAS sol (i), as well as by a sol mixture constituted from all three precursors (Ag–RB–FAS, procedure 1S) (ii), and secondly, two stage treatment of cotton by Ag–RB sol and than by FAS sol (Ag–RB + FAS, procedure 2S) (iii). The hydrophobic and oleophobic properties of cotton fabrics treated by procedures (i)–(iii) before and after consecutive (up to 10) washings were established from contact angle measurements (water, diiodomethane and n-hexadecane) and correlated with infrared and XPS spectroscopic measurements. The results revealed that even after 10 washing cycles cotton treated with Ag–RB + FAS (2S) retained an oleophobicity similar to that of the FAS treated cotton, while the Ag–RB–FAS (1S) cotton fibres exhibited a loss of oleophobicity already after the second washing, even though fluorine and C–F vibrational bands were detected in the corresponding XPS and IR spectra. The antibacterial activity of cotton treated by procedures (i)–(iii) was tested by its reduction of the bacteria Escherichia coli and Staphylococcus aureus following the AATCC 100-1999 standard method and EN ISO 20743:2007 transfer method. The reduction in growth of both bacteria was nearly complete for the unwashed Ag–RB and Ag–RB–FAS (S1), but for the unwashed Ag–RB + FAS (S2) treated cotton no reduction of S. aureus and 43.5 ± 6.9% reduction of E. coli was noted. After the first washing, the latter two finishes exhibited nearly a complete reduction of E. coli but for the Ag–RB treated cotton the reduction dropped to 88.9 ± 3.4. None of the finishes retained antibacterial properties after 10 repetitive washings. The beneficial and long-lasting low surface energy effect of FAS finishes in the absence of Ag nanoparticles, which led to the “passive” antibacterial properties of FAS treated cotton fabrics, was established by applying the EN ISO 20743:2007 transfer method. The results revealed a reduction in bacteria of about 21.9 ± 5.7% (FAS), 13.1 ± 4.8% (Ag–RB–FAS (S1)) and 41.5 ± 3.7% (Ag–Rb + FAS (S2)), while no reduction of the growth of bacteria was observed for cotton treated with Ag nanoparticles after 10 repetitive washings. The physical properties (bending rigidity, breaking strength, air permeability) of finished cotton samples were determined, and showed increased fabric softness and flexibility as compared to the Ag–RB treated cotton, but a slight decrease of breaking strength in the warp and weft directions, while air permeability decreased for all type of finishes.

In a continuation of previous studies, the wetting properties of the hydrophobic diureapropyltriethoxysilane [bis(aminopropyl)-terminated polydimethylsiloxane (1000)] (PDMSU) sol-gel hybrid, which forms washing-resistant water-repellent finishes on cotton fabrics, were further investigated. The addition of 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) to PDMSU resulted in a highly apolar low-energy surface on aluminum with gammaStotal equal to 14.5 mJ/m2 and a DetlaGiwi value of -82 mJ/m2. Mixed PFOTES-PDMSU finishes applied on cotton fabrics increased the water contact angles (thetaw) from approximately 130 degrees (PDMSU) to 147 degrees, also imparting oleophobicity (thetadiiodomethane=130 degrees, thetan-hexadecane=120 degrees) to the finished cotton fabrics. Washing caused breakage of the coating's integrity as established from SEM, which was attributed to the partial removal of PFOTES from the composite films, also shown by subtractive IR attenuated total reflectance (ATR) and XPS spectral measurements made on washed and unwashed fabrics. The antibacterial properties of the PFOTES-PDMSU-finished fabrics were assessed with the transfer method (EN ISO 20743:2007), revealing that the reduction of Escherichia coli bacteria on unwashed cotton fabrics was nearly 100%. Moreover, for washed (10 times) cotton fabrics a much higher bacterial reduction was noted for the PFOTES-PDMSU finishes (60.6+/-10.8%), surpassing PDMSU (30.4+/-6.1%) and commercial fluoroalkoxysilane (FAS) (21.9+/-5.7%) finishes. The structure of PFOTES-PDMSU gels, xerogels, and the corresponding coatings was investigated by analyzing the 29Si NMR and IR ATR spectra and comparing them with the spectra of PFOTES and octameric (T8) PFOTES based polyhedra. The results revealed the tendency of PFOTES to condense in octameric silsesquioxane polyhedra (T8), coexisting in the PDMSU sol-gel network with cyclic tetramers (T4(OH)4) and open cube-like species (T7(OH)3). The presence of -OH-functionalized PFOTES silsesquioxanes, established even in coatings heat-treated at 140 degrees C (15 min), also explained the excellent washing fastness of PFOTES finishes on cotton fabrics. The regenerative nature of the water- and oil-repellent properties of washed PFOTES-PDMSU-finished cotton fabrics was attributed to the surface mobility of the T8 PFOTES based polyhedra, ousted from the coating interior during consecutive washings.

A novel bifunctional polyhedral oligomeric silsesquioxane (POSS) based silane precursor R(x)R'(y)(SiO(3/2))(8), (x + y = 8), bearing 3-(N-(3-triethoxysilylpropyl)ureido)propyl (ureasil - U) and isooctyl (IO) groups (i.e., U(2)IO(6) POSS) was synthesized, and the corresponding coatings, prepared under the acid hydrolysis conditions, were studied in order to assess their corrosion inhibition of the AA 2024-T3 alloy. The U(2)IO(6) POSS precursor was made in two steps: in the first, an appropriate stoichiometric (2:6) mixture of 3-aminopropyltriethoxysilane (AP(2)) and isooctyltrimethoxysilane (IO(6)) was autoclaved under basic hydrolysis conditions giving AP(2)IO(6)(SiO(3/2))(8) cubes, which were reacted in the second step with 3-isocyanatopropyltriethoxysilane (ICPTES), leading to the bis end-capped sol-gel precursor U(2)IO(6) POSS having a cube-like structure. Coatings were made from sols catalyzed with acidified water. IR and (29)Si NMR spectroscopic studies combined with mass spectrometric measurements were employed to confirm the cube-like structure of AP(2)IO(6) and U(2)IO(6) POSS. The structure and morphology of the U(2)IO(6) POSS coatings were studied with the help of infrared reflection-absorption (IR RA) spectroscopic measurements combined with XPS and AFM measurements, providing information about the formation of partially self-assembled coatings. The degree of corrosion inhibition was assessed from the potentiodynamic measurements showing around 10 times smaller current densities for the coatings only 30-40 nm thick. Ex situ IR RA spectroelectrochemical measurements were performed by consecutive measurements of the IR RA spectra of U(2)IO(6) POSS coatings which were chronocoulometrically charged at different potentials. At potentials more positive than the corrosion potential (E(corr) approximately -0.5 V), the amide I bands shifted, indicating the formation of new urea-urea aggregations and associations, with the newly formed strong band at 1680-1690 cm(-1) suggesting the formation of amidonium ions. These results showed that the urea groups represented the weakest part of the coatings due to their tendency to protonation.

ABSTRACT An electrochemical and in-situ Raman spectroelectrochemical study of 1-methyl-3-propylimidazolium iodide ionic liquid electrolyte (MPIm+Ix-) in the absence (x=1) and presence (x=3) of iodine is presented. Cyclic voltammetric measurements in combination with a platinum disk microelectrode revealed a remarkable difference before and after addition of iodine to the ionic liquid, implying the electrochemical formation of polyiodide ions (I5-) at potentials more positive than +0.6V in the presence of an equimolar amount of iodine. To verify this presumption, we performed in-situ Raman spectroelectrochemical measurements of MPIm+I− and MPIm+I−+I2 ionic liquids in a laboratory-made spectroelectrochemical cell, while stepwise changing the potential of the working platinum disk electrode. The results obtained were in good accordance with the above-mentioned postulate about the presence of polyiodide species (I5-), and can be conveniently employed in further investigations to elucidate of the Grotthus mechanism, associated with increasing conductivity as a result of the formation of polyiodides.