ATR-IR Spectroscopy Research Articles

Synthesis and Characterization of Solvated Lanthanide(II) Bis(triisopropylsilyl)phosphide Complexes.

Lanthanide (Ln) silylamide chemistry is well-developed, but the corresponding silylphosphide chemistry is immature; there are only ten structurally characterized examples of Ln(II) bis(trimethylsilyl)phosphide complexes to date and no reported derivatives with bulkier R-groups. Here, we report the synthesis of the first f-block bis(triisopropylsilyl)phosphide complexes, [Ln{P(SiiPr3)2}2(THF)x] (1-Ln; Ln = Sm, Eu, x = 3; Ln = Yb, x = 2), by the respective salt metathesis reactions of parent [LnI2(THF)2] with 2 equiv of [Na{P(SiiPr3)2}]n in toluene. Complexes 1-Ln were characterized by a combination of NMR, EPR, ATR-IR, electronic absorption and emission spectroscopies, elemental analysis, SQUID magnetometry, and single crystal X-ray diffraction. These data contrast with those obtained for related Ln(II) bis(trimethylsilyl)phosphide complexes due to the bulkier ligands in 1-Ln and also with Ln(II) bis(triisopropylsilyl)amide complexes due to a combination of longer Ln-P vs. Ln-N bonds and the softer nature of P- vs. N-donor ligands.

Investigation and kinetics of hydrogel scaffold with sustained release ciprofloxacin hydrochloride

AbstractControlled drug delivery is the mechanism that determines the frequency of the drug as well as the side effect that can be occurred. Many approaches studied the encapsulation of the drug in a polymer matrix to achieve a controlled released drug by the effect crosslinking network. In this work, a loaded hydrogel with ciprofloxacin hydrochloride has been prepared as an incremental effect on the antibacterial properties. So, four formulations named, hydrogel 1, hydrogel 2, hydrogel 3, and hydrogel 4 were prepared using different polymers concentrations (chitosan, gelatin, iota carrageenan (IC), and glutaraldehyde as crosslinking agents) ciprofloxacin hydrochloride was used as a drug model. The obtained data revealed that the hydrogels prepared from chitosan/gelatin/IC hydrogels are porous and have interconnected microstructures. The hydrogels structure was evaluated by ATR-IR spectroscopy, EDX, Swelling rate, SEM, porosity, antibacterial properties as well as drug release and kinetics. The hydrogels fractured at stresses of 0.1665 to 0.0358 Kgf / mm2. The swelling rates (SR %) after 24 h. were 412%, 362%, 383%, 375% and 407% for of hydrogel 1, hydrogel 2, hydrogel 3, hydrogel 4 and ciprofloxacin hydrochloride loaded hydrogel 1, respectively. The porosity of the prepared hydrogels was increased as the concentration of IC increased from 72.4 to 78%. Loading of ciprofloxacin hydrochloride was confirmed by the presence of fluorine in the EDX measurement. The ciprofloxacin hydrochloride loaded hydrogel 1 has a sustained release of ciprofloxacin hydrochloride over a time of about 10 h. The first-order kinetic model is the best model for the release of ciprofloxacin hydrochloride from the prepared ciprofloxacin hydrochloride loaded hydrogel 1 with a regression coefficient (R2) of 0.9814. The unloaded samples of hydrogels had almost the same antibacterial properties regardless of the amount of IC. Loading the hydrogel with ciprofloxacin hydrochloride has an incremental effect on the antibacterial properties.

Base-free trifluoroacetylation: From methyl glucopyranoside to cellulose nanofibers

Trifluoroacetic anhydride (TFAA) reacts smoothly with low molecular weight carbohydrates and cellulose nanofibers (CNFs) under base-free conditions. Methyl α- and β-d-glucopyranoside were used as model compounds to optimize reaction conditions, which were then applied to lyophilized CNFs for surface modification. ATR-IR spectroscopy and powder X-ray diffraction were employed to characterize the modified CNFs. Trifluoroacetylation for 4 h yields a degree of substitution (DS) of 0.4 acyl groups per anhydroglucose unit while maintaining a crystallinity index near 50 %. DS values were quantified by gravimetry, acid–base titration after saponification, and a novel approach utilizing solution 19F NMR spectroscopy which offers greater accuracy than the other techniques. This study presents an efficient, base-free method for derivatizing carbohydrates as well as surface functionalization of CNFs with trifluoroacetyl groups, potentially expanding their application in fiber-reinforced thermoplastic composites.

Comparative study of metal-organic frameworks synthesized via imide condensation and coordination assembly.

A series of metal-organic frameworks (1-XDI) have been synthesized by imide condensation reactions between an amine-functionalized pentanuclear zinc cluster, Zn4Cl5(bt-NH2)6, (bt-NH2 = 5-aminobenzotriazolate), and organic dianhydrides (pyromellitic dianhydride (PMDA), naphthalenetetracarboxylic dianhydride (NDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (HFIPA)). The properties of the 1-XDI MOFs have been compared with analogues (2-XDI) prepared using traditional coordination assembly. The resulting materials have been characterized by ATR-IR spectroscopy, acid-digested 1H NMR spectroscopy, elemental analysis, and gas adsorption measurements. N2 adsorption isotherm data reveal modest porosities and BET surface areas (30-552 m2 g-1). All of the new 1-XDI and 2-XDI MOFs show selective adsorption of C2H2 over CO2 while 2-PMDI and 2-BPDI exhibit high selectivity toward C3H6/C3H8 separation. This study establishes imide condensation of preformed metal-organic clusters with organic linkers as a viable route for MOF design.

Ultrathin Film Antimony-Doped Tin Oxide Prevents [NiFe] Hydrogenase Inactivation at High Electrode Potentials.

For hydrogenases to serve as effective electrocatalysts in hydrogen biotechnological devices, such as enzymatic fuel cells, it is imperative to design electrodes that facilitate stable and functional enzyme immobilization, efficient substrate accessibility, and effective interfacial electron transfer. Recent years have seen considerable advancements in this area, particularly concerning hydrogenases. However, a significant limitation remains: the inactivation of hydrogenases at high oxidative potentials across most developed electrodes. Addressing this issue necessitates a thorough understanding of the interactions between the enzyme and the electrode surface. In this study, we employ ATR-IR spectroscopy combined with electrochemistry in situ to investigate the interaction mechanisms, electrocatalytic behavior, and stability of the oxygen-tolerant membrane-bound [NiFe] hydrogenase from Cupriavidus necator (MBH), which features a His-tag on its small subunit C-terminus. Antimony-doped tin oxide (ATO) thin films were selected as electrodes due to their protein compatibility, suitable potential window, conductivity, and transparency, making them an ideal platform for spectroelectrochemical measurements. Our comprehensive examination of the physiological and electrochemical processes of [NiFe] MBH on ATO thin film electrodes demonstrates that by tuning the electron transport properties of the ATO thin film, we can prevent MBH inactivation at extended oxidative potentials while maintaining direct electron transfer between the enzyme and the electrode.

Energetic Coordination Compounds: Investigation of Aliphatic Ligands and Development of Prototype Detonators.

In this work, energetic coordination compounds (ECCs) of transition metals (Fe, Ni, Cu, Zn) containing aliphatic amines as ligands were synthesized: ethylenediamine; 1,3-diaminopropane; tris(2-aminoethyl)amine; tris(3-aminopropyl)amine. The compounds were investigated in terms of ignition/explosion temperature, friction and impact sensitivity. For selected compounds, structural characterisation was presented (IR-ATR spectroscopy, Raman spectroscopy) and their morphology was determined (SEM, powder XRD). They were also investigated by differential scanning calorimetry (DSC). In order to assess the potential application of selected ECCs in detonators, underwater explosion tests were carried out, determining energetic performance. The results achieved for detonators containing ECCs were compared with those for reference detonators (containing pentaerythritol tetranitrate, PETN), indicating their potential use as a "green" alternative to nitric acid esters.

Controlling Hybrid Polyhydroxyurethane Adhesive and Rheological Properties by Partial Carbonation of Biobased Epoxy Monomer.

Controlling hybrid material properties by simple monomer design offers an elegant pathway to prepare thermoset adhesives with tunable properties. Herein, biobased hybrid polyhydroxyurethane/polyepoxy is prepared starting from partially carbonated cashew nut shell epoxy derivatives (NC514) and m-xylene diamine (MXDA). The curing reactions, that is, epoxy-amine and cyclic carbonate aminolysis, monitored by ATR-IR spectroscopy at 50°C are found to be concomitant yielding highly homogeneous materials. Hybrid networks are extensively characterized by swelling tests, TGA, DMA, DSC, tensile tests, rheology, and lap-shear-test on aluminum substrates. The introduction of hydroxyurethane moieties within the epoxy-amine networks enhanced the adhesion properties (up to 20% compare to neat epoxy resins) by combining hydrogen bonding capability and vitrimeric properties (thermoset able to flow). Rheological characterizations and reprocessing tests demonstrated that hybrid adhesives with up to 47 mol% of cyclic carbonate groups are capable of covalent exchange (internally catalyzed by tertiary amine) while keeping similar thermomechanical properties and enhanced adhesion strength compare to the permanent epoxy network.

Rare earth mixed sandwich complexes with tetraalkylphospholide and cyclooctatetraenide ligands

A series of rare earth (mono)phospholide mixed sandwich complexes of the general form [M(PC4R4)(COT)(THF)n] (M = Sc, Y, La, Lu; R = Me, Et; COT = cyclooctatetraenide, {C8H8}2–; n = 0 to 2) have been isolated by the treatment of iodide precursors, [M(COT)(I)(THF)n], (1M, M = Sc, Y, Lu, n = 2; M = La, n = 3) with potassium phospholide salts, [K(PC4R4)]n (R = Me, Et). The solid-state molecular structures and speciation of these sandwich complexes depends upon both the ionic radius of the rare earth metal, along with small steric and solubility differences which arise between the two per-alkylated phospholide ligands. The smaller {PC4Me4} ligand gave monomeric Lewis-base free [M(C8H8)(PC4Me4)] (2M, M = Sc, Lu) with smaller rare earths Sc(III) and Lu(III), but moving to larger ions Y(III) and La(III), the products were poorly soluble and could only be isolated as THF-adducts, [Y(C8H8)(PC4Me4)(THF)] (3) and [La(C8H8)(PC4Me4)(THF)2] (4). The slightly increased steric demands of {PC4Et4} gave monomeric Lewis-base free complexes for Sc(III), Lu(III), and Y(III) in [M(C8H8)(PC4Et4)] (5M, M = Sc, Y, Lu), whereas for La(III) a dimeric complex was isolated, [La(C8H8)(µ-PC4Et4)]2 (6). We also report the synthesis and molecular structures of 1Sc and 1Lu, as well as [LuI3(THF)3] (7) for the first time. All complexes were characterised by single crystal X-ray diffraction, multi-nuclear NMR, UV-Vis-NIR and ATR-IR spectroscopies in addition to elemental analysis.

Soft confinement of water in aliphatic alcohols: MIR/NIR spectroscopic and DFT studies

Here, we present the first examination of the state of water under a soft confinement in eight aliphatic alcohols including cyclopentanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-octanol and 3-octanol. Due to relatively large size of the aliphatic part, water has limited solubility in all studied alcohols. Water content in saturated solutions was determined by Karl Fischer titration and correlated with the spectroscopic data. This way, we determined the molar absorptivity of the ν2+ν3 combination mode. The effect of addition of water and temperature variation was monitored by ATR-IR and NIR spectroscopy. Analysis of the experimental results was guided by DFT calculations, which provided the structures, harmonic MIR spectra and binding energies of selected alcohol-water complexes.Our studies demonstrated that the state of water in alcohols is related to its solubility, which depends on structure of solvent molecules. The solubility of water in 1-alcohols decreases on increasing of the chain length, but for long chain alcohols this effect is less evident. More apparent solubility reduction appears in going from the primary to secondary alcohols. The effective shielding of the OH group in the linear alcohols is achieved when on both sides of the OH group are ethyl or longer substituents, while the shielding by methyl groups is less efficient. Water is much better soluble in the cyclic alcohols as compared with the linear ones due to better accessibility of the OH group.The soft confinement of water in aliphatic alcohols allows for flexible structural arrangements and interactions. Even at low water content, we did not observe free molecules of water. At these conditions, the molecules of water are singly or doubly bonded to the OH groups from the alcohol. Increasing solubility of water reduces the number of the free OH groups and leads to formation of water clusters. Obtained results allow concluding that in alcohols with sizable aliphatic part the molecules of water are confined in the vicinity of the OH groups.

Insight on Zn-Al LDH as electrocatalyst for CO2 reduction reaction: An in-situ ATR-IR study

Electrochemical reduction of CO2 (CO2RR) is expected to play a key role among the various strategies being explored to limit global warming. In this scenario, Layered Double Hydroxides (LDHs) are emerging as a promising class of electrocatalysts to replace the most used noble metals. In this work three Zn-Al LDH with different Zn2+/Al3+ ratio were synthesized and characterized by means of XRD, STEM-EDX and HR-TEM. Their suitability for CO2RR to CO was assessed by means of a custom-made three-compartment cell, showing an increase in CO selectivity by decreasing the Zn2+/Al3+ ratio. The CO2 interaction with the samples was firstly characterized by means of volumetric adsorption measurements, exhibiting an increase in capture capacity by decreasing the Zn2+/Al3+ ratio. The evolution of the samples in interaction with a CO2-saturated liquid flow was then deeply investigated by means of in-situ ATR-IR spectroscopy. The samples displayed a different evolution in the vibrational region of the carbonate-like species (1800–1200 cm−1). To better discriminate the different carbonate cyclohexane was also employed. A definitive assignment of the main IR bands of the carbonate was carried out by studying the spectral behavior of the different bands observed in the ATR-IR experiments and by comparing these results with the existing literature. Interestingly, Zn-Al 1:2 LDH, the most efficient electrocatalyst for CO2RR, is also the sole sample exhibiting a higher monodentate to total bidentate carbonates ratio, suggesting that the existence of a higher content of low coordination oxygen anions with stronger basic character can influence the final catalytic activity.

Investigation on the Durability of a Polypropylene Geotextile under Artificial Aging Scenarios

Geosynthetics are widely used in various civil engineering applications, such as geotextiles in coastal protection, and display a sustainable alternative to natural mineral materials. However, the full benefits of using geosynthetics can only be gained with a long service lifetime of the products. With the use of added stabilizers to the polymers, service lifetimes can be achieved in the range of 100 years. Therefore, accelerated aging methods are needed for the assessment of the long-term performance of geotextiles. In the present study, the behavior of geosynthetic materials made of polypropylene was investigated under artificial aging conditions involving elevated temperatures ranging from 30 to 80 °C, increased oxygen pressures ranging from 10 to 50 bar in water-filled autoclaves, and UV irradiation under atmospheric conditions. ATR-IR spectroscopy was employed to detect the increase in the carbonyl index over various aging durations, indicating the oxidative degradation of the geotextile. The most pronounced increase was observed in the case of aging through UV irradiation, followed by thermal aging. Elevated pressure, on the other hand, had a lower impact on oxidation. High-temperature size exclusion chromatography was utilized to follow the reduction in molar mass under different degradation conditions, and the results were consistent with those obtained from ATR-IR spectroscopy. In polyolefins such as polypropylene, Hindered Amine Stabilizers (HAS) are used to suppress oxidation caused by UV radiation. The quantitative analysis of HAS was carried out using a UV/Vis method and HPLC. The degradation of UV stabilizers during the aging of geotextiles is responsible for the oxidation and the reduction in the molar mass of polypropylene. From the results, it can be concluded that applications of PP geotextile without soil or sand cover might cause the risk of the formation of microplastic particles. Material selection, design, and maintenance of the construction must follow best practices, including the system’s removal or replacement at end-of-life. Otherwise, a sustainable use of geotextiles in civil engineering is not possible.

Lutetium-Induced Ultrafine PtRu Nanoclusters with a High Electrochemical Surface Area for Direct Methanol Fuel Cells at Alleviated Temperatures.

PtRu alloys have been recognized as the state-of-the-art catalysts for the methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). However, their applications in DMFCs are still less efficient in terms of both catalytic activity and durability. Rare earth (RE) metals have been recognized as attractive elements to tune the catalytic activity, while it is still a world-class challenge to synthesize well-dispersed Pt-RE alloys. Herein, we developed a novel hydrogen-assisted magnesiothermic reduction strategy to prepare a highly dispersed carbon-supported lutetium-doped PtRu catalyst with ultrafine nanoclusters and atomically dispersed Ru sites. The PtRuLu catalyst shows an outstanding high electrochemical surface area (ECSA) of 239.0 m2 gPt-1 and delivers an optimized MOR mass activity and specific activity of 632.5 mA mgPt-1 and 26 A cmPt-2 at 0.4 V vs saturated calomel electrode (SCE), which are 3.6 and 3.5 times of commercial PtRu-JM and an order higher than PtLu, respectively. These novel catalysts have been demonstrated in a high-temperature direct methanol fuel cell running in a temperature range of 180-240 °C, achieving a maximum power density of 314.3 mW cm-2. The AC-STEM imaging, in situ ATR-IR spectroscopy, and DFT calculations disclose that the high performance is resulted from the highly dispersed PtRuLu nanoclusters and the synergistic effect of the atomically dispersed Ru sites with PtRuLu nanoclusters, which significantly reduces the CO* intermediates coverage due to the promoted water activation to form the OH* to facilitate the CO* removal.

Synthesis and Magnetic Properties of Bis-Halobenzene Decamethyldysprosocenium Cations.

The decamethyldysprosocenium cation, [Dy(Cp*)2]+ (Cp* = {C5Me5}), was a target single-molecule magnet (SMM) prior to the isolation of larger dysprosocenium cations, which have recently shown magnetic memory effects up to 80 K. However, the relatively short Dy···Cp*centroid distances of [Dy(Cp*)2]+, together with the reduced resonance of its vibrational modes with electronic states compared to larger dysprosocenium cations, could lead to more favorable SMM behavior. Here, we report the synthesis and magnetic properties of a series of solvated adducts containing bis-halobenzene decamethyldysprosocenium cations, namely [Dy(Cp*)2(PhX-κ-X)2][Al{OC(CF3)3}4] (X = F or Cl) and [Dy(Cp*)2(C6H4F2-κ2-F,F)(C6H4F2-κ-F)][Al{OC(CF3)3}4]. These complexes were prepared by the sequential reaction of [Dy(Cp*)2(μ-BH4)]∞ with allylmagnesium chloride and [NEt3H][Al{OC(CF3)3}4], followed by recrystallization from parent halobenzenes. The complexes were characterized by powder and single crystal X-ray diffraction, NMR and ATR-IR spectroscopy, elemental analysis, and SQUID magnetometry; experimental data were rationalized by a combination of density functional theory and ab initio calculations. We find that bis-halobenzene adducts of the [Dy(Cp*)2]+ cation exhibit highly bent Cp*···Dy···Cp* angles; these cations are also susceptible to decomposition by C-X (X = F, Cl, Br) activation and displacement of halobenzenes by O-donor ligands. The effective energy barrier to reversal of magnetization measured for [Dy(Cp*)2(PhF-κ-F)2][Al{OC(CF3)3}4] (930(6) cm-1) sets a new record for SMMs containing {Dy(Cp*)2} fragments, though all SMM parameters are lower than would be predicted for an isolated [Dy(Cp*)2]+ cation, as expected due to transverse ligand fields introduced by halobenzenes and the large deviation of the Cp*···Dy···Cp* angle from linearity promoting magnetic relaxation.

Effects of alloying palladium with gold in furfural hydrogenation:An in situ ATR-IR spectroscopy and density functional theory study

Furfural is a versatile platform molecule and a model compound to explore the key factors influencing activity and selectivity in heterogeneous catalysis. In this study, Pd and AuPd nanoparticles (average size 3.5–4 nm) were deposited on TiO2 by sol immobilization method and were evaluated for liquid-phase furfural hydrogenation. Alloying Au and Pd caused a decrease in activity, an enhancement in stability, and a change in selectivity, favouring the complete hydrogenation of furfural over the decarbonylation reaction. These variations in catalytic performance were elucidated by combining in situ attenuated total reflectance infrared spectroscopy and density functional theory studies.

Photophysical properties of tris(benzoyltrifluoroacetonate)Eu(III) with pyrazole complex and its precursor

The precursor, [Eu(btfa)3(H2O)2] with yield of 84 % and its complex with monodentate pyrazole, [Eu(btfa)3(pz)2] were isolated successfully. To the best of our knowledge, no previous reports of such synthesis with a high yield of [Eu(btfa)3(H2O)2] exist in literature. Single crystal X-ray diffraction (SC-XRD) analysis demonstrates, octa-coordinate environment of Eu (III) in both the complexes. The geometry of these complexes was obtained from SHAPE v2.1 and found triangular dodecahedron (D2d) and square antiprism (D4d) for [Eu(btfa)3(H2O)2] and [Eu(btfa)3(pz)2], respectively. These complexes were further characterized by elemental, thermal analysis (TGA/DTA) and ATR-IR spectroscopy. The lifetime of [Eu(btfa)3(pz)2] (546 ± 0.35 μs) is much longer than that of its precursor [Eu(btfa)3(H2O)] (335 ± 0.11 μs). The overall quantum yield of [Eu(btfa)3(pz)2] complex (21 %) is seven times larger than its precursor (3 %). The Judd-Ofelt intensity parameters accredit that [Eu(btfa)3(pz)2] is more polarizable (Ω2 = 33.56 × 10-20 cm2) than its precursor, [Eu(btfa)3(H2O)2] (Ω2 = 13.95 × 10-20 cm2).

Influence of weakly coordinating anions binding to the hexa-tert-butyl dysprosocenium cation.

Complexes containing isolated dysprosocenium cations, [Dy(CpR)2][WCA] (CpR = substituted cyclopentadienyl, WCA = weakly coordinating anion), have recently emerged as leading examples of high-temperature single-molecule magnets (SMMs) due to a combination of the axial orientation and rigidity of the CpR rings. However, our understanding of the effects of transverse fields on the magnetic properties of [Dy(CpR)2]+ cations is underdeveloped. Here we investigate the impact of equatorially-bound WCAs via the synthesis of the Dy(III) bis-CpR complexes [Dy(Cpttt)2{AlCl[OC(CF3)3]3-κ-Cl}] (1) and [Dy(Cpttt)2{AlCl(C2H5)[OC(C6F5)3]2-κ-Cl}] (2), and their characterisation by single crystal XRD, elemental analysis, ATR-IR and NMR spectroscopy, and ab initio calculations. Despite the similarity of the Dy coordination spheres in 1 and 2 we find that their effective energy barriers to reversal of magnetisation are vastly different (Ueff = 886(17) cm-1 and 559(18) cm-1, respectively) and they both show waist-restricted magnetic hysteresis at 2 K. Together, these data provide fresh insights into the sensitivity of the magnetic properties of [Dy(CpR)2]+ cations to relatively weak equatorial interactions.

In situ dissolved polypropylene prediction by Raman and ATR-IR spectroscopy for its recycling.

Monitoring the dissolution of polyolefins using online spectroscopy analysis is addressed in this work, with the aim of optimizing plastic recycling processes. Two in situ spectroscopic methods are used to predict the dissolved polymer content: Raman spectroscopy and attenuated total reflectance infrared spectroscopy. Commercially available polypropylenes are considered. Different solvents are selected based on their affinity with polypropylene. Partial least squares regression is employed to identify models predicting the polymer concentration for each solvent from the online spectra. Raman spectroscopy was found to give a better prediction. It was therefore used to study different parameters influencing the dissolution process, such as solvent type, temperature and polymer form.

Surface Modification of Lignite with Alkyl and Mixed Alkyl-Aryl Films Generated from an Aryl Diazonium Salt and Alkyl Halides: Experimental Results and Theoretical Analyses.

In search of new possible uses of cheap lignite from the Kosova Bassin, the surface of lignite powders is modified with alkyl or mixed alkyl-aryl layers. Modification is performed in aqueous acid solution containing an aryl diazonium salt and an alkyl halide compound in millimolar concentration, in the presence of potassium iodide as a reducing agent at equimolar concentration. Attachment of alkyl films substituted with carboxylic groups and aryl films with nitro or bis-trifluoromethyl groups is characterized by IRATR and XPS spectroscopy. The formation of a stable interface during the grafting reactions of alkyl and aryl moieties with lignite surface has been confirmed by theoretical calculations. Aryl diazonium salts once chemically or spontaneously reduced are a source of aryl radicals, able to attach chemically to the material surface or to react with alkyl halides by abstracting the halogen atom. If the aryl diazonium salts are unable to graft to the coal surface due to steric hindrance, they can, nevertheless, abstract an iodine or bromine atom to generate alkyl radicals that react with the material surface.

Effects of ZnO/trimethylsilyl cellulose nano-composite coating on anti-UV and anti-fungal properties of papers

Trimethylsilyl cellulose (TMSC) was employed as the coating matrix for the application of zinc oxide nanoparticles (ZnO) onto paper surfaces and the protections of ZnO/TMSC coating against UV-induced damages and fungal spoilage were evaluated. Filter papers were immersed in 2% w/v TMSC solution loaded with ZnO and air-dried. Three ZnO/TMSC suspensions were prepared with 0.1, 0.5, and 1% w/v ZnO NPs. The presences of ZnO/TMSC protective layers were confirmed with ATR-IR spectroscopy. The coated papers exhibited high surface hydrophobicities. After the coated papers were subject to 365-nm UV irradiation at 400 W for 3 h, the contact angles dramatically dropped. The trimethylsilyl (TMS) groups exposed on the surface formed a moisture barrier and were partially removed on UV exposure. ATR-IR revealed that more TMS groups were removed in the protective layer with no ZnO. UV-irradiated papers turned yellow and papers protected with 1% ZnO/TMSC exhibited significantly lower color changes than that of the uncoated one. Compared to the TMSC-coated paper, the addition of ZnO resulted in a significant reduction in tensile strength at maximum. However, after UV irradiation, significant increases in both the strain at break and strength at maximum were only observed in 1% ZnO/TMSC-protected papers. Regarding their anti-fungal properties, the 1% ZnO/TMSC films were effective in growth inhibitions of Aspergillus sp. and Penicillium sp. on the nonirradiated papers. Despite being hydrophilic after UV-irradiation, growths of the molds were severely suppressed on the UV-irradiated paper.

Effect of Composition and Surface Microstructure in Self-Polarized Ferroelectric Polymer Films on the Magnitude of the Surface Potential.

The values of the surface potentials of two sides of films of polyvinylidene fluoride, and its copolymers with tetrafluoroethylene and hexafluoropropylene, were measured by the Kelvin probe method. The microstructures of the chains in the surfaces on these sides were evaluated by ATR IR spectroscopy. It was found that the observed surface potentials differed in the studied films. Simultaneously, it was observed from the IR spectroscopy data that the microstructures of the chains on both sides of the films also differed. It is concluded that the formation of the surface potential in (self-polarized) ferroelectric polymers is controlled by the microstructure of the surface layer. The reasons for the formation of a different microstructure on both sides of the films are suggested on the basis of the general regularities of structure formation in flexible-chain crystallizing polymers.