Volume 96, Issue 12

Materials chemistry is focused on the design, preparation, and understanding of innovative materials. It is an emerging area of research where definitions are not well established. This document defines the area of materials chemistry for the benefit of chemistry communities and the general public worldwide interested in this discipline. This recommendation defines the term “materials chemistry” as the “scientific discipline that designs, synthesizes, and characterizes materials, with particular interest on processing and understanding of useful or potentially useful properties displayed by the materials designed and synthesized for specific applications.”

A previously published paper provided six examples of spontaneous processes for ideal systems that cannot be explained using classical thermodynamics. These six examples include free expansion of an ideal gas, mixing of ideal gases, diffusion of an ideal solute, mixing of ideal solutes, osmosis with ideal solutions, and free discharge of a concentration battery with ideal solutions. The previous paper demonstrated how energy was not a driving force in any of these examples and then proceeded to develop a positional entropy model, S D , that explains why these spontaneous processes occur. This new paper provides a method for calculating positional entropy, S D , for the same six systems, but for real particles that include nonzero volumes, particles with different volumes, and particles with different particle-particle interactions. The important outcome of this work shows that spontaneous discharge of these six example systems, either for ideal or real particles, is the result of a probability field created by the non-equilibrium distribution of the microstates that exists after the constraints on the system are changed, e.g., by removal of a separating partition or the shorting of a concentration cell. The probability field biases the movement of the particles toward the equilibrium distribution, where the bias is a consequence of an increased probability and not because of a decrease in energy. An additional conclusion of this work shows that the discharge of the probability field to the final equilibrium distribution of positional microstates removes the potential energy in the system but does not violate the law of conservation of energy.

In this study, we present a synthetic route for the preparation of a novel 1,10- phenanthroline-based tetraza-macrocyclic ligand, 5,12,25,28-tetraazaheptacyclo [14.8.4.2⁴,⁷.2 10 , 13 .0⁶, 11 .0 19 , 27 .0 22 , 26 ]dotriaconta-1 (25),4,6,8,10,12,16(28),17,19(27),20,22(26),23,29, 31-tetradecaene, 3 and its corresponding nickel complex, (28Z)-1,3,6,31-tetraaza-2-nickelaoctacyclo [17.9.3.2⁷, 28 .0³, 16 .0⁴, 13 .0⁵, 10 .0 22 , 30 .0 25 , 29 ]tritriaconta-4(13),5(10),6,8,11,14,16,19(31),20,22(30), 23,25(29),26,28(32)-tetradecaene, 8. The ligand was synthesized via a condensation reaction involving 2,9-dimethyl-1,10-phenanthroline and 2,9-dicarbaldehyde-1,10 phenanthroline, followed by nickel metal complexation. Fourier-transformed infrared (FT-IR) spectroscopy, gas chromatography-mass spectrometry (GC-MS), 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and thermal analyses were employed to characterize the ligand and its Ni complex. Their ADMET parameters and potential macromolecular targets calculations showed they have therapeutic potentials. The antioxidant assay shows that Ni-complex is approximately 9 times more potent than the ligand with IC 50 values of 0.045 mg/ml and 0.404 mg/ml, respectively. Their microspecies distribution which was predicted using ChemAxon Predictor revealed their catalytic potentials The reaction mechanisms involved are discussed. The 1,10-phenanthroline-based macrocyclic ligand and its nickel complex significantly expand the structural diversity within the tetraza-macrocyclic ligand system and serve as base ligands for the development of possible derivatives, with concomitant applicability in drug development and catalysis.

The aim of this research was to assess the impact of the components of alkanolamine deep eutectic solvents (DESs) on the physical properties of those DESs and their carbon dioxide capacity. To achieve this goal, novel deep eutectic solvents were synthesized by using 2-(butylamino)ethanol (BAE) as the hydrogen bond donor (HBD), along with tetrabutylammonium bromide TBAB), tetrabutylammonium chloride (TBAC), or tetraethylammonium chloride (TEAC) as the hydrogen bond acceptors (HBA) at various molar ratios (1:6, 1:8, and 1:10). To confirm the presence of hydrogen bond interactions between the components Fourier Transform Infrared Spectroscopy measurements were conducted. Furthermore, thermal properties, including melting points and thermal stability, of these deep eutectic solvents as well as key physical properties, such as density, viscosity, refractive index, and sound velocity, within the temperature range of 293.15–333.15 K and at a pressure of 0.1 MPa were examined. The effect of the molar ratio of HBA to HBD, the type of anion, and the length of the alkyl chain were studied and analysed in regard to physicochemical properties. In this work, the solubility of carbon dioxide in DESs derived from 2-(butylamino)ethanol, 3-aminopropan-1-ol (AP), and 2-(methylamino)ethanol (MAE) was measured. The highest CO 2 capacity was found for TEAC:MAE 1:10 DES characterized by the shortest alkyl chain length in both HBA and HBD molecules, the highest amine content, and the lowest viscosity. Additionally, the effect of water addition on carbon dioxide solubility was explored. The results showed that the influence of water on CO 2 solubility varies with the type of DES. In general, this work highlighted that DESs can serve as effective media for carbon dioxide capture, and their performance can be tailored by changing the type of hydrogen bond acceptor or donor, their molar ratio and by the addition of water.

A newly synthesis composite thin films of poly(vinyl chloride) has been refinement with ionic liquid, where PVC dissolved in THF with various concentrations of IL by casting method to form the composite thin films, without any reaction and IL dangles within PVC matrix. The thin films were examined by the diffusive reflectance device under the wavelength range (238–1300 nm). The XRD, EDX, and AFM techniques were utilized to discover the structure of the PVC matrix after additive IL. The XRD analysis illustrated the amorphous structure of the films, while the EDS analysis illustrated the main composition of pure PVC and composite PVC/IL. The optical properties and optical parameters were studied. The reflectance, extinction factor, transmittance, and imaginary dielectric constant declined, the absorption value was between (80–89 %), and the refractive index, real dielectric constant, and optical conductivity were increased. The indirect energy gap declined from 4.2 eV to 2.2 eV and the direct energy gap declined from 3.7 eV to 2.6 eV. The Urbach energy was increased from 2.09 eV to 15.45 eV revealing an increase in the disorders of electrons. The E d increased from 23.42 eV to 70.68 eV and E o increased from 7.00 eV to 10.88 eV. AFM analysis illustrated the roughness of the films increased after additive IL to the PVC Matrix from 1.08 nm to 4.45 nm and the root mean square of the particles ranged from 1.57 nm to 5.56 nm. The PVC composite thin films are utilized in solar cell and sodium-ion battery applications.

This study examines the morphology and various thermal, mechanical, and rheological properties of polylactic acid (PLA)-based nanobiocomposites. The objective of this investigation is to evaluate the potential of modified Algerian clay as a nanofiller through an examination of the characteristics of PLA/Mag-CTA and PLA/CMC nanobiocomposites with varying levels of prepared fillers. This study is concerned with the synthesis of poly(lactic acid)/Maghnite-CTA (PLA/Mag-CTA) and poly(lactic acid)/microcrystalline cellulose (CMC) nanobiocomposites, with two distinctive catalysts and organic reinforcements produced in solution. The outcomes of the various techniques employed demonstrate that PLA nanobiocomposites exhibit a mixed morphology, comprising intercalation and exfoliation. The results from the diverse techniques used show that the PLA nanobiocomposites developed have a mixed intercalated-exfoliated morphology. The dispersion of the Maghnite-CTA filler and microcrystalline cellulose was enhanced during the production of the various materials, as well as the presence of aggregates at high levels. The best rheological performance, corresponding to the optimal dispersion of the nanofiller, was observed for a low quantity of organic filler. Thermal behavior properties were significantly enhanced with the incorporation of the two nanofillers. Analysis by steric exclusion chromatography showed that the fillers used in the nanobiocomposite synthesis increased the average molecular weights of the PLA chains, while the polydispersity index remained constant.

This paper reviews observations on processes involving concentration gradients to show that (1) Concentration gradients can do external work during discharge if the system is arranged in a manner that requires it. (2) Work has to be done on the system (i.e. energy has to be added) to create a concentration gradient. (3) Concentration gradients can spontaneously discharge with no change in energy except interaction energy. These three observations are significant since, together, these observations demonstrate an apparent violation of the law of conservation of energy which is resolved by proposing that a probability field is a common element for all concentration gradients. This paper thus introduces two new concepts into thermodynamics: (1) Many spontaneous processes occur because of an increase in probability, not because of a decrease in the energy state of the system. (2) Concentration gradients coincide with a probability field and a constraint-dependent and temperature-dependent potential energy.

In this study modified cellulose based adsorbent was prepared from Populus nigra plant, and used for elimination of metaldehyde (herbicide) from model waste water. The adsorbent was characterized through analytical technique such as FTIR, SEM, EDX and XRD for structural adsorption related parameters. The results of SEM showed the suitability of the material to be used as adsorbent and FTIR showed successful crosslinking of polyvinyl alcohol into cellulose structure. In order to get maximum reclamation benefits from adsorbent it was subjected to a number of tests evaluating the effect of metaldehyde concentration, sorbent dose, contact time, initial pH of solution and temperature. The maximum removal of 70 % was achieved under conditions of 80 mg/L metaldehyde concentration, 60 min contact time, pH of 8, 0.08 g sorbent dosage, and room temperature (25 °C). The Langmuir isotherm model with correlation coefficients of 0.9855 and maximum adsorption capacity recorded was 8.32 mg/g, while excellent agreement was shown by kinetic data with pseudo second order kinetic model with R 2  = 0.9876. Thermodynamic study indicated enthalpy change (Δ H ° = −129 kJ/mol) to be negative, entropy change (Δ S ° = 161.7 j/mol) positive, and the Gibbs free energy (Δ G ) as negative showing that the process to be exothermic and feasible/spontaneous with an increase of randomness at solid liquid interface. The finding indicated that modified cellulose could be used as an efficient adsorbent for removal of metaldehyde from model waste water. However, further validation with other pollutants will be helpful in checking reproducibility of the present findings.

In this work, we describe the synthesis and characterisation of the starting materials [Cp*IrCl 2 ] 2 and four new ruthenium(II) and iridium(III) complexes half sandwich, contain the fragments [(p-cymene)Ru] 2+ and [Cp*Ir] 2+ ; (Cp* = Cp Me4Et ) of stoichiometry: [Cp*IrCl 2 (2-aminopyridine)] (I), [Cp*IrCl 2 (4-aminopyridine)] (II), [Cp*IrCl 2 (adenine)] (III) and [( p -cymene)RuCl 2 (adenine)] (IV). The new compounds have been characterised by C, H, and N elemental analysis; infrared and 1 H NMR spectroscopy with 1 H– 1 H COSY, ESI/TOF mass spectrometry and thermogravimetry. A study of the cytotoxicity of these compounds against the Hela cell line was carried out, with results indicating a low activity.