Deep Cracking of Bulky Hydrocarbons into Light Products via Tandem Catalysis over Uniform Interconnected ZSM-5@AlSBA-15 Composites.

Deep cracking of bulky hydrocarbons on zeolite-containing catalysts into light products with high activity, desired selectivity, and long-term stability is demanded but challenging. Herein, the efficient deep cracking of 1,3,5-triisopropylbenzene (TIPB) on intimate ZSM-5@AlSBA-15 composites via tandem catalysis is demonstrated. The rapid aerosol-confined assembly enables the synthesis of the composites composed of a continuous AlSBA-15 matrix decorated with isolated ZSM-5 nanoparticles. The two components at various ZSM-5/AlSBA-15 mass ratios are uniformly mixed with chemically bonded pore walls, interconnected pores, and eliminated external surfaces of nanosized ZSM-5. The typical composite with a ZSM-5/AlSBA-15 mass ratio of 0.25 shows superior performance in TIPB cracking with outstanding activity (≈100% conversion) and deep cracking selectivity (mass of propylene + benzene > 60%) maintained for a long time (> 6 h) under a high TIPB flux (2 mL h-1), far better (several to tens of times higher) than the single-component and physically mixed catalysts and superior to literature results. The high performance is attributed to the cooperative tandem catalytic process, that is, selective and timely pre-cracking of TIPB to isopropylbenzene (IPB) in AlSBA-15 and subsequently timely diffusion and deep cracking of IPB in nanosized ZSM-5.

Flexible Mesopores in Nanoscrolls: Extraordinarily Large Alteration of Pore Sizes and Their Reversibility.

Flexible porous materials have gained considerable interest for their potential applications in selective absorption and controlled release/storage of specific molecules or compounds. Here, nanoscrolls are proposed as a type of inorganic solids with reversibly flexible mesopores. Nanoscrolls exhibit a rolled-up structure composed of nanosheets with a 1D rod-like morphology, possessing two distinct nanospaces. The first space comprises 1D tubular mesopores located at the center of the rod, while the second space exists in the interlayer regions on the wall of the mesopore, resulting from the layer stacking caused by the scrolling of nanosheets. By replacing the interlayer cations on the nanoscroll walls with other cations, a drastic alteration in the size of the 1D mesopores is observed. For instance, exchanging bulky dodecylammonium cations with small NH4 + cations leads to a substantial change in pore size, with differences ranging from 10 to 20 nm-a notably larger variation compared to previous reports on flexible porous materials. Importantly, the alteration of pore size induced by the exchange reaction is found to be reversible. This reversible alteration in pore size holds promise for applications in host-guest chemistry involving large moieties such as nanoparticles and enzymes.

Hierarchically Superstructured Anisotropic Carbon Particles by Multiscale Assembly Driven by Spinodal Decomposition.

Hierarchical superstructures have novel shape-dependent properties, but well-defined anisotropic carbon superstructures with controllable size, shape, and building block dimensionality have rarely been accomplished thus far. Here, a hierarchical assembly technique is presented that uses spinodal decomposition (SD) to synthesize anisotropic oblate particles of mesoporous carbon superstructure (o-MCS) with nanorod arrays by integrating block-copolymer (BCP) self-assembly and polymer-polymer interface behaviors in binary blends. The interaction of major and minor phases in binary polymer blends leads to the formation of an anisotropic oblate particle, and the BCP-rich phase enables ordered packing and unidirectional alignment of carbon nanorods. Consequently, this approach enables precise control over particles' size, shape, and over the dimensionality of their components. Exploiting this functional superstructure, o-MCS are used as an anode material in potassium-ion batteries, and achieve a notable specific capacity of 156 mA h g-1 at a current density of 2 A g-1, and long-term stability for 3000 cycles. This work presents a significant advancement in the field of hierarchical superstructures, providing a promising strategy for the design and synthesis of anisotropic carbon materials with controlled properties, offering promising applications in energy storage and beyond.

Enhanced Ion Transport Through Mesopores Engineered with Additional Adsorption of Layered Double Hydroxides Array in Alkaline Flow Batteries.

Efficient mass transfer in electrodes is essential for the electrochemical processes of battery charge and discharge, especially at high rates and capacities. This study introduces a 3D electrode design featuring layered double hydroxides (LDHs) nanosheets array grown in situ on a carbon felt surface for flow batteries. The mesoporous structure and surface characteristic of LDH nanosheets, especially, the hydroxyl groups forming a unique "H-bonding-like" geometry with ferrous cyanide ions, facilitate efficient adsorption and ion transport. Thus, the designed LDHs electrode enables the alkaline zinc-iron flow battery to maintain a voltage efficiency of 81.6% at an ultra-high current density of 320 mA cm-2, surpassing the values reported in previous studies. The energy efficiency remains above 84% after 375 cycles at a current density of 240 mA cm-2. Molecular dynamics simulations verify the enhanced adsorption effect of LDH materials on active ions, thus facilitating ion transport in the battery. This study provides a novel approach to improve mass transport in electrodes for alkaline flow batteries and other energy storage devices.

Photocatalytic Hydrogen Evolution Using Mesoporous Honeycomb Iron Titanate.

Mesoporous honeycomb iron titanate using a sol-gel, evaporation-induced self-assembly method is synthesized. A triblock copolymer, F127, serves as a structure-directing agents, with iron chloride and titanium (IV) isopropoxide as inorganic precursors. The strong intermolecular force of attraction among urea, metal precursors, and polymer led to the formation of the mesoporous honeycomb structure. The study of physicochemical properties using different techniques reveals the formation of microstructures with a remarkable degree of porosity. The amorphous iron titanate outperforms the photochemical generation of H2 due to its disorderly structural arrangement and incomplete crystal formation. The randomness on the structure provides more area for catalytic reaction by providing more contact with the reactant and superior light absorption capability. The high amount of hydrogen gas, 40.66 mmolg-1h-1, is observed in the investigation over 3 h of activity for the iron titanate honeycomb sample. This yield is a more significant amount compared to the obtained for the commercially available TiO2 (23.78 mmolg-1h-1). The iron titanate materials synthesized with low-cost materials and methods are very effective and have the potential for hydrogen generation.

Mesoporous Metal Nanomaterials: Developments and Electrocatalytic Applications.

Mesoporous metal nanomaterials (MPMNs) are pivotal in nanotechnology, especially in electrochemical applications, due to their unique structure. Unlike traditional nanomaterials, MPMNs possess hierarchical and mesoporous characteristics, providing more active sites for improved mass and electron transfer. This distinctive composition offers dual benefits, enhancing activity, stability, and selectivity for specific reactions. The intricate architecture, featuring interconnected pores, amplifies surface area, ensuring efficient use of active sites and boosting reactivity in electrocatalytic processes. Additionally, the mesoporous nature promotes superior diffusion kinetics, facilitating better transport of reactants and products. This intricate interplay of structural elements contributes not only to the increased efficiency of electrochemical reactions but also to the extended durability of MPMNs during prolonged usage. This concept focus on the synthesis and design strategies of MPMNs, aligning with the dynamic requirements of diverse electrocatalytic applications. The synergy resulting from these advancements not only accentuates the intrinsic properties of MPMNs but also broadens their scope for practical implementation in emerging fields of electrochemistry.

Mesoporous Metal Sponges Produced by Explosive Decomposition.

The formation of mesoporous gold sponges by explosive decomposition of 'knallgold' (also known as 'fulminating' gold) is studied. Proof-of-principle experiments are conducted and then the phenomena are further investigated using 'toy physics' molecular dynamics simulations. The simulations invoked various ratios of a volatile Lennard-Jones element G and a noble metal element N. In both experiment and simulation the morphology of the resulting sponge is found to depend on the stoichiometry of the starting material. As the mole fraction of G (χG) is increased from 0.5 to close to 1.0 in the simulations, the morphology of the sponges changes from closed to open, with a corresponding increase in the average mean curvature from 0 to +0.12 inverse Lennard-Jones length (L) units. The average Gaussian curvature of the simulated sponges is always negative, with the minimum value of 0.05 L-2 being found for χG≈0.65. In broad agreement with experiment, sponge formation in the simulations is bounded by stoichiometry; no sponges form if χG is <0.52, for χG between 0.52 and 0.70 the sponge is characterized by vermicular cavities whereas classic bicontinuous fibrous sponges form for 0.70<χG<0.85 and, finally, discrete particles result if χG>0.85.

Composite Silica-Based Films as Platforms for Electrochemical Sensors.

Sol-gel-derived silica thin films generated onto electrode surfaces in the form of organic-inorganic hybrid coatings or other composite layers have found tremendous interest for being used as platforms for the development of electrochemical sensors and biosensors. After a brief description of the strategies applied to prepare such materials, and their interest as electrode modifier, this review will summarize the major advances made so far with composite silica-based films in electroanalysis. It will primarily focus on electrochemical sensors involving both non-ordered composite films and vertically oriented mesoporous membranes, the biosensors exploiting the concept of sol-gel bioencapsulation on electrode, the spectroelectrochemical sensors, and some others.

Application of Stemphylium lycopersici Extracts Immobilized on MCM-48type Mesoporous Materials as Biocatalysts for Monoacylglycerol Production.

Monoacylglycerols are eco-friendly and inexpensive emulsifiers with a range of applications. The traditional synthetic route is not eco-friendly, while enzymatic catalysis offers milder reaction conditions and higher selectivity. However, its application still is limited due to the costs. In this context, endophytic fungi can be source to new biocatalysts with enhanced catalytic activity. Based on this perspective, the aim of this study was perform the synthesis of MAG's through transesterification reactions of solketal and different vinyl esters, using crude and immobilized lipolytic extracts from the endophytic fungi Stemphylium lycopersici, isolated from Humiria balsamifera. The reactions were conducted using 100 mg of biocatalyst, 1 mmol of substrates, 9 : 1 n-heptane/acetone, at 40 °C, 200 rpm for 96 h. In the reactions using the ILE and stearate, laureate and decanoate vinyl esters it was possible to obtain the correspondent products with conversion rates of 52-75 %. Also, according to the structure drivers used in MCM-48 synthesis, different morphologies and conversions rates were observed. Employing [C16MI] Cl, [C14MI] Cl and [C4MI] Cl, the 1-lauroyl- glycerol conversion was 36 %, 79 % and 44 %, respectively. This is the first work involving the immobilization of an endophytic fungi and its utilization as a biocatalyst in the production of MAG's.

Highly Efficient Separation of Ethanol Amines and Cyanides via Ionic Magnetic Mesoporous Nanomaterials.

Simple and efficient sample pretreatment methods are important for analysis and detection of chemical warfare agents (CWAs) in environmental and biological samples. Despite many commercial materials or reagents that have been already applied in sample preparation, such as SPE columns, few materials with specificity have been utilized for purification or enrichment. In this study, ionic magnetic mesoporous nanomaterials such as poly(4-VB)@M-MSNs (magnetic mesoporous silicon nanoparticles modified by 4-vinyl benzene sulfonic acid) and Co2+@M-MSNs (magnetic mesoporous silicon nanoparticles modified by cobalt ions) with high absorptivity for ethanol amines (EAs, nitrogen mustard degradation products) and cyanide were successfully synthesized. The special nanomaterials were obtained by modification of magnetic mesoporous particles prepared based on co-precipitation using -SO3H and Co2+. The materials were fully characterized in terms of their composition and structure. The results indicated that poly(4-VB)@M-MSNs or Co2+@M-MSNs had an unambiguous core-shell structure with a BET of 341.7 m2·g-1 and a saturation magnetization intensity of 60.66 emu·g-1 which indicated the good thermal stability. Poly(4-VB)@M-MSNs showed selective adsorption for EAs while the Co2+@M-MSNs were for cyanide, respectively. The adsorption capacity quickly reached the adsorption equilibrium within the 90 s. The saturated adsorption amounts were MDEA = 35.83 mg·g-1, EDEA = 35.00 mg·g-1, TEA = 17.90 mg·g-1 and CN-= 31.48 mg·g-1, respectively. Meanwhile, the adsorption capacities could be maintained at 50-70% after three adsorption-desorption cycles. The adsorption isotherms were confirmed as the Langmuir equation and the Freundlich equation, respectively, and the adsorption mechanism was determined by DFT calculation. The adsorbents were applied for enrichment of targets in actual samples, which showed great potential for the verification of chemical weapons and the destruction of toxic chemicals.

Optimization of Cyanocobalamin (Vitamin B12) Sorption onto Mesoporous Superparamagnetic Iron Oxide Nanoparticles.

The techniques used to detect and quantify cyanocobalamin (vitamin B12) vary considerably in terms of detection sensitivity, from the most sensitive, based on radioisotopes and mass spectrometry (MS) with limits of detection (LOD) in fg mL-1, to fluorescence (FL) and surface plasmon resonance (SPR) biosensors with LOD values in the range of a few µg mL-1. For accurate quantification of an analyte present at trace levels in complex biological matrices, a selective separation and enrichment step is required to overcome matrix interferences and ensure sufficient detection sensitivity. In this study, iron oxide magnetic nanoparticles (IONPs) were used for the extraction and initial preconcentration of cyanocobalamin (vitamin B12). In the dependence of the magnetization on the H-field (hysteresis loop), no coercivity and remanence values were found at 300 K, indicating the superparamagnetic properties of the tested IONPs. Perfluorinated acids were used as amphiphilic agents to allow the sorption of cyanocobalamin onto the IONPs. FT-IR/ATR spectroscopy was used to confirm the sorption of cyanocobalamin on the IONPs. The influence of the addition of a homologous series of perfluorinated acids such as trifluoroacetic acid (TFAA), heptafluorobutyric acid (HFBA), and trichloroacetic acid (TCAA) to the extraction mixture was tested considering their type, mass, and time required for effective sorption. The adsorption kinetics and isotherm, described by the Freundlich and Langmuir equations, were analyzed. The maximum adsorption capacity (qm) exceeded 6 mg g-1 and was 8.9 mg g-1 and 7.7 mg g-1 for HFBA and TCAA, respectively, as the most efficient additives. After the desorption process using aqueous KH2PO4 solution, the sample was finally analyzed spectrophotometrically and chromatographically. The IONP-based method was successfully applied for the isolation of cyanocobalamin from human urine samples. The results showed that the developed approach is simple, cheap, accurate, and efficient for the determination of traces of cyanocobalamin in biological matrices.

Freestanding Block Copolymer Membranes with Tunable Pore Sizes Promoted by Subnanometer Nanowires.

Block copolymers (BCPs) have enduring appeal for its intriguing assembly behaviors. Nevertheless, the unsatisfactory mechanical properties of BCPs make it a problem to fabricate freestanding membranes and hindered practical applications. Herein, a freestanding membrane with tunable pore size is prepared simply by co-assembly of BCPs and subnanometer nanowires (SNWs), combining the abundant function of BCPs and prominent mechanical properties of SNWs. Benefited from synergy of the components and the hierarchical structure, the tensile strength of composite membrane is promoted by two orders of magnitude compared to that of BCPs. With the columnar pores aligning vertically to surfaces and the pore size regulated by processing conditions, the membranes exhibit precise size-selected effect in ultrafiltration of Au nanoparticles (Au NPs) and can distinct NPs with diameter difference as tiny as 5 nm, demonstrating the promising prospect in separation technology and even widespread fields.

Micellar Nanoreactors Enabled Site-Selective Decoration of Pt Nanoparticles Functionalized Mesoporous SiO2 /WO3-x Composites for Improved CO Sensing.

Site-selective and partial decoration of supported metal nanoparticles (NPs) with transition metal oxides (e.g., FeOx ) can remarkably improve its catalytic performance and maintain the functions of the carrier. However, it is challenging to selectively deposit transition metal oxides on the metal NPs embedded in the mesopores of supporting matrix through conventional deposition method. Herein, a restricted in situ site-selective modification strategy utilizing poly(ethylene oxide)-block-polystyrene (PEO-b-PS) micellar nanoreactors is proposed to overcome such an obstacle. The PEO shell of PEO-b-PS micelles interacts with the hydrolyzed tungsten salts and silica precursors, while the hydrophobic organoplatinum complex and ferrocene are confined in the hydrophobic PS core. The thermal treatment leads to mesoporous SiO2 /WO3-x framework, and meanwhile FeOx nanolayers are in situ partially deposited on the supported Pt NPs due to the strong metal-support interaction between FeOx and Pt. The selective modification of Pt NPs with FeOx makes the Pt NPs present an electron-deficient state, which promotes the mobility of CO and activates the oxidation of CO. Therefore, mesoporous SiO2 /WO3-x -FeOx /Pt based gas sensors show a high sensitivity (31 ± 2 in 50 ppm of CO), excellent selectivity, and fast response time (3.6 s to 25 ppm) to CO gas at low operating temperature (66 °C, 74% relative humidity).

Pt-Pd Nanoalloys Functionalized Mesoporous SnO2 Spheres: Tailored Synthesis, Sensing Mechanism, and Device Integration.

Methane (CH4 ), as the vital energy resource and industrial chemicals, is highly flammable and explosive for concentrations above the explosive limit, triggering potential risks to personal and production safety. Therefore, exploiting smart gas sensors for real-time monitoring of CH4 becomes extremely important. Herein, the Pt-Pd nanoalloy functionalized mesoporous SnO2 microspheres (Pt-Pd/SnO2 ) were synthesized, which show uniform diameter (≈500 nm), high surface area (40.9-56.5 m2 g-1 ), and large mesopore size (8.8-15.8 nm). The highly dispersed Pt-Pd nanoalloys are confined in the mesopores of SnO2 , causing the generation ofoxygen defects and increasing the carrier concentration of sensitive materials. The representative Pt1 -Pd4 /SnO2 exhibits superior CH4 sensing performance with ultrahigh response (Ra /Rg = 21.33 to 3000 ppm), fast response/recovery speed (4/9 s), as well as outstanding stability. Spectroscopic analyses imply that such an excellent CH4 sensing process involves the fast conversion of CH4 into formic acid and CO intermediates, and finally into CO2 . Density functional theory (DFT) calculations reveal that the attractive covalent bonding interaction and rapid electron transfer between the Pt-Pd nanoalloys and SnO2 support, dramatically promote the orbital hybridization of Pd4 sites and adsorbed CH4 molecules, enhancing the catalytic activation of CH4 over the sensing layer.

Oxalate-Assisted Synthesis of Hollow Carbon Nanocage With Fe Single Atoms for Electrochemical CO2 Reduction.

Metal single-atom catalysts are promising in electrochemical CO2 reduction reaction (CO2 RR). The pores and cavities of the supports can promote the exposure of active sites and mass transfer of reactants, hence improve their performance. Here, iron oxalate is added to ZIF-8 and subsequently form hollow carbon nanocages during calcination. The formation mechanism of the hollow structure is studied in depth by controlling variables during synthesis. Kirkendall effect is the main reason for the formation of hollow porous carbon nanocages. The hollow porous carbon nanocages with Fe single atoms exhibit better CO2 RR activity and CO selectivity. The diffusion of CO2 facilitated by the mesoporous structure of carbon nanocage results in their superior activity and selectivity. This work has raised an effective strategy for the synthesis of hollow carbon nanomaterials, and provides a feasible pathway for the rational design of electrocatalysts for small molecule activation.

Establishing Transition Metal Phosphides as Effective Sulfur Hosts in Lithium-Sulfur Batteries through the Triple Effect of "Confinement-Adsorption-Catalysis".

Structurally optimized transition metal phosphides are identified as a promising avenue for the commercialization of lithium-sulfur (Li-S) batteries. In this study, a CoP nanoparticle-doped hollow ordered mesoporous carbon sphere (CoP-OMCS) is developed as a S host with a "Confinement-Adsorption-Catalysis" triple effect for Li-S batteries. The Li-S batteries with CoP-OMCS/S cathode demonstrate excellent performance, delivering a discharge capacity of 1148 mAh g-1 at 0.5 C and good cycling stability with a low long-cycle capacity decay rate of 0.059% per cycle. Even at a high current density of 2 C after 200 cycles, a high specific discharge capacity of 524 mAh g-1 is maintained. Moreover, a reversible areal capacity of 6.56 mAh cm-2 is achieved after 100 cycles at 0.2 C, despite a high S loading of 6.8 mg cm-2 . Density functional theory (DFT) calculations show that CoP exhibits enhanced adsorption capacity for sulfur-containing substances. Additionally, the optimized electronic structure of CoP significantly reduces the energy barrier during the conversion of Li2 S4 (L) to Li2 S2 (S). In summary, this work provides a promising approach to optimize transition metal phosphide materials structurally and design cathodes for Li-S batteries.

Organic-Inorganic Phenolic/POSS Hybrids Provide Highly Ordered Mesoporous Structures Templated by High Thermal Stability of PS-b-P4VP Diblock Copolymer.

Anionic living polymerization was used to prepare a diblock copolymer of poly(styrene-b-4-vinyl pyridine) (PS-b-P4VP), and a phenolic resin with a double-decker silsesquioxane (DDSQ) cage structure was used to form a phenolic/DDSQ hybrid (PDDSQ-30 with 30 wt.% DDSQ). Strong intermolecular hydrogen bonding could be confirmed through the hydroxyl (OH) groups of PDDSQ hybrid with the pyridine group of the P4VP block in PDDSQ-30/PS-b-P4VP blends based on Fourier transform infrared spectroscopy analyses, where increasing PDDSQ concentrations resulted in a higher proportion of hydrogen-bonded pyridine groups. After thermal polymerization at 180 °C, the self-assembled structures of these PDDSQ/PS-b-P4VP blends were revealed by data from small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), where the d-spacing increased with raising PDDSQ concentration. Because relatively higher thermal stability of the PDDSQ hybrid than pure phenolic resin and PS-b-P4VP template, we can obtain the long ranger order of mesoporous PDDSQ hybrids after removing the PS-b-P4VP template, which reveals the high surface area and high pore volume with cylindrical and spherical structures corresponding to the PDDSQ compositions that are rarely observed by using pure phenolic resin as the matrix and could be used in supercapacitor application.

Materials used to prevent adhesion, growth, and biofilm formation of Candida species.

The species of the Candida genus are opportunistic pathogenic fungi found in humans and are responsible for ∼80% of worldwide fungal infections. Aimed at diminishing and preventing Candida adhesion to cells or implanted devices in the human host, a large diversity of materials has been developed and functionalized that have attracted much interest. Furthermore, these materials have been focused almost exclusively on Candida albicans, followed by C. glabrata, C. parapsilosis, and C. tropicalis. Although an important diversity of materials has been synthesized to prevent adherence and formation of biofilms by Candida species, it is however important to evaluate the capacity of each material in terms of its property to diminish the adherence of Candida. These materials are discussed in this review.

Synthesis, thermal evolution and magnetic investigations of SBA-15 silica functionalized with anchored iron phosphonate molecules.

In the current work, we report on the synthesizing of a series of novel nanocomposite materials obtained by functionalizing the SBA-15 silica matrix with anchored iron phosphonate molecules and the following thermal treatment. The obtained results reveal the formation of a unique amorphic layer of Fe-based compounds on the surface of silica walls of SBA-15 channels as a result of the organic groups' decomposition after moderate thermal treatment. Due to their unique structure, represented in an active Fe-containing amorphous coating spread over a large surface area, these materials are of great interest for their potential applications in fields such as catalysis, adsorption, and non-linear optics. The obtained materials remain amorphous, preserving the SBA-15 mesoporous structure up to temperatures of approximately 800 °C, after which the partial melting of the silica backbone is observed with the simultaneous formation of nanocrystals inside the newly-formed glassy mass. All obtained materials were characterized using such techniques as thermogravimetry, transmission and scanning electron microscopy combined with energy dispersive x-ray spectroscopy mapping, Raman spectroscopy, N2sorption analysis, x-ray diffraction, x-ray photoelectron spectroscopy, Mössbauer spectroscopy, and SQUID measurements.

Mechanism of Cs Immobilization within a Sodalite Framework: The Role of Alkaline Cations and the Si/Al Ratio.

Conditioning of radioactive waste generated from the operation of medical institutions, nuclear cycle facilities, and nuclear facilities is important for the safety of the environment. One of the most hazardous radionuclides is radioactive cesium. There is a need for more effective solutions to contain radionuclides, especially cesium (Cs+). Geopolymers are promising inorganic materials that can provide a large active surface area with adjustable porosity and binding capacity. The existence of nanosized zeolite-like structures in aluminosilicate gels was shown earlier. These structures are candidates for immobilizing radioactive cesium (Cs+). However, the mechanisms of their interactions with the aluminosilicate framework related to radionuclide immobilization have not been well studied. In this work, the influence of alkaline cations (Na+ or K+) and the aluminosilicate framework structure on the binding capacity and mechanism of interaction of geopolymers with Cs+ is explored in the example of a sodalite framework. The local structure of the water molecules and alkaline ions in the equilibrium state and its behavior when the Si/Al ratio was changed were studied by DFT.