Presence Of Alkali Research Articles

Kinetics and Mechanism of Cation-Induced Guest Release from Cucurbit[7]uril.

The release of two organic guests from cucurbit[7]uril (CB7) was selectively monitored by the stopped‐flow method in aqueous solutions of inorganic salts to reveal the mechanistic picture in detail. Two contrasting mechanisms were identified: The symmetric dicationic 2,7‐dimethyldiazapyrenium shows a cation‐independent complex dissociation mechanism coupled to deceleration of the ingression in the presence of alkali and alkaline earth cations (Mn+) due to competitive formation of CB7–Mn+ complexes. A much richer, unprecedented kinetic behaviour was observed for the ingression and egression of the monocationic and non‐symmetric berberine (B+). The formation of ternary complex B+–CB7–Mn+ was unambiguously revealed. A difference of more than two orders of magnitude was found in the equilibrium constants of Mn+ binding to B+–CB7 inclusion complex. Large cations, such as K+ and Ba2+, also promoted B+ expulsion from the ternary complex in a bimolecular process. This study reveals a previously hidden mechanistic picture and motivates systematic kinetic investigations of other host–guest systems.

Improved physical properties of konjac glucomannan gels by co-incubating composite konjac glucomannan/xanthan systems under alkaline conditions

Alkali induced konjac glucomannan (KGM) gels have been a popular food item in many Asian nations since ancient times. However, there exist a few drawbacks for this type of gels, including significant syneresis and inferior gel strength, etc. In this study, due to relatively strong alkali resistance, xanthan was selected to be incorporated into KGM sol systems, and the composite KGM/xanthan systems were then allowed to gel by subjecting to a protocol consisting of incubating at 90 °C for 2 h and then cooling to room temperature. It was found that the gelation process consisted of two steps: during incubation at 90 °C, KGM gel network was predominantly formed, and the incorporation of xanthan caused a slower gelling rate of the KGM gel network. In the subsequent cooling process, xanthan synergistically bound with the KGM network, thereby strengthening the composite gels, with the binding process beginning at ~60 °C. When the KGM/xanthan ratio was 7:3, the highest gel strength (~1200 g) of the composite gel was obtained, which is much higher than the pure KGM gel (KGM/xanthan ratio 10:0, and the gel strength was ~44 g). Moreover, xanthan addition also decreased the syneresis rate of the composite gels during freeze-thaw treatment. Overall, the present study highlighted an applicable way to tailor the physical properties of KGM gels by co-incubating a composite KGM/xanthan system in the presence of alkali.

Bio-energy with carbon capture and storage via alkaline thermal Treatment: Production of high purity H2 from wet wheat straw grass with CO2 capture

Biomass has a unique potential for “negative emissions” of CO2 if carbon capture and storage are integrated into the biomass conversion. While a large body of research has explored biomass conversion, challenges such as low energy density and high moisture content persist. This study proposes and investigates a novel single-step reaction scheme called Alkaline Thermal Treatment (ATT) to convert a real biomass feedstock (e.g. wet wheat straw grass) into high purity H2 in the presence of alkali (e.g., NaOH) at a moderate temperature of 500 °C and ambient pressure. Importantly, negligible CO and a very low percentage of CO2 (0.3%) were detected in the product gas stream, thus rendering gas products from the ATT reaction usable in various applications including fuel cells without further gas purification steps. The solid residue contained a very high percentage of carbonate, confirming the in-situ carbon capture effect.

Reaction Behavior of Glucose and Fructose in Subcritical Water in the Presence of Various Salts.

Glucose and fructose were treated in subcritical water in the presence of alkali or alkaline earth metal chlorides. All salts accelerated the conversion of saccharides, and alkaline earth metal chloride greatly promoted the isomerization of glucose to fructose. In contrast, alkali metal salts only slightly promoted this isomerization and facilitated the decomposition of glucose to byproducts such as organic acids. The selectivity of the glucose-to-fructose isomerization was higher at lower conversions of glucose and in the presence of alkaline earth metal chlorides. The pH of the reaction mixture also greatly affected the selectivity, which decreased rapidly at lower pH due to the generated organic acids. At low pH, decomposition of glucose became dominant over isomerization, but further conversion of glucose was suppressed. This result was elucidated by the suppression of the alkali-induced isomerization of glucose at low pH. Fructose underwent decomposition during the treatment of the fructose solution, but its isomerization to glucose was not observed. The added salts autocatalytically promoted the decomposition of fructose, and the reaction mechanism of fructose decomposition differed from that of glucose.

Further interpretation of the underlying causes of the strengthening effect of alkali on gluten and noodle quality: Studies on gluten, gliadin, and glutenin

Alkali significantly enhanced gluten strength and noodle texture. To further understand the underlying mechanisms of the gluten strengthening effect of alkali, the macroscopic rheological properties, microstructure, intermolecular interactions, water mobility, molecular weight distribution (MWD) and structure, and the molecular chain morphology changes of gluten and its subfractions (glutenin and gliadin) were separately investigated. Alkali increased the G′ and G″ of gluten and glutenin fractions. Scanning electron microscopy (SEM) images confirmed that alkali induced a more compact structure in all fractions and a membrane-like structure in gluten and glutenin. Quartz crystal microbalance with dissipation (QCM-D) results demonstrated that alkali promoted alkali/protein-protein interactions in gluten and glutenin fractions. Hydrophobic interactions and water-solids interaction were enhanced by alkali in all fractions. Glutenin fraction was shown to play a key role in the protein polymerization of fresh gluten samples in the presence of alkali, while both glutenin and gliadin contributed to the enhanced polymerization during cooking. Atomic force microscopy (AFM) images showed that alkali induced remarkable aggregations of protein molecular chains in gluten system.

Конденсация S-замещенных 6-амино-2-тиоурацилов с бензальдегидами

In the present study 5,5'-(phenylmethylene) bis (2-organylsulfanyl-6-aminopyrimidin-4(3 H )-ones) were obtained by the interaction of 2-allylsulfanyl-, 2-methallylsulfanyl- and 2-propargylsulfanyl-6-aminopyrimidin-4(3 H )-ones with benzaldehyde with ratio of 2:1 in concentrated acetic acid at room temperature. At the same conditions 5,5'-((4-(dimethylamino)phenyl)methylene) bis (2-organylsulfanyl-6-aminopyrimidin-4(3 H )-ones) and 5,5'-((3,4-dimethoxyphenyl)methylene) bis (2-benzylsulfanyl-6-aminopyrimidin-4(3 H )-one) were prepared by the reaction of 2-allylsulfanyl-, 2-benzylsulfanyl-, 2-propargylsulfanyl-6-aminopyrimidin-4(3 H )-ones with 4,4-dimethylaminobenzaldehyde and 2-benzylsulfanyl-6-aminopyrimidin-4(3 H )-one with 3,4-dimethoxybenzaldehyde, respectively. The initial 2-organylsulfanyl-6-aminopyrimidin-4(3 H )-ones were prepared by the known method of 6-amino-2-thiouracil alkylation by organylhalides (allyl bromide, methallyl chloride, propargyl bromide, benzyl chloride) in aqueous ethanol at room temperature in the presence of alkali. The structures of dipyrimidines were confirmed by 1 H NMR spectroscopy and gas chromatography–mass spectrometry. The NMR spectra were recorded on a Bruker DRX-400 and a Bruker AVANCE-500 spectrometers. The mass spectra were obtained on a Shimadzu GCMS-QP2010 Ultra instrument. The 1 H NMR spectra of obtained dipyrimidines contained no singlets of the pyrimidine ring characteristic for the 5-H proton at δ 4.90–5.05 ppm, but they contained the signals of the CHPh proton at δ 5.35–5.50 ppm. The monosubstituted phenyl ring had signals at δ 7.00–7.25 ppm, while the protons of di- and trisubstituted phenyl ring characteristically appeared in a higher field at δ 6.55–6.90 ppm and 6.60–6.70 ppm, respectively. The characteristic features of all analyzed mass spectra were the molecular ion peak, as well as the C 5 -CHPh bond rupture and formation of phenyl cation. The mass spectra of all studied compounds contained peaks, characteristic for fragmentation of initial 2-organylsulfanyl-6-aminopyrimidin-4(3 H )-ones. Interaction with aromatic aldehydes proceeded in two stages, which was proved by the formation of 6-amino-5-(hydroxy(phenyl)methyl)-2-methallylsulfanylpyrimidin-4(3 H )-one and 5,5'-(phenylmethylene) bis (2-­methallylsulfanyl-6-aminopyrimidin-4(3 H )-one) mixture in the reaction of 2-methallylsulfanyl-6-aminopyrimidin-4(3 H )-one with benzaldehyde with equimolar ratio. All attempts to obtain the tricyclic system, namely, substituted pyrido[2,3- d :6,5- d ’] dipyrimidines by the intermolecular elimination of the ammonia molecule were unsuccessful. The reaction of 5,5'-(phenylmethylene) bis (2-allylsulfanyl-6-aminopyrimidin-4(3 H )-one with iodine led to formation of 6,6'-(phenylmethylene) bis (5-amino-3-(iodomethyl)-7-oxo-2,3,7,8-tetrahydrothiazolo[3,2- a ]pyrimidinium) iodide, as proved by 1 H NMR. The 1 H NMR spectrum contained the characteristic signal of the NCH + proton at δ 5.29 ppm.

The dissolution of simulant vitrified intermediate level nuclear waste in young cement water

AbstractIt is pertinent to the safety case for geological disposal in the UK that the behaviour of vitrified wastes in proximity to cementitious materials is understood. In this study, vitrified simulant intermediate level nuclear waste (ILW) was subject to dissolution in a synthetic cement water solution to simulate disposal conditions. Results show that the presence of alkali / alkaline earth elements in the cementitious solution can be favourable, at least in the short-term, leading to lower dissolution rates associated with incorporation of these elements into the altered layer of the glass.

Study of wheat straw delignification in a rotary-pulsation apparatus

This paper presents the results of studies of isolation lignin and hemicelluloses efficiency during the pre-treatment of wheat straw for hydrolysis in a rotary-pulsation apparatus. The pre-treatment of lignocellulosic raw materials for hydrolysis is a necessary step in the second-generation bioethanol production technology. The lignocellulose complex is destroyed during this process, and this allows hydrolytic enzymes access to the surface of cellulose fibers. The pre-treatment is the most energy-consuming stage in bioethanol production technology, since it usually occurs at high temperature and pressure for a significant time. One of the ways to improve the efficiency of this process is the use of energy-efficient equipment that allows intensifying heat and mass transfer. An example of such equipment is a rotary-pulsation apparatus, which are effective devices in stirring, homogenization, dispersion technologies, etc. The treatment of wheat straw in a rotary-pulsation apparatus was carried out under atmospheric pressure without external heat supply at solid/water ratios of 1:10 and 1:5 in the presence of alkali. It was determined that the treatment of the water dispersion of straw at ratio of 1:10 due to the energy dissipation during 70 minutes leads to the release of 42 % of lignin and 25.76 % of easily hydrolyzed polysaccharides. Changing the solid / water ratio from 1:10 to 1:5 leads to an increase in the yield of lignin and easily hydrolyzed polysaccharides to 58 and 33.38 %, respectively.

Extraction Properties of 4-Tetra(hydroxyphenyl)BTPhen in Liquid-Liquid Extraction Systems with Cyclohexanone/Octanol or in a Solid-Phase Extraction System

The extraction properties of tetra(4-hydroxyphenyl)BTPhen have been investigated. Liquid-liquid extraction studies in proposed SANEX diluents, cyclohexanone and 1-octanol, indicate that actinide-lanthanide separation is superior in cyclohexanone; whereas actinide-actinide separation is more efficient in 1-octanol. Immobilization of the ligand onto a silica support results in the separation factor becoming dependent upon the concentration of nitrate anions in the aqueous phase. The immobilized ligand was also applied to the extraction of transition metals, resulting in >70% uptake of all transition metals examined, in the presence of alkali and alkaline earth metals.

Synthesis of New Dihydroquinopimaric Acid Analogs with Nitrile Groups as Apoptosis-Inducing Anticancer Agents.

Cyan-containing compounds are of great interest as potential anticancer agents. Terpenoids can severe as a natural matrix for the development of promising derivatives with antitumor activity. The 2-cyanoethoxy methyl dihydroquinopimarate derivatives (5-9) were synthesized by the reaction of the intermediates (1-4) with acrylonitrile in the presence of alkali (30% KOH solution) using triethylbenzylammonium chloride. The cytotoxicity evaluation was carried out according to the National Cancer Institute (NCI) Protocol, while apoptosis was studied by flow cytometric analysis of Annexin V and 7-aminoactinomycin D staining and cell cycle was analyzed using the method of propidium iodide staining. Synthesis of new dihydroquinopimaric acid derivatives with nitrile groups was carried out. The obtained cyanoethyl derivatives were converted into tetrazole, amine, oxadiazole and amidoxime analogs. The primary screening for antitumor activity showed the highest cytotoxic potency of the cyanoethyl-substituted compounds. The introduction of cyanoethyl groups at C-1, C-4 and C-1, C-4, C-20 positions of dihydroquinopimaric acid methyl ester provided antiproliferative effect towards the Jurkat, K562, U937, and HeLa tumor cell cultures (CC50=0.045-0.154µM). These nitrile derivatives are effective inducers of tumor cell apoptosis affecting the S and G2 phases of the cell cycle in a dose-dependent manner. The cyanoethyl analogs of dihydroquinopimaric acid reported herein are apoptosis inducers and cytotoxic agents. These findings will be useful for the further design of more potent cytotoxic agents based on natural terpenes.

Nanoscale Ordering and Depolymerization of Calcium Silicate Hydrates in the Presence of Alkalis

Increasing cement production and its substantial contribution to anthropogenic CO2 emissions (∼5–8%) have led to the pursuit of alternative, sustainable cements. These sustainable cements often con...

Novel tribenzylaminobenzolsulphonylimine based on their pyrazine and pyridazines: Synthesis, characterization, antidiabetic, anticancer, anticholinergic, and molecular docking studies

A new method of obtaining multifunctional pyrazoles by the reaction of 1,3-dipolar addition of tribenzylsulfonyliminochloride to polarophiles has been developed. This imine is obtained by reacting tribenzylamine with N-chlorobenzene sulfamide (chloramine-B). Regardless of the structure and composition of polarophiles, the cyclization reaction takes place in the presence of alkali in 6–8 h of boiling, which proves the activation of the methylene groups of tribenzylamine using the electron-withdrawing sulfonamide group. These novel derivatives were effective inhibitors of the α-glycosidase, butyrylcholinesterase (BChE), and acetylcholinesterase enzymes (AChE) with Ki values in the range of 0.45 ± 0.08–1.24 ± 0.27 µM for α-glycosidase, 6.04 ± 0.95–11.61 ± 2.84 µM for BChE, and 2.04 ± 0.24–4.23 ± 1.02 µM for AChE, respectively. The biological activities of the studied molecules against enzyme molecules were investigated by molecular docking calculations. The enzymes studied were AChE for ID 4M0E, BChE for ID 5NN0 BChE, and α-Glycosidase for ID 1XSI (α-Gly) respectively.

Alkali‐Driven Assembly of Protein‐Rich Biomass Boosts the Electrocatalytic Activity of the Derived Carbon Materials for Oxygen Reduction

AbstractThough of great significance, it is still a challenge to facilely engineer biomass into heteroatom‐doped porous carbon materials (HPCs)‐based electrocatalysts with high activity and durability to replace Pt‐based ones for oxygen reduction reaction (ORR). Herein, alkali‐driven assembly strategy is proposed to boost the ORR catalytic performance of the HPCs derived from protein‐rich biomass. Egg white for instance, can self‐assemble into a hydrogel with 3D networks in the presence of alkali. The formed hydrogel can work as a self‐heteroatom (N, S) doped and self‐activated precursor for fabricating HPCs. The as‐obtained NSPC‐1‐900 ORR catalyst has onset potential (Eonset) and half‐wave potential (E1/2) values of 1.03 and 0.88 V (vs. RHE) respectively, and it represents an air electrode catalyst for Zn‐air batteries with high power density and durability. This work affords a facile and effective strategy of utilizing low‐cost, abundant and sustainable biomass to prepare HPCs for energy storage and conversion.

Ethanol steam reforming over Co[sbnd]Ru nanoparticles supported on highly porous polymer-based carbon material

A novel one-step method for the preparation of highly porous metal-carbon nanocomposites, based on bimetallic CoRu nanoparticles supported on activated polyacrylonitrile-derived carbon, was proposed for ethanol steam reforming (ESR). After applying infrared heating on a precursor based on polyacrylonitrile (PAN) and metal Co/Ru) compounds in solution and in the presence of alkali, this led to the formation of active CoRu solid solution nanoparticles supported on polymer-based carbon. This synthesis approach allows to reduce the fabrication time of the given nanocomposite catalytic material significantly. It was found that the metal loading influences the specific surface area and porosity-type of material. The nanocomposites were tested as potential catalysts for hydrogen production through the ESR reaction. High yields of hydrogen (5.88 mol H2/mol EtOH at 520 °C and GHSV of 89.4 h−1) and relatively low yields of by-products were obtained over the IR-PAN-Co-Ru (10%) catalyst.

A crosslinking-induced precipitation process for the simultaneous removal of poly(vinyl alcohol) and reactive dye: The importance of covalent bond forming and magnesium coagulation

High chemical oxygen demand (COD) and a strong color, which primarily originates from desizing and dyeing operations, are two major removal objectives in textile wastewater treatment. In this study, crosslinking-induced precipitation via the covalent bonding between –OH groups of PVA and vinyl sulfone groups of reactive dyes is proposed to simultaneously remove poly(vinyl alcohol) (PVA) and reactive dyes. Due to the nucleophilic addition reaction under an alkaline condition, PVA polymers can be efficiently crosslinked by dye molecules and destabilized in the presence of alkali and Na2SO4. Additionally, due to the high coagulation efficiency under the alkaline conditions, MgSO4 was used as a coagulant to facilitate the removal of the residual color after precipitation. After a two-step process, whereby coagulation was followed by crosslinking-induced precipitation, the maximum efficiencies of the removal of COD, PVA, and color attained 88.9%, 86.3%, and 99.2%, respectively, when the PVA monomer/RB5 mole ratio was 400. We hope that this technically feasible, highly efficient, and cost-effective process provides a basis for the practical application of the simultaneous treatment of desizing and dyeing wastewater.

Adsorption Characteristics of Starch Digested with Alkali on Fine Hematite Particles

In this paper, the influence of alkali on the flocculation of starch on fine hematite was investigated through a series of tests, like turbidities, paste titration, adsorption, conductance, scanning electron microscope (SEM) measurement, and Fourier transforms infrared spectroscopic analysis (FTIR) as well. The results pointed out that alkali concentration has a strong influence on physicochemical changes of starch granules, inducing different adsorption densities on mineral surfaces. A maximum amount of adsorption density on mineral particles was harvested for the starch digested with sodium hydroxide at a concentration of 0.4 N/g starch. It is worthy to note that starch is not fully digested in the presence of alkali at a concentration of less than 0.4 N/g starch. Higher concentration of hydroxide ions, however, tends to obtain less adsorption density of starch on hematite because too small remnants in the starch gel have inverse effects on adsorption capacity.

Study of surfactant alternating gas injection (SAG) in gas-flooded oil-wet, low permeability carbonate rocks

Many low permeability carbonate reservoirs are gasflooded but leave behind a large amount of residual oil. Surfactant solutions can be injected with gas to improve recovery. Surfactants and gas have the potential to form foam that can improve both oil displacement efficiency and sweep efficiency in oil reservoirs. However, in many carbonate reservoirs, foams need to overcome two adverse conditions: oil-wettability and low permeability. This study investigates the performance of 2 surfactant formulations in gas-flooded low permeability, oil-wet carbonate cores: one that combine wettability alteration, low interfacial tension (IFT), and coarse foaming and the other that is only foaming. Phase behavior experiments were performed to determine the optimal salinity for low oil-water IFT. Contact angle and imbibition experiments were performed on initially oil-wet media to identify surfactants for wettability altering capabilities. Coinjection coreflood experiments of surfactant solution and gas (with no crude oil) were performed at a constant injection rate with varying gas/water ratio and at varying injection rates to determine the critical foam parameters. Finally, oil displacement experiments were performed in low permeability limestone cores using the promising surfactant formulations to study the effect on incremental oil recovery after gas EOR injection process. In addition, dynamic adsorption tests were performed to estimate the adsorption of surfactants in limestone rocks. Mobility reduction factors obtained in coinjection experiments were low (less than 10 in most cases) in tight carbonate cores. The foaming was very coarse or weak, if any. There was a significant hysteresis effect at higher foam injection velocity; the foaming behavior in low permeability carbonate rocks were very weak and very different compared to those in high permeability rocks. Wettability alteration and low IFT can be achieved with anionic surfactants that generate coarse foam and help in fluid diversion. Adsorption of the anionic surfactants studied was between 0.04 and 0.11 mg/gm of rock in presence of alkali and EDTA in tight carbonate formations. Oil displacement experiments in oil-wet carbonate cores revealed that tertiary oil-recovery with injection of wettability-altering, low IFT surfactant can recover a significant amount of oil (about 28–70% ROIP) over the secondary gas flood. The pressure drops in the presence of oil suggested rapid foam coalescence and unstable foam in oil-wet carbonate cores. Good foaming surfactant that does not change wettability or achieve low IFT recovered less oil. Low IFT and wettability alteration in synergy with coarse foaming improves incremental oil recovery significantly and is crucial for higher oil recovery in oil-wet porous media.

Evaluation of Interfacial Properties of Aqueous Solutions of Anionic, Cationic and Non-ionic Surfactants for Application in Enhanced Oil Recovery

AbstractSurfactants play an important role in enhanced oil recovery by reducing the interfacial tension (IFT) between oil and water and changing the wettability of reservoir rock. Studies have been made to determine the effect of temperature, salt, alkali and polymer on IFT in the presence of anionic (SDS), cationic (CTAB) and nonionic (Tween 80) surfactants. The experimental data reveal that with increase in temperature the surface tension and IFT of the above surfactants are significantly reduced. IFT values of surfactants are also affected by the presence of polymer, alkali and salt. The results show that the addition of polymer increases the IFT as well as the contact angle of all the surfactant solutions. On the other hand, the presence of alkali in surfactant solution reduces the IFT between crude oil and water as alkali reacts with the acidic components of crude oil to form additional in-situ surfactants. It has been found that the presence of salt in an aqueous solution of different surfactants reduces IFT and contact angle as the salt increases the tendency of the surface active agents to accumulate at the interface. Sand pack flooding in presence of different chemical combinations has also been investigated. It has been found that the enhanced oil recovery by alkali-surfactant-polymer flooding is better than the corresponding surfactant and surfactant-polymer flooding.

Pyrolysis and combustion kinetics of lignocellulosic biomass pellets with calcium-rich wastes from agro-forestry residues

The pyrolysis and combustion kinetics of biomass pellets (i.e., rice husk, herb residue, and wood residue) with the calcium-rich wastes (i.e., CaO, CaCO3, and eggshell) from agro-forestry residues were comparatively studied. During pyrolysis or combustion of biomass, the Ca-rich wastes could slightly influence the decomposition rate in the stage of devolatilization at relatively lower temperatures (e.g., <400 °C). However, the lignin decomposition and the char combustion were obviously influenced by the calcium-based catalysis at higher temperatures (>700 °C). Particularly, the eggshell had a lowest activation energy in the stage of char combustion. The presence of alkali and alkaline-earth metals (AAEMs) in the eggshells might have positive effects on volatile and char combustion. During the combustion, the decomposition temperatures of CaCO3 and eggshell were decreased, thereby favoring to uptake CO2. Furthermore, by identifying the small molecular products, it was found that both CaCO3 and CaO can improve the pyrolysis of RH, but CaCO3 showed better performances, especially on CO2 capture at lower temperatures and on the enhancement of CO production.

Structural insights of hierarchically engineered feldspars by confocal Raman microscopy

AbstractA structural and compositional characterization of fast‐sintered Na‐rich feldspar is carried out by means of the confocal Raman microscopy. The analysis of the main Raman modes (νa = 512 cm−1 and νb = 480 cm−1) determines that feldspar crystallizations correspond to a sodic‐plagioclase group, with an anorthite proportion estimated of 25–45%. The presence of alkali and alkaline earth in the formulated composition leads to albite type feldspar with slightly Al–Si disordered distribution in tetrahedral sites. Raman shift of the main Raman mode νa reveals differences in crystal stresses between nanograins and micrograins. The Rayleigh light‐scattering microscopy shows up lamellar domains of ~2–3 μm resulting from unmixing by spinodal decomposition. Combining Raman spectroscopy and X‐ray diffraction versus temperature significant structural changes are confirmed. This structural change correlates with a stress release and thermally activated conduction. This research gives fundamental understanding of structure, chemical composition, and micro‐nanostructure of engineered glass–ceramics, which may allow tailoring them: for example, to modulate spinodal decomposition regions and interphases.