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By reaction of sodium electride or NaC2H with the anhydrous sodium salt of propiolic acid, Na(OOC-C≡C-H), in liquid ammonia crystalline powders of Na2C3O2 were obtained. The structure analysis based on synchrotron powder diffraction data revealed that Na2C3O2 crystallizes in a monoclinic unit cell (I2/a, Z=4) exhibiting the elusive Y-shaped -C≡C-COO- anion, which is unprecedented in a crystalline compound up to now. IR/Raman and solid-state NMR spectroscopic investigations with assignments supported by DFT-based ab initio calculations confirm this finding. Reaction with sodium electride led to a higher crystallinity of the product, but additionally a by-product apparently due to decomposition and polymerization of Na2C3O2 was formed. No such by-product was observed in the reaction with NaC2H, which turned out to be a milder metalation route. However, the product of the latter reaction is less crystalline.
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Sulfonated, cross-linked porous polymers are promising frameworks for aqueous high-performance electrolyte-host systems for electrochemical energy storage and conversion. The systems offer high proton conductivities, excellent chemical and mechanical stabilities, and straightforward water management. However, little is known about mass transport mechanisms in such nanostructured hosts. We report on the synthesis and postsynthetic sulfonation of an aromatic framework (SPAF-2) with a 3D-interconnected nanoporosity and varying sulfonation degrees. Water adsorption produces the system SPAF-2H20. It features proton exchange capacities up to 6 mequiv g-1 and exceptional proton conductivities of about 1 S cm-1. Two contributions are essential for the highly efficient transport. First, the nanometer-sized pores link the charge transport to the diffusion of adsorbed water molecules, which is almost as fast as bulk water. Second, continuous exchange between interface-bound and mobile species enhances the conductivities at elevated temperatures. SPAF-2H20 showcases how to tailor nanostructured electrolyte-host systems with liquid-like conductivities.
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An isotopic effect of normal (H2O) vs. heavy water (D2O) is well known to fundamentally affect the structure and chemical properties of proteins, for instance. Here, we correlate the results from small angle X-ray and neutron scattering (SAXS, SANS) with high-resolution scanning transmission electron microscopy to track the evolution of CdS nanoparticle size and crystallinity from aqueous solution in the presence of the organic ligand ethylenediaminetetraacetate (EDTA) at room temperature in both H2O and D2O. We provide evidence via SANS experiments that exchanging H2O with D2O impacts nanoparticle formation by changing the equilibria and dynamics of EDTA clusters in solution as investigated by nuclear magnetic resonance analysis. The colloidal stability of the CdS nanoparticles, covered by a layer of [Cd(EDTA)]2- complexes, is significantly reduced in D2O despite the strong stabilizing effect of EDTA in suspensions of normal water. Hence, conclusions about nanoparticle formation mechanisms from D2O solutions reveal limited transferability to reactions in normal water due to isotopic effects, which thus need to be discussed for contrast match experiments.
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The solution chemistry of aluminum is highly complex and various polyoxocations are known. Here we report on the facile synthesis of a cationic Al24 cluster that forms porous salts of composition [Al24 (OH)56 (CH3 COO)12 ]X4 , denoted CAU-55-X, with X=Cl- , Br- , I- , HSO4 - . Three-dimensional electron diffraction was employed to determine the crystal structures. Various robust and mild synthesis routes for the chloride salt [Al24 (OH)56 (CH3 COO)12 ]Cl4 in water were established resulting in high yields (>95 %, 215â g per batch) within minutes. Specific surface areas and H2 O capacities with maximum values of up to 930â m2 g-1 and 430â mg g-1 are observed. The particle size of CAU-55-X can be tuned between 140â nm and 1250â nm, permitting its synthesis as stable dispersions or as highly crystalline powders. The positive surface charge of the particles, allow fast and effective adsorption of anionic dye molecules and adsorption of poly- and perfluoroalkyl substances (PFAS).
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Patient education (PE) is vital in reducing anxiety, increasing satisfaction with treatment, helping with self-management, and creating a sense of control for cancer patients. Patients access much of their material from health care providers through in-person visits, patient libraries, and in-person classes. Due to reductions in in-person visits throughout the pandemic, we sought to understand how PE programs responded under varying levels of COVID-19 restrictions to meet the information needs of patients and families. A cross-sectional survey was distributed to members of the Cancer Patient Education Network (CPEN) and the Health Care Education Association (HCEA) via the respective listservs. The survey consisted of five sections that included closed and opened questions. Participants were asked questions to describe their PE programs and how their duties were affected during the pandemic. Forty-two CPEN members completed the survey (N = 42, 66%) with a 35% response rate and a 55% completion rate, and 19 HCEA members completed the survey (N = 19, 30%) with a 5% response rate and 16% completion rate. The majority of staff surveyed were not furloughed (N = 57/64, 89%). Just under half reported a change in daily PE program activities (N = 23/52, 44%) and most reported a change in developing PE materials (e.g., pamphlets) (N = 10/26, 63%), finding information for patients/families (N = 11/19, 58%), and delivering classes (N = 12/21, 57%). COVID-19 has ushered in a new era in the delivery of PE with the rapid deployment of digital cancer patient education. Results can inform future directions for the delivery of PE post-pandemic.
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COVID-19 , Neoplasias , Humanos , COVID-19/epidemiología , Pandemias , Estudios Transversales , Encuestas y Cuestionarios , Ansiedad , Neoplasias/terapiaRESUMEN
A diode requires the combination of p- and n-type semiconductors or at least the defined formation of such areas within a given compound. This is a prerequisite for any IT application, energy conversion technology, and electronic semiconductor devices. Since the discovery of the pnp-switchable compound Ag10 Te4 Br3 in 2009, it is in principle possible to fabricate a diode from a single material without adjusting the semiconduction type by a defined doping level. Often a structural phase transition accompanied by a dynamic change of charge carriers or a charge density wave within certain substructures are responsible for this effect. Unfortunately, the high pnp-switching temperature between 364 and 580 K hinders the application of this phenomenon in convenient devices. This effect is far removed from a suitable operation temperature at ambient conditions. Ag18 Cu3 Te11 Cl3 is a room temperature pnp-switching material and the first single-material position-independent diode. It shows the highest ever reported Seebeck coefficient drop that takes place within a few Kelvin. Combined with its low thermal conductivity, it offers great application potential within an accessible and applicable temperature window. Ag18 Cu3 Te11 Cl3 and pnp-switching materials have the potential for applications and processes where diodes, transistors, or any defined charge separation with junction formation are utilized.
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The enzymatic degradation of aliphatic polyesters offers unique opportunities for various use cases in materials science. Although evidently desirable, the implementation of enzymes in technical applications of polyesters is generally challenging due to the thermal lability of enzymes. To prospectively overcome this intrinsic limitation, we here explored the thermal stability of proteinase K at conditions applicable for polymer melt processing, given that this hydrolytic enzyme is well established for its ability to degrade poly(l-lactide) (PLLA). Using assorted spectroscopic methods and enzymatic assays, we investigated the effects of high temperatures on the structure and specific activity of proteinase K. Whereas in solution, irreversible unfolding occurred at temperatures above 75-80 °C, in the dry, bulk state, proteinase K withstood prolonged incubation at elevated temperatures. Unexpectedly little activity loss occurred during incubation at up to 130 °C, and intermediate levels of catalytic activity were preserved at up to 150 °C. The resistance of bulk proteinase K to thermal treatment was slightly enhanced by absorption into polyacrylamide (PAM) particles. Under these conditions, after 5 min at a temperature of 200 °C, which is required for the melt processing of PLLA, proteinase K was not completely denatured but retained around 2% enzymatic activity. Our findings reveal that the thermal processing of proteinase K in the dry state is principally feasible, but equally, they also identify needs and prospects for improvement. The experimental pipeline we establish for proteinase K analysis stands to benefit efforts directed to this end. More broadly, our work sheds light on enzymatically degradable polymers and the thermal processing of enzymes, which are of increasing economical and societal relevance.
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Poliésteres , Polímeros , Endopeptidasa K/metabolismo , Poliésteres/química , Polímeros/química , TemperaturaRESUMEN
Swelling of clays is hampered by increasing layer charge. With vermiculite-type layer charge densities, crystalline swelling is limited to the two-layer hydrate, while osmotic swelling requires ion exchange with bulky and hydrophilic organic molecules or with Li+ cations to trigger repulsive osmotic swelling. Here, we report on surprising and counterintuitive osmotic swelling behavior of a vermiculite-type synthetic clay [Na0.7]inter[Mg2.3Li0.7]oct[Si4]tetO10F2 in mixtures of water and dimethyl sulfoxide (DMSO). Although swelling in pure water is restricted to crystalline swelling, with the addition of DMSO, osmotic swelling sets in at some threshold composition. Finally, when the DMSO concentration is increased further to 75 vol %, swelling is restricted again to crystalline swelling as expected. Repulsive osmotic swelling thus is observed in a narrow composition range of the binary water-DMSO mixture, where a freezing point suppression is observed. This suppression is related to DMSO and water molecules exhibiting strong interactions leading to stable molecular clusters. Based on this phenomenological observation, we hypothesize that the unexpected swelling behavior might be related to the formation of different complexes of interlayer cations being formed at different compositions. Powder X-ray diffraction and 23Na magic angle spinning-NMR evidence is presented that supports this hypothesis. We propose that the synergistic solvation of the interlayer sodium at favorable compositions exerts a steric pressure by the complexes formed in the interlayer. Concomitantly, the basal spacing is increased to a level, where entropic contributions of interlayer species lead to a spontaneous thermodynamically allowed one-dimensional dissolution of the clay stack.
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Weathering of microplastics made of commodity plastics like polystyrene, polypropylene and polyethylene introduces polar polymer defects as a result of photooxidation and mechanical stress. Thus, hydrophobic microplastic particles gradually become hydrophilic, consisting of polar oligomers with a significant amount of oxygen-bearing functional groups. This turnover continuously changes interactions between microplastics and natural colloidal matter. To be able to develop a better understanding of this complex weathering process, quantification of the corresponding defect proportions is a first and essential step. Using polystyrene, 13C enriched at the α position to 23%, we demonstrate that 13C cross polarisation (CP) NMR spectroscopy allows for probing the typical alcohol, peroxo, keto and carboxyl defects. Even the discrimination between in- and end-chain ketones, carboxylic acids and esters as well as ketal functions was possible. Combined with multiCP excitation, defect proportions could be determined with excellent accuracy down to 0.1%. For materials with 13C in natural abundance, this accounts for a detection limit of roughly 1%. The best trade-off between measurement time and accuracy for the quantification of the defect intensities for multiCP excitation was obtained for CP block lengths shorter than 250 µs and total build-up times longer than 2 ms. Further measurement time reduction is possible by using multiCP excitation to calibrate intensities obtained from series of 13C CP MAS NMR spectra. As photooxidation is an important degradation mechanism for microplastics in the environment, we expect these parameters to be transferable for probing defect proportions of weathered microplastics in general.
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Porphyrin-based metal-organic frameworks (MOFs), exemplified by MOF-525, PCN-221, and PCN-224, are promising systems for catalysis, optoelectronics, and solar energy conversion. However, subtle differences between synthetic protocols for these three MOFs give rise to vast discrepancies in purported product outcomes and description of framework topologies. Here, based on a comprehensive synthetic and structural analysis spanning local and long-range length scales, we show that PCN-221 consists of Zr6O4(OH)4 clusters in four distinct orientations within the unit cell, rather than Zr8O6 clusters as originally published, and linker vacancies at levels of around 50%, which may form in a locally correlated manner. We propose disordered PCN-224 (dPCN-224) as a unified model to understand PCN-221, MOF-525, and PCN-224 by varying the degree of orientational cluster disorder, linker conformation and vacancies, and cluster-linker binding. Our work thus introduces a new perspective on network topology and disorder in Zr-MOFs and pinpoints the structural variables that direct their functional properties.
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Spin-ices are frustrated magnets that support a particularly rich variety of emergent physics. Typically, it is the interplay of magnetic dipole interactions, spin anisotropy, and geometric frustration on the pyrochlore lattice that drives spin-ice formation. The relevant physics occurs at temperatures commensurate with the magnetic interaction strength, which for most systems is 1-5 K. Here, we show that non-magnetic cadmium cyanide, Cd(CN)2, exhibits analogous behaviour to magnetic spin-ices, but does so on a temperature scale that is nearly two orders of magnitude greater. The electric dipole moments of cyanide ions in Cd(CN)2 assume the role of magnetic pseudospins, with the difference in energy scale reflecting the increased strength of electric vs magnetic dipolar interactions. As a result, spin-ice physics influences the structural behaviour of Cd(CN)2 even at room temperature.
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Acetic acid, an alternative green solvent, was utilized for the solvothermal synthesis of four 2D materials of composition [Zr2O2(OAc)2(BDC-F)], [Zr2O2(OAc)2(BDC-F4)], [Zr2O2(OAc)2(BDC)], and [Zr2O2(OAc)2(NDC)] (BDC, terephthalate; BDC-F, 2-fluoroterephthalate; BDC-F4, tetrafluoroterephthalate; NDC, 2,6-naphthalenedicarboxylate). The first three compounds were subsequently reacted with terephthalic acid in solid-state reactions to form porous MIL-140A-type metal-organic frameworks and mixed-linker derivatives ([ZrO(BDC)1-x(BDC-Y)x], x = 0-0.18, Y = F, F4). The reaction kinetics of the formation of MIL-140A were investigated with the aid of time-resolved synchrotron and temperature-resolved in-house X-ray powder diffraction experiments. Thorough compositional analyses and solid-state NMR spectroscopic experiments were used to assess the crystallographic ordering of the different linker molecules. Additionally, acetic acid-based routes for the direct synthesis of MIL-140A-NO2 and a novel MIL-140A-(CH3)2 derivative were discovered.
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BACKGROUND: Oncology nurses are challenged to coordinate an effective, evidence-based approach to comprehensive patient education, symptom management, and psychosocial support for patients with pancreatic and colorectal cancers during chemotherapy. OBJECTIVES: The purpose of the study was to develop and evaluate a nurse-led psychoeducational intervention using a multimedia tool. METHODS: Development and testing of the intervention was grounded in the Science and Practice Aligned Within Nursing model for evidence-based practice implementation. FINDINGS: Forty-five participants completed the study (29 with pancreatic cancer and 16 with colorectal cancer). Patient knowledge increased significantly in patients with pancreatic cancer following the intervention (p = 0.05).
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Atención Ambulatoria , Cuidados Paliativos , Práctica Clínica Basada en la Evidencia , Humanos , Enfermería OncológicaRESUMEN
La3 B6 O13 (OH) was obtained by a high-pressure/high-temperature experiment at 6â GPa and 1673â K. The compound crystallizes in the space group P21 (no. 4) with the lattice parameters a=4.785(2), b=12.880(4), c=7.433(3)â Å, and ß=90.36(10)°, and is built up of corner- as well as edge-sharing BO4 tetrahedra. It represents the first acentric high-pressure borate containing these B2 O6 entities. The compound develops borate layers of "sechser"-rings with the La3+ cations positioned between the layers. Single-crystal and powder X-ray diffraction, vibrational and MAS NMR spectroscopy, second-harmonic generation (SHG) and thermoanalytical measurements, as well as computational methods were used to affirm the proposed structure and the B2 O6 entities.
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Herein is reported the utilization of acetonitrile as a new solvent for the synthesis of the three significantly different benchmark metal-organic frameworks (MOFs) CAU-10, Ce-UiO-66, and Al-MIL-53 of idealized composition [Al(OH)(ISO)], [Ce6 O4 (OH)4 (BDC)6 ], and [Al(OH)(BDC)], respectively (ISO2- : isophthalate, BDC2- : terephthalate). Its use allowed the synthesis of Ce-UiO-66 on a gram scale. While CAU-10 and Ce-UiO-66 exhibit properties similar to those reported elsewhere for these two materials, the obtained Al-MIL-53 shows no structural flexibility upon adsorption of hydrophilic or hydrophobic guest molecules such as water and xenon and is stabilized in its large-pore form over a broad temperature range (130-450â K). The stabilization of the large-pore form of Al-MIL-53 was attributed to a high percentage of noncoordinating -COOH groups as determined by solid-state NMR spectroscopy. The defective material shows an unusually high water uptake of 310â mg g-1 within the range of 0.45 to 0.65â p/p°. In spite of showing no breathing effect upon water adsorption it exhibits distinct mechanical properties. Thus, mercury intrusion porosimetry studies revealed that the solid can be reversibly forced to breathe by applying moderate pressures (≈60â MPa).
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Solving the structure of carbon nitrides has been a long-standing challenge due to the low crystallinity and complex structures observed within this class of earth-abundant photocatalysts. Herein, we report on two-dimensional layered potassium poly(heptazine imide) (K-PHI) and its proton-exchanged counterpart (H-PHI), obtained by ionothermal synthesis using a molecular precursor route. We present a comprehensive analysis of the in-plane and three-dimensional structure of PHI. Transmission electron microscopy and solid-state NMR spectroscopy, supported by quantum-chemical calculations, suggest a planar, imide-bridged heptazine backbone with trigonal symmetry in both K-PHI and H-PHI, whereas pair distribution function analyses and X-ray powder diffraction using recursive-like simulations of planar defects point to a structure-directing function of the pore content. While the out-of-plane structure of K-PHI exhibits a unidirectional layer offset, mediated by hydrated potassium ions, H-PHI is characterized by a high degree of stacking faults due to the weaker structure directing influence of pore water. Structure-property relationships in PHI reveal that a loss of in-plane coherence, materializing in smaller lateral platelet dimensions and increased terminal cyanamide groups, correlates with improved photocatalytic performance. Size-optimized H-PHI is highly active toward photocatalytic hydrogen evolution, with a rate of 3363 µmol/gh H2 placing it on par with the most active carbon nitrides. K- and H-PHI adopt a uniquely long-lived photoreduced polaronic state in which light-induced electrons are stored for more than 6 h in the dark and released upon addition of a Pt cocatalyst. This work highlights the importance of structure-property relationships in carbon nitrides for the rational design of highly active hydrogen evolution photocatalysts.
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Exploring the reasons for the initiation of Al-O-Al bond formation in alkali-earth alumino silicate glasses is a key topic in the glass-science community. Evidence for the formation of Al-O-Al and Al-NBO bonds in the glass composition 38.7CaO-9.7MgO-12.9Al2O3-38.7SiO2 (CMAS, mol%) has been provided based on Molecular Dynamics (MD) simulations. Analyses in the short-range order confirm that silicon and the majority of aluminium cations form regular tetrahedra. Well-separated homonuclear (Si-O-Si) and heteronuclear (Si-O-Al) cluster regions have been identified. In addition, a channel region (C-Region), separated from the network region, enriched with both NBO and non-framework modifier cations, has also been identified. These findings are in support of the previously proposed extended modified random network (EMRN) model for aluminosilicate glasses. A detailed analysis of the structural distributions revealed that a majority of Al, 51.6%, is found in Si-O-Al links. Although the formation of Al-O-Al and Al-NBO bonds is energetically less favourable, a significant amount of Al is found in Al-O-Al links (33.5%), violating Lowenstein's rule, and the remainder is bonded with non-bridging oxygen (NBO) in the form of Al-NBO (Al-O-(Ca, Mg)). The conditions necessary for the formation of less favourable bonds are attributed to the presence of a high amount of modifier cations in current CMAS glass and their preferable coordination.
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Two new chalcogenogallates Cs4 Ga6 Q11 (Q=S, Se) were obtained by a controlled thermal treatment of CsN3 in the presence of stoichiometric amounts of Ga2 Q3 and the elemental chalcogens at elevates temperatures. Both isotypic compounds crystallize in the space group P 1 â¾ (no. 2). The most prominent structural feature in these chalcogenogallates are the complex anionic Dreier double chains 1 ∞ [Ga6 Q11 4- ] formed by condensed GaQ4 tetrahedra. The semiconductors Cs4 Ga6 S11 (Eg =3.14â eV) and Cs4 Ga6 Se11 (Eg =2.41â eV) were further studied by using UV/Vis, 133 Cs and 71 Ga solid-state NMR spectroscopy, and complementary DFT calculations. The 133 Cs MAS NMR spectra are characteristic for cationic cesium and vibrational spectra show two distinct regions, attributed to the Ga-Q valence and deformation vibrations, respectively. High-temperature studies revealed incongruent melting of both solids, which is also depicted in updated binary phase-diagrams Cs2 Q-Ga2 Q3 (Q=S, Se).
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Proton-containing point defects in solid materials are important for a variety of properties ranging from ionic transport over thermal conductivity up to compressibility. Ultrafast magic-angle spinning techniques nowadays offer high-resolution solid-state NMR spectra, even for 1H, and thus open up possibilities to study the underlying defect chemistry. Nevertheless, disorder within such defects again leads to heavy spectral overlap of 1H resonances, which prevents quantitative analysis of defect concentrations, if several defect types are present. Here, we present a strategy to overcome this limitation by simulating the 1H lineshape as well as 1H-1H double-quantum buildup curves, which we then validate against the experimental data in a joint cost function. To mimic the local structural disorder, we use molecular dynamics simulations at the DFT level. It turned out to be advantageous for the joint refinement to put the computational effort into the structural optimisation to derive accurate proton positions and to use empirical correlations for the relation between isotropic and anisotropic 1H chemical shifts and structural elements. The expressiveness of this approach is demonstrated on ringwoodite's (γ-Mg2SiO4) OH defect chemistry containing four different defect types in octahedral and tetrahedral voids with both pure Mg and mixed Si and Mg cation environments. Still, we determine the ratio for each defect type with an accuracy of about 5% as a result of the minimization of the joint cost function. We expect that our approach is generally applicable for local proton disorder and might prove to be a valuable alternative to the established AIRSS and Monte Carlo methods, respectively.
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Aluminosilicate glasses are considered to follow the Al-avoidance principle, which states that Al-O-Al linkages are energetically less favorable, such that, if there is a possibility for Si-O-Al linkages to occur in a glass composition, Al-O-Al linkages are not formed. The current paper shows that breaching of the Al-avoidance principle is essential for understanding the distribution of network-forming AlO4 and SiO4 structural units in alkaline-earth aluminosilicate glasses. The present study proposes a new modified random network (NMRN) model, which accepts Al-O-Al linkages for aluminosilicate glasses. The NMRN model consists of two regions, a network structure region (NS-Region) composed of well-separated homonuclear and heteronuclear framework species and a channel region (C-Region) of nonbridging oxygens (NBOs) and nonframework cations. The NMRN model accounts for the structural changes and devitrification behavior of aluminosilicate glasses. A parent Ca- and Al-rich melilite-based CaO-MgO-Al2O3-SiO2 (CMAS) glass composition was modified by substituting MgO for CaO and SiO2 for Al2O3 to understand variations in the distribution of network-forming structural units in the NS-region and devitrification behavior upon heat treating. The structural features of the glass and glass-ceramics (GCs) were meticulously assessed by advanced characterization techniques including neutron diffraction (ND), powder X-ray diffraction (XRD), 29Si and 27Al magic angle spinning (MAS)-nuclear magnetic resonance (NMR), and in situ Raman spectroscopy. ND revealed the formation of SiO4 and AlO4 tetrahedral units in all the glass compositions. Simulations of chemical glass compositions based on deconvolution of 29Si MAS NMR spectral analysis indicate the preferred formation of Si-O-Al over Si-O-Si and Al-O-Al linkages and the presence of a high concentration of nonbridging oxygens leading to the formation of a separate NS-region containing both SiO4 and AlO4 tetrahedra (Si/Al) (heteronuclear) in addition to the presence of Al[4]-O-Al[4] bonds; this region coexists with a predominantly SiO4-containing (homonuclear) NS-region. In GCs, obtained after heat treatment at 850 °C for 250 h, the formation of crystalline phases, as revealed from Rietveld refinement of XRD data, may be understood on the basis of the distribution of SiO4 and AlO4 structural units in the NS-region. The in situ Raman spectra of the GCs confirmed the formation of a Si/Al structural region, as well as indicating interaction between the Al/Si region and SiO4-rich region at higher temperatures, leading to the formation of additional crystalline phases.