Colloidal Metal Research Articles

Rapid Synthesis of Noble Metal Colloids by Plasma-Liquid Interactions.

The interactions between plasma and liquids cause complex physical and chemical reactions at the gas-liquid contact surface, producing numerous chemically active particles that can rapidly reduce noble metal ions. This study uses atmospheric-pressure surface dielectric barrier discharge (DBD) plasma to treat ethanol aqueous solutions containing noble metal precursors, and stable gold, platinum, and palladium colloids are obtained within a few minutes. To evaluate the mechanism of the reduction of noble metal precursors by atmospheric-pressure surface DBD plasma, the corresponding metal colloids are prepared first by activating an ethanol aqueous solution with plasma and then adding noble metal precursors. It is found that the long-lived active species hydrogen peroxide (H2O2) plays a dominant role in the synthesis process, which has distinct effects on different metal ions. When HAuCl4 and H2PdCl4 are used as precursors, H2O2 acts as a reducing agent, and AuCl4- and PdCl42- ions can be reduced to metallic Au and Pd. However, when AgNO3 is the precursor, H2O2 acts as an oxidising agent, and Ag+ ions cannot be reduced to obtain metal colloids because metallic Ag can be dissolved in H2O2 under acidic conditions. A similar phenomenon was also observed for the preparation of Pd colloid-PA with a plasma-activated ethanol aqueous solution using Pd(NO3)2 as a Pd precursor.

Molar excess of coordinating N-heterocyclic carbene ligands triggers kinetic digestion of gold nanocrystals.

There has been much interest in evaluating the strength of the coordination interactions between N-heterocyclic carbene (NHC) molecules and transition metal ions, nanocolloids and surfaces. We implement a top-down core digestion test of Au nanoparticles (AuNPs) triggered by incubation with a large molar excess of poly(ethylene glycol)-appended NHC molecules, where kinetic dislodging of surface atoms and formation of NHC-Au complexes progressively take place. We characterize the structure and chemical nature of the generated PEG-NHC-Au complexes using 1D and 2D 1H-13C NMR spectroscopy, supplemented with matrix assisted laser desorption/ionization mass spectrometry, and transmission electron microscopy. We further apply the same test using thiol-modified molecules and find that though etching can be measured the kinetics are substantially slower. We discuss our findings within the classic digestion of transition metal ores and colloids induced by interactions with sodium cyanide, which provides an insight into the strength of coordination between the strong σ-donating (soft Lewis base) NHC and Au surfaces (having a soft Lewis acid character), as compared to gold-to-gold covalent binding.

Plasmon resonances of GZO core-Ag shell nanospheres, nanorods, and nanodisks for biosensing and biomedical applications in near-infrared biological windows I and II.

There is currently a great deal of interest in realizing localized surface plasmon resonances (LSPRs) in two distinct windows in the near-infrared (NIR) spectrum for in vivo biosensing and medical applications, the biological window (BW) I and II (BW I, 700-900 nm; BW II, 1000-1700 nm). This study aims to demonstrate that LSPRs of Ga-doped ZnO (GZO) core-silver (Ag) shell structures exhibit promising features for biological applications in the NIR BW I and II. Here, we study three different shapes for nanoshells: the core-shell nanosphere, nanorod, and nanodisk. In the calculation of the optical response of these nanoshells, an effective medium approach is first used to reduce the dielectric function of a nanoshell to that of an equivalent homogenous NP with an effective dielectric function. Then, the LSPR spectra of nanoshells are calculated using the modified long-wavelength approximation (MLWA), which corrects the polarizability of the equivalent NP as obtained by Gans theory. Through numerical investigations, we examine the impacts of the core and shell sizes of the proposed nanoshells as well as the medium refractive index on the position and line width of the plasmon resonance peaks. It is shown that the plasmon resonances of the three proposed nanoshells exhibit astonishing resonance tunability in the NIR region by varying their geometrical parameters. Specifically, the improved spectrum characteristics and tunability of its plasmon resonances make the GZO-Ag nanosphere a more viable platform for NIR applications than the spherical metal colloid. Furthermore, we demonstrate that the sensitivity and figure of merit (FOM) of the plasmon resonances may be significantly increased by using GZO-Ag nanorods and nanodisks in place of GZO-Ag nanospheres. It is found that the optical properties of the transverse plasmon resonance of the GZO-Ag nanodisk are superior to all plasmon resonances produced by the GZO-Ag nanorods and GZO-Ag nanospheres in terms of sensitivity and FOM. The FOM of the transverse plasmon mode of the GZO-Ag nanodisk is almost two orders of magnitude higher than that of the longitudinal and transverse plasmon modes of the GZO-Ag nanorod in BW I and BW II. And it is 1.5 and 2 times higher than the plasmon resonance FOM of GZO-Ag nanospheres in BW I and BW II, respectively.

Water Dispersible Colloidal Metal and Metal Oxide Nanoparticles Synthesis for Agarwood Inoculation: A Review

Agarwood is one of the most expensive natural products, produced from Aquilaria Spp. These plants produce agar resin through mechanical, biological, or chemical stress. Besides these, the particles having size in the range of 1-100 nm, are known as nanoparticles, have ultra-high surface area and surface plasmon resonance, can create stress on living plants when incorporated into the plant body. Adopting this concept, we intend to produce agarwood by inoculating water-dispersible metal/metal oxide nanoparticles. Therefore, we aim to synthesize water-dispersible four noble metals (Au, Ag, Pt, Pd) and five metal oxides (Fe3O4, TiO2, SnO2, MnO2, CuO) nanoparticles in aqueous colloidal states for application in biotechnology, considering the facile synthetic routes, readily available and inexpensive precursors, and stability of the products under normal laboratory conditions for an extended period, utilizing the synthesis methods of precipitation of metal/metal oxide nanoparticles from an aqueous solution, microwave and ultrasound-assisted rapid heating methods, sol-gel methods, and surfactant-assisted microemulsion methods. We believe that by applying any of these methods, water-dispersible, long-lasting colloidal metal/metal oxide nanoparticles can be synthesized using a simple laboratory setup, without the need for sophisticated tools or instruments. IUBAT Review, 6(2): 41-76

In Situ Sol-Gel Assembly of Graphitic Carbonitride Nanosheet-Supported Colloidal Binary Metal Sulfide into Nanosandwich-Like Multifunctional 3D Macroporous Aerogel Catalysts for Asymmetric Supercapacitor and Electrocatalytic Oxygen and Hydrogen Evolution

It is challenging to develop scalable and stable multifunctional catalysts for energy storage and conversion applications. To address the above challenges, we designed 3D macroporous nanosandwich-like aerogels using an in situ sol-gel assembly for 2D g-C3N4 nanosheet-supported NiCo2S4 nanoporous aerogels. The resultant in situ method not only assembles NiCo2S4 but also 2D g-C3N4 into the sandwich-like 3D network, allowing rapid ion and electron transport. The potential of g-C3N4 and NiCo2S4 in electrochemical energy storage and electrocatalysis is promising for improving its electrochemical activities. The synthesized 3D NiCo2S4/g-C3N4 (3%) composite aerogel electrode achieved a remarkable specific capacitance value, 1083 F·g-1 at 5 mA·cm-2 current density with 87.03% cyclic stability. Furthermore, the asymmetric electrochemical supercapacitor device was fabricated with a maximum specific energy of 43 Wh·kg-1, with outstanding electrochemical stability of about 97% over 10,000 charge/discharge cycles. In addition, NiCo2S4/g-C3N4 (3%) catalysts achieved 294 and 155 mV as oxygen and hydrogen evolution reaction overpotentials, respectively, at 20 and 10 mA·cm-2 current density values. This study provides a new method for the conversion of 2D sheets and 0D colloidal network into 3D macroporous nanocomposite aerogels in multifunctional applications.

High Q-Factor Plasmonic Surface Lattice Resonances in Colloidal Nanoparticle Arrays.

Surface lattice resonances (SLRs) sustained by ordered metal arrays are characterized by their narrow spectral features, remarkable quality factors, and the ability to tune their spectral properties based on the periodicity of the array. However, the majority of these structures are fabricated using classical lithographic processes or require postannealing steps at high temperatures to enhance the quality of the metal. These limitations hinder the widespread utilization of these periodic metal arrays in various applications. In this work, we use the scalable technique of template-assisted assembly of metal colloids to produce plasmonic supercrystals over centimeter areas capable of sustaining SLRs with high Q factors reaching up to 270. Our approach obviates the need for any postprocessing, offering a streamlined and efficient fabrication route. Furthermore, our method enables extensive tunability across the entire visible and near-infrared spectral ranges, empowering the design of tailored plasmonic resonant structures for a wide range of applications.

Nanostructure Tuning of Gold Nanoparticles Films via Click Sintering.

Colloidal metal nanoparticles dispersions are commonly used to create functional printed electronic devices and they typically require time-, energy- and equipment-consuming post-treatments to improve their electrical and mechanical properties. Traditional methods, e.g. thermal, UV/IR, and microwave treatments, limit the substrate options and may require expensive equipment, not available in all the laboratories. Moreover, these processes also cause the collapse of the film (nano)pores and interstices, limiting or impeding its nanostructuration. Finding a simple approach to obtain complex nanostructured materials with minimal post-treatments remains a challenge. In this study, a new sintering method for gold nanoparticle inks that called as "click sintering" has been reported. The method uses a catalytic reaction to enhance and tune the nanostructuration of the film while sintering the metallic nanoparticles, without requiring any cumbersome post-treatment. This results in a conductive and electroactive nanoporous thin film, whose properties can be tuned by the conditions of the reaction, i.e., concentration of the reagent and time. Therefore, this study presents a novel and innovative one-step approach to simultaneously sinter gold nanoparticles films and create functional nanostructures, directly and easily, introducing a new concept of real-time treatment with possible applications in the fields of flexible electronics, biosensing, energy, and catalysis.

Terrigenous humic substances regulate the concentrations of dissolved Fe and Cu (but not Al, Mn, Ni or Zn) in the Gaoping River plume

The small mountainous rivers of Oceania discharge a large fraction of their dissolved and particulate load of materials within a very small percentage of the time. As a result, the yearly inputs and physicochemical forms of dissolved metals exported to the ocean by these rivers are poorly quantified. We investigated the wet-season distribution patterns of metals and fluorescent organic substances in the surface waters of the Gaoping River plume, SW Taiwan, under both moderate (Sep 2020) and strong flow conditions (Aug 2021). The mixing behaviour of both soluble (<5 kDa) and colloidal (>5 kDa) metals and fluorescent components was examined over the salinity range 3.0–32.2 in 2020 and 5.8–31.1 in 2021. We detected two humic-like and one protein-like fluorescent components, the same on both surveys. The humic-like components, C1 and C3, originated from the Gaoping River and correlated strongly with Cu and Fe, respectively. Component C3 showed a greater enrichment relative to C1 in the colloidal (C3/C1 > 0.8) than in the soluble phase (C3/C1 = 0.4). The protein-like component, C2, came from both terrestrial and marine sources and displayed a more complex mixing behaviour than the other two. One striking result was that the effective zero-salinity concentrations of Fe (∼300 nM) and Cu (∼23 nM) did not change significantly in response to a 10-fold increase in river discharge between Sep 2020 and Aug 2021. Similarly to Fe and Cu, the distribution patterns of Components C1 and C3 did not change significantly between the moderate and the strong plume, and C3 and C1 correlated strongly with Fe and Cu, respectively. We conclude that subtropical mountainous rivers can provide soil-derived humic substances which facilitate and regulate the delivery of Fe and Cu to the ocean, provided mountain forests are preserved.

Overcoming Charge Confinement in Perovskite Nanocrystal Solar Cells.

The small nanoparticle size and long-chain ligands in colloidal metal halide perovskite quantum dots (PeQDs) cause charge confinement, which impedes exciton dissociation and carrier extraction in PeQD solar cells, so they have low short-circuit current density Jsc , which impedes further increases in their power conversion efficiency (PCE). Here, a re-assembling process (RP) is developed for perovskite nanocrystalline (PeNC) films made of colloidal perovskite nanocrystals to increase Jsc in PeNC solar cells. The RP of PeNC films increases their crystallite size and eliminates long-chain ligands, and thereby overcomes the charge confinement in PeNC films. These changes facilitate exciton dissociation and increase carrier extraction in PeNC solar cells. By use of this method, the gradient-bandgap PeNC solar cells achieve a Jsc = 19.30mA cm-2 without compromising the photovoltage, and yield a high PCE of 16.46% with negligible hysteresis and good stability. This work provides a new strategy to process PeNC films and pave the way for high performance PeNC optoelectronic devices.

Surface-Enhanced Raman Spectroscopy of Benzylpenicillin Using Silver Nanocrystals Modified with Moroccan Plant Extracts

Green chemical routes for the synthesis of colloidal metal nanocrystals have been of great interest, namely in the context of nanosciences associated with biological applications. Among these methods, the synthesis of metal colloids using medicinal plant extracts originates nanocrystals having surfaces modified with chemical compounds of biological origin, which can be further explored in association with conventional pharmaceutics. In this context, the development of spectroscopic methods that seeks for understanding the potential benefits of using formulations that contain natural compounds and metal nanoparticles with therapeutic properties is of relevance. This research describes the chemical synthesis of silver colloids via the reduction of Ag(I) in the presence of distinct aqueous plant extracts. The selected extracts were obtained from Moroccan plants that have been used in traditional therapeutic practices over the centuries. The method led to stable colloids comprising polydispersed Ag nanocrystals that show surface-enhanced Raman scattering (SERS) activity. As an illustrative scenario, these colloids have been applied to the SERS detection of the natural β-lactam antibiotic benzylpenicillin, also known as penicillin G (PG). Our results indicate that all the Ag colloids tested with the different plant extracts are SERS-active for PG without showing detrimental interference from chemical adsorbates originated from the extracts. Therefore, this spectroscopic method can be further explored for monitoring nanoformulations of pharmaceuticals and metal colloids obtained using biological synthesis.

Colloidal Synthesis of Multinary Alkali-Metal Chalcogenides Containing Bi and Sb: An Emerging Class of I-V-VI2 Nanocrystals with Tunable Composition and Interesting Properties.

The growth mechanism and synthetic controls for colloidal multinary metal chalcogenide nanocrystals (NCs) involving alkali metals and the pnictogen metals Sb and Bi are unknown. Sb and Bi are prone to form metallic nanocrystals that stay as impurities in the final product. Herein, we synthesize colloidal NaBi1-xSbxSe2-ySy NCs using amine-thiol-Se chemistry. We find that ternary NaBiSe2 NCs initiate with Bi0 nuclei and an amorphous intermediate nanoparticle formation that gradually transforms into NaBiSe2 upon Se addition. Furthermore, we extend our methods to substitute Sb in place of Bi and S in place of Se. Our findings show the initial quasi-cubic morphology transforms into a spherical shape upon increased Sb substitution, and the S incorporation promotes elongation along the <111> direction. We further investigate the thermoelectric transport properties of the Sb-substituted material displaying very low thermal conductivity and n-type transport behavior. Notably, the NaBi0.75Sb0.25Se2 material exhibits an ultralow thermal conductivity of 0.25 W·m-1·K-1 at 596 K with an average thermal conductivity of 0.35 W·m-1·K-1 between 358 and 596 K and a ZTmax of 0.24.

Direct and Indirect Evolution of Photoluminescent SemiconductorCdS Magic-Size Clusters through Their Precursor Compounds.

Colloidal semiconductor II-VI metal chalcogenide (ME) magic-size clusters (MSCs) exhibit either an optical absorption singlet or doublet. In the latter case, a sharp photoluminescence (PL) signal is observed. Whether the PL-inactive MSCs transform to the PL-active ones is unknown. We show that PL-inactive CdS MSC-322 transforms to PL-active CdS MSC-328 and MSC-373 in the presence of acetic acid (HOAc). MSC-322 displays a sharp absorption at ~322 nm, whereas MSC-328 and MSC-373 both have broad absorptions respectively around 328 and 373 nm. In a reaction of cadmium myristate and S powder in 1-octadecene, MSC-322 develops; with HOAc, MSC-328 and MSC-373 are present. We propose that the MSCs evolve from their relatively transparent precursor compounds (PCs). The PC-322 to PC-328 quasi-isomerization involves monomer substitution, while monomer addition occurs for the PC-328 to PC-373 transformation. Our findings suggest that S dominates the precursor self-assembly quantitatively, and ligand-bonded Cd mainly controls MSC optical properties.

Transfer of Metals under Hydrothermal Conditions in the Form of Colloidal Particles and Supersaturated True Solutions

Colloids of metals have been studied much more poorly in hydrothermal solutions than in surface and underground waters. Nevertheless, literature data indicate that colloidal particles containing metals are present in hydrothermal minerals, in geogas, in groundwaters above orebodies, in fluid inclusions of minerals, and in geothermal solutions. These particles are usually thought to be formed at nucleation in supersaturated solution, which is generated in conversion reactions of minerals or when fluids boil. Published experimental data confirm that colloidal particles can be formed and preserved in hydrothermal conditions. Experimental data on the filtration of supersaturated and colloidal solutions in porous media at elevated temperatures are still too scarce to enable a comprehensive and reasonably accurate assessment of the mobility of colloidal particles under these conditions. The involvement of colloids in the hydrothermal ore-forming process is most clearly manifested at formation of rich epithermal Au deposits. The example of a quartz geothermometer is employed to demonstrate that metals can be transferred in true supersaturated solution, and this mechanism may be even more efficient than colloidal transfer. Metals can thus be transferred in the hydrothermal process in significantly higher concentrations than it follows from the traditional approach based on equilibrium thermodynamics.

The Evolution from Superatom- to Plasmon-Mediated Magnetic Circular Dichroism in Colloidal Metal Nanoparticles Spanning the Nonmetallic to Metallic Limits.

The magneto-optical absorption properties of colloidal metal nanoclusters spanning nonmetallic to metallic regimes were examined using variable-temperature variable-field magnetic circular dichroism (VTVH-MCD) spectroscopy. Charge neutral Au25(SC8H9)18 exhibited MCD spectra dominated by Faraday C-terms, consistent with expectations for a nonmetallic paramagnetic nanocluster. This response is reconciled by the open-shell superatom configuration of Au25(SC8H9)18. Metallic and plasmon-supporting Au459(pMBA)170 exhibited temperature-independent VTVH-MCD spectra dominated by Faraday A-terms. Au144(SC8H9)60, which is intermediate to the metallic and nonmetallic limits, showed the most complex VTVH-MCD response of the three nanoclusters, consisting of 19 distinguishable peaks spanning the visible and near-infrared (3.0-1.4 eV). Variable-temperature analysis suggested that none of these transitions originated from plasmon excitation. However, evidence for both paramagnetic and mixed (i.e., nondiscrete) transitions of Au144(SC8H9)60 was observed. These results highlight the complexity of gold nanocluster electronic transitions that emerge as sizes approach metallic length scales. Nanoclusters in this regime may provide opportunities for tailoring the magneto-optical properties of colloidal nanostructures.

Systematic literature electrocoagulation for wastewater treatment: Mini-review

Electrocoagulation is a method that can be used to remove pollutants and nutrients from liquid waste. This method has been found for a long time but has exclusively recently been developed for wastewater treatment after a lengthy process. Electrocoagulation can remove colloidal materials, i.e., suspended solids, metals, and other dissolved solids in wastewater. Several studies have shown that electrocoagulation has been successfully operated in various industrial wastewaters, i.e., bakery, chocolate, cork boiling, olive, biodiesel, Etc. This review uses the systematic review scale mini-review method. Literature was collected from various databases using Harzing's Publish or Perris Software and analyzed by Mendeley Software. The results indicate that the electrocoagulation method has received excellent attention for development, i.e., the effectiveness and energy that must be consumed, and that research is evolving to show the best performance of electrocoagulation.

Heading toward Miniature Sensors: Electrical Conductance of Linearly Assembled Gold Nanorods.

Metal nanoparticles are increasingly used as key elements in the fabrication and processing of advanced electronic systems and devices. For future device integration, their charge transport properties are essential. This has been exploited, e.g., in the development of gold-nanoparticle-based conductive inks and chemiresistive sensors. Colloidal wires and metal nanoparticle lines can also be used as interconnection structures to build directional electrical circuits, e.g., for signal transduction. Our scalable bottom-up, template-assisted self-assembly creates gold-nanorod (AuNR) lines that feature comparably small widths, as well as good conductivity. However, the bottom-up approach poses the question about the consistency of charge transport properties between individual lines, as this approach leads to heterogeneities among those lines with regard to AuNR orientation, as well as line defects. Therefore, we test the conductance of the AuNR lines and identify requirements for a reliable performance. We reveal that multiple parallel AuNR lines (>11) are necessary to achieve predictable conductivity properties, defining the level of miniaturization possible in such a setup. With this system, even an active area of only 16 µm2 shows a higher conductance (~10-5 S) than a monolayer of gold nanospheres with dithiolated-conjugated ligands and additionally features the advantage of anisotropic conductance.

Colloidal metal nanocatalysts to advance orange II hydrogenolysis tracked by a microplate reader

The thermal reduction method was applied to synthesize metal nanoparticles using poly(1-vinyl-2-pyrrolidone) as an organic stabilizer to control metal nanoparticle agglomeration. Colloidal metal nanoparticles, gold, palladium, and gold–palladium nanoparticles were synthesized, and UV–visible spectrophotometry and high-resolution transmission electron microscopy analyses were conducted to characterize them. The metal nanoparticle micrographs showed well-dispersed particles with an average size of 9.6 nm (Au), 15.4 nm (Pd), and 10.6 nm (AuPd). All the colloidal metal nanoparticles served as nanocatalysts to advance a reductive degradation of orange II in presence of borohydride ions. For a prompt screening of catalytic activity, the microplate reader system was considered at a fixed maximum absorbance wavelength of λ 489 nm respected by orange II. Excess borohydride ions were used to construct pseudo-first kinetic conditions. The Langmuir–Hinshelwood model allowed the finding of kinetic activity on the surface of metal nanoparticles. AuPd nanocatalyst interface exhibited low activation energy (5.38 kJ mol−1) compared to the one on Au (8.19 kJ mol−1) and Pd (7.23 kJ mol−1).Graphical

Plate-Like Colloidal Metal Nanoparticles.

The pseudo-two-dimensional (2D) morphology of plate-like metal nanoparticles makes them one of the most anisotropic, mechanistically understood, and tunable structures available. Although well-known for their superior plasmonic properties, recent progress in the 2D growth of various other materials has led to an increasingly diverse family of plate-like metal nanoparticles, giving rise to numerous appealing properties and applications. In this review, we summarize recent progress on the solution-phase growth of colloidal plate-like metal nanoparticles, including plasmonic and other metals, with an emphasis on mechanistic insights for different synthetic strategies, the crystallographic habits of different metals, and the use of nanoplates as scaffolds for the synthesis of other derivative structures. We additionally highlight representative self-assembly techniques and provide a brief overview on the attractive properties and unique versatility benefiting from the 2D morphology. Finally, we share our opinions on the existing challenges and future perspectives for plate-like metal nanomaterials.

Theory of Anisotropic Metal Nanostructures

A significant challenge in the development of functional materials is understanding the growth and transformations of anisotropic colloidal metal nanocrystals. Theory and simulations can aid in the development and understanding of anisotropic nanocrystal syntheses. The focus of this review is on how results from first-principles calculations and classical techniques, such as Monte Carlo and molecular dynamics simulations, have been integrated into multiscale theoretical predictions useful in understanding shape-selective nanocrystal syntheses. Also, examples are discussed in which machine learning has been useful in this field. There are many areas at the frontier in condensed matter theory and simulation that are or could be beneficial in this area and these prospects for future progress are discussed.

Rapid and Direct Liquid-Phase Synthesis of Luminescent Metal Halide Superlattices.

The crystallization of nanocrystal building blocks into artificial superlattices has emerged as an efficient approach for tailoring the nanoscale properties and functionalities of novel devices. To date, ordered arrays of colloidal metal halide nanocrystals have mainly been achieved by using post-synthetic strategies. Here, a rapid and direct liquid-phase synthesis is presented to achieve a highly robust crystallization of luminescent metal halide nanocrystals into perfect face-centered-cubic (FCC) superlattices on the micrometer scale. The continuous growth of individual nanocrystals is observed within the superlattice, followed by the disassembly of the superlattices into individually dispersed nanocrystals owing to the highly repulsive interparticle interactions induced by large nanocrystals. Transmission electron microscopy characterization reveals that owing to an increase in solvent entropy, the structure of the superlattices transforms from FCC to hexagonal close-packed (HCP) and the nanocrystals disassemble. The FCC superlattice exhibits a single and slightly redshifted emission, due to the reabsorption-free property of the building block units. Compared to individual nanocrystals, the superlattices have three times higher quantum yield with improved environmental stability, making them ideal for use as ultrabright blue-light emitters. This study is expected to facilitate the creation of metamaterials with ordered nanocrystal structures and their practical applications.