Anhydrous Crystals Research Articles

Electroformation of Giant Unilamellar Vesicles from Damp Films in Conditions Involving High Cholesterol Contents, Charged Lipids, and Saline Solutions.

Giant unilamellar vesicles (GUVs) are frequently used as membrane models in studies of membrane properties. They are most often produced using the electroformation method. However, there are a number of parameters that can influence the success of the procedure. Some of the most common conditions that have been shown to have a negative effect on GUV electroformation are the presence of high cholesterol (Chol) concentrations, the use of mixtures containing charged lipids, and the solutions with an elevated ionic strength. High Chol concentrations are problematic for the traditional electroformation protocol as it involves the formation of a dry lipid film by complete evaporation of the organic solvent from the lipid mixture. During drying, anhydrous Chol crystals form. They are not involved in the formation of the lipid bilayer, resulting in a lower Chol concentration in the vesicle bilayer compared to the original lipid mixture. Motivated primarily by the issue of artifactual Chol demixing, we have modified the electroformation protocol by incorporating the techniques of rapid solvent exchange (RSE), ultrasonication, plasma cleaning, and spin-coating for reproducible production of GUVs from damp lipid films. Aside from decreasing Chol demixing, we have shown that the method can also be used to produce GUVs from lipid mixtures with charged lipids and in ionic solutions used as internal solutions. A high yield of GUVs was obtained for Chol/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) samples with mixing ratios ranging from 0 to 2.5. We also succeeded in preparing GUVs from mixtures containing up to 60 mol% of the charged lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-L-serine (POPS) and in NaCl solutions with low ionic strength (<25 mM).

Effects of structure similar additive on the crystallization of L-phenylalanine from aqueous solution

A comprehensive understanding of the effect of structure similar additives on the nucleation and growth of amino acid in aqueous solution is of great significance for the crystallization of L-phenylalanine and industrial production of anhydrous L-phenylalanine. This paper mainly focuses on the influence of L-tyrosine on the crystallization process of L-phenylalanine by investigating the variation and typical phenomenon in solubility, metastable zone width, crystal nucleation and growth process, and crystal morphology. The results show that the existence of L-tyrosine can obviously increase the solubility and narrow the metastable zone of L-phenylalanine thus promote the nucleation process. Meanwhile, L-tyrosine can also selectively inhibit the formation of monohydrate and improve the purity of industry-favored anhydrous L-phenylalanine in the final product. In order to explore the inhibiting effect of L-tyrosine in crystallization process, the molecular configurations in two different crystallization states were simulated by using Molecular Dynamics.The results show that water and L-phenylalanine molecules tend to form anhydrous crystals when the addition proportion of L-tyrosine increases. The theoretical calculations are in good agreement with the experimental data. The conclusions of this paper will provide new ideas and effective controlling approaches for L-phenylalanine crystals’ morphology and amino acids’ crystallization process.

Synthesis of Chlorophylls-Doped Guanine Crystals with High Reflection and Depolarization for Green Camouflage Coating.

Hyperspectral imaging technology can record the spatial and spectral information of the targets and significantly enhance the levels of military reconnaissance and target detection. It has scientific importance to mimic "homochromatic and homospectral" camouflage materials that have hyperspectral similarity with the green vegetation, one of the most common natural backgrounds. It is a big challenge to exquisitely simulate the spectral of green vegetation in visible and near-infrared windows because of the slight differences between the artificial green dyes and vegetation, the instability of chlorophylls, and the easy loss of hydroxide bands due to the loss of water from the camouflage materials. Herein, a novel kind of biomimetic material of green vegetation was designed through the incorporation of chlorophylls into the crystal lattices of single-crystalline anhydrous guanine microplates for the first time. The synthesized chlorophylls-doped anhydrous guanine crystals exhibit high reflectance intensity and depolarization effect, thus can be applied as biomimetic camouflage materials that mimic green vegetation with high reflectivity and low polarization in the visible and near-infrared regions. The factors influencing the formation of dye-doped organic crystals under mild conditions were thoroughly investigated and the characterizations using electron microscopies and fluorescence confocal laser scanning microscopy clearly confirm the occlusion of chlorophylls into the crystal lattices of guanine crystals. The thermal stability experiments clearly indicate that the chlorophylls-doped guanine crystals possess long-term stability at high temperature. This study provides a new strategy for the synthesis of multifunctional materials comprised of organic crystals.

Efficient Determination of Critical Water Activity and Classification of Hydrate-Anhydrate Stability Relationship

For a pair of hydrated and anhydrous crystals, the hydrate is more stable than the anhydrate when the water activity is above the critical water activity (awc). Conventional methods to determine awc are based on either hydrate-anhydrate competitive slurries at different aw or solubilities measured at different temperatures. However, these methods are typically resource-intensive and time-consuming. Here, we present simple and complementary solution- and solid-based methods and illustrate them using carbamazepine and theophylline. In the solution-based method, awc can be predicted using intrinsic dissolution rate (IDR) ratio or solubility ratio of the hydrate-anhydrate pair measured at a known water activity. In the solid-based method, awc is predicted as a function of temperature from the dehydration temperature and enthalpy obtained by differential scanning calorimetry (DSC) near a water activity of unity. For carbamazepine and theophylline, the methods yielded awc values in good agreement with those from the conventional methods. By incorporating awc as an additional variable, the hydrate-anhydrate relationship is categorized into four classes based on their dehydration temperature (Td) and enthalpy (ΔHd) in analogy with the monotropy/enantiotropy classification for crystal polymorphs. In Class 1 (ΔHd< 0 and Td ≥ 373 K), no awc exists. In Class 2 (ΔHd>0andTd≥373K), awc always exists under conventional crystallization conditions. In Class 3 (ΔHd<0andTd<373K), awc exists when T>Td. In Class 4 (ΔHd>0andTd<373K), awc exists only when T<Td. The hydrate-anhydrate pairs of carbamazepine and theophylline belong to Class 4.

Bio-Inspired Synthesis of Square-Shaped Anhydrous Hypoxanthine Nanoplatelet Crystals with Superior Optical Properties

Bio-Inspired Synthesis of Square-Shaped Anhydrous Hypoxanthine Nanoplatelet Crystals with Superior Optical Properties

Electroformation of Giant Unilamellar Vesicles from Damp Lipid Films with a Focus on Vesicles with High Cholesterol Content.

Giant unilamellar vesicles (GUVs) are membrane models used to study membrane properties. Electroformation is one of the methods used to produce GUVs. During electroformation protocol, dry lipid film is formed. The drying of the lipid film induces the cholesterol (Chol) demixing artifact, in which Chol forms anhydrous crystals which do not participate in the formation of vesicles. This leads to a lower Chol concentration in the vesicle bilayers compared to the Chol concentration in the initial lipid solution. To address this problem, we propose a novel electroformation protocol that includes rapid solvent exchange (RSE), plasma cleaning, and spin-coating methods to produce GUVs. We tested the protocol, focusing on vesicles with a high Chol content using different spin-coating durations and vesicle type deposition. Additionally, we compared the novel protocol using completely dry lipid film. The optimal spin-coating duration for vesicles created from the phosphatidylcholine/Chol mixture was 30 s. Multilamellar vesicles (MLVs), large unilamellar vesicles (LUVs) obtained by the extrusion of MLVs through 100 nm membrane pores and LUVs obtained by extrusion of previously obtained LUVs through 50 nm membrane pores, were deposited on an electrode for 1.5/1 Chol/phosphatidylcholine (POPC) lipid mixture, and the results were compared. Electroformation using all three deposited vesicle types resulted in a high GUV yield, but the deposition of LUVs obtained by the extrusion of MLVs through 100 nm membrane pores provided the most reproducible results. Using the deposition of these LUVs, we produced high yield GUVs for six different Chol concentrations (from 0% to 71.4%). Using a protocol that included dry lipid film GUVs resulted in lower yields and induced the Chol demixing artifact, proving that the lipid film should never be subjected to drying when the Chol content is high.

Formation of compounds with diverse polyelectrolyte morphologies and nonlinear ion conductance in a two-dimensional nanofluidic channel.

Aqueous electrolytes subjected to angstrom-scale confinement have recently attracted increasing interest because of their distinctive structural and transport properties, as well as their promising applicability in bioinspired nanofluidic iontronics and ion batteries. Here, we performed microsecond-scale molecular dynamics simulations, which provided evidence of nonlinear ionic conductance under an external lateral electric field due to the self-assembly of cations and anions with diverse polyelectrolyte morphologies (e.g., extremely large ion clusters) in aqueous solutions within angstrom-scale slits. Specifically, we found that the cations and anions of Li2SO4 and CaSO4 formed chain-like polyelectrolyte structures, whereas those of Na2SO4 and MgSO4 predominantly formed a monolayer of hydrated salt. Additionally, the cations and anions of K2SO4 assembled into a hexagonal anhydrous ionic crystal. These ion-dependent diverse polyelectrolyte morphologies stemmed from the enhanced Coulomb interactions, weakened hydration and steric constraints within the angstrom-scale slits. More importantly, once the monolayer hydrated salt or ionic crystal structure was formed, the field-induced ion current exhibited an intriguing gating effect at a low field strength. This abnormal ion transport was attributed to the concerted movement of cations and anions within the solid polyelectrolytes, leading to the suppression of ion currents. When the electric field exceeded a critical strength, however, the ion current surged rapidly due to the dissolution of many cations and anions within a few nanoseconds in the aqueous solution.

Rectal Bioavailability of Amoxicillin from Hollow-Type Suppositories: Effect of Chemical Form of Amoxicillin.

Rectal drug administration could offer advantages in the delivery of medicines for children by avoiding swallowability issues, improving stability and enabling administration by caregivers. This study aimed to evaluate the rectal bioavailability of hollow-type suppositories (HTS) and understand the effect of two chemical forms of amoxicillin: amoxicillin sodium (AS) or amoxicillin trihydrate (AMT). HTS were prepared by incorporating a lipophilic core containing the antibiotic with a polyethylene glycol (PEG) shell. Formulations were characterised in vitro, and the absolute bioavailability was determined in a rabbit model, while drug-base interactions were evaluated using X-ray diffraction crystallography (XRD), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy. The in vitro amoxicillin release from AMT HTS was delayed, taking 27.3 ± 4.9 h to release 50% drug compared with 1.7 h for the AS HTS, likely due to solubility differences between AMT and AS. The presence of orthorhombic AMT and anhydrous AS crystals in respective HTS was confirmed via XRD and DSC. PEG shells were able to protect the drug chemical stability when stored at 25 °C/60% RH. Despite the difference in their in vitro release rates, a similar rectal bioavailability was found in both forms of amoxicillin (absolute bioavailability 68.2 ± 6.6% vs. 72.8 ± 32.2% for AMT HTS and AS HTS, respectively; p = 0.9682). Both HTS formulations showed little or no irritation to the rectal mucosa following a single dose.

Petrology of the explosive deposits from the April 2021 eruption of La Soufrière volcano, St Vincent: a time-series analysis of microlites

Abstract After more than three months of lava dome extrusion, La Soufrière (St Vincent) transitioned to a series of explosive eruptions in April 2021. Here we present a time-series petrologic analysis of the phenocryst and microlite populations during the first c. 48 h of explosivity to constrain ascent conditions and processes that drove changes in behaviour. Primary eruptive products were crystal-rich (45–50 vol%) basaltic andesites with similar phenocryst phase assemblages and compositions. The change in eruptive style is consistent with overpressurization as a consequence of second boiling from anhydrous microlite crystallization. The microlites display variation between the explosive phases, with two populations: (1) ‘inherited’ − normally zoned high-An plagioclase (&gt;An 70 ) + olivine (Fo 62–79 ) + clinopyroxene + titanomagnetite, inferred to have crystallized at depths &gt;15 km and high water pressures; (2) ‘juvenile’ − unzoned plagioclase (An 45–65 ) + clinopyroxene + orthopyroxene + intermediate pyroxene (Wo 12–38 ) + titanomagnetite, inferred to have crystallized upon ascent due to decompression and degassing. Scoria from the first explosions featured extensive groundmass crystallization and a significant ‘inherited’ microlite population. Later explosions had a more abundant ‘juvenile’ microlite population and lower crystallinity, consistent with more rapid ascent from depth, initiated by decompression following initial blasts and destruction of the lava dome.

Biomimetic Synthesis of Organic Molecular-Doped Fluorescent Guanine Crystals with Pearlescence.

Biomimetic synthesis of guanine crystals has been focused on in the last years. However, multi-functional guanine crystals occluded with fluorescent molecules have not been realized in the laboratory. Here, the controllable synthesis of guanine crystal microplatelets with fluorescence and pearlescence was achieved for the first time by incorporating Nile red (NR) or fluorescein isothiocyanate (FITC) molecules into guanine crystals. The synthesized fluorescent guanine crystals are pure β-phase anhydrous guanine single crystals. Aqueous suspensions with NR- and FITC-doped guanine crystals exhibit distinct pearlescence. The fluorescence intensities of NR and FITC were greatly enhanced after being doped into guanine crystals due to the inhibition of aggregation-caused quenching. Moreover, films composed of fluorescent guanine microplatelets exhibit high diffuse reflection intensity (70 %). This work provides a strategy to synthesize multifunctional materials composed of organic crystals occluded with dyes.

Electroformation of Giant Unilamellar Vesicles from Damp Lipid Films Formed by Vesicle Fusion.

Giant unilamellar vesicles (GUVs) are artificial membrane models which are of special interest to researchers because of their similarity in size to eukaryotic cells. The most commonly used method for GUVs production is electroformation. However, the traditional electroformation protocol involves a step in which the organic solvent is completely evaporated, leaving behind a dry lipid film. This leads to artifactual demixing of cholesterol (Chol) in the form of anhydrous crystals. These crystals do not participate in the formation of the lipid bilayer, resulting in a decrease of Chol concentration in the bilayer compared to the initial lipid solution. We propose a novel electroformation protocol which addresses this issue by combining the rapid solvent exchange, plasma cleaning and spin-coating techniques to produce GUVs from damp lipid films in a fast and reproducible manner. We have tested the protocol efficiency using 1/1 phosphatidylcholine/Chol and 1/1/1 phosphatidylcholine/sphingomyelin/Chol lipid mixtures and managed to produce a GUV population of an average diameter around 40 µm, with many GUVs being larger than 100 µm. Additionally, compared to protocols that include the dry film step, the sizes and quality of vesicles determined from fluorescence microscopy images were similar or better, confirming the benefits of our protocol in that regard as well.

Viscosity of crystal-free silicate melts from the active submarine volcanic chain of Mayotte

Following an unprecedented seismic activity that started in May 2018, a new volcanic edifice, now called Fani Maoré, was constructed on the ocean floor 50 km east of the island of Mayotte (Indian Ocean). This volcano is the latest addition to a volcanic chain characterized by an alkaline basanite-to-phonolite magmatic differentiation trend. Here, we performed viscosity measurements on five silicate melts representative of the East-Mayotte Volcanic Chain compositional trend: two basanites from Fani Maoré, one tephriphonolite and two phonolites from different parts of the volcanic chain. A concentric cylinder viscometer was employed at super-liquidus conditions between 1500 K and 1855 K and a creep apparatus was used for measuring the viscosity of the undercooled melts close to the glass transition temperature in the air. At super-liquidus temperatures, basanites have the lowest viscosity (0.11–0.34 to 0.99–1.16 log10 Pa⸱s), phonolites the highest (1.75–1.91 to 3.10–3.89 log10 Pa⸱s), while the viscosity of the tephriphonolite falls in between (0.89–1.97 log10 Pa⸱s). Near the glass transition, viscosity measurements were performed for one phonolite melt because obtaining pure glass samples for the basanite and tephriphonolite compositions was unsuccessful. This is due to the formation of nanolites upon quench as evidenced by Raman spectroscopy. The phonolite viscosity ranges from of 10.19 log10 Pa⸱s at 1058 K to 12.30 log10 Pa⸱s at 986 K. Comparison with existing empirical models reveals an underestimation of 1.2 to 2.0 log units at super-liquidus and undercooled temperatures, respectively, for the phonolite. This emphasizes (i) the lack of data falling along the alkaline basanite-to-phonolite magmatic differentiation trend to calibrate empirical models, and (ii) the complexity of modeling viscosity variations as a function of temperature and chemical composition for alkaline compositions. The new measurements indicate that, at eruptive temperatures between 1050 °C and 1150 °C (1323–1423 K), the oxidized, anhydrous, crystal-free and bubble-free basanite melt have a viscosity around 2.6 log10 Pa⸱s. In contrast, the anhydrous phonolite crystal- and bubble-free melt would have a viscosity around 6–10 log10 Pa⸱s at expected eruptive temperatures, from 800 to 1000 °C (1073–1273 K). Considering that both basanite and phonolite lavas from the Mayotte submarine volcanic chain contain <6% crystals and a significant amount of water (1-2.3 wt% and 0.8-1.2 wt%, respectively), such viscosity values are probably upper limits. The new viscosity measurements are essential to define eruptive models and to better understand the storage and transport dynamics of Comoros Archipelago magmas, and of alkaline magmas in general, from the source to the surface.

C-H▪▪▪S Hydrogen Bonds in Ampicillin and Amoxicillin Crystals Investigated by Sulfur K-Edge X-Ray Absorption Near-Edge Structure Spectroscopy and Single-Crystal X-Ray Structure Analysis.

Sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy was evaluated for its ability to detect non-conventional C-H▪▪▪S hydrogen bonds in crystals of the sulfur-containing penam antibiotics ampicillin and amoxicillin. The XANES spectra of the nearly isomorphous crystals of ampicillin trihydrate and amoxicillin trihydrate were very similar, whereas that of ampicillin anhydrate displayed unique features. Single-crystal X-ray structure analyses revealed that the C-H▪▪▪S hydrogen bond geometries and the chemical types of the hydrogen donors differed between the isomorphous trihydrate crystals and ampicillin anhydrate crystal. These observations demonstrate that the shapes of the sulfur K-edge XANES spectra are dependent on the nature of the C-H▪▪▪S hydrogen bonds. Sulfur K-edge XANES spectroscopy shows promise for use in the detection and analysis of non-covalent interactions, including hydrogen bonds to sulfur atoms, within active pharmaceutical ingredients.

Short-Chain Mono-Alkyl β-D-Glucoside Crystals-Do They Form a Cubic Crystal Structure?

Three-dimensional liquid crystal (LC) phases, cubic LC phases, have been extensively studied as fascinating molecular assembled systems formed by amphiphilic compounds. However, similar structures have only been seen in rare instances in lipid crystal states in glycolipid crystal studies. In this study, we prepared short-chain n-alkyl β-D-glucosides (CnG) with an alkyl chain length n ranging from 4 to 6 and investigated their crystal structures. First, differential thermal analysis (DTA) and thermogravimetric analysis (TG) measurements showed the formation of hydrated crystals for C4G and C5G, respectively. Second, the crystal structures of CnG (n = 4, 5, 6) in both anhydrous and hydrated states were examined using a temperature-controlled powder X-ray diffraction (PXRD) measurement. Both hydrate and anhydrous crystals of C4G and C5G with critical packing parameters (CPPs) less than 0.33 formed cubic crystal phases. Bilayer lengths, calculated from the main diffraction peaks in each PXRD profile, depended on crystalline moisture for C5G, but no significant change was confirmed for C4G, indicating that the properties of each hydrophilic layer differ. However, C6G with a CPP of 0.42 formed a crystal structure with a modulated lamellar structure similar to C7G and C8G with similar CPP values. Thus, a glycolipid motif concept with a cubic crystal structure was demonstrated.

Zircon Reveals Diverse Trends of Magma Crystallization from Two Types of Early Post-Collisional Diorites (Variscan Orogen, NE Bohemian Massif)

Abstract Amphibole- and clinopyroxene-bearing monzodiorites were emplaced at 340 Ma (CA-ID-TIMS zircon age), suggesting the formation of hydrous and dry magmas closely related in space and time in the NE Bohemian Massif. Hafnium and oxygen isotopes of zircon in less evolved rocks (&amp;lt;55 wt% SiO2) are similar between Amp and Cpx monzodiorites (εHf = −3.3 ± 0.5 and − 3.5 ± 0.8; δ18O = 6.4 ± 1.0 and 6.8 ± 0.7, respectively), consistent with a common source—a contaminated mafic magma derived from an enriched mantle. At the same time, the conditions of crystallization are distinct and zircon appears to be an excellent tool for distinguishing between hydrous and anhydrous crystallization conditions, a process that may be more ambiguously recorded by whole rock and major mineral chemistry. In particular, elements fractionated by either amphibole or plagioclase crystallization, such as Hf, Dy, and Eu, differ in zircon from amphibole- and clinopyroxene-bearing rocks, and Zr/Hf, Yb/Dy, and Eu/Dy are therefore useful indices of crystallization conditions. We show that the composition of zircon from hydrous dioritic magmas is not comparable with that of typical zircon from dioritic-granitic suites worldwide, suggesting a specific process involved in their formation. Here, we propose that fluid-present remelting of a mafic underplate is necessary to explain the rock textures as well as the composition of the whole rock, zircon, and other minerals of amphibole-bearing monzodiorites and that a similar process may control the formation of amphibole-rich dioritic rocks worldwide, including appinitic suites. Overall, we show that dioritic rocks represent snapshots of differentiation processes that occur in the early stages of magma evolution before the magma is homogenized into large-scale batholiths.

Polarizable force fields for accurate molecular simulations of aqueous solutions of electrolytes, crystalline salts, and solubility: Li+, Na+, K+, Rb+, F−, Cl−, Br−, I−

We develop and study polarizable microscopic models, force fields, for molecular simulations of alkali-halide electrolyte aqueous solutions, their crystals, and phase equilibria. We start from the AH/BK3 force fields of Kiss and Baranyai (P. T. Kiss and A. A. Baranyai, J. Chem. Phys. 2014, 141, 114501), which we refine using an approach for determining ion-ion interaction parameters, directly targeting experimental values of the lattice energy, pressure at a given density, and bulk and shear moduli of anhydrous electrolyte crystals. We apply the approach to 16 alkali-halide salts crystallizing in the face-centered cubic rock salt structure. As a result, we obtain force fields which predict rather accurately properties of crystals including their chemical potentials, properties of aqueous solutions including their static permittivity, and aqueous solubility. The force fields can thus find applications in molecular simulations of alkali-halide aqueous electrolytes, their interfaces, phase equilibria, metastable states, and other cases where less accurate models may exhibit various undesirable features such as excessive ion pairing, spurious precipitation, or incorrect low mobility.

Optical absorption measurements and optoelectronic DFT calculations for ethanol solvated quercetin and anhydrous/hydrated quercetin crystals

UV–vis optical absorption measurements of the ethanol solvated quercetin molecule and the dihydrate triclinic quercetin crystal were performed, as well as the electronic structure of the ethanol solvated quercetin molecule and the properties of anhydrous and mono(di)hydrated quercetin crystals employing Density Functional Theory (DFT) calculations with a dispersion correction scheme. Unit cell geometry optimization of the anhydrous crystal has elucidated the structure of the anhydrous quercetin crystal (space group P21/a, monoclinic). Anhydrous quercetin exhibits a direct bandgap of 2.17 ​eV with large valence band dispersion, suggesting a semiconductor behavior for hole transport. Monohydrate quercetin has an indirect gap of 1.84 ​eV, while the solid dihydrate form has a Kohn-Sham indirect electronic bandgap of 2.00 ​eV, smaller than the experimental optical absorption bandgap of 2.40 ​eV. Applying the Δ-sol gap correction scheme, the bandgaps increase by about 1 ​eV. There is a significant optical anisotropy for all quercetin systems in the solid state, especially for the anhydrous form.

Anhydrous calcium phosphate crystals stabilize DNA for dry storage.

The resilience of ancient DNA (aDNA) in bone gives rise to the preservation of synthetic DNA with bioinorganic materials such as calcium phosphate (CaP). Accelerated aging experiments at elevated temperature and humidity displayed a positive effect of co-precipitated, crystalline dicalcium phosphate on the stability of synthetic DNA in contrast to amorphous CaP. Quantitative PXRD in combination with SEM and EDX measurements revealed distinct CaP phase transformations of calcium phosphate dihydrate (brushite) to anhydrous dicalcium phosphate (monetite) influencing DNA stability.

Anhydrous fat crystallization of ultrasonic treated goat milk: DSC and NMR relaxation studies

Methods of NMR relaxation and differential scanning calorimetry (DSC) were used to study the crystallization of anhydrous milk fat (AMF) obtained from milk and subjected to ultrasonic (US) processing. Amongst the changes in the crystallization nature under the influence of ultrasound are the decrease in the crystallization temperature and the increase in the melting enthalpy of the anhydrous milk fat samples. The increase is ∼30% at 20 min of isothermal crystallization and is presumably explained by the additional formation of β'-form crystals from the melt. The parameters of the Avrami equation applied to the description of experimental data show an increase in the crystallization rate in samples with ultrasonic treatment and a change in the dimension of crystallization with a change in melting temperature.

Morphology control of laser-induced dandelion-like crystals of sodium acetate through the addition of acidic polymers

Crystal growth speeds, crystal sizes and the morphology of sodium acetate (CH3COONa) crystals in the presence of polymaleic acid and polyacrylic acid with different concentrations were investigated in supersaturated solutions of sodium acetate. The technique of non-photochemical laser-induced nucleation (NPLIN) was used to produce initial crystallites of anhydrous CH3COONa. The anhydrous CH3COONa crystal growth in solution after laser irradiation resembled the formation of dandelion seed heads. Even though NPLIN could offer temporal–spatial control of crystal nucleation without the addition of acidic polymers, the crystal growth rates were heterogeneous for crystallites along the laser pathway, which led to irregular crystalline sizes and morphologies. Here, a controllable approach from crystal nucleation to crystal growth has been designed through the addition of acidic polymers in the laser-induced growth of anhydrous CH3COONa crystals. In the presence of an acidic polymer, both the crystal growth and the morphological modification were controlled from tuft-shaped crystals to dandelion-like crystals. As bulk solid thicknesses and crystal growth speeds can be modified by different mass fractions of acidic polymer, a mathematical model was established to analyse the dynamics of crystal growth under the effect of acidic polymers. The model reproduces remarkably well the experimental trend and predicts experimental results. The changes in supersaturation and the number of nuclei through the addition of acidic polymers were analysed to investigate the underlying mechanism of morphological difference.