Inhibition of jarosite heterogeneous crystallization on anglesite via in-situ formation of competitive substrate.

Heterogeneous crystallization is a common occurrence during the formation of solid wastes. It leads to the encapsulation of valuable/hazardous metals within the primary phase, presenting significant challenges for waste treatment and metal recovery. Herein, we proposed a novel method involving the in-situ formation of a competitive substrate during the precipitation of jarosite waste, which is an essential process for removing iron in zinc hydrometallurgy. We observed that the in-situ-formed competitive substrate effectively inhibits the heterogeneous crystallization of jarosite on the surface of anglesite, a lead-rich phase present in the jarosite waste. As a result, the iron content on the anglesite surface decreases from 34.8% to 1.65%. The competitive substrate was identified as schwertmannite, characterized by its loose structure and large surface area. Furthermore, we have elucidated a novel mechanism underlying this inhibition of heterogeneous crystallization, which involves the local supersaturation of jarosite caused by the release of ferric and sulfate ions from the competitive substrate. The local supersaturation promotes the preferential heterogeneous crystallization of jarosite on the competitive substrate. Interestingly, during the formation of jarosite, the competitive substrate gradually vanished through a dissolution-recrystallization process following the Ostwald rule, where a metastable phase slowly transitions to a stable phase. This effectively precluded the introduction of impurities and reduced waste volume. The goal of this study is to provide fresh insights into the mechanism of heterogeneous crystallization control, and to offer practical crystallization strategies conducive to metal separation and recovery from solid waste in industries.

Controllable Iodoplumbate-Coordination of Hybrid Lead Iodide Perovskites via Additive Engineering for High-Performance Solar Cells.

The crystallization and growth of perovskite crystals are two crucial factors influencing the performance of perovskite solar cells (PSCs). Moreover, iodoplumbate complexes such as PbI2, PbI3-, and PbI42- in perovskite precursor solution dictate both the quality of perovskite crystals and the optoelectrical performance of PSCs. Here, we propose an iodoplumbate-coordination strategy that employs pentafluorophenylsulfonyl chloride (PTFC) as an additive to tailor the crystal quality. This strategy directly affects the thermodynamics and kinetics of perovskite crystal formation by regulating hydrogen bonds or coordination bonds with Pb2+ or I- ions. Subsequently, the synergistic effect of the PTFC and FA+ complex was beneficial for intermediate-to-perovskite phase transition, improving the crystalline quality and reducing the defect density in the perovskite film to suppress nonradiative recombination loss. Consequently, the treated PSCs achieved a power conversion efficiency (PCE) of 24.61%, demonstrating enhanced long-term stability under both light and thermal stress. The developed device retained 92.53% of its initial PCE after 1200 h of continuous illumination and 88.6% of its initial PCE after 600 h of 85 °C thermal stability tests, respectively, both conducted in N2 atmospheres.

Preparation of debranched starch with high thermal stability and crystallinity using a novel thermal cycling treatment.

Herein, the effects of temperature cycling (4 °C/50 °C/100 °C) on the recrystallization, physicochemical properties, and digestibility of debranched starch (DBS) were investigated. Temperature cycling involved heating DBS to 100 °C to dissociate weak heat-sensitive crystalline structures and cooling to 4 °C to induce the rapid growth of crystal nuclei, followed by maintaining the temperature at 50 °C to promote orderly crystalline growth. This procedure aimed to increase the degree of crystalline structure in recrystallized DBS, thereby resulting in DBS that was heat- and digestion-resistant. Temperature cycling increased the dissociation temperature of DBS, and temperatures of up to 114.8 °C were attained after five cycling times. With increasing cycles, the crystalline structure of DBS transitioned from B-type to the more robust and compact A-type, and the crystallinity increased to ∼81.9 % (after seven cycles). Raman and Fourier transform infrared (FTIR) spectra indicated that temperature cycling enhanced the short-range ordered structure of DBS. Moreover, in vitro digestion experiments demonstrated that the resistant starch content of DBS increased to ∼61.9 % after eight cycles. To summarize, this study demonstrated a green and effective method for preparing heat-and digestion-resistant recrystallized DBS, which can be used for developing dietary supplements and low gastrointestinal staples.

Physicochemical properties of starch of four varieties of native potatoes.

The limited industrial use of indigenous varieties of native potatoes has caused a decrease in its cultivation, restricting it to the self-consumption of the Andean population. The present study analyzed the physicochemical, thermal, and structural properties of the starches extracted from four of these varieties Aq'hu Pukucho, Yurakk Kkachun Wakkachi, Yurac Anca, and Huarmi Mallco, as a potential source of be used in industries such as food, pharmaceutical and, bioplastics. The percentage yield in wet extraction ranged between 14.53 and 20.26 %. The luminosity L* and whiteness index (WI) values were observed in ranges of 90.75-92.71 and 90.05-91.50, respectively. The Finding revealed various techno-functional properties, since the level of amylose varied between 36.29 and 43.97 %, an average zeta potential of -22 mV, and a maximum viscosity between 19,450-14,583 cP. The starches showed consistent thermal behavior since the TGA curves showed three stages with gelatinization temperatures that ranged between 54.9 and 59.75 °C, an enthalpy of 3.60-6.62 J/g, and various shapes of particles such as circular, elliptical, and oval. In conclusion, the relationships between variables such as water absorption index, swelling power, viscosity, crystallinity, enthalpy, and gelatinization temperature reveal different characteristics of each type of starch, which can influence its use.

A crystal engineering approach for rational design of curcumin crystals for Pickering stabilization of emulsions.

Emulsions stabilized via Pickering particles are becoming more and more popular due to their high stability and biocompatibility. Hence, developing new ways to produce effective Pickering particles is essential. In this work, we present a crystal engineering approach to obtain precise control over particle properties such as size, shape, and crystal structure, which may affect wettability and surface chemistry. A highly reproducible synthesis method via anti-solvent crystallization was developed to produce sub-micron sized curcumin crystals of the metastable form III, to be used as Pickering stabilizers. The produced crystals presented a clear hydrophobic nature, which was demonstrated by their preference to stabilize water-in-oil (W/O) emulsions. A comprehensive experimental and computational characterization of curcumin crystals was performed to rationalize their hydrophobic nature. Analytical techniques including Raman spectroscopy, powder X-ray diffraction (PXRD), Solid-State Nuclear Magnetic Resonance (SSNMR), scanning electron microscopy (SEM), Differential Scanning Calorimetry (DSC), confocal fluorescence microscopy and contact angle measurements were used to characterize curcumin particles in terms of shape, size and interfacial activity. The attachment energy model was instead applied to study relevant surface features of curcumin crystals, such as topology and facet-specific surface chemistry. This work contributes to the understanding of the effect of crystal properties on the mechanism of Pickering stabilization, and paves the way for the formulation of innovative products in fields ranging from pharmaceuticals to food science.

Impact of Drug Conjugation Site and Corona Chemistry on the Therapeutic Activity of Polymer Nanorod - Drug Conjugates.

Biocompatible rod-shaped nanoparticles of controlled length can be produced through the heat-induced "living" seeded crystallization-driven self-assembly (CDSA) of poly(2-isopropyl-2-oxazoline)-containing block copolymers. With a hydrophilic poly(2-methyl-2-oxazine) or poly(2-methyl-2-oxazoline) corona, these nanorods have proven non-cytotoxic, non-hemolytic, and ideal for use as a polymer-based drug delivery system. This study demonstrates a facile, one-pot method for the synthesis of mycophenolic acid (MPA)-conjugated block copolymer "unimers" for use in seeded CDSA. Through altering block order during sequential monomer addition cationic ring-opening polymerization (CROP), MPA is conjugated to either the chain end of the core-forming or corona-forming block. This allows bioactive polymer nanorods to be prepared with MPA positioned at either the periphery of the corona, or at the core-corona interface of the nanorod formed during seeded CDSA. In vitro, these nanorods arrest growth in human T and B lymphocytes, with reduced effect in "off-target" monocytes when compared with unconjugated MPA. Furthermore, the conjugation of MPA to the core-corona interface of the nanorods leads to a slower release and reduced cytostatic effect. This study offers a robust investigation into the effect of steric hindrance and corona chemistry on the therapeutic potential of drug-conjugated CDSA nanorods and demonstrates the potential of poly(2-oxazoline)/poly(2-oxazine)-based CDSA nanomaterials as effective drug delivery platforms.

Efficient and Stable Red Perovskite Light-Emitting Diodes via Thermodynamic Crystallization Control.

Efficient and stable red perovskite light-emitting diodes (PeLEDs) demonstrate promising potential in high-definition displays and biomedical applications. Although significant progress has been made in device performance, meeting commercial demands remains a challenge in the aspects of long-term stability and high external quantum efficiency (EQE). Here, an in situ crystallization regulation strategy is developed for optimizing red perovskite films through ingenious vapor design. Mixed vapor containing dimethyl sulfoxide and carbon disulfide (CS2) is incorporated to conventional annealing, which contributes to thermodynamics dominated perovskite crystallization for well-aligned cascade phase arrangement. Additionally, the perovskite surface defect density is minimized by the CS2 molecule adsorption. Consequently, the target perovskite films exhibit smooth exciton energy transfer, reduced defect density, and blocked ion migration pathways. Leveraging these advantages, spectrally stable red PeLEDs are obtained featuring emission at 668, 656, and 648 nm, which yield record peak EQEs of 30.08%, 32.14%, and 29.04%, along with prolonged half-lifetimes of 47.7, 60.0, and 43.7 h at the initial luminances of 140, 250, and 270 cd m-2, respectively. This work provides a universal strategy for optimizing perovskite crystallization and represents a significant stride toward the commercialization of red PeLEDs.

Robust Imidazole-Linked Covalent Organic Framework Enabling Crystallization Regulation and Bulk Defect Passivation for Highly Efficient and Stable Perovskite Solar Cells.

The low crystallinity of the perovskite layers and many defects at grain boundaries within the bulk phase and at interfaces are considered huge barriers to the attainment of high performance and stability in perovskite solar cells (PSCs). Herein, a robust photoelectric imidazole-linked porphyrin-based covalent organic framework (PyPor-COF) is introduced to precisely control the perovskite crystallization process and effectively passivate defects at grain boundaries through a sequential deposition method. The 1D porous channels, abundant active sites, and high crystallization orientation of PyPor-COF offer advantages for regulating the crystallization of PbI2 and eliminating defects. Moreover, the intrinsic electronic characteristics of PyPor-COF endow a more closely matched energy level arrangement within the perovskite layer, which promotes charge transport and thereby suppresses the recombination of photogenerated carriers. The champion PSCs containing PyPor-COF achieved power conversion efficiencies of 24.10% (0.09 cm2) and 20.81% (1.0 cm2), respectively. The unpackaged optimized device is able to maintain its initial efficiency of 80.39% even after being exposed to air for 2000 h. The device also exhibits excellent heating stability and light stability. This work gives a new impetus to the development of highly efficient and stable PSCs via employing COFs.

Use of Differential ScanninTableg Calorimetry as a Rapid, Effective In-process Check Method for Impurity Quantitation of an Early Clinical Batch of Giredestrant (GDC-9545).

Giredestrant (GDC-9545) is a selective estrogen receptor degrader (SERD) that was developed for treatment of ER+/HER2- metastatic breast cancer. An anhydrous crystalline tartrate salt was identified as the solid form suitable for clinical development. An early clinical batch of the active pharmaceutical ingredient (API)/drug substance failed to pass the GMP purity specifications owing to the presence of a substantial amount of high molecular weight impurities (oligomers), as determined by size exclusion chromatography. Several trial rework batches were manufactured using various re-slurry and recrystallization conditions to purge impurities in the drug substance to adhere to purity specifications. Based on the melting point depression of the API in presence of oligomers in these rework batches, a differential scanning calorimetry method was developed to quantify impurity content as a function of melting point onset of the API. This thermal analysis method was used as a surrogate for chromatography as a rapid, effective in-process check method for impurity quantitation to enable the timely release of the final reworked clinical batch. Post release, the % w/w oligomer value determined by calorimetry was in excellent agreement to that obtained by size exclusion chromatography.

Preparation of tenofovir amibufenamide fumarate spherical particles to improve tableting performance and sticking propensity by designing a spherical crystallization process.

Tenofovir amibufenamide fumarate (TMF) is the first oral drug developed in Asia for the treatment of adult patients with chronic viral hepatitis B, however, further applications are limited by poor tableting performance and high sticking propensity. In this work, the spherulitic growth process of TMF has been designed and explored with the help of molecular dynamics simulation and process analysis technologies (ATR-FTIR, FBRM and EasyViewer). The spherical particles with high bulk density, good flowability and uniform particle size distribution are prepared by a simple quenching process. More importantly, experimental results show that spherical particles have higher average tensile strength (100.8% increase), higher plastic deformability and lower amount of punch sticking (87.4% decrease in 30 tablets) compared to the commercial powder products. These contributions not only shed light on the design principle of drug spherulitic growth processes, but also provide guidance for the manufacture of high-quality tablet products.

Structural analysis of the TPI-Manchester, a thermolabile variant of human triosephosphate isomerase.

Human triosephosphate isomerase G122R, also known as TPI-Manchester, is a thermolabile variant detected in a screening of more than 3400 individuals from a population in Ann Arbor, Michigan. Here, the crystallographic structure of G122R was solved to determine the molecular basis of its thermal stability. Structural analysis revealed an increase in the flexibility of residues at the dimer interface, even though R122 is about 20 Å away, suggesting that long-range electrostatic interactions may play a key role in the mutation effect.

The direct inhibitory effects of Lactobacillus acidophilus, a commensal urinary bacterium, on calcium oxalate stone development.

BACKGROUND: Lactobacillus acidophilus is a commensal urinary bacterium found more abundantly in healthy individuals than in stone patients. Hence, it has been proposed to play an inhibitory role in kidney stone disease (KSD) but with unclear mechanisms. We therefore investigated the direct effects of L. acidophilus on calcium oxalate (CaOx) stone development compared with Escherichia coli, which is known to promote CaOx stone formation. RESULTS: L. acidophilus at 1 × 103 CFU/ml  significantly reduced the abundance of newly formed crystals, enlargement and aggregation of seeded crystals, and crystal adhesion on renal cell membranes. By contrast, E. coli at 1 × 103 CFU/ml significantly enhanced crystal growth and aggregation but did not affect crystallization and crystal-cell adhesion. Oxalate consumption assay showed that neither L. acidophilus nor E. coli significantly reduced the remaining oxalate level after 1 - 3 h incubation. However, both of them adhered to CaOx crystals. Surface component detection revealed that only L. acidophilus expressed S-layer protein, whereas only E. coli exhibited flagella on their surfaces. Removal of L. acidophilus S-layer protein and E. coli flagella completely abolished the inhibitory and promoting effects of L. acidophilus and E. coli, respectively. CONCLUSIONS: L. acidophilus inhibits CaOx stone development by hampering crystallization, growth, aggregation and cell-adhesive ability of CaOx. By contrast, E. coli enhances CaOx stone development by promoting CaOx growth and aggregation. Their contradictory effects are most likely from differential surface components (i.e., S-layer protein on L. acidophilus and flagella on E. coli) not from oxalate-degrading ability. Video Abstract.

Basic Theory of Ice Crystallization Based on Water Molecular Structure and Ice Structure.

Freezing storage is the most common method of food preservation and the formation of ice crystals during freezing has an important impact on food quality. The water molecular structure, mechanism of ice crystal formation, and ice crystal structure are elaborated in the present review. Meanwhile the methods of ice crystal characterization are outlined. It is concluded that the distribution of the water molecule cluster structure during the crystallization process directly affects the formed ice crystals' structure, but the intrinsic relationship needs to be further investigated. The morphology and distribution of ice crystals can be observed by experimental methods while simulation methods provide the possibility to study the molecular structure changes in water and ice crystals. It is hoped that this review will provide more information about ice crystallization and promote the control of ice crystals in frozen foods.

Comparison of two crystal polymorphs of NowGFP reveals a new conformational state trapped by crystal packing.

Crystal polymorphism serves as a strategy to study the conformational flexibility of proteins. However, the relationship between protein crystal packing and protein conformation often remains elusive. In this study, two distinct crystal forms of a green fluorescent protein variant, NowGFP, are compared: a previously identified monoclinic form (space group C2) and a newly discovered orthorhombic form (space group P212121). Comparative analysis reveals that both crystal forms exhibit nearly identical linear assemblies of NowGFP molecules interconnected through similar crystal contacts. However, a notable difference lies in the stacking of these assemblies: parallel in the monoclinic form and perpendicular in the orthorhombic form. This distinct mode of stacking leads to different crystal contacts and induces structural alteration in one of the two molecules within the asymmetric unit of the orthorhombic crystal form. This new conformational state captured by orthorhombic crystal packing exhibits two unique features: a conformational shift of the ß-barrel scaffold and a restriction of pH-dependent shifts of the key residue Lys61, which is crucial for the pH-dependent spectral shift of this protein. These findings demonstrate a clear connection between crystal packing and alternative conformational states of proteins, providing insights into how structural variations influence the function of fluorescent proteins.

The Role of Metal Nanoparticles in the Pathogenesis of Stone Formation.

The process of stone formation in the human body remains incompletely understood, which requires clinical and laboratory studies and the formulation of a new endogenous, nanotechnological concept of the mechanism of origin and formation of crystallization centers. Previously, the mechanism of sialolithiasis was considered a congenital disease associated with the pathology of the ducts in the structure of the glands themselves. To date, such morphological changes of congenital nature can be considered from the position of the intrauterine formation of endogenous bacterial infections complicated by the migration of antigenic structures initiating the formation of crystallization centers. The present work is devoted to the study of the morphology and composition of stones obtained as a result of surgical interventions for sialolithiasis. Presumably, nanoparticles of metals and other chemical compounds can be structural components of crystallization centers or incorporated into the conditions of chronic endogenous inflammation and the composition of antigenic structures, in complexes with protein and bacterial components. X-ray microtomography, X-ray fluorescence analysis, scanning transmission electron microscopy and microanalysis, mass spectrometry, and Raman spectroscopy were used to study the pathogenesis of stone formation. Immunoglobulins (Igs) of classes A and G, as well as nanoparticles of metals Pb, Fe, Cr, and Mo, were found in the internal structure of the stones. The complex of antigenic structures was an ovoid calcified layered matrix of polyvid microbial biofilms, with the inclusion of metal nanoparticles and chemical elements, as well as immunoglobulins. The obtained results of clinical and laboratory studies allow us to broaden the view on the pathogenesis of stone formation and suggest that the occurrence of the calcification of antigenic structures may be associated with the formation of IgG4-associated disease.

Effects of Carbon Fiber Content on the Crystallization and Rheological Properties of Carbon Fiber-Reinforced Polyamide 6.

Carbon fiber (CF)-reinforced polyamide 6 (PA6) composites have an excellent performance, attributed to properties such as light quality, high strength, and vibration reduction, and they are widely used in fields such as aerospace and transportation. Four kinds of carbon fiber-reinforced polyamide 6 (CF/PA6) composite pellets with carbon fiber contents of 20, 30, 40, and 50 wt.% were prepared using twin screw extrusion. The results were characterized using a simultaneous thermal analyzer, capillary rheometer, electronic universal material testing machine, and scanning electron microscope (SEM); their crystallization, rheological behavior, mechanical properties, surface structure, etc., were studied. DSC results indicate that an increase in carbon fiber content enhances the thermal stability of CF/PA6 and narrows the crystallization window but has a minor effect on the molecular chain diffusion time. The crystallinity reaches its maximum at a carbon fiber content of 40 wt.%, reaching 55.16%. The steady-state rheological behavior reveals that CF/PA6 behaves as a pseudoplastic fluid, exhibiting shear-thinning behavior. When the carbon fiber content is 40 wt.%, the power law exponent (n) reaches its maximum, and the consistency coefficient (K) decreases by 300 Pa⋅sn compared to the 30 wt.% content. With increasing temperature, n increases while K decreases. SEM observations reveal that samples with carbon fiber contents of 20 wt.% and 40 wt.% exhibit better fiber dispersion and orientation. However, the interfacial bonding strength is superior in the 40 wt.% sample. When the carbon fiber content reaches 50 wt.%, significant injection molding defects occur at the clamping end, leading to extensive matrix tearing during tension testing.

A Comparative Study on the Melt Crystallization of Biodegradable Poly(butylene succinate-co-terephthalate) and Poly(butylene adipate-co-terephthalate) Copolyesters.

As an important biodegradable and partially biobased copolyester, poly(butylene succinate-co-terephthalate) (PBST) possesses comparable thermal and mechanical properties and superior gas barrier performance when compared with poly(butylene adipate-co-terephthalate) (PBAT), but it was found to display poorer melt processability during pelletizing and injection molding. To make clear its melt crystallization behavior under rapid cooling, PBST48 and PBST44 were synthesized, and their melt crystallization was investigated comparatively with PBAT48. PBST48 showed a PBAT48-comparable melt crystallization performance at a cooling rate of 10 °C/min or at isothermal conditions, but it showed a melt crystallization ability at a cooling rate of 40 °C/min which was clearly poorer. PBST44, which has the same mass composition as PBAT48, completely lost its melt crystallization ability under the rapid cooling. The weaker chain mobility of PBST, resulting from its shorter succinate moiety, is responsible for its inferior melt crystallization ability and processability. In comparison with PBAT48, PBST48 displayed higher tensile modulus, and both PBST48 and PBST44 showed higher light transmittance. The findings in this study deepen the understanding of PBST's properties and will be of guiding significance for improving PBST's processability and application development.

Improvement of Hydrogen-Resistant Gas Turbine Engine Blades: Single-Crystal Superalloy Manufacturing Technology.

This paper presents the results of an analysis of resistance to hydrogen embrittlement and offers solutions and technologies for manufacturing castings of components for critical applications, such as blades for gas turbine engines (GTEs). The values of the technological parameters for directional crystallization (DC) are determined, allowing the production of castings with a regular dendritic structure of the crystallization front in the range of 10 to 12 mm/min and a temperature gradient at the crystallization front in the range of 165-175 °C/cm. The technological process of making GTE blades has been improved by using a scheme for obtaining disposable models of complex profile castings with the use of 3D printing for the manufacture of ceramic molds. The ceramic mold is obtained through an environmentally friendly technology using water-based binders. Short-term tensile testing of the samples in gaseous hydrogen revealed high hydrogen resistance of the CM-88 alloy produced by directed crystallization technology: the relative elongation in hydrogen at a pressure of 30 MPa increased from 2% for the commercial alloy to 8% for the experimental single-crystal alloy.

Application and development of ultrasound in industrial crystallization.

Crystallization is an important process that affects the properties of final products and is essential in nearly all chemical processing industries. In recent years, ultrasonic technology has received widespread attention due to its ability to enhance crystallization yield, improve crystal morphology and shape, and regulate the particle size and distribution of crystal products. It holds promising prospects for industrial crystallization. In this work, the ultrasonic cavitation effect and ultrasonic crystallization mechanism are described, and the influence of ultrasound on the crystallization effect of products is analysed and discussed. In addition, the application status of ultrasonic reactors and ultrasonic crystallization processes is introduced in detail, and the change trend from laboratory to industrialization is analyzed. Finally, the challenges and opportunities facing the industrialization of ultrasonic crystallization in future developments are discussed. The purpose of this work is to make the selective promotion or inhibition of ultrasound more helpful for industrial crystallization.