Shape change of calcite single crystals to accommodate interfacial curvature: Crystallization in presence of Mg2+ ions and agarose gel-networks

Synthetic calcite single crystals,due to their strong crystal habit,tend to grow into characteristic rhombohedra.In the nature,biogenic calcite crystals form composites together with biomacromolecular materials,spurring investigations of how the growing calcite single crystals change their habit to satisfy the curvature of the organic phase.In this work,we examine calcite crystallization on a flat surface of glass slide and a curved surface of polystyrene(PS)sphere.The crystals exhibit tiny contact area onto the glass substrate that is averagely only 15% of their projected area on the substrate.In sharp contrast,the contact area greatly increase to above 75% of the projected area,once magnesium ions or agarose gel networks are introduced into the crystallization media.Furthermore,the calcite crystals form rough and step-like interfaces with a curved surface.However,the interfaces become smooth and curved as the crystals grow in presence of magnesium ions or agarose gel networks.The discrepancy between the interfacial structures implies kinetic effects of the additives on the crystallization around the surfaces. This work may provide implications for understanding the formation mechanisms of single-crystal composite materials.     

Hydrogels coupled with self-assembled monolayers: an in vitro matrix to study calcite biomineralization

This paper describes the control of the nucleation and growth of calcite crystals by a matrix composed of an agarose hydrogel on top of a carboxylate-terminated self-assembled monolayer (SAM). The design of this matrix is based upon examples from biomineralization in which hydrogels are coupled with functionalized, organic surfaces to control, simultaneously, crystal morphology and orientation. In the synthetic system, calcite crystals nucleate from the (012) plane (the same plane that is observed in solution growth). The aspect ratio (length/width) of the crystals decreases from 2.1 +/- 0.22 in solution to 1.2 +/- 0.04 in a 3 w/v % agarose gel. One possible explanation for the change in morphology is the incorporation of gel fibers inside of the crystals during the growth process. Etching of the gel-grown crystals with deionized water reveals an interpenetrating network of gel fibers and crystalline material. This work begins to provide insight into why organisms use hydrogels to control the growth of crystals.     

The Effect of Additives on the Early Stages of Growth of Calcite Single Crystals

As crystallization processes are often rapid, it can be difficult to monitor their growth mechanisms. In this study, we made use of the fact that crystallization proceeds more slowly in small volumes than in bulk solution to investigate the effects of the soluble additives Mg²⁺ and poly(styrene sulfonate) (PSS) on the early stages of growth of calcite crystals. Using a “Crystal Hotel” microfluidic device to provide well‐defined, nanoliter volumes, we observed that calcite crystals form via an amorphous precursor phase. Surprisingly, the first calcite crystals formed are perfect rhombohedra, and the soluble additives have no influence on the morphology until the crystals reach sizes of 0.1–0.5 μm for Mg²⁺ and 1–2 μm for PSS. The crystals then continue to grow to develop morphologies characteristic of these additives. These results can be rationalized by considering additive binding to kink sites, which is consistent with crystal growth by a classical mechanism.     

Growth of gamma glycine crystal and its characterisation

Single crystal of γ-glycine, an organic nonlinear optical material, has been grown by solvent evaporation technique from a mixture of aqueous solutions of glycine and potassium nitrate, lithium nitrate at room temperature. Gamma glycine crystals have been grown up to the dimension of 20 mm × 15 mm × 12 mm. Powder X-ray diffraction of the grown crystal was recorded and indexed. Single crystal X-ray diffraction studies were carried out and the unit cell parameters were compared with the literature values. The γ-phase of glycine is confirmed by single crystal XRD and FTIR spectral analysis. The crystals were characterised by UV–vis–NIR transmission spectrum in the range 200–1100 nm. The second harmonic generation conversion efficiency of γ-glycine crystal was twice the efficiency of KDP crystal. Thermal characteristics of γ-glycine crystals were determined by thermogravimetric analysis (TGA) and differential thermal analysis, which shows the thermal stability of the grown crystals. Dielectric constant and dielectric loss measurements were carried out at different temperatures and frequencies. The microhardness of the grown crystals has been studied using Vicker's microhardness tester.     

Calcium Carbonate Scale Formation in Pipes: Effect of Flow Rates,Temperature, and Malic Acid as Additives on the Mass and Morphology of the Scale

It is well recognized that calcium carbonates (CaCO₃) is one of the main components of scale that is commonly encountered in chemical and related industries. The calcium carbonate scale often grows extensively on equipment and parts, causing major operational difficulties. This paper presents experiments on calcium carbonate scale formation and control in a piping system where the scale-forming solution flowed in a laminar manner: 30, 40, and 50 mL/min, respectively. Other parameters evaluated were: solution temperature (25, 30 and 40 °C), and concentrations of malic acid (C₄H₆O₅) added as impurities (3.00 and 5.00 ppm). The scale-forming solution was made by mixing equimolar solutions of CaCl2 and Na2CO3, respectively. The scale formation process was monitored by measuring the conductivity of the solution coming out of the piping system. It was found that in all experiments, conductivity decreased abruptly after a certain induction period, during which time the conductivity remained steady. The induction period varied from 17 min to 34 min, which means that the scale starts forming 17 min to 34 min after the mixing of the solution. Higher flow rates resulted in more calcium carbonate scale mass, which indicate that the fluid flow enhances the scale formation. Similarly, increasing the temperature of the solution (25, 30, and 40 °C) resulted in the increase of the scale mass. Overall, higher malic acid concentrations resulted in longer induction time and less scale mass. Depending on the temperature and the malic acid concentration tested, the reduction in scale mass could be ≥ 200%. This drastic reduction in scale mass suggests that malic acid could be an effective anti-scalant for calcium carbonate scale. SEM imaging and its associated EDS analysis confirmed that the scale formed corresponds to that of calcite (CaCO3). The X-ray diffraction analysis of the scale showed that the scale consisted of crystalline matter which corresponds to the powder diffraction data for calcium carbonate. The addition of malic acid in trace amounts (0.00 to 5.00 ppm) was able to alter the morphology of the scale crystals, indicating the preference adsorption of malic acid on specific crystal surface.     

Green synthesis of plant-stabilized Au nanoparticles for the treatment of gastric carcinoma

In this study, gold nanoparticles (AuNPs) were green synthesized using plant extract. The obtained nanoparticles (Au NPs) were characterized by advanced physical and chemical techniques like TEM, FTIR, UV–vis, SEM, XRD and EDX. SEM image displayed the quasi-spherical shaped nanoparticles of mean diameter 20–50 nm. All the particles were of uniform shape and texture. From the XRD pattern, four distinct diffraction peaks at 38.2°, 44.2°, 64.7° and 77.4° are indexed as (1 1 1), (2 0 0), (2 2 0) and (3 1 1) planes of fcc metallic gold. The in vitro cytotoxic and anti-gastric carcinoma effects of biologically synthesized Au NPs against cancer cell lines were assessed. The IC₅₀ of the Au NPs were 192, 149, 76 and 85 µg/mL against NCI-N87, MKN45, GC1401 and GC1436 gastric cancer cell lines. The anti-gastric carcinoma properties of the Au NPs could significantly remove the cancer cell lines in a time and concentration-dependent manner. So, the findings of the recent research show that biologically synthesized Au NPs might be used to cure cancer.     

One-pot photoreduction to prepare NIR-absorbing plasmonic gold nanoparticles tethered by amphiphilic polypeptide copolymer for synergistic photothermal-chemotherapy

We developed one-pot photoreduction strategy to fabricate the NIR-absorbing plasmonic PLC-b-PEO@Au NPs. It possessed strong NIR absorption at 700-1100 nm, an ultrahigh photothermal conversion efficiency of 62.1%, and good photostability.     

Thermally induced transformations of calcium carbonate polymorphs precipitated selectively in ethanol/water solutions

For the precipitation of calcium carbonate polymorphs in ethanol/water solutions of calcium chloride by the diffusion of the gases produced by sublimation–decomposition of solid ammonium carbonate, polymorph selection and morphology control of the precipitates were demonstrated by the effect of ethanol/water ratio in the mother liquor. The precipitated phases change systematically from gel-like aggregates of hydrated amorphous calcium carbonate in the absolute ethanol solution to well-shaped rhombohedral particles of calcite in the absolute aqueous solution via almost pure phase of vaterite with dendrite structure in 75%-ethanol/25%-aqueous and 50%-ethanol/50%-aqueous solutions. On heating the precipitated sample in flowing dry nitrogen, all the samples transformed to calcite before the thermal decomposition, where the thermal decomposition temperature shifts to higher temperatures with increasing the water content in the mother liquor due to the systematic increase in the particle size of calcite. Accordingly, the present method of controlled precipitation of calcium carbonate polymorphs is also useful to control the particle size and reactivity of calcite produced by heating the precipitates. Selecting vaterite with dendrite structure from the present series of precipitated samples, the structural phase transition to calcite was characterized as the three-dimensional growth of rhombohedral particles of calcite with the enthalpy change ΔH = ? 2.8 ± 0.1 kJ mol^?1 and the apparent activation energy E_a = 289.9 ± 5.8 kJ mol^?1.     

Radiation hydrolysate of tuna cooking juice with enhanced antioxidant properties

Tuna protein hydrolysates are of increasing interest because of their potential application as a source of bioactive peptides. Large amounts of tuna cooking juice with proteins and extracts are produced during the process of tuna canning, and these cooking juice wastes cause environmental problems. Therefore, in this study, cooking juice proteins were hydrolyzed by irradiation for their utilization as functional additives. The degree of hydrolysis of tuna cooking juice protein increased from 0% to 15.1% at the absorbed doses of 50 kGy. To investigate the antioxidant activity of the hydrolysate, it was performed the ferric reducing antioxidant power (FRAP) assay, and the lipid peroxidation inhibitory and superoxide radical scavenging activities were measured. The FRAP values increased from 1470 μM to 1930 μM and IC₅₀ on superoxide anion was decreased from 3.91 μg/mL to 1.29 μg/mL at 50 kGy. All of the antioxidant activities were increased in the hydrolysate, suggesting that radiation hydrolysis, which is a simple process that does not require an additive catalysts or an inactivation step, is a promising method for food and environmental industries.     

High pressure effects on benzoic acid dimers: Vibrational spectroscopy

To understand pressure effects on dimer structure stability, Raman and FTIR spectroscopies were used to examine changes in H-bonded dimers of benzoic acid (BA). Experiments were performed on single crystals compressed to 33 GPa in a diamond anvil cell (DAC). Several changes in Raman spectra were observed in the range 6–8 GPa indicating modification in the dimer structure suggesting the lowering of molecular symmetry. Pressure increase above 15 GPa induced strong luminescence and a gradual change of the crystal color from white to yellow/brownish. FTIR measurements on the sample released from 33 GPa indicated formation of a new compound. It is proposed that molecules of this compound are composed of the hydroxyl group associated with alcohol, carbonyl group associated with ketone, and the sp³ hydrocarbon groups. This study demonstrates that sufficient high pressure compression and subsequent decompression can lead to significant changes in the H-bonded dimer structure, including the breaking of bonds and formation of new chemical compound.     

Impact of Fe3+ on UV absorption of K2Al2B2O7 crystals

K₂Al₂B₂O₇ (KABO) is a new nonlinear optical crystal capable of laser harmonic generation in the UV range. However, abnormal UV absorption prevents its application in effectively generating UV light with wavelength shorter than 300 nm. The transmittance spectra of the grown crystals show distinct absorption bands at 216 nm and 264 nm. It is observed that the UV absorption is strongly correlated with iron impurity at a parts per million (ppm) level. Furthermore, electron paramagnetic resonance (EPR) spectra of the absorbing crystals show a strong signal at g = 2.00 position corresponding to a Fe³⁺ center. A new crystal growth method which reduces the iron content has been proposed and results show that the new KABO crystal is free from the Fe³⁺ UV absorptions.     

Morphology and properties of hollow-fiber membrane made by PAN mixing with small amount of PVDF

In this paper, the morphological structure and properties such as, miscibility, tensile strength, flux and retention ratio of hollow-fiber membranes manufactured by PAN mixing with small amounts of PVDF have been studied. The hollow fiber was made from a spinning solution composed of polymer (PAN : PVDF=10 : 0, 9 : 1, 7 : 3), additive (PVP, PEG-600) and solvent (DMAC) when immersed in water. The spinnability of blend polymer and the influences of blending on spinning technology have been observed; the morphology of membranes were examined by SEM. The blend membranes possess much higher flux than PAN membrane and fairly good retention ratio especially for the membrane made by PAN : PVDF=9 : 1.     

Reactive poly（divinyl benzene-co-maleic anhydride） nanoparticles：Preparation and characterization

Polymeric nanoparticles（NPs）have drawn great interest in the past few years due to their potential applications in the felds of biomedical and optical technologies.However,it is still a challenge to prepare functional polymeric NPs,especially for particle diameters smaller than 50 nm.In this work,we demonstrate a one-pot method to fabricate reactive poly（divinyl benzene-co-maleic anhydride）NPs（PDVBMAH NPs）through a self-stable precipitation polymerization process.The size and morphology of these PDVBMAH NPs were characterized in detail by scanning electronic microscopy,and their chemical structure was determined by IR.The results showed that these NPs were highly cross-linked and their diameter was about 30 nm with narrow distribution.Additionally,the DVB and MAH endow the NPs with reactive surface anhydride and pendant vinyl groups,and these particles could be further functionalized through reaction of these groups.A plausible pathway was proposed for the formation of PDVBMAH NPs.     

Photoelectrochemical determination of inorganic mercury ions based on energy transfer between CdS quantum dots and Au nanoparticles

A novel photoelectrochemical (PEC) sensor for mercury ions (Hg^2 +) was fabricated based on the energy transfer (ET) between CdS quantum dots (QDs) and Au nanoparticles (NPs) with the formation of T–Hg^2 +–T pairs. In the presence of Hg^2 + ions, a T-rich single-strand (ss) DNA labeled with Au NPs could hybridize with another T-rich ssDNA anchored on the CdS QDs modified electrode, through T–Hg^2 +–T interactions, rendering the Au NPs in close proximity with the CdS QDs and hence the photocurrent decrease due to the ET between the CdS QDs and the Au NPs. Under the optimal condition, the photocurrent decrease was proportional to the Hg^2 + concentration, ranging from 3.0 × 10^− 9 to 1.0 × 10^− 7 M, with the detection limit of 6.0 × 10^− 10 M.     

Effect of Additional Poly Vinyledene Fluoride (PVDF) on LiCoO2 Cathodes

LiCoO2 as one of cathodes in lithium ion battery was prepared using ball mill on 800 Hz for 10 h, followed by ultra–sonic process in order to form LiCoO2 nanoparticle. Poly(vinyledene fluoride) PVDF was added into LiCoO2 nanoparticle using dimethylsulfoxide (DMSO) to form LiCoO2/PVDF composite. The addition of PVDF was able to fill the voids on LiCoO2 matrix, therefore the space gap between particles in the matrix could be eliminated. The morphology, crystal structure and composite conductivity of LiCoO2/PVDF were analysed using scanning electron microscope (SEM), X-ray diffraction (XRD) and conductivity meter. The results showed that LiCoO2 with PVDF had bigger conductivity value than LiCoO2 without PVDF.     

One-step synthesis of hollow structured Si/C composites based on expandable microspheres as anodes for lithium ion batteries

Si/C composites of carbon hollow structures loaded with Si nanoparticles (NPs) (Si/C-HSs) were prepared by one-step pyrolysis of a mixture of Si NPs and expandable microspheres (EMs). For the Si/C-HSs, hollow carbon shells with rough surfaces were formed by directly carbonizing the polymer shells of EMs, and the Si NPs fell into the void space or were loaded on the rough surfaces of the carbon shells. The EM-based carbon shells accommodated the volume expansion of the Si NPs and improved the electrical conductivity of the composites. As a result, the Si/C-HSs exhibited a high capacity (initial reversible capacity: 854.4 mAh g^− 1 at 300 mA g^− 1), stable cycling performance (capacity retention: 80% after 50 cycles), and excellent rate capability.     

Spectrofluorimetric determination of fexofenadine hydrochloride in pharmaceutical preparation using silver nanoparticles

A novel sensitive fluorimetric method was investigated for the assay of fexofenadine hydrochloride (FEX) using silver nanoparticles (NPs) as a fluorescence probe. The NPs, which were prepared by chemical reduction of silver nitrate with sodium borohydride (reducing agent) in aqueous solution (without organic stabilizers) were water soluble, stable and had narrow emission band. The addition of drug to NPs solution caused considerable quenching of the emission band of silver NPs, which was likely due to the complexation of the drug to silver NPs. Under the optimum conditions, the quenched fluorescence (FL) intensity was linear with the concentration of FEX in the range of 1 × 10^?7 to 2.5 × 10^?5 mol L^?1 (0.9985) with a detection limit of 1.2 × 10^?8 mol L^?1. The quenching mechanism of the studied drug on the emission band of silver NPs was explained by Stern–Volmer law. The developed method was applied to FEX determination in a pharmaceutical formulation (allegra tablets) and biological fluids (human serum and urine).     

Morphosynthesis of poly(ether ketone) by reaction-induced crystallization during polymerization

Morphology control of poly(ether ketone) (PEK) was examined by using the crystallization during the nucleophilic aromatic substitution reaction of potassium salt of 4-fluoro-4′-hydroxybenzophenone. Polymerizations were carried out at 290 °C. The PEK was obtained as precipitates and its morphology was highly influenced by the polymerization condition such as the solvent, the concentration and the polymerization time. High crystalline spindle-like crystals were obtained by the polymerization in diphenyl sulfone (DPS) at a concentration of 5.0% for 2 h with the yield of 86%. The average length and width were 1.4 μm and 300 nm respectively, and the maximum thickness was 130 nm. The surface was not smooth and it was hilly. The spindle-like crystal was likely consisted of multilayered lamellae comprised of the microcrystallites. The molecules were oriented perpendicular to the lamella. The polymerization in DPS at a higher concentration of 10.0% afforded the networks of nanofibres, of which the diameter was 100–250 nm. The obtained PEK precipitates possessed excellent thermal properties.     

Electrodeposition of PtCo alloy nanoparticles on inclusion complex film of functionalized cyclodextrin–ionic liquid and their application in glucose sensing

Platinum–cobalt (PtCo) alloy nanoparticles (NPs) are successfully fabricated by ultrasonic-electrodeposition method, using an inclusion complex (IC) film of functionalized cyclodextrin (CD)–ionic liquid (IL) as support. The morphology and composition of the PtCo alloy NPs are characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction, respectively. It is found that they are well-dispersed on the CD–IL surface and exhibit many unique features. The resulting modified glassy carbon electrode shows excellent catalytic activity for glucose oxidation. Under the physiological condition, the oxidation current of glucose is linear to its concentration up to 20 mM with sensitivity of 13.7 μA mM^?1 cm^?2. In addition, the interference from the oxidation of ascorbic acid and uric acid could be effectively avoided. Therefore, it is promising as a nonenzymatic glucose sensor.     

Decomposition of p-nonylphenols in water and elimination of their estrogen activities by 60Co γ-ray irradiation

Concentration of p-nonylphenols (NPs) in water at 1 μmol dm⁻³ was decreased exponentially with absorbed dose when NPs were irradiated by ⁶⁰Co γ-rays. Two products having molecular weight of 236, presumably OH adducts of NPs, were detected by LC–MS analyses. The elimination of estrogen activity of aqueous NPs solution including such irradiation products at 5000 Gy (J kg⁻¹) was confirmed by the yeast two-hybrid assay. These results should expand the application of ionizing radiation to the treatment of NPs.