The impact of the crystalline or amorphous structure of a solid on the solubility and pharmacokinetic properties of a drug candidate is always considered by the pharmaceutical industry during the development of a new drug, however, it is not so frequently considered during the early discovery process by organic and medicinal chemists, particularly working at the academia. We want to share, as an example case, the false negative obtained in the biological testing of a solid sample of a tyrosine kinase inhibitor due to an unexpected crystallinity with respect to a solid amorphous batch of the same compound and the experimentation carried out to establish the origin of such inconsistency.

: The stability of semiconductor catalysts is a very important property in the field of catalytic reactions. Materials necessitate resistance to mechanical abrasion and chemical erosion for better overall performance. In this work, high crystallinity BiOCl nanosheets were prepared by a simple hydrothermal method. The photocatalysts demonstrate full UV light absorption ability and excellent photocatalytic norfloxacin degradation performance. 84 % of highly toxic norfloxacin were photocatalytically eliminated within 180 min. The internal structure and surface chemical state of BiOCl were analyzed by SEM, TEM, Raman, FTIR, UV-vis, XPS, and other techniques. Such high crystallinity makes BiOCl molecules closely arranged and the molecular chains strongly connected, thus exhibiting a high level of photocatalytic stability and recyclability.

Bulk metallic glass matrix composites have emerged as competent structural material of future bearing potential structural applications. However, the optimum percentage of crystallinity required to produce enough toughness that it can serve as structural component is still a matter of debate. In this study, an effort is made to address this problem by inoculation. A controlled amount of carefully selected inoculant is introduced in Zr_47.5Cu_45.5Al₅Co₂ bulk metallic glass matrix composite during melting and solidification. Its effect in promoting crystallinity is checked by detailed electron back scatter diffraction (EBSD) mapping. Proper pattern capture, background correction, binning, Hough space transformation, step size selection, indexing and matching with well-defined crystal structure files have shown to reflect upon map quality. This shows and bears direct relation with effect of inoculation. Results from two independent laboratories are reported. Inoculation treatment is shown to be advantageous.

Polyethylene terephthalate (PET) is nowadays one of the most used polymers for packaging applications. Modifications induced by service conditions and the optimal mean to recycle this matter several times have to be perfectly understood to allow a reuse for similar application (from bottle to bottle for example). The present study aims to compare physico-chemical properties, crystalline organization, and mechanical behaviour of virgin (vPET) and recycled PET (rPET). Using different combined experimental methods (Calorimetry, Small Angle X-ray Scattering, Atomic Force Microscopy, DMA, and uni-axial tensile test), it has been proven that even if there is no change in the crystallinity of PET, the crystallisation process shows some differences (size and number of spherulites). The potential impact of these differences on local mechanical characterization, at the lamella scale, is explored and tends to demonstrate the development of homogeneous microstructure, leading to well-controlled and relevant local mechanical properties. This approach increases the understanding of crystallisation of PET and recycled PET during forming processes such as thermoforming or injection stretch blow moulding (ISBM) where elongation at break can depend on the microstructure conditioned by the crystallisation process.

The effect of Mg particles on PLA's thermal, chemical, physical, and mechanical properties has been studied. The thermal and physical properties have been studied by differential scanning calorimetry, analysing the stability of the α and α’-crystals of the PLA. A colloidal route was used to introduce Mg particles inside the PLA matrix, ensuring a good dispersion of the particles. Materials with Mg contents from 0 to 10 wt.% have been prepared, with additions of polyethyleneimine (PEI) and polyethylene glycol (PEG). Fourier Transform Infrared Spectroscopy has been used to confirm the influence of Mg, PEI, and PEG on PLA properties. The mechanical properties have been measured with a universal tensile test machine on printed filaments via Fused Filament Fabrication (FFF), which were naturally aged to stable conditions. Filaments with and without a notch were studied to obtain the materials' tensile strength, elastic modulus, and fracture toughness. Different analytical models to explain the results of the PLA-Mg were studied, in which the interface strength of the PLA-Mg composites was calculated.

Two-phase olive pomace is a byproduct of the olive-oil extraction process that is sometimes processed further to recover more oil. During pomace oil production, especially in the early stages of olive processing, odours can be produced. These odours are a serious nuisance especially in and around the processing facilities, as well as for nearby communities. These odours can be strong and unpleasant, and they may result in various issues, including environmental concerns. Thus, in this paper, the effect of storage and drying on the composition of two-phase olive pomace was investigated. Several physicochemical and instrumental analyses were performed and it was concluded that the structural elements of pomace are not the ones who are affected during storage and drying. Storage and drying mainly impact the oil content of pomace, leading to an acidity increase and to the production of odorous oxidation compounds. Volatile acids, methyl and ethyl esters are released into the atmosphere causing serious environmental nuisance.

The global development of bioeconomy is impossible without technologies for comprehensive processing of plant renewable resources. The use of proven pretreatment technologies raises the possibility of industrial implementation of enzymatic conversion of polysaccharides from lignocellulose considering the process complexity. For instance, a well-tuned kraft pulping produces a substrate easily degraded by cellulases and hemicelulases. Enzymatic hydrolysis of bleached hardwood kraft pulp was carried out using an enzyme complex of endoglucanases, cellobiohydrolases, b-glucosidases and xylanases produced by recombinant strains of Penicillium verruculosum at a 10 FPU/g mixture rate and a 10 % substrate concentration. As a result of biocatalysis the following products are obtained: sugar solution, mainly glucose, xylobiose, xylose, as well as other minor reducing sugars; modified complex based on cellulose and xylan. The composition of biomodified kraft pulp was determined involving the use of HPLC. The method for determining the degree of crystallinity on an X-ray diffractometer was used to characterize the properties. The article shows the possibility of producing modified cellulose cryogels by amorphization with concentrated 85 % H3PO4 followed by precipitation with water and supercritical drying. Analysis of the enzymatic hydrolysate composition reveals the predominance of glucose (55...67 %) in reducing sugars with a maximum content of up to 6 % in the solution after 72 hours. The properties and structure of modified kraft pulp were shown to change during biocatalysis, in particular, the degree of crystallinity increased by 5 % after 3 hours of enzymatic hydrolysis. We obtained cryogels based on the initial and biomodified kraft pulp with conversion rates of 35, 50 and 70 %. The properties of these cryogels are not inferior to those based on industrial microcrystalline cellulose, as confirmed by the specific surface area, degree of swelling, porosity and SEM images. Thus, kraft pulp enzymatic hydrolysis offers prospects not only for producing sugar-rich hydrolysates for microbiological synthesis, but also for producing cellulose powders and cryogels with specified properties.

In order to study the crystallinity of different density polyethylenes, the experimental study on the transformation of the conductance mechanism under high electric field was carried out. The X-ray Diffraction(XRD), Different Scanning Calorimeter(DSC), Direct Current(DC) breakdown of Low-density polyethylene(LDPE), Linear low density polyethylene(LLDPE), Medium density polyethylene(MDPE) and High-density polyethylene(HDPE) and the electric field of 5-200kV/mm were tested. Conductivity characteristics experiments, in addition, using the mathematical formula of a variety of conductance mechanisms, the electric field-current density curves of the four kinds of polyethylene were fitted to analyze the conductance transition of the above four kinds of polyethylene in non-ohmic regions under different high field strengths. mechanism. The experimental results show that as the density of polyethylene increases, the crystallinity increases continuously, and the continuous increase of crystallinity causes the electric conduction flow under the same field strength to decrease significantly. The field strength corresponding to the two turning points in the conductance characteristic curve increases simultaneously. Large, the breakdown field strength increases; through analysis, it is found that in the high field, as the electric field increases, the conductance mechanism develops from the ohmic conductance of the low field strength region to the bulk effect of the high field strength region (Poole-Frenkel). Then the electrode effect to the high field strength (Schottky), and the threshold field strength of this conductance mechanism transition increases with the increase of crystallinity.

Ionic liquids have been recognised as interesting solvents applicable in the efficient lignocellulosic biomass valorisation, especially in the biomass fractionation into individual polymeric components or direct hydrolysis some of biomass fractions. Considering the chemical character of ionic liquids, two different approaches, paved the way for a fractionation of biomass. The first strategy integrated a pre-treatment, hydrolysis and conversion of biomass through the employment of hydrogen-bond acidic 1-ethyl-3-methyimidazolim hydrogen sulfate ionic liquid. The second one relied on the use of a three-step fractionation process with hydrogen-bond basic 1-ethyl-3-methylimidazolium acetate to produce high purity cellulose, hemicellulose and lignin fractions. The proposed approaches were scrutinised for wheat straw and eucalyptus residues. Those different biomasses allowed understanding that enzymatic hydrolysis yields are dependent on the crystallinity of pre-treated biomass. The use of acetate based ionic liquid allowed to change crystalline cellulose I to cellulose II and consequently enhanced glucan to glucose yield to 93.14.1 mol% and 82.91.2 mol% for wheat straw and eucalyptus, respectively. Whereas for hydrogen sulfate ionic liquid, the same enzymatic hydrolysis yields were 61.6  0.2 mol% for wheat straw and only 7.90.3 mol% for eucalyptus residues. These results demonstrate the importance of either ionic liquid character or biomass type on the efficient biomass processing.

Microplastics (MPs) and nanoplastics (NPs) are distributed and transferred among the four major environmental compartments (air, water, soil, and biota) and have been already found in humans, making crucial to develop remediation technologies to tackle this kind pollution. Photocatalysis can be used to eliminate MPs present in contaminated wastewater effluents before their discharge into waterbodies. In this work, several green TiO2-based semiconductors were prepared using the extrapallial fluid (EPF) of Mytilus edulis sea water mussels as doping precursor. The semiconductors were then used as films or powders to photocatalytically degrade polystyrene (PS) NPs and MPs and polyethylene (PE) MPs. It was found that the obtention of green TiO2-based semiconductors with good characteristics for photocatalytic purposes (anatase crystalline phase, presence of porosity, activity in visible light and high surface area) seems not enough to achieve high degradation efficiency. The operational conditions of the reaction system should be also taken into account. For instance, the convenience of using semiconductors in the form of films can be overcome by their limited exposed surface area or the null adsorption of the semiconductor in the MPs particles. Additionally, crystallinity of the semiconductor can be a more determinant factor to take into account when performing photocatalysis of MPs.

Recent advances and demands in clinical applications drive a large amount of research to hydroxyapatite (HA) composite coatings fabricated by plasma spray. However, lower degree of HA crystallinity related to high temperature exposure in plasma spray usually leads to rapid weakening and disintegration of HA coatings and often promotes inflammatory responses in the surrounding tissue. In this research, graphene nanosheet (GNS) reinforced HA coatings were fabricated using plasma spray and followed by heat and hydrothermal treatment (hereafter referred to as thermal treatment). The addition of GNSs resulted in competing phenomenon to influence HA crystallinity viz. increased portion of the partially melted/unmelted zones and higher cooling rate during splat formation, leading to slight increase in HA crystallinity (~46.0-51.3%) in the as-sprayed coating. XRD and FTIR results showed that thermal treatment was capable of inducing significant transformation of amorphous HA to the crystalline form and removing other foreign non-HA compounds through regaining OH- ion, and therefore HA coatings displayed ~45.5-47.1% improvements in HA crystallinity regardless of addition or not of the GNS nanofillers. Microstructure observations revealed that thermal treatment enabled microcrack propagation due to stresses caused by crystallisation and phase transformations, and the residual partially melted/unmelted zone of the thermally treated GNS/HA coating was significantly decreased in size. More importantly, the added GNSs contributed greatly to the significant increase in surface nanoroughness of the thermally treated HA coatings owing to the fact that much more structural defects along with the GNSs mainly induced by thermal treatment might act as nucleation sites to accelerate HA nanoparticle precipitation, which would be beneficial for the improved adhesion strength of the osteoblast cells on the coating surface.

As a widely used plastic, the aging and degradation of polyethylene (PE) are inevitable problems, whether the goal is to prolong the life of PE products or address the issue of white pollution. Molecular simulation is a vital scientific tool in elucidating the mechanisms and processes of chemical reactions. To obtain the distribution and evolution process of PE's thermal oxidation products, this work employs the self-consistent charge density functional tight binding (SCC-DFTB) method to perform molecular simulations of the thermal oxidation of PE with different crystallinity and branched structures. We discovered that crystallinity does not affect the thermal oxidation mechanism of PE, but higher crystallinity makes PE more susceptible to cross-linking and carbon chain growth, reducing the degree of PE carbon chain breakage. The branched structure of PE results in differences in pore size between the carbon chains, with larger pores leading to a concentrated distribution of O2 and free radicals subsequently formed. The breakdown of PE is slowed down when free radicals are localized in low-density regions of the carbon chain. The specifics and mechanism of PE's thermal oxidation are clearly revealed in this paper, which is essential for understanding the process in-depth and for the development of anti-aging PE products.

Polyamide 11 (PA11) is a plant-based nylon made from castor beans. Powder bed fusion laser sintering (PBF-LS) is an additive manufacturing process used for PA11 which allows the reuse of the unsintered powder. The unsintered powder is mixed with virgin powders at different refresh rates which has been studied extensively for most semi-crystalline polyamides. However, there is lack of information on the effect of using 100% reused PA11 powder and the number of times it is reused on its own during powder bed fusion laser sintering. This paper investigates the effect of reusing PA11 powder in PBF-LS and number of times it is reused on the dimensional accuracy, density, thermal and tensile properties. From 100% virgin powder to 3rd use of the powder, there is a decrease in powder wastage, decrease in crystallinity and tensile strength. These was associated with the polymerisation and cross-linking process of polymer chains, upon exposure to high temperature. This results in a higher molecular weight and hence density. From the 4th use to 10th reuse, the opposite was observed which was associated to an increase in high-viscosity and un-molten particles which resulted in defects in the PBF-LS parts.

To determine the metamorphic ages of the accretionary complexes in the Northern Chichibu Belt in SW Japan, K–Ar dating was conducted using weakly metamorphosed sedimentary rocks collected from the Kanto Mountains, Central Japan. Whole-rock ages were obtained for chert and red shale samples, and the mineral ages of fine-grained illite with the grain size less than 4 μm were obtained for chert, red shale, mudstone, acidic tuff, and basic tuff. The K–Ar ages of chert and red shale presented large variations, with systematically older ages compared to those of mudstone and tuff in the same strata. The influence of submarine hydrothermal activities on chert and red shale before subduction is a possible cause of this deviation. The illite samples, which were fractionated into four grain-size classes using a suspension method, yielded older ages and higher illite crystallinity (i.e., smaller values of Kübler’s crystallinity index) for larger grain-size classes. The peak metamorphic ages were determined from the K–Ar ages of the 3–4 μm class illite in mudstone and tuff. The Late Jurassic to the Earliest Cretaceous accretionary complex of the lowest structural unit (Kashiwagi Unit) was dated within a small range between 117–110 Ma, which is distinctly older than the K–Ar ages of white mica reported from the Sanbagawa Belt. The peak metamorphic age of acidic tuff (113 Ma) at the type locality of the Mikabu Greenstones indicates that the subducted Mikabu seamount is a constituent of the Kashiwagi Unit. The peak metamorphic ages of the Manba and Kamiyoshida Units were obtained as 132–107 Ma and 163–144 Ma, respectively. Major structural discontinuity is suggested within the Middle Jurassic accretionary complexes.

Films prepared from poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymers produced by Aneurinibacillus sp. H1 using an automatic film applicator were homogeneous and had a defined thickness, which allowed a detailed study of physicochemical properties. Their properties were compared with a poly (3-hydroxybutyrate) homopolymer film prepared by the same procedure, which proved to be significantly more crystalline by DSC and XRD. Structural differences between samples had a major impact on their properties. With increasing 4-hydroxybutyrate content, the ductility and release rate of the model hydrophilic active ingredient increased significantly. Other observed properties, such as the release of the hydrophobic active substance, the contact angle with water and ethylene glycol, or the surface morphology and roughness, were also affected by the composition. The identified properties predetermine these copolymers for wide use in areas such as biomedicine or smart biodegradable packaging for food or cosmetics. The big advantage is the possibility of fine-tuning properties simply by changing the fermentation conditions.

Free volume is an extremely important intrinsic defect in polymers. Structurally, the free volume is the randomly distributed holes in the polymer molecular chain segments. From the perspective of molecular movement, it is also the space needed for the movement of molecular segments. In proton exchange membrane fuel cells, the free volume is also the space needed for the directional conduction of protons. Irradiation grafting sulfonated polyvinylidene fluoride (PVDF) is one of the methods to produce proton exchange membrane with good proton channel rate. Using the LYS-1 program, based on the linear absorption coefficient and backscatter coefficient models, the percentage of annihilated positrons in PVDF in the two-layer model and the three-layer model was studied, and comparing the two fitting results it is determined that the model closest to the positron annihilation percentage required by the PALS experiment is the two-layer model, which allows the percentage of positrons that are annihilated in PVDF films with a thickness of 100 μm to reach 46% using the high energy positron source ⁴⁴Ti without using the positron moderator. Using positron annihilation lifetime spectrum (PALS) analysis methods, based on Eldrup's classical model of free volume, the influence of absorbed doses of α particles on the free volume and crystallinity of PVDF was investigated, respectively. Based on the two test results the model of cross-linking and degradation of polyvinylidene fluoride irradiated by α particles was determined. Afterwards, X-ray diffraction (XRD) methods was used to study the change of PVDF crystal area before and after irradiation. The XRD results are consistent with the results measured by PALS.

The morphology of virgin reactor powder (RP) of high-density polyethylene HDPE with MW = 160,000 g/mol was investigated with the help of DSC, SEM, SAXS and WAXS methods. The morphological SEM analysis showed, that the main morphological units of RP are macro- and micro-shish kebab structures with significantly different geometric dimensions, as well as individual lamellae of folded chain crystals. Quantitative analysis of an asymmetric SAXS reflection made it possible to reveal the presence of several periodic morphoses in the RP with long periods from 20 nm to 60 nm and to correlate them with the observed powder morphology. According to the DSC crystallinity data, the thickness of the lamellae in each long period was estimated. Their surface energy was calculated in the framework of the Gibbs-Thompson theory. The presence of regular and irregular folds on the surface of the different shish-kebab lamellae is discussed. The percentage of identified morphoses in the RP was calculated. It has been suggested that the specific structure of HDPE RP is due to the peculiarity of polymer crystallization during suspension synthesis in a quasi-stationary regime, in which local overheating and inhomogeneous distribution of shear stresses in a chemical reactor are possible.