Survey on chemical,physical, and thermal prediction behaviors for sequential chemical treatments used to obtain cellulose from Imperata Brasiliensis

Journal of Thermal Analysis and Calorimetry - The effects of chemical treatment sequences on the chemical, physical, and mainly the thermal properties of Imperata Brasiliensis grass in the process...     

Hofmeister effects on the colloidal stability of poly(ethylene glycol)-decorated nanoparticles

The colloidal stability of poly(ethylene glycol)-decorated poly(methyl methacrylate), PMMA/Tween-20, particles was investigated by means of phase separation measurements, in the presence of sodium fluoride (NaF), sodium chloride, sodium bromide, sodium nitrate, or sodium thiocyanate (NaSCN) at 1.0?mol?L^?1. Following Hofmeister's series, the dispersions of PMMA/Tween-20 destabilized faster in the presence of NaF than with NaSCN. After the phase separation, the systems were homogenized and except for the dispersions in NaF, re-dispersed particles took longer to destabilize, indicating that anions adsorbed on the particles, creating a new surface. Except for F^? ions, the adsorption of anions on the polar outmost shell was evidenced by means of tensiometry and small-angle X-ray scattering measurements. Fluoride ions induced the dehydration of the polar shell, without affecting the polar shell electron density, and the formation of very large aggregates. A model was proposed to explain the colloidal behavior in the presence of Hofmeister ions.     

Synthesis,Mechanism Elucidation and Biological Insights of Tellurium(IV)-Containing Heterocycles

Inspired by the synthetic and biological potential of organotellurium substances, a series of five- and six-membered ring organotelluranes containing a Te−O bond were synthesized and characterized. Theoretical calculations elucidated the mechanism for the oxidation-cyclization processes involved in the formation of the heterocycles, consistent with chlorine transfer to hydroxy telluride, followed by a cyclization step with simultaneous formation of the new Te−O bond and deprotonation of the OH group. Moreover, theoretical calculations also indicated anti-diastereoisomers to be major products for two chirality center–containing compounds. Antileishmanial assays against Leishmania amazonensis promastigotes disclosed 1,2λ⁴-oxatellurane LQ50 (IC₅₀=4.1±1.0; SI=12), 1,2λ⁴-oxatellurolane LQ04 (IC₅₀=7.0±1.3; SI=7) and 1,2λ⁴-benzoxatellurole LQ56 (IC₅₀=5.7±0.3; SI=6) as more powerful and more selective compounds than the reference, being up to four times more active. A stability study supported by ¹²⁵Te NMR analyses showed that these heterocycles do not suffer structural modifications in aqueous-organic media or at temperatures up to 65 °C.     

Cannabidiol Discovery and Synthesis—a Target-Oriented Analysis in Drug Production Processes

The current state of evidence and recommendations for cannabidiol (CBD) and its health effects change the legal landscape and aim to destigmatize its phytotherapeutic research. Recently, some countries have included CBD as an antiepileptic product for compassionate use in children with refractory epilepsy. The growing demand for CBD has led to the need for high-purity cannabinoids on the emerging market. The discovery and development of approaches toward CBD synthesis have arisen from the successful extraction of Cannabis plants for cannabinoid fermentation in brewer's yeast. To understand different contributions to the design and enhancement of the synthesis of CBD and its key intermediates, a detailed analysis of the history behind cannabinoid compounds and their optimization is provided herein.     

Interplay of colloidal stability of cellulose nanocrystals and their dispersibility in cellulose acetate butyrate matrix

Cellulose nanocrystals (CNC) prepared from eucalyptus cellulose CNCs were modified by the reaction with methyl adipoyl chloride, CNCm, or with a mixture of acetic and sulfuric acid, CNCa. The CNC were either dispersed at 0.1 wt% in the pure solvents ethyl acetate (EA), tetrahydrofuran (THF) and dimethylformamide (DMF) or in cellulose acetate butyrate (CAB) solutions prepared in these solvents at 0.9 wt%. The colloidal behavior of these dispersions was systematically investigated using a phase separation analyzer LUMiReader^®. The mechanical properties and morphological features of the films resulting from the mixtures of CAB and CNC were determined by dynamic mechanical analysis, optical microscopy and atomic force microscopy, respectively. Regardless the functional group attached to the surface of CNC, the best colloidal stability was observed for dispersions prepared in CAB/DMF solution. Higher degree of substitution of modified CNCs favored the colloidal stability in EA and THF. Composite films prepared from CAB/DMF solutions were more homogeneous and presented better mechanical performance than those prepared in CAB/EA or CAB/THF. The mechanical performance of composites and neat CAB prepared from DMF was CAB/CNCs > CAB/CNCm > CAB/CNCa > CAB, indicating that the modification weakens the percolation process, which is mediated by H bonding.     

Determination of polycyclic aromatic hydrocarbons in fractions in asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization

An analytical method using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization for the determination of polycyclic aromatic hydrocarbons in asphalt fractions has been developed. The 14 compounds determined, characterized by having two or more condensed aromatic rings, are expected to be present in asphalt and are considered carcinogenic and mutagenic. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all of the compounds. The limits of detection ranged from 0.5 to 346.5 μg/L and the limits of quantification ranged from 1.7 to 1550 μg/L. The method was validated against a diesel particulate extract standard reference material (NIST SRM 1975), and the obtained concentrations agreed with the certified values. The method was applied to asphalt samples after its fractionation according to ASTM D4124 and the method of Green. The concentrations of the seven polycyclic aromatic hydrocarbons quantified in the sample ranged from 0.86 mg/kg for benzo[ghi]perylene to 98.32 mg/kg for fluorene.     

Self-assembling of phenothiazine compounds investigated by small-angle X-ray scattering and electron paramagnetic resonance spectroscopy

Small-angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) have been carried out to investigate the structure of the self-aggregates of two phenothiazine drugs, chlorpromazine (CPZ) and trifluoperazine (TFP), in aqueous solution. In the SAXS studies, drug solutions of 20 and 60 mM, at pH 4.0 and 7.0, were investigated and the best data fittings were achieved assuming several different particle form factors with a homogeneous electron density distribution in respect to the water environment. Because of the limitation of scattering intensity in the q range above 0.15 A(-1), precise determination of the aggregate shape was not possible and all of the tested models for ellipsoids, cylinders, or parallelepipeds fitted the experimental data equally well. The SAXS data allows inferring, however, that CPZ molecules might self-assemble in a basis set of an orthorhombic cell, remaining as nanocrystallites in solution. Such nanocrystals are composed of a small number of unit cells (up to 10, in c-direction), with CPZ aggregation numbers of 60-80. EPR spectra of 5- and 16-doxyl stearic acids bound to the aggregates were analyzed through simulation, and the dynamic and magnetic parameters were obtained. The phenothiazine concentration in EPR experiments was in the range of 5-60 mM. Critical aggregation concentration of TFP is lower than that for CPZ, consistent with a higher hydrophobicity of TFP. At acidic pH 4.0 a significant residual motion of the nitroxide relative to the aggregate is observed, and the EPR spectra and corresponding parameters are similar to those reported for aqueous surfactant micelles. However, at pH 6.5 a significant motional restriction is observed, and the nitroxide rotational correlation times correlate very well with those estimated for the whole aggregated particle from SAXS data. This implies that the aggregate is densely packed at this pH and that the nitroxide is tightly bound to it producing a strongly immobilized EPR spectrum. Besides that, at pH 6.5 the differences in motional restriction observed between 5- and 16-DSA are small, which is different from that observed for aqueous surfactant micelles.     

The two-echelon production-routing problem

This paper introduces the Two-Echelon Production-Routing Problem. This problem is motivated from the petrochemical industry, enlarging the supply chain integration by taking into account production, inventory, and routing decisions in a two-echelon vendor-managed inventory system. We describe, model, and design a branch-and-cut (B&C) to solve the problem under different inventory policies. We also propose a novel exact algorithm, by employing parallel computing techniques, in order to combine local search procedures within a traditional B&C scheme. We evaluate the performance of our methods through extensive computational experiments, both by comparing the algorithms, the effectiveness of the different inventory policies, and the impact of these policies on the partial costs. We derive many managerial insights based on the results. We also validate our new exact algorithm by solving similar problems from the literature, such as the two-echelon multi-depot inventory-routing (2E-MDIRP) and the classical multi-vehicle production-routing problem (MV-PRP). Computational experiments show that our method is very competitive. Based on 512 experiments for the 2E-MDIRP, our algorithm was able to find 111 new best known solutions (BKS), besides proving 412 optimal solutions, against 298 from the literature. For 336 experiments over small and medium size MV-PRP instances, we proved 242 optimal solutions, 11 more than the exact methods from the literature, besides providing 95 new BKS. Moreover, we were the first to tackle large MV-PRP instances exactly, and in this case, our algorithm provides all BKS for instances up to 50 customers, 20 periods and 5 vehicles, outperforming all meta/matheuristics procedures from the literature.