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The application of process analysis and control is essential to enhance process understanding and ensure output material quality. The present study focuses on the stability of the feedback control system for a fluidized bed granulation process. Two strategies of dynamic moisture control (DMC) and static moisture control (SMC) were established based on the in-line moisture value obtained from the near-infrared sensor and control algorithm. The performance of these strategies on quality consistency control was examined using process moisture similarity analysis and principal component analysis. The stable moisture control performance and low batch-to-batch variability indicated that the DMC method was significantly better than other granulation methods. In addition, the investigation of robustness further showed that the implemented DMC method was able to produce predetermined target moisture values by varying process parameters. This study provides an advanced and simple control method for fluidized bed granulation quality assurance.
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The spontaneous zwitterionic copolymerization (SZWIP) of 2-oxazolines and acrylic acid affords biocompatible but low molecular weight linear N-acylated poly(amino ester)s (NPAEs). Here, we present a facile one-step approach to prepare functional higher molar mass cross-linked NPAEs using 2,2'-bis(2-oxazoline)s (BOx). In the absence of solvent, insoluble free-standing gels were formed from BOx with different length n-alkyl bridging units, which when butylene-bridged BOx was used possessed an inherent green fluorescence, a behavior not previously observed for 2-oxazoline-based polymeric materials. We propose that this surprising polymerization-induced emission can be classified as nontraditional intrinsic luminescence. Solution phase and oil-in-oil emulsion approaches were investigated as means to prepare solution processable fluorescent NPAEs, with both resulting in water dispersible network polymers. The emulsion-derived system was investigated further, revealing pH-responsive intensity of emission and excellent photostability. Residual vinyl groups were shown to be available for modifications without affecting the intrinsic fluorescence. Finally, these systems were shown to be cytocompatible and to function as fluorescent bioimaging agents for in vitro imaging.
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Amidas , Ésteres , Fluorescência , Polimerização , PolímerosRESUMO
CsPbI3 perovskite nanocrystals are a promising optoelectronic material when stabilized in their cubic phase. While ongoing efforts have addressed this structural challenge through a variety of meta-stabilization approaches, the postsynthesis purification of these nanocrystal dispersions has remained a challenge. In this article, we undertake a detailed investigation into the chemical, optical, and structural changes that arise during purification of CsPbI3 nanocrystals. It is found that nanocrystal degradation can only be avoided through the judicious control of additives within each purification cycle. Under optimized additive-to-nanocrystal ratios, multiple purification cycles can be readily achieved, while retaining the quality and phase stability of the CsPbI3. This facile purification protocol ensures the preparation of high purity and high quality CsPbI3 nanocrystal inks that are suitable for better characterization or integration in optoelectronic devices. The approach has been generalized for CsPbX3 (X = Cl-, Br-, and I-).
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Monitoring the particle size distribution (PSD) is crucial for controlling product quality during fluidized bed granulation. This paper proposed a rapid analytical method that quantifies the D10, D50, and D90 values using a Convolutional Block Attention Module-Convolutional Neural Network (CBAM-CNN) framework tailored for deep learning with near-infrared (NIR) spectroscopy. This innovative framework, which fuses CBAM with CNN, excels at extracting intricate features while prioritizing crucial ones, thereby facilitating the creation of a robust multi-output regression model. To expand the training dataset, we incorporated the C-Mixup algorithm, ensuring that the deep learning model was trained comprehensively. Additionally, the Bayesian optimization algorithm was introduced to optimize the hyperparameters, improving the prediction performance of the deep learning model. Compared with the commonly used Partial Least Squares (PLS), Support Vector Machine (SVM), and Artificial Neural Network (ANN) models, the CBAM-CNN model yielded higher prediction accuracy. Furthermore, the CBAM-CNN model avoided spectral preprocessing, preserved the spectral information to the maximum extent, and returned multiple predicted values at one time without degrading the prediction accuracy. Therefore, the CBAM-CNN model showed better prediction performance and modeling convenience for analyzing PSD values in fluidized bed granulation.
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Química Farmacêutica , Espectroscopia de Luz Próxima ao Infravermelho , Química Farmacêutica/métodos , Espectroscopia de Luz Próxima ao Infravermelho/métodos , Tamanho da Partícula , Teorema de Bayes , Redes Neurais de ComputaçãoRESUMO
The preparation of diclofenac sodium spheres by fluidized bed is a common production mode for the pharmaceutical preparations at present, but the critical material attributes in the production process is mostly analyzed off-line, which is time-consuming and laborious, and the analysis results lag behind. In this paper, the real-time in-line prediction of drug loading of diclofenac sodium and the release rate during the coating process was realized by using near infrared spectroscopy. For the best near infrared spectroscopy (NIRS) model of drug loading, R2cv, R2p, RMSECV, RMSEP were 0.9874, 0.9973, 0.002549 mg/g, 0.001515 mg/g respectively. For the best NIRS model of three release time points, the R2cv, R2p, RMSECV and RMSEP were 0.9755, 0.9823, 3.233%, 4.500%; 0.9358, 0.9965, 2.598%, 0.7939% and 0.9867, 0.9927, 0.4085%, 0.4726% respectively. And the analytical ability of these model was verified. The organic combination of these two parts of work constituted an important basis for ensuring the safety and effectiveness of diclofenac sodium spheres from the perspective of production process.
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Diclofenaco , Espectroscopia de Luz Próxima ao Infravermelho , Espectroscopia de Luz Próxima ao Infravermelho/métodos , Diclofenaco/química , Análise dos Mínimos QuadradosRESUMO
Near-infrared spectroscopy (NIRS) is an excellent process analytical technology (PAT) tool for active pharmaceutical ingredient (API) quantification during fluidized granulation. Therefore, a portable near-infrared spectrometer combined with a new innovative method of extended iterative optimization technique (EIOT) was used to in-line monitor the API content uniformity during fluidized bed granulation. The principal component analysis (PCA) and partial least squares regression (PLSR) were also used to characterize and predict API concentration with changes from 75% to 125% of the label claim to prove the superiority of EIOT. The API content prediction accuracy of the EIOT method was verified through offline High Performance Liquid Chromatography (HPLC) measurement. Also, the spatial distribution of API in granules was visualized by Raman imaging technology. The results showed that the established NIRS method was suitable for the prediction of API content in fluidized bed granulation, which provides a new idea for the determination of API content during granulation.
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Espectroscopia de Luz Próxima ao Infravermelho , Cromatografia Líquida de Alta Pressão , Análise dos Mínimos Quadrados , Análise de Componente Principal , Espectroscopia de Luz Próxima ao Infravermelho/métodosRESUMO
Accumulation of heavy metal ions, including copper ions (Cu2+), presents a serious threat to human health and to the environment. A substantial amount of research has focused on detecting such species in aqueous solutions. However, progress towards ultrasensitive and easy-to-use sensors for non-aqueous solutions is still limited. Here, we focus on the detection of copper species in hexane, realising ultra-sensitive detection through a fluorescence-based approach. To achieve this, a novel macroporous composite material has been developed featuring luminescent CsPbBr3 nanocrystals (NCs) chemically adhered to a polymerized high internal phase emulsion (polyHIPE) substrate through surface thiol groups. Due to this thiol functionality, sub-monolayer NC formation is realised, which also renders outstanding stability of the composite in the ambient environment. Copper detection is achieved through a direct solution based immersion of the CsPbBr3-(SH)polyHIPE composite, which results in concentration-dependent quenching of the NC photoluminescence. This newly developed sensor has a limit of detection (LOD) for copper as low as 1 × 10-16 M, and a wide operating window spanning 10-2 to 10-16 M. Moreover, the composite exhibits excellent selectivity among different transition metals.
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The extensive use of halomethanes (CH3X, X = F, Cl, Br, I) as refrigerants, propellants, and pesticides has drawn serious concern due to their adverse biological and atmospheric impact. However, there are currently no portable rapid and accurate monitoring systems for their detection. This work introduces an approach for the selective and sensitive detection of halomethanes using photoluminescence spectral shifts in cesium lead halide perovskite nanocrystals. Focusing on iodomethane (CH3I) as a model system, it is shown that cesium lead bromide (CsPbBr3) nanocrystals can undergo rapid (<5 s) halide exchange, but only after exposure to oleylamine to induce nucleophilic substitution of the CH3I and release the iodide species. The extent of the halide exchange is directly dependent on the CH3I concentration, with the photoluminescence emission of the CsPbBr3 nanocrystals exhibiting a redshift of more than 150 nm upon the addition of 10 ppmv of CH3I. This represents the widest detection range and the highest sensitivity to the detection of halomethanes using a low-cost and portable approach reported to date. Furthermore, inherent selectivity for halomethanes compared to other organohalide analogues is achieved through the dramatic differences in their alkylation reactivity.
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The ligand assisted reprecipitation (LARP) technique is an accessible and facile method that can synthesize metal halide perovskite nanocrystals (PNCs) under ambient conditions. However, low product yields of less than 30% for LARP and its contemporary methods are indicative of highly inefficient reactions. In this work we apply the principles of green chemistry to the LARP technique for synthesizing CsPbBr3 PNCs and help address this issue. Through these efforts, high product yields of â¼70% are achieved using stochiometric Cs : Pb precursor ratios. This is realized by (i) substituting the conventional toluene (TOL) anti-solvent with ethyl acetate (EA) and (ii) replacing the conventionally used unsaturated oleylamine ligand with the shorter saturated octylamine ligand. These changes also result in a 60% molar reduction in total ligand concentration and a 62.5% reduction in solvent waste during purification. The synthesized PNCs are comparable to the TOL-LARP reference in crystal quality, morphology and phase, with their photoluminescence quantum yields being readily enhanced to over 80% through additions of RNH3Br ligands. The spectral versatility of these materials is demonstrated through post-synthetic chloride and iodide halide anion exchange, which readily yields tunable CsPbX3 derivatives across the visible spectrum. Our EA-LARP protocol is further shown to be readily upscaled to â¼0.5 L, while maintaining good nanocrystal properties and a product yield of 60%.
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Improving the stability and tuning the optical properties of semiconducting perovskites are vital for their applications in advanced optoelectronic devices. We present a facile synthetic method for hybrid composites of perovskites and metal-organic frameworks (MOFs). A simple two-step solution-based method without organic surfactants was employed to make all-inorganic lead-halide perovskites (CsPbX3; X = Cl, Br, I, or mixed halide compositions) form directly in the pores of MIL-101 MOF. That is, a polar organic solution of lead halide (PbX2) was impregnated into the MOF pores to give PbX2@MIL-101, which was then subjected to a perovskite-formation reaction with cesium halide (CsX) dissolved in methanol. The compositions of the halogen anions in the perovskites can be modulated with various halide precursors, leading to CsPbX3@MIL-101 composites with X3 = Cl3, Cl2Br, Br2Cl, Br3, Br2I, I2Br, and I3 that exhibit gradual variation of band gap energies and tuned emission wavelengths from 417 to 698 nm.
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Currently, the most efficient perovskite solar cells (PSCs) mainly use planar and mesoporous titanium dioxide (TiO2) as an electron-transport layer (ETL). However, because of its intrinsic photocatalytic properties, TiO2 can decompose perovskite absorber and lead to poor stability under solar illumination (ultraviolet light). Herein, a simplified architectural ETL-free PSC with enhanced efficiency and outstanding photostability is produced by the facile deposition of a bathocuproine (BCP) interlayer. Power conversion efficiency of the ETL-free PSC improves from 15.56 to 19.07% after inserting the BCP layer, which is the highest efficiency reported for PSCs involving an ETL-free architecture, versus 19.03% for the n-i-p full device using TiO2 as an ETL. The BCP interlayer has been demonstrated to have several positive effects on the photovoltaic performances of devices, such as "modulation doping" of the perovskite layer, modification of FTO surface work function, and enhancing the charge-transfer efficiency between FTO and perovskite. Moreover, the BCP-based ETL-free devices exhibit outstanding photostability: the unencapsulated BCP-based ETL-free PSCs retain over 90% of their initial efficiencies after 1000 h of storage in air and maintain 92.2% after 450 h of exposure to full solar irradiation (without a UV filter), compared to only 14.1% in the n-i-p full cells under the same condition.
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The fluidized bed granulation and pellets coating technologies are widely used in pharmaceutical industry, because the particles made in a fluidized bed have good flowability, compressibility, and the coating thickness of pellets are homogeneous. With the popularization of process analytical technology (PAT), real-time analysis for critical quality attributes (CQA) was getting more attention. Near-infrared (NIR) spectroscopy, as a PAT tool, could realize the real-time monitoring and control during the granulating and coating processes, which could optimize the manufacturing processes. This article reviewed the application of NIR spectroscopy in CQA (moisture content, particle size and tablet/pellet thickness) monitoring during fluidized bed granulation and coating processes. Through this review, we would like to provide references for realizing automated control and intelligent production in fluidized bed granulation and pellets coating of pharmaceutical industry.
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Espectroscopia de Luz Próxima ao Infravermelho , Tecnologia Farmacêutica , Química Farmacêutica , Excipientes , Tamanho da Partícula , ComprimidosRESUMO
High-quality and millimeter-sized perovskite single crystals of CsPbBr3 and Cs4PbBr6 were prepared in organic solvents and studied for correlation between photocurrent generation and photoluminescence (PL) emission. The CsPbBr3 crystals, which have a 3D perovskite structure, showed a highly sensitive photoresponse and poor PL signal. In contrast, Cs4PbBr6 crystals, which have a 0D perovskite structure, exhibited more than 1 order of magnitude higher PL intensity than CsPbBr3, which generated an ultralow photoresponse under illumination. Their contrasting optoelectrical characteristics were attributed to different exciton binding energies, induced by coordination geometry of the [PbBr6]4- octahedron sublattices. This work correlated the local structures of lead in the primitive perovskite and its derivatives to PL spectra as well as photoconductivity.
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In CH3NH3PbI3-based high efficiency perovskite solar cells (PSCs), tiny amount of PbI2 impurity was often found with the perovskite crystal. However, for two-step solution process-based perovskite films, most of findings have been based on the films having different morphologies between with and without PbI2. This was mainly due to the inferior morphology of pure perovskite film without PbI2, inevitably produced when the remaining PbI2 forced to be converted to perovskite, so advantages of pure perovskite photoactive layer without PbI2 impurity have been overlooked. In this work, we designed a printing-based two-step process, which could not only generate pure perovskite crystal without PbI2, but also provide uniform and full surface coverage perovskite film, of which nanoscale morphology was comparable to that prepared by conventional two-step solution process having residual PbI2. Our results showed that, in two-step solution process-based PSC, pure perovskite had better photon absorption and longer carrier lifetime, leading to superior photocurrent generation with higher power conversion efficiency. Furthermore, this process was further applicable to prepare mixed phase pure perovskite crystal without PbI2 impurity, and we showed that the additional merits such as extended absorption to longer wavelength, increased carrier lifetime and reduced carrier recombination could be secured.
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We report on the fabrication of PbS/CH3NH3PbI3 (=MAP) core/shell quantum dot (QD)-sensitized inorganic-organic heterojunction solar cells on top of mesoporous (mp) TiO2 electrodes with hole transporting polymers (P3HT and PEDOT: PSS). The PbS/MAP core/shell QDs were in situ-deposited by a modified successive ionic layer adsorption and reaction (SILAR) process using PbI2 and Na2S solutions with repeated spin-coating and subsequent dipping into CH3NH3I (=MAI) solution in the final stage. The resulting device showed much higher efficiency as compared to PbS QD-sensitized solar cells without a MAP shell layer, reaching an overall efficiency of 3.2% under simulated solar illumination (AM1.5, 100 mW·cm(-2)). From the measurement of the impedance spectroscopy and the time-resolved photoluminescence (PL) decay, the significantly enhanced performance is mainly attributed to both reduced charge recombination and better charge extraction by MAP shell layer. In addition, we demonstrate that the MAP shell effectively prevented the photocorrosion of PbS, resulting in highly improved stability in the cell efficiency with time. Therefore, our approach provides method for developing high performance QD-sensitized solar cells.