New methods for resolution of hydroxychloroquine by forming diastereomeric salt and adding chiral mobile phase agent on RP-HPLC.

Hydroxychloroquine (HCQ), 2-([4-([7-Chloro-4-quinolyl]amino)pentyl]ethylamino)ethanol, exhibited significant biological activity, while its side effects cannot be overlooked. The RP-HPLC enantio-separation was investigated for cost-effective and convenient optical purity analysis of HCQ. The thermodynamic resolution of Rac-HCQ, driven by enthalpy and entropy, was achieved on the C18 column using Carboxymethyl-ß-cyclodextrin (CM-ß-CD) as the chiral mobile phase agent (CMPA). The effects of CCM-ß-CD, pH, and triethylamine (TEA) V% on the enantio-separation process were explored. Under the optimum conditions at 24°C, the retention times for the two enantiomers were t R 1 = 29.39 min $$ {t}_{R1}=29.39\ \min $$ and t R 2 = 32.42 min $$ {t}_{R2}=32.42\ \min $$ , resulting in R s = 1.87 $$ {R}_s=1.87 $$ . The resolution via diastereomeric salt formation of Rac-HCQ was developed to obtain the active pharmaceutical ingredient of single enantiomer S-HCQ. Di-p-Anisoyl-L-Tartaric Acid (L-DATA) was proved effective as the resolution agent for Rac-HCQ. Surprisingly, it was found that refluxing time was a key fact affecting the resolution efficiency, which meant the kinetic dominate during the process of the resolution. Four factors-solvent volume, refluxing time, filtration temperature, and molar ratio-were optimized using the single-factor method and the response surface method. Two cubic models were established, and the reliability was subsequently verified. Under the optimal conditions, the less soluble salt of 2L-DATA:S-HCQ was obtained with a yield of 96.9% and optical purity of 63.0%. The optical purity of this less soluble salt increases to 99.0% with a yield of 74.2% after three rounds recrystallization.

Enantiomeric separation of tryptophan via novel chiral polyamide composite membrane.

The separation of chiral drugs continues to pose a significant challenge. However, in recent years, the emergence of membrane-based chiral separation has shown promising effectiveness due to its environmentally friendly, energy-efficient, and cost-effective characteristics. In this study, we prepared chiral composite membrane via interfacial polymerization (IP), utilizing ß-cyclodextrin (ß-CD) and piperazine (PIP) as mixed monomers in the aqueous phase. The chiral separation process was facilitated by ß-CD, serving as a chiral selective agent. The resulting membrane were characterized using SEM, FT-IR, and XPS. Subsequently, the chiral separation performance of the membrane for DL-tryptophan (Trp) was investigated. Lastly, the water flux, dye rejection, and stability of the membrane were also examined. The results showed that the optimized chiral PIP0.5ß-CD0.5 membrane achieved an enantiomeric excess percentage (ee%) of 43.0% for D-Trp, with a solute flux of 66.18 nmol·cm-2·h-1, and maintained a good chiral separation stability. Additionally, the membrane demonstrated positive performance in the selective separation of mixed dyes, allowing for steady operation over a long period of time. This study offers fresh insights into membrane-based chiral separations.

Novel ethylenediamine-ß-cyclodextrin grafted membranes for the chiral separation of mandelic acid and its derivatives.

In the present study, flat cellulose acetate ultrafiltration membranes were prepared first by nonsolvent induced phase separation method. Then chiral membranes for separating the enantiomers were prepared by grafting the ultrafiltration membranes using ethylenediamine-ß-cyclodextrin as the chiral selector and epichlorohydrin as the spacer arm. The pure water permeability of the ultrafiltration membrane was around 115 L·m-2·h-1·bar-1. The properties of the chiral membranes were characterized using infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The chiral membrane performance in enantiomer separation was evaluated with racemates, such as mandelic acid (MA), 2-chloromandelic acid (2-ClMA), 4-chloromandelic acid (4-ClMA), and methyl mandelate (MM). The influence of feed concentration on the separation efficiency was also investigated. The results indicated that the enantiomeric excess percentages (e.e%) of the racemic mixtures for these four chiral compounds were up to 31.8%, 25.4%, 17.8%, and 32.6%, respectively. The binding free energy of the chiral selector with the (S)-enantiomer calculated by molecular dynamics simulations was stronger than that with the (R)-enantiomer, which was consistent with the experimental results (higher concentration of (R)-enantiomer in the permeate). This supports the affinity absorption-separation mechanism.

Resolution of trans-1,2-cyclohexanedicarboxylic acid containing two carboxylic groups by forming diastereomeric salts based on feeding molar ratio control.

To investigate the thermodynamic and molecular self-assembly mechanism of trans-1,2-cyclohexane dicarboxylic acid containing two carboxylic acid groups in the chiral resolution process, (S)-phenylethylamine was used as the chiral resolving agent. Two stoichiometric salts were formed when the raw materials were fed at different molar ratios: cyclohexane dicarboxylate monophenylethylamine salt and cyclohexane dicarboxylate diphenylethylamine salt. When the molar ratio of the (S)-phenylethylamine to trans-1,2-cyclohexane dicarboxylic acid was less than 3:1, trans-(1S,2S)-cyclohexane dicarboxylic acid was obtained with 97 e.e% purity. But when the molar ratio exceeded 3:1, the product was the racemic trans-(1,2)-cyclohexane dicarboxylic acid. In addition, single crystal structures of more soluble mono-salt, less soluble mono-salt, and less soluble di-salt were obtained. The weak intermolecular interactions and the way of the molecules packing in the crystals were analyzed. The hydrogen bond was stronger in the less soluble salt than that in the more soluble salt. And a "lock-and-key" structure in the hydrophobic layers makes it more tightly packed through the van der Waals interaction, which is responsible for the stability of less soluble salts.

Computational fluid dynamics simulation and the experimental verification of protein adsorption on a hollow fiber membranes module.

Immobilized metal affinity chromatography (IMAC) ensures the specific purification of proteins containing histidine tags through high affinity with transition metal chelators, which has various applications in biological protein separation. Most chromatographic separations currently use a fixed bed. In this form, internal flow pressure drops very sharply, accompanied by uneven solution flow, pore blockages, etc., all of which greatly reduce separation efficiency. Therefore, this study uses hollow fiber membranes (HFMs) with micron-scale inner diameters as a base, thus reducing operating pressure and significantly enhancing mass transmission. Batch adsorption experiments were performed using flat plate membranes to obtain the reaction's thermodynamic and kinetic model parameters for use in a dynamic column breakthrough simulation. The numerical simulation was based on a single HFM model and established a mathematical model for computational fluid dynamics (CFD) in ANSYS Fluent software. Model accuracy was validated by combining the simulation with experiments. The effects of different module and process parameters on the breakthrough curve were investigated by varying parameters such as flow rate, initial feed concentration, and HFM inner diameter. Design parameters and operating conditions contributing to module utilization were subsequently obtained.

The mechanism of low-dose radiation-induced upregulation of immune checkpoint molecule expression in lung cancer cells.

INTRODUCTION: This study explored the effect of low-dose radiation on the expression of immune checkpoint molecules in lung cancer cells and its mechanism, as well as the antitumour effect of combined low-dose radiation and immune checkpoint inhibitors. METHODS: Western blot analysis was used to assess the expression of the immune checkpoint molecules CD47, PD-L1, FGL-1 and CD155 in lung cancer cells after radiation. Western blotting was also used to explore changes in the JAK2/STAT3 pathway. CD8+ T lymphocyte infiltration in tumour tissues were assessed by immunohistochemistry in a mouse model. The inhibitory effect of low-dose radiation combined with PD-L1 or CD47 inhibitors on tumor growth was evaluated by measuring tumor volume. RESULTS: In response to low-dose irradiation, the expression of CD47 and PD-L1 in A549 and LLC cells was increased, the expression of p-JAK2 and p-STAT3 was also increased. AG490-mediated inhibition of the JAK2/STAT3 pathway before irradiation significantly reduced the expression of p-JAK2 and p-STAT3 in lung cancer cells, in the meantime, expression of CD47 and PD-L1 was also reduced. Conventional dose exposure exhibited the same trend. PD-L1 and CD47 protein levels increased after low-dose irradiation in an LLC tumour-bearing mouse model. Low-dose irradiation combined with PD-L1 or CD47 inhibitor treatment reduced levels of PD-L1 or CD47 in tumour tissues, increased the proportion of CD8+ T lymphocytes, and significantly inhibited tumour growth. CONCLUSIONS: Both low-dose and regular-dose irradiation upregulate expression of the immune checkpoint molecules CD47 and PD-L1 in lung cancer cells, and the mechanism may be related to the JAK2/STAT3 pathway. Furthermore, low-dose irradiation combined with PD-L1 or CD47 inhibitors significantly inhibits tumour growth.

Detection of Specific Building in Remote Sensing Images Using a Novel YOLO-S-CIOU Model. Case: Gas Station Identification.

The specific building is of great significance in smart city planning, management practices, or even military use. However, traditional classification or target identification methods are difficult to distinguish different type of buildings from remote sensing images, because the characteristics of the environmental landscape around the buildings (like the pixels of the road and parking area) are complex, and it is difficult to define them with simple rules. Convolution neural networks (CNNs) have a strong capacity to mine information from the spatial context and have been used in many tasks of image processing. Here, we developed a novel CNN model named YOLO-S-CIOU, which was improved based on YOLOv3 for specific building detection in two aspects: (1) module Darknet53 in YOLOv3 was replaced with SRXnet (constructed by superimposing multiple SE-ResNeXt) to significantly improve the feature learning ability of YOLO-S-CIOU while maintaining the similar complexity as YOLOv3; (2) Complete-IoU Loss (CIoU Loss) was used to obtain a better regression for the bounding box. We took the gas station as an example. The experimental results on the self-made gas station dataset (GS dataset) showed YOLO-S-CIOU achieved an average precision (AP) of 97.62%, an F1 score of 97.50%, and had 59,065,366 parameters. Compared with YOLOv3, YOLO-S-CIOU reduced the parameters' number by 2,510,977 (about 4%) and improved the AP by 2.23% and the F1 score by 0.5%. Moreover, in gas stations detection in Tumshuk City and Yanti City, the recall (R) and precision (P) of YOLO-S-CIOU were 50% and 40% higher than those of YOLOv3, respectively. It showed that our proposed network had stronger robustness and higher detection ability in remote sensing image detection of different regions.

Structure and Properties of PSf Hollow Fiber Membranes with Different Molecular Weight Hyperbranched Polyester Using Pentaerythritol as Core.

A homologous series of hyperbranched polyesters (HBPEs) was successfully synthesized via an esterification reaction of 2,2-bis(methylol)propionic acid (bis-MPA) with pentaerythritol. The molecular weights of the HBPEs were 2160, 2660, 4150 and 5840 g/mol, respectively. These HBPEs were used as additives to prepare polysulfone (PSf) hollow fiber membranes via non-solvent induced phase separation. The characteristic behaviors of the casting solution were investigated, as well as the morphologies, hydrophilicity and mechanical properties of the PSf membranes. The results showed that the initial viscosities of the casting solutions were increased, and the shear-thinning phenomenon became increasingly obvious. The demixing rate first increased and then decreased when increasing the HBPE molecular weight, and the turning point was 2660 g/mol. The PSf hollow fiber membranes with different molecular weights of HBPEs had a co-existing morphology of double finger-like and sponge-like structures. The starting pure water contact angle decreased obviously, and the mechanical properties improved.

A polyethersulfone-bisphenol sulfuric acid hollow fiber ultrafiltration membrane fabricated by a reverse thermally induced phase separation process.

A novel antifouling polyethersulfone (PES) hollow fiber membrane was modified by the addition of bisphenol sulfuric acid (BPA-PS) using a reverse thermally induced phase separation (RTIPS) process. BPA-PS was synthesized by click chemistry and was blended to improve the hydrophilicity of PES hollow fiber membranes. The performance of PES/BPA-PS hollow fiber membranes, prepared with different contents of BPA-PS and at different temperatures of the coagulation water bath, was characterized by scanning electron microscopy (SEM), pure water flux (J w), BSA rejection rate (R), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and water contact angle measurements. SEM morphologies revealed that a finger-like cross-section emerged in the hollow fiber membrane by a non-solvent induced phase separation (NIPS) mechanism while a sponge-like cross-section appeared in the hollow fiber membrane via the RTIPS method. Both FTIR and XPS analysis indicated that the sulfate group in BPA-PS was successfully blended with the PES membranes. The results from AFM and water contact angle measurements showed that the surface roughness increased and the hydrophilicity of the PES/BPA-PS hollow fiber membrane was improved with the addition of BPA-PS. The results demonstrated that the PES/BPA-PS membrane with 1 wt% BPA-PS via RTIPS exhibited optimal properties.

[Hyperspectral Detection Model for Soil Dispersion in Zhouqu Debris Flow Source Region].

Sensitive band positions, models and the principles of soil dispersion detected by hyperspectral remote sensing were firstly discussed according to the results of soil dispersive hyperspectral remote sensing experiment. Results showed that, (1) signals and noises could be separated by Fourier transformation. A finely mineral identification system was developed to remove spectral noises and provide highly accurate data for establishing soil dispersive model; (2) Soil dispersive hyperspectral remote sensing model established by the multiple linear regression method was good at soil dispersion forecasting for the high correlation between sensitive bands and the soil dispersions. (3) According to mineral spectra, soil minerals and their absorbed irons were reflected by sensitive bands which revealed reasons causing soils to be dispersive. Sodium was the closest iron correlated with soil dispersion. The secondary was calcite, montmorillonite and illite. However, the correlation between soil dispersion and chlorite, kaolinite, PH value, quartz, potassium feldspar, plagioclase was weak. The main reason was probably that sodium was low in ionic valence, small ionic radius and strong hydration forces; calcite was high water soluble and illite was weak binding forces between two layers under high pH value.

FAS Grafted Electrospun Poly(vinyl alcohol) Nanofiber Membranes with Robust Superhydrophobicity for Membrane Distillation.

This study develops a novel type of electrospun nanofiber membranes (ENMs) with high permeability and robust superhydrophobicity for membrane distillation (MD) process by mimicking the unique unitary microstructures of ramee leaves. The superhydrophobic ENMs were fabricated by the eletrospinning of poly(vinyl alcohol) (PVA), followed by chemical cross-linking with glutaraldehyde and surface modification via low surface energy fluoroalkylsilane (FAS). The resultant FAS grafted PVA (F-PVA) nanofiber membranes were endowed with self-cleaning properties with water contact angles of 158° and sliding angles of 4° via the modification process, while retaining their high porosities and interconnected open structures. For the first time, the robust superhydrophobicity of the ENMs for MD was confirmed by testing the F-PVA nanofiber membranes under violent ultrasonic treatment and harsh chemical conditions. Furthermore, vacuum membrane distillation experiments illustrated that the F-PVA membranes presented a high and stable permeate flux of 25.2 kg/m2 h, 70% higher than those of the commercial PTFE membranes, with satisfied permeate conductivity (<5 µm/cm) during a continuous test of 16 h (3.5 wt % NaCl as the feed solution, and feed temperature and permeate pressure were set as 333 K and 9 kPa, respectively), suggesting their great potentials in myriad MD processes such as high salinity water desalination and volatile organiccompounds removal.

Processing-structure-property correlations of polyethersulfone/perfluorosulfonic acid nanofibers fabricated via electrospinning from polymer-nanoparticle suspensions.

Polyethersulfone (PES)/perfluorosulfonic acid (PFSA) nanofiber membranes were successfully fabricated via electrospinning method from polymer solutions containing dispersed calcium carbonate (CaCO(3)) nanoparticles. ATR-FTIR spectra indicated that the nanoparticles mainly existed on the external surface of the nanofibers and could be removed completely by acid treatment. Surface roughness of both the nanofibers and the nanofiber membranes increased with the CaCO(3) loading. Although FTIR spectra showed no special interaction between sulfonic acid (-SO(3)) groups and CaCO(3) nanoparticles, XPS measurement demonstrated that the content of -SO(3) groups on external surface of the acid-treated nanofibers was enhanced by increasing CaCO(3) loading in solution. Besides, the acid-treated nanofiber membranes were performed in esterification reactions, and exhibited acceptable catalytic performance due to the activity of -SO(3)H groups on the nanofiber surface. More importantly, this type of membrane was very easy to separate and recover, which made it a potential substitution for traditional liquid acid catalysts.

[A rapid quantificational identification model of minerals and its applications].

Rapid identification of minerals is the key point for enhancing the efficiency of mineral exploration by remote sensing, mineral mapping by remote sensing and many geological investigations. Because of the limitation of technology and other aspects, the amount of models and software concerning rapid identification of minerals is very small. Since 1990s the development in spectrometers and computers has made it possible to apply near infrared spectrum technology to identify minerals. Two models have emerged. Model I is based on analyzing the position of absorption bands, while Model II is founded on waveform matching. In the present paper, characteristic spectrum linear inversion modeling was built. Validated by the data gained from end-members of USGS mineral spectrum library by mixing randomly, this model with the accuracy being approximately 100% is much better than Model I and II. Used to analyze the 23 samples selected in Baogutu area in Xinjiang, the model we built with the accuracy of 64.6% is superior to Model I (the accuracy is 33.8%) and Model II (the accuracy is 8.1%). Though the accuracy of our model is not as high as that of identification by microscope at present, using our model is much more effective and convenient, and there also will be less artificial error and smaller workload. The good performance of our model in the mineral exploration work by remote sensing in Baogutu area in Xinjiang shows wide popularizing prospects.

[Alteration mineral mapping method based on statistical analysis of field measured spectra].

The present paper presents a new alteration mineral mapping method based on statistical analysis of field measured spectra. First of all, this method processes a cluster of measurement data of spectra of field samples, in order to distinguish different sample area from the overall types. Second, the results of the clustering of different mineral alterations established their respective discriminant functions. Thus, mapping major alteration type accords with the clustered reference spectra by given remote sensing images. Finally mapping further alteration types was based on the discriminant function of second step, which leads to final alteration map. This method takes full account of the different combination of alteration types, as well as the regional differences of alterations, and the establishment of the discriminant function for alteration minerals is more scientific. Moreover, the authors accessed the reliability of mapping to a certain extent. The method was applied to a study area of Baogutu in Xinjiang Province, which represents a good result.

[An algorithm for highlightling structure in multispectral remote sensing].

Based on the principle of mineral generation, structures could provide not only passage ways for ore-forming fluid, but also space for them to aggregate. So, it was very important to study the feature of structures in study area before mineral exploration. In order to highlight structures using multispectral remote sensing data, an algorithm integrating principle component analysis (PCA), maximum noise fraction transformation (MNF) and original image data was proposed here. In the algorithm, the original image was firstly transformed by PCA and MNF; then all bands were normalized to reduce errors caused by different band dimensions, and three bands containing detailed structure information were selected to form the false color image in which structures in study area were highlighted. Results of transformation on enhanced thematic mapper (ETM) data acquired on June 27th 2000 in Hatu area, Xinjiang province, China showed that (1) the transformed image was not only more colorful than the original data, but also more gradational than the original data. (2) The color difference among objects was enhanced by the algorithm. (3) Structrues were highlighted by the algorithm. Therefore, the algorithm's effect of highlighting structures in study area was noticeable.