SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Bingbing Liu,Yifei Zhang,Peidong Yang,Yanfang Huang,Yubin Xue,Hu Sun,Shuzhen Yang,Guihong Han
Zinc electrolyte crystallization sediment (ZECS) generated in the zinc hydrometallugy industry contains valuable metals of strontium (Sr), manganese (Mn), and zinc (Zn), which has economical value but poses potential detrimental to the environment. However, the extraction and recovery of Sr is extremely difficult due to the thermodynamically stable Ca and Sr sulfate cocrystallization structure in ZECS. The destruction of refractory sulfate cocrystallization structure is a prerequisite for Sr extraction, and the carbothermal reduction roasting method is demonstrated to be efficient for the phase reconstruction. In this study, a stepwise Sr, Mn, and Zn recovery process from ZECS via carbothermal reduction roasting-acid leaching-selective precipitation-multistage extraction was proposed. In the reduction roasting procedure, all the sulfates including CaSO 4 , SrSO 4 , and Ca 0.7 Sr 0.3 SO 4 are reduced to soluble sulfides. Meanwhile, most MnO 2 is converted to a low-valence Mn product (MnO) that is soluble in acid, and the reduced Zn (g) is volatilized which can be collected from the flue dust. In the acid leaching procedure, the leaching efficiencies of Sr, Ca, and Mn are as high as 97.34%, 97.44%, and 95.49% respectively, while 99.50% Si in the form of silica is enriched in the leaching residue. After that, high-purity Sr solution was obtained after selective precipitation for Mn removal and D2EHPA multistage extraction for Ca removal. 97.41% Mn in the leaching solution is precipitated by adjusting the pH value to 9.5 with NaOH solution. After four-stage extraction, 79.60% Sr and only 0.35% Ca are retained in the aqueous phase. The purified solution contains 2.88 g/L Sr, 0.052 g/L Ca, and 0.014 g/L Mn, which can be used to prepare industrial SrCO 3 product via the carbonation operation. Thermodynamic behavior and reduction roasting reconstruction mechanism of Ca and Sr sulfate cocrystallization structure in ZECS were discussed in this work. The distributions of main metal elements (Sr, Ca, Mn, and Zn) in ZECS during the carbothermal reduction roasting-acid leaching-selective precipitation-multistage extraction process were also systematically studied.
研究领域:
冶金学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF DRUG DELIVERY SCIENCE AND TECHNOLOGY
·
2022
·
IF 5.062
Lixin Liu,Qi An,Yunan Zhang,Weitong Sun,Jinjing Li,Yanru Feng,Yiding Geng,Guangdong Cheng
With the purpose of improving the solubility and reducing the hygroscopicity of enrofloxacin (ENR), an unreported pharmaceutical salt cocrystal of enrofloxacin with both neutral and anionic p-nitrobenzoic acid (PNB) (ENR-PNB, C 19 H 23 FN 3 O 3 ·C 7 H 4 NO 4 ·C 7 H 5 NO 4 ) was designed and synthesized by changing the reaction molar ratio (1:2) of ENR and coformer PNB on the basis of summarizing the past experience of our group, and its crystal structure was characterized. Single-crystal X-ray diffraction (SCXRD) analysis revealed that the salt cocrystal consists of ENR + , PNB − and PNB neutral molecule in a 1:1:1 ratio. The two asymmetric units that become centrosymmetric form an X-shaped structure centered on the ENR dimer R 2 2 (20). The adjacent X-shaped structures are interconnected by hydrogen bonds to form 1D chain and form the octamer R 8 8 (42) at the same time. As we expected, the formation of the salt cocrystal ENR-PNB results in a simultaneous improvement in the solubility and hygroscopicity of ENR. This may be the fact that ENR and PNB depend on CAHBs to raise the hydrous enthalpy of salt cocrystal. And the presence of PNB neutral molecules lower hygroscopicity of ENR in high humidity environments. Unexpectedly, the permeability of ENR-PNB was also increased compared to that of pure ENR. It is speculated that the number of polar sites in the system is greatly reduced because of hydrogen bonds formation, which increases the permeability of the ENR salt cocrystal. In addition, the in vitro antibacterial activities of ENR-PNB are enhanced at different concentrations compared to ENR. The present study implies that it is possible to improve the solubility, hygroscopic stability, permeability and antibacterial activity of enrofloxacin by changing the chemical reaction molar ratio to form salt cocrystal containing both neutral and anionic coformers, which provides a new strategy and insight to simultaneously improve the solubility and hygroscopicity and even permeability of the active ingredients of solid drugs.
研究领域:
药物化学
·
晶体学
✓ 已验证
产品关联
DOI
高影响因子
CRYSTAL GROWTH & DESIGN
·
2024
·
IF 3.2
Yujiao Li,Yunan Zhang,Qi An,Jingwen Shi,Lixin Liu
Based on the study of the effect of positional isomerism of coformer functional groups on the cocrystallization and physicochemical properties of the active pharmaceutical ingredients, the impact of cis–trans isomeric butenedioic acid as coformers on the conformation, crystal structure, and its physicochemical properties of marbofloxacin was further explored. In this work, fumaric acid (FA) and maleic acid (MA) with different configurations were chosen as coformers to synthesize the pharmaceutical salt cocrystal (MBF-FA-H2FA) and salt (MBF-MA) of marbofloxacin (MBF), and their structures were fully characterized. Significant differences between the conformations of marbofloxacin in the salt cocrystal and in salt were found. In the salt cocrystal, the N atom of the piperazine group from marbofloxacin is coplanar with the pyridone ring, and the whole is straight like fumaric acid, whereas the marbofloxacin piperazine group in the salt is bent like the maleic acid configuration. Furthermore, the conformational variability of marbofloxacin in the salt cocrystal and the salt resulted in different crystal structures and opposite physicochemical properties. Notably, both multicomponent crystals have a surface hydrophilic intercalation structure. However, the salt cocrystal and salt exhibited different solubility and permeability. Specifically, the MBF-MA salt showed improved solubility and permeability, while the MBF-FA-H2FA salt cocrystal showed a decreased solubility and permeation rate compared to MBF. In addition, in vitro bacterial inhibitory activity assays indicated that the MBF-MA salt has stronger inhibitory activity against Gram-negative and Gram-positive bacterial strains than the MBF-FA-H2FA salt cocrystal and pure MBF.
研究领域:
药学
·
晶体学
·
生物化学
✓ 已验证
产品关联
DOI
高影响因子
CRYSTAL GROWTH & DESIGN
·
2022
·
IF 4.01
Su-Su Meng,Yue-Ming Yu,Fan-Zhi Bu,Cui-Wei Yan,Zhi-Yong Wu,Yan-Tuan Li
A cocrystallization tactic of double optimization and synergistic enhancement efficacy has been proposed, aiming at maximizing the benefits of phenolic acid nutriment syringic acid (HSA) to perfect biopharmaceutical features of antibacterial drug ofloxacin (OA). This strategy utilizes the salt-forming function and cocrystallization ability of HSA interplaying with OA to assemble into a salt cocrystal, thus ameliorating OA’s physicochemical properties in vitro, which, in turn, can optimize its pharmacokinetic characteristics in vivo, making OA’s pharmaceutical peculiarities be doubly optimized on both in vivo and in vitro levels. Ulteriorly, the antibacterial potency of OA is heightened by stimulating the auxiliary antibacterial ability of HSA, fulfilling the cooperativeness of OA and HSA in antibacterial efficacy. Taking this tactic as orientation, the first OA– nutriment salt cocrystal, viz., [HOA+-SA–]-HSA-H2O, is directionally synthesized and structurally identified. Single-crystal X-ray diffraction substantiates that the salt cocrystal has a bilayer hole structure, wherein, a hexahelical hydrogen-bonding motif of [HOA+-SA–] salts situates outside with a double spiral of neutral HSA and H2O molecules inside, thus endowing the salt cocrystal with the capacity to simultaneously enhance solubility and permeability compared with OA itself, which achieves positive correlations with theoretical investigations. Intriguingly, the strengthened in vitro properties of the salt cocrystal have been effectually turned into in vivo pharmacokinetic advantages, displaying an advanced peak plasma concentration and protracted half-life along with raised relative bioavailability. More meaningfully, the antibacterial capacity of the salt cocrystal has also attained significant enhancement owing to the congenerous antibacterial action of OA and HSA. Therefore, this investigation not only offers a novice strategy for optimizing in vitro/vivo pharmaceutical characteristics and concurrently elevating antibacterial efficacy of OA through formation of the salt cocrystal but also fulfills a breakthrough in developing new salt cocrystal systems of antibacterial drugs.
研究领域:
药学
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生物医学工程
✓ 已验证
DOI
高影响因子
Materials
·
2021
·Vol. 14
·期 19
·5737
·
IF 3.623
Zhiyu Tong,Linfeng Li,Yuanyuan Li,Qingmeng Wang,Xiaomin Cheng
The multiple eutectic nitrates with a low melting point are widely used in the field of solar thermal utilization due to their good thermophysical properties. The addition of nanoparticles can improve the heat transfer and heat storage performance of nitrate. This article explored the effect of MgO nanoparticles on the thermal properties of ternary eutectic nitrates. As a result of the decomposition reaction of the Mg(OH)2precursor at high temperature, MgO nanoparticles were synthesized in situ in the LiNO3–NaNO3–KNO3ternary eutectic nitrate system. XRD and Raman results showed that MgO nanoparticles were successfully synthesized in situ in the ternary nitrate system. SEM and EDS results showed no obvious agglomeration. The specific heat capacity of the modified salt is significantly increased. When the content of MgO nanoparticles is 2 wt %, the specific heat of the modified salt in the solid phase and the specific heat in the liquid phase increased by 51.54% and 44.50%, respectively. The heat transfer performance of the modified salt is also significantly improved. When the content of MgO nanoparticles is 5 wt %, the thermal diffusion coefficient of the modified salt is increased by 39.3%. This study also discussed the enhancement mechanism of the specific heat capacity of the molten salt by the nanoparticles mainly due to the higher specific surface energy of MgO and the semi-solid layer that formed between the MgO nanoparticles and the molten salt.Keywords:MgO nanoparticles;eutectic nitrates;in situ;specific heat capacity;thermal diffusion coefficient
研究领域:
材料科学
·
能源工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CRYSTAL GROWTH & DESIGN
·
2020
·
IF 4.089
Ling-Yang Wang,Fan-Zhi Bu,Yan-Tuan Li,Zhi-Yong Wu,Cui-Wei Yan
A novel cocrystallization form of amantadine hydrochloride (AMNH) with sulfathiazole (SUZ), as the first example of dual-drug cocrystal simultaneously containing antiviral drug and antibacterial agent, is designed and successfully synthesized. The structure of resulting cocrystal SUZ–AMNH is thoroughly characterized. The single crystal X-ray diffraction reveals that a 1:1 ratio of the two components exists in the cocrystal structure, in which the interactions between SUZ and AMNH molecules are mainly dominated by N–H···O hydrogen bonds and N–H+(AMNH)···Cl–···H–N(SUZ) charge-assisted hydrogen bonds, constructing a three-dimensional supramolecular structure. The dissolubility and permeability of the cocrystal are systematically studied under physiological pH environments. It has been found that SUZ in the cocrystal shows a 1.83–5.23 times increase in water solubility and ca. 2-fold enhancement in penetrability compared with pure SUZ. Intriguingly, the simultaneously improved physicochemical properties for SUZ can bring about the strengthening in antibacterial activities, displaying enhanced inhibition of bacterial strains and lower values of minimum inhibitory concentration. The present investigation not only provides a promising method for therapeutic hybridization of antiviral and antibacterial drugs against coinfection, but also exploits a new pathway of the drug–drug cocrystallization strategy toward widening new applications for conventional drugs.
研究领域:
药学
·
材料科学
✓ 已验证
DOI
高影响因子
MOLECULAR PHARMACEUTICS
·
2023
·
IF 4.9
Su-Su Meng,Yue-Ming Yu,Fan-Zhi Bu,Cui-Wei Yan,Zhi-Yong Wu,Yan-Tuan Li
The current research leverages the structural features and property superiorities along with benefits in protecting cardiovascular system of gallic acid (GLC) and gentisic acid (HGA) to optimize in vitro/vivo peculiarities of cardiotonic drug milrinone (MIL) through developing a stratagem of cocrystallization-driven double-optimized ternary salt cocrystal. This strategy assembles MIL ternary salt cocrystal by shaping a cocrystallization moiety relying on noncovalent interplays with GLC to obtain permeability advancement and molding a salt segment via the salification of proton transfer between HGA and MIL molecules to facilitate solubility enhancement. While the ameliorative in vitro properties further modulate the in vivo pharmacokinetic behaviors, thus fulfilling a dual optimization of MIL’s biopharmaceutical characteristics on both in vitro and in vivo aspects. Along this line, the first MIL ternary salt cocrystal, viz., [HMIL+-GA–]-MIL-GLC-H2O (denoted as MTSC hereinafter), has been satisfactorily constructed and precisely structurally identified by diversified techniques. The single-crystal X-ray diffraction experiment validates that a molecular salt [HMIL+-GA–] species cocrystallizes with one neutral MIL, two GLC, and five solvent water molecules, among which the organic constituents compose laminated hydrogen bond networks, and then are self-assembled by water molecules to a 3D supramolecular structure. The unique structural feature and stacking pattern of MTSC make both the permeability and solubility be respectively enhanced by 9.69 times and 5.17- to 6.03-fold compared with the parent drug per se. The experimental outcomes are powerfully supported by associated calculations based on density functional theory. Intriguingly, these optimal in vitro physicochemical natures of MTSC have been potently converted into strengths of in vivo pharmacokinetics, showcasing the elevated drug plasma concentration, elongated half-life, alongside advanced bioavailability. Consequently, this presentation not just contributes a brand-new crystalline form with utility values, but ushers in a new dimension of ternary salt cocrystals for improving in vitro/vivo limitations of poor drug bioavailability.
研究领域:
药剂学
·
药物化学
·
药物递送
·
生物药剂学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2024
·
IF 4
Fan-Zhi Bu,Su-Su Meng,Ling-Yang Wang,Zhi-Yong Wu,Yan-Tuan Li
For the sake of fully laying stress on the advantages of multi-component cocrystals in ameliorating limitations of poor pharmaceutical peculiarities, and further offering fresh insights for the application of salt-type cocrystals in the optimization of anti-heart failure medication milrinone (MIL), the present project exploits the structural characteristic and property preponderance of gallic acid (GLC) and 3,5-dinitrobenzoic acid (HBA) to design and assemble MIL ternary salt cocrystal via a combination tactic of cocrystallization and salification. This strategy organizes the ternary salt-cocrystal by fashioning a salt portion to foster solubility enhancement and shaping a cocrystal moiety to achieve permeability advancement. Following this thread, the MIL ternary salt-cocrystal, namely [HMIL + -BA − ]-GLC H 2 O (indicated as TSC there-in-after), is accurately authenticated by comprehensive characterization means. Single-crystal X-ray diffraction affirms that the asymmetric unit of TSC comprises a [HMIL + -BA − ] salt, one neutral GLC molecule along with three water molecules, all of which build a three-dimensional hydrogen-bonding network containing electrostatic forces and π-π stacking interactions. Such unique structural feature and aggregation motif make MIL in TSC achieve a coinstantaneous elevation of 10.59 times in permeability and 4.76−5.15 folds in solubility versus the parent medicine itself at different physiological pH, which supports well agreement with the DFT-based theoretical investigations including reduced density gradient, molecular electrostatic potential surface, topology, Hirshfeld surface analysis, together with Gibbs free energy of solvation. All of these not only contribute a completely new cocrystalline model for MIL with synchronously optimizing dissolubility and permeability, but demonstrate the feasibility and effectiveness of ternary salt cocrystals in modifying the properties of anti-heart failure medicines.
研究领域:
药学
·
材料科学
·
理论化学
·
晶体学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）