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Journal of the American Chemical Society Apr 2023Organic hierarchical branch micro/nanostructures constituted by single crystals with inherent multichannel characteristics exhibit superior potential in regulating...
Organic hierarchical branch micro/nanostructures constituted by single crystals with inherent multichannel characteristics exhibit superior potential in regulating photon transmission for photonic circuits. However, organic branch micro/nanostructures with precise branch positions are extremely difficult to achieve due to the randomness of the nucleation process. Herein, by taking advantage of the dislocation stress field-impurity interaction that solute molecules deposit preferentially along the dislocation line, twinning deformation was introduced into microcrystals to induce oriented nucleation sites, and ultimately organic branch microstructures with controllable branch sites were fabricated. The growth mechanism of these controllable single crystals with an angle of 140° between trunk and branch is attributed to the low lattice mismatching ratio (η) of 4.8%. These as-prepared hierarchical branch single crystals with asymmetrical optical waveguide characteristics have been demonstrated as an optical logic gate with multiple input/out channels, which provides a route to command the nucleation sites and offers potential applications in the organic optoelectronics at the micro/nanoscale.
PubMed: 37040147
DOI: 10.1021/jacs.3c02061 -
Bioprocess and Biosystems Engineering Jul 2015Since about 170 years, salts were used to create supersaturated solutions and crystallize proteins. The dehydrating effect of salts as well as their kosmotropic or... (Review)
Review
Since about 170 years, salts were used to create supersaturated solutions and crystallize proteins. The dehydrating effect of salts as well as their kosmotropic or chaotropic character was revealed. Even the suitability of organic solvents for crystallization was already recognized. Interestingly, what was performed during the early times is still practiced today. A lot of effort was put into understanding the underlying physico-chemical interaction mechanisms leading to protein crystallization. However, it was understood that already the solvation of proteins is a highly complex process not to mention the intricate interrelation of electrostatic and hydrophobic interactions taking place. Although many basic questions are still unanswered, preparative protein crystallization was attempted as illustrated in the presented case studies. Due to the highly variable nature of crystallization, individual design of the crystallization process is needed in every single case. It was shown that preparative crystallization from impure protein solutions as a capture step is possible after applying adequate pre-treatment procedures like precipitation or extraction. Protein crystallization can replace one or more chromatography steps. It was further shown that crystallization can serve as an attractive alternative means for formulation of therapeutic proteins. Crystalline proteins can offer enhanced purity and enable highly concentrated doses of the active ingredient. Easy scalability of the proposed protein crystallization processes was shown using the maximum local energy dissipation as a suitable scale-up criterion. Molecular modeling and target-oriented protein engineering may allow protein crystallization to become part of a platform purification process in the near future.
Topics: Crystallization; Molecular Weight; Organic Chemicals; Proteins; Salts; Solubility; Temperature
PubMed: 25700885
DOI: 10.1007/s00449-015-1374-y -
Chemical Society Reviews Jun 2024Seawater electrolysis for the production of fuels and chemicals involved in onshore and offshore plants powered by renewable energies offers a promising avenue and... (Review)
Review
Seawater electrolysis for the production of fuels and chemicals involved in onshore and offshore plants powered by renewable energies offers a promising avenue and unique advantages for energy and environmental sustainability. Nevertheless, seawater electrolysis presents long-term challenges and issues, such as complex composition, potential side reactions, deposition of and poisoning by microorganisms and metal ions, as well as corrosion, thus hindering the rapid development of seawater electrolysis technology. This review focuses on the production of value-added fuels (hydrogen and beyond) and fine chemicals through seawater electrolysis, as a promising step towards sustainable energy development and carbon neutrality. The principle of seawater electrolysis and related challenges are first introduced, and the redox reaction mechanisms of fuels and chemicals are summarized. Strategies for operating anodes and cathodes including the development and application of chloride- and impurity-resistant electrocatalysts/membranes are reviewed. We comprehensively summarize the production of fuels and chemicals (hydrogen, carbon monoxide, sulfur, ammonia, ) at the cathode and anode seawater electrolysis, and propose other potential strategies for co-producing fine chemicals, even sophisticated and electronic chemicals. Seawater electrolysis can drive the oxidation and upgrading of industrial pollutants or natural organics into value-added chemicals or degrade them into harmless substances, which would be meaningful for environmental protection. Finally, the perspective and prospects are outlined to address the challenges and expand the application of seawater electrolysis.
PubMed: 38855878
DOI: 10.1039/d3cs00822c -
Se Pu = Chinese Journal of... Apr 2021Istradefylline is a novel selective adenosine A receptor antagonist that is used to treat Parkinson's disease and improve motor dysfunction in the early stage of this...
Istradefylline is a novel selective adenosine A receptor antagonist that is used to treat Parkinson's disease and improve motor dysfunction in the early stage of this disease. During the synthesis of intermediate A1 (6-amino-1,3-diethyl-2,4-(1,3)-pyrimidinedione), at least two by-products were formed under alkaline or high-temperature conditions. In a previous study, one of the by-products in the synthesis of the intermediate was studied, and its structure was identified as ()-ethyl-2-cyano-3-ethylamino-2-butene amide. In this study, we used high performance liquid chromatography (HPLC) to analyze another impurity formed during the synthesis of A1, and the following steps were executed: 0.4 g of intermediate was weighed and added to a 50 mL beaker, followed by the sequential addition of 8 mL water and 8 mL acetonitrile, and then, ultrasonic dissolution was performed. Finally, the solution was filtered through a 0.45-μm organic membrane and the test sample solution was obtained. We used the Agilent zorbax C18 chromatography column, with acetonitrile (A)/water(B) as the mobile phase under gradient elution ((/A∶B)=/20∶80, /60∶40, -/90∶10). The detector wavelength is 268 nm. In order to separate the impurity from A1, we used a Ceres B preparative column, with acetonitrile-water (30/70, v/v) as the mobile phase. The flow rate was set at 30 mL/min, and the detection wavelength was 268 nm. The structure of the impurity was confirmed by high-resolution mass spectrometry (HRMS), one-dimensional nuclear magnetic resonance (NMR), and two-dimensional nuclear magnetic resonance (2D NMR), and characterized by single-crystal X-ray diffraction (XRD). In MS experiments, an electrospray ionization (ESI) source was used with positive ion scanning. In the NMR experiments, we used tetramethylsilane (TMS) as the internal standard and deuterated dimethyl sulfoxide (DMSO-d) as the solvent to obtain the spectra. The results of preparative high performance liquid chromatography (Prep-HPLC) showed that good separation effect could be achieved by isocratic elution, and the impurity was perfectly separated. TheH-NMR spectral data are as follows:H-NMR (600 MHz, DMSO): 1.01 (q, =6.9 Hz, 3H), 1.02 (q, =6.9 Hz, 3H), 1.07 (t, =6.9 Hz, 3H), 3.04 (p, =6.8 Hz, 2H), 3.74 (q, =7.0 Hz, 2H), 3.94 (q, =7.1 Hz, 2H), 5.85 (s, 1H). The C-NMR spectral data are summarized as follows: C-NMR (150 MHz, DMSO): 13.9, 14.1, 15.9, 34.6, 34.9, 36.9, 81.9, 152.2, 153.3, 159.3, 162.0. The impurity was characterized by single-crystal XRD, and its spatial structure was further verified and determined as 1-(1,3-diethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-yl)-3-ethylurea. Based on the chemical structure of the impurity, we propose the following mechanism for the impurity: when A1 is synthesized under alkaline conditions or at high temperature, excessive diethylurea continues to undergo amidation with A1 to obtain this by-product. Although the formation mechanism of the impurity studied in this paper is different from that of the intermediate A1 impurity ()-ethyl-2-cyano-3-ethylamino-2-butene amide, both the impurities are formed at high temperatures. Both will be accompanied by A1 in the subsequent reaction of istradefylline synthesis. The relationship between drug impurities and drug safety is a complex relationship that is affected by many factors. Generally, most impurities in drugs have potential biological activities, and some even interact with the drugs, thus affecting their efficacy and safety and inducing toxic effects. Therefore, to ensure the quality of istradefylline, it is necessary to control the impurity content during the production. The findings of this paper may provide guidelines for controlling the impurity content in istradefylline.
Topics: Chromatography, High Pressure Liquid; Drug Contamination; Mass Spectrometry; Purines
PubMed: 34227764
DOI: 10.3724/SP.J.1123.2020.10013 -
ACS Applied Materials & Interfaces Oct 2020High-entropy oxides (HEOs) have attracted increasing interest owing to their unique structures and fascinating physicochemical properties. Spherical mesoporous HEOs...
High-entropy oxides (HEOs) have attracted increasing interest owing to their unique structures and fascinating physicochemical properties. Spherical mesoporous HEOs further inherit the advantages of spherical mesoporous materials including high surface area and tunable pore size. However, it is still a huge challenge to construct HEOs with uniform spheres and a mesoporous framework. Herein, a wet-chemistry sol-gel strategy is demonstrated for the synthesis of spherical mesoporous HEOs (e.g., Ni-Co-Cr-Fe-Mn oxide) with high specific surface area (42-143 m/g), large pore size (5.5-8.3 nm), unique spherical morphology (∼55 nm), and spinel structure without any impure crystal phase using polyphenol as a polymerizable ligand. The metal/polyphenol-formaldehyde resin colloidal spheres are first synthesized via a sol-gel process. Because of their abundant catechol groups and strong chelating ability with different metal species, polyphenols can not only accommodate five different metal ions in their networks but also be well polymerized by formaldehyde to form colloidal spheres. After calcination, the metal species aggregate together to form HEOs, while the organic resin is fully decomposed to produce mesopores. Because of the open framework with accessible mesopores, they could be used as a peroxymonosulfate catalyst for degradation of organic pollutants and a nanoplatform for efficient detection of DNA. This work demonstrates a straightforward sol-gel strategy for design and synthesis of spherical mesoporous high-entropy materials, which would promote the exploration of new properties of high-entropy materials and extend their application.
PubMed: 32915530
DOI: 10.1021/acsami.0c11899 -
Biomedical Chromatography : BMC Dec 2021Midostaurin (MDS) is used for the treatment of acute myeloid leukemia, myelodysplastic syndrome, and advanced systemic mastocytosis. MDS softgel capsule samples were...
Impurity profiling and stability-indicating method development and validation for the estimation of assay and degradation impurities of midostaurin in softgel capsules using HPLC and LC-MS.
Midostaurin (MDS) is used for the treatment of acute myeloid leukemia, myelodysplastic syndrome, and advanced systemic mastocytosis. MDS softgel capsule samples were subjected to stress testing per International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use guidelines for impurity profiling study. MDS underwent extensive degradation under stress testing (acid, alkaline, oxidative, photolytic, thermolytic, and hydrolysis conditions) and formed four degradation products (DPs). MDS and its DPs were separated well from one another with good resolution using reserved-phase HPLC using an Inertsil ODS-3V column (250 × 4.6 mm, 5 μm) and a mobile phase of ammonium formate (40 mM) and acetonitrile. The stability-indicating characteristic of the newly developed method was proven for the estimation of MDS assay, and its organic impurities were free from interference. The validated method exhibited excellent linearity, accuracy, precision, specificity, detection limit, and quantitation limit within 25 min run time. Stress testing, robustness, and solution stability were performed to ensure the continuous performance of the developed method. The peak fractions of DPs formed under stress testing were isolated and characterized using LC-MS, H and C NMR, IR, and UV-Vis. The structure of the major DPs was predicted as DP1 based on the spectral data. The proposed method is effectively used for MDS in bulk drug and finished formulations in the pharmaceutical industry.
Topics: Capsules; Chromatography, High Pressure Liquid; Drug Contamination; Limit of Detection; Linear Models; Mass Spectrometry; Reproducibility of Results; Staurosporine
PubMed: 34331472
DOI: 10.1002/bmc.5222 -
Environmental Pollution (Barking, Essex... Mar 2024The removal and recovery of uranium [U(VI)] from organic containing wastewater has been a challenging in radioactive wastewater purification. Here, we designed a...
The removal and recovery of uranium [U(VI)] from organic containing wastewater has been a challenging in radioactive wastewater purification. Here, we designed a polyamine/amidoxime polyacrylonitrile fiber (PAN-AO-A) with high removal efficiency, excellent selectivity, excellent organic resistance and low cost by combining the anti-organic properties of amidoxime polyacrylonitrile fiber (PAN-AO-A) with the high adsorption capacity of polyamine polyacrylonitrile fiber, which is used to extract U(VI) from low-level uranium-containing wastewater with high ammonia nitrogen and organic content. PAN-AO-A adsorbent with high grafting rate (86.52%), high adsorption capacity (q = 618.8 mg g), and strong resistance to organics and impurity interference is achieved. The adsorption rate of U(VI) in both real organic and laundry wastewater containing uranium is as high as 99.7%, and the partition coefficients (K) are 7.61 × 10 mL g and 9.16 × 10 mL g, respectively. The saturated adsorption capacity of PAN-AO-A in the continuous system solution can reach up to 505.5 mg g, and the concentration of U(VI) in the effluent is as low as 1 μg L. XPS analysis and Density functional theory (DFT) studies the coordination form between U(VI) and PAN-AO-A, where the most stable structure is η-AO(UO)(CO). The -NH-/-NH and -C(NH)N-OH groups of PAN-AO-A exhibit a synergistic complex effect in the U(VI) adsorption process. PAN-AO-A is a material with profound influence and limitless potential that can be used for wastewater containing U(VI) and organic matter.
Topics: Wastewater; Uranium; Polyamines; Oximes; Adsorption
PubMed: 38159627
DOI: 10.1016/j.envpol.2023.123269 -
The Journal of Physical Chemistry... Oct 2021Narrow bandgap donor-acceptor organic semiconductors are generally considered to show a closed-shell singlet ground state, and their radicals are reported as impurities,...
Narrow bandgap donor-acceptor organic semiconductors are generally considered to show a closed-shell singlet ground state, and their radicals are reported as impurities, defects, polarons, and charge transfer monoradicals. Herein, we systematically investigated the open-shell singlet diradical electronic ground state of two diketopyrrolopyrrole-based compounds via the combination of electron spin resonance (ESR), nuclear magnetic resonance, superconducting quantum interference device magnetometry, and theoretical calculations. It is widely known that the quinoidal character will be significantly enhanced in the aggregation state accompanied by improved planarity and enhanced delocalization. We proposed an aggregation-induced radical and captodative effect as the driving force for the formation and stabilization of the open-shell quinoid diradical based on the ESR test in different proportions of mixed solvents. Our results provided a novel view for understanding the intrinsic chemical structure of donor-acceptor organic semiconductors, the open-shell singlet and thermally excited triplet electronic states, and the unexpected physical processes between the ground state and the excited state.
PubMed: 34596405
DOI: 10.1021/acs.jpclett.1c02463 -
Angewandte Chemie (International Ed. in... Dec 2023Accidentally, it was found that triphenylamine (TPA) from commercial sources shows ultralong yellow-green room temperature phosphorescence (RTP) like commercial...
Accidentally, it was found that triphenylamine (TPA) from commercial sources shows ultralong yellow-green room temperature phosphorescence (RTP) like commercial carbazole, which however disappears for lab-synthesized TPA with high purity. Herein, we for the first time identify the impurity types that cause RTP of commercial TPA, which are two N, N-diphenyl-naphthylamine isomers. Due to similar molecular polarity and very trace amount (≈0.8 ‰, molar ratio), these naphthyl substituted impurities can be easily overlooked. We further show that even at an extremely low amount (1000000 : 1, mass ratio) of impurities, RTP emission is still generated, attributed to the triplet-to-triplet energy transfer mechanism. Notably, this doping strategy is also applicable to the triphenylphosphine and benzophenone host systems, of which strong RTP emission can be activated by simply doping the corresponding naphthyl substituted analogues into them. This work therefore provides a general and efficient host/guest strategy toward high performance and diverse organic RTP materials.
PubMed: 37905301
DOI: 10.1002/anie.202315911 -
Biotechnology Progress Jul 2022Cell culture medium (CCM) formulations are chemically defined to reduce lot-to-lot variability and complexity of the medium while still providing all essential nutrients...
Cell culture medium (CCM) formulations are chemically defined to reduce lot-to-lot variability and complexity of the medium while still providing all essential nutrients supporting cell growth and productivity of various cell lines. However, raw material impurities may still introduce variations and inconsistencies to final CCM formulations. In one of our previous studies (Weiss et al. Biotechnol Prog. 2021;37(4):e3148), we have demonstrated the impact of iron raw material impurity on Chinese hamster ovary (CHO) cell performance and critical quality attributes (CQAs) of recombinant proteins within the Cellvento® 4CHO CCM platform by identifying manganese impurity as the main root cause for improved cell performance and altered glycosylation profiles. This study sought to investigate the impact of iron raw material impurities within another medium platform, namely EX-CELL® Advanced CHO Fed-Batch-Medium. As opposed to previously published results, in this platform, copper instead of manganese impurity present within the used ferric ammonium citrate (FAC) iron source was responsible for an improved cell performance of a CHOZN® cell line and a slight difference in CQAs of the produced recombinant protein. The use of tightly controlled raw material specifications or the use of low impurity iron sources is therefore crucial to minimize the impact of impurities on cell performance in any CCM platform and thereby guarantee consistent and reproducible cell culture processes.
Topics: Animals; CHO Cells; Cell Culture Techniques; Copper; Cricetinae; Cricetulus; Culture Media; Iron; Manganese; Recombinant Proteins
PubMed: 35318833
DOI: 10.1002/btpr.3251