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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Preparation of titanium (IV) immobilized core-shell magnetic covalent organic framework nanospheres for highly selective enrichment of nucleotides from human serum

Xiaoxia Zhang,Jiwei Shen,Yinmao Wei,Chaozhan Wang

In this work, a titanium (IV) immobilized covalent organic framework (COF) was developed and used as an efficient adsorbent for highly selective enrichment of nucleotides from human serum. Firstly, an amino-functionalized magnetic COF (Fe 3 O 4 @TpBD(NH 2 ) 2 ) was synthesized by the in situ growth strategy. Alendronate sodium (AS) was then modified on the surface of the Fe 3 O 4 @TpBD(NH 2 ) 2 via Schiff base reaction. Finally, Ti 4+ was chelated to obtain immobilized metal ion affinity chromatography (IMAC) adsorbent (denoted as Fe 3 O 4 @COF-AS-Ti 4+ ). Its adsorption performances toward nucleotides including adenosine triphosphate (ATP), adenosine-5′-diphosphate (ADP) and adenosine-5′-monophosphate (AMP) were investigated, their maximum adsorption capacity were 36.7, 39.0 and 49.6 μmol/g, respectively. The adsorption and desorption can be achieved very fast (in 1 min). In addition, the Fe 3 O 4 @COF-AS-Ti 4+ can still selectively adsorb nucleotides in the presence of other analogues, such as nucleosides, phenols, aromatic amines and phenol amines. It can be served as a good adsorbent for selective enrichment of nucleotides and simultaneous exclusion of biomacromolecules. It has also good synthesis reproducibility and reusability. These features suggest that the Fe 3 O 4 @COF-AS-Ti 4+ nanospheres are of great benefit for pretreatment prior to instrument analysis of nucleotides.

研究领域: 分析化学 · 生物化学
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FOOD CHEMISTRY · 2024 · IF 8.5

Profiling the differential phosphoproteome between breast milk and infant formula through a titanium (IV)-immobilized magnetic nanoplatform

Pengcheng Xie,Jialiang Liu,Zonggao Liao,Qi Zhou,Jiajiu Sun,Zheyi Liu,Huihuang Xiong,Hao Wan

Breast milk (BM) fulfills the nutritional needs of infants and sets the standard for infant formula (IF). However, profiling the differential phosphoproteome between BM and IF remains unclear. Herein, a titanium (IV) (Ti 4+ )-immobilized magnetic nanoplatform (Fe 3 O 4 @GO@PDA-Ti 4+ ) was constructed by self-assembly polymerization of dopamine on magnetic graphene oxide, followed by immobilizing Ti 4+ through chelation for phosphopeptide enrichment. Fe 3 O 4 @GO@PDA-Ti 4+ possessed outstanding selectivity (1/1000, a molar ratio of β-casein digests to bovine serum albumin digests) and favorable sensitivity (2.5 fmol/μL), along with rapid magnetic separation. Excellent phosphopeptide capture efficiencies were obtained for BM and IF using Fe 3 O 4 @GO@PDA-Ti 4+ as an adsorbent coupled with liquid chromatography-mass spectrometry/mass spectrometry. There were 191 and 239 phosphopeptides found in BM and IF, respectively, with 36 phosphoproteins identified in both. However, BM and IF shared only 17 phosphopeptides and 4 phosphoproteins. The variation in the phosphoproteome between BM and IF provides valuable insights into the optimization of IF humanization.

CAS / MDL: 62-31-7 490-79-9 64-18-6
研究领域: 生物化学 · 营养学 · 分析化学
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JOURNAL OF ORGANOMETALLIC CHEMISTRY · 2019 · IF 2.066

Air-stable μ-oxo-bridged binuclear titanium(IV) salophen perfluorooctanesulfonate as a highly efficient and recyclable catalyst for the synthesis of bis(indolyl) methane derivatives

Jie Qiao,Shan Gao,Lingxiao Wang,Jiancong Wei,Ningbo Li,Xinhua Xu

An air-stable μ -oxo-bridged binuclear Lewis acid of titanium(IV) salophen perfluorooctanesulfonate [{Ti(salophen)H 2 O} 2 O][OSO 2 C 8 F 17 ] 2 ( 1 ) was successfully synthesized by the reaction of Ti IV (salophen)Cl 2 with AgOSO 2 C 8 F 17 and characterized by different techniques such as IR, NMR and HRMS . TG-DSC analysis showed that this complex was thermally stable at 220 °C. Meanwhile, it exhibited good solubility in polar organic solvents and good ionic dissociation in CH 3 CN solution. Fluorescence spectra and Hammett indicator results indicated that the complex had relatively strong acidity. And it showed high catalytic efficiency for the synthesis of bis(indolyl) methane derivatives through Friedel-crafts reaction of aldehyde/ketone with indoles . Moreover, it can be reused five times with minimal changes in catalytic efficiency.

研究领域: 化学 · 材料科学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Titanium (IV) hydroxide-modified biochar electrode for efficient and selective fluorine removal by flow-electrode capacitive deionization

Bin Xu,Zilong Han,Yonghai Gan,Hongcen Zhen,Zhe Li,Jun Luo,Kaixiang Jiang,Changhai Ji,Wenzhong Yang,Xinzhe Lu,Rongting Ji

Flow-electrode capacitive deionization (FCDI) can be a promising technology for fluorine removal from groundwater. In this study, a new kind of titanium (IV) hydroxide modified biochar (Ti-BC) was prepared by a simple method and used as FCDI electrode materials to selectively remove F - at the first time. Ti-BC exhibited superior defluorination capabilities due to the its unique mesoporous structure and the introduction of hydroxyl functional groups. The optimal F - removal performance was obtained by optimizing the operation parameters and the parameter of applied voltage had the greatest impact. Ti-BC electrode performed excellent electrosorption capacity of 9.65 mg/g and electrosorption efficiency of 96.5 %. Besides, the energy consumption was as low as 0.002 kWh/m 3 . Furthermore, the remarkable selectivity for F - even in mixed ions systems was confirmed, and the actual fluorine-containing groundwater could be effectively treated to meet the WHO drinking water standard. With the help of characterization techniques and theoretical calculation, the detailed fluorine removal mechanisms were obtained, including physical adsorption, electrostatic attraction, capacitive adsorption and ligand exchange. This work not only proposed new insights into the efficient and selective fluorine removal, but also promoted the development of targeted electrodes for practical application in treating fluorine pollution in groundwater.

CAS / MDL: 7681-49-4
研究领域: 环境科学 · 材料科学
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MICROCHIMICA ACTA · 2020 ·Vol. 187 ·期 10 ·1-9 · IF 6.232

Targeted immobilization of titanium (IV) on magnetic mesoporous nanomaterials derived from metal-organic frameworks for high-efficiency phosphopeptide enrichment in biological samples

Pu Chenlu,Zhao Hongli,Gu Qinying,Zheng Yu,Lan Minbo

A selectively modified porous metal/carbon nanocomposite was fabricated to enhance the enrichment of low-abundance phosphopeptides from biological samples. The carbon matrix derived from the metal-organic framework provides a suitable pore size to allow the diffusion of peptides, while the deliberately modified metal nanoparticles within the pores enhance their interaction with the phosphopeptides. This nanocomposite shows extremely high enrichment selectivity for phosphopeptides in the MALDI-TOF MS detection, even when the molar ratio of α-casein digests versus bovine serum albumin digests was up to about 1:20,000. By combining such nanocomposite with nano-LC-MS/MS, 4556 unique phosphopeptides were identified with high selectivity (95.2%) from HeLa cell extracts. Furthermore, phosphopeptides from prostate tissue digests were also determined. A total of 277 and 1242 phosphopeptides were identified from normal and tumor tissues of a patient with prostate cancer, respectively. This indicates that phosphorylation and prostate cancer can be related to each other.

CAS / MDL: 693-98-1 67-56-1 83-86-3
研究领域: 分析化学 · 生物医学
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RSC Advances · 2022 ·Vol. 12 ·期 19 ·11715-11721 · IF 4.036

Synthesis of ultrahigh-molecular-weight ethylene/1-octene copolymers with salalen titanium(IV) complexes activated by methyaluminoxane

Baokang Zou,Yipeng Zhan,Xiuli Xie,TongTong Zhang,Runkai Qiu,Fangming Zhu

Two salalen titanium(IV) complexes ((H-salalen)TiCl2 and (F-salalen)TiCl2) containing hydrogen and fluorine respectively on the phenolate ring close to the imine were synthesized for the copolymerization of ethylene with 1-octene to prepare poly(ethylene-co-1-octene) in the presence of methylaluminoxane (MAO). The (F-salalen)TiCl2/MAO showed higher catalytic activity and better copolymer characteristics such as a higher molecular weight, narrower molecular weight distribution, and higher 1-octene incorporation than (H-salalen)TiCl2/MAO, which revealed that the electron-withdrawing conjugated effect introduced by fluorine substituents led to improvements on catalytic performance and thermal stability. The influences of copolymerization conditions including temperature, Al/Ti molar ratios and comonomer feed ratios on the copolymerization behavior of (F-salalen)TiCl2/MAO and the copolymer microstructure were investigated in detail. Under the activation of MAO, the (F-salalen)TiCl2 could produce ultrahigh molecular weight poly(ethylene-co-1-octene) with 1-octene incorporation ratios in the range of 0.9–3.1 mol% and exhibit relatively high activity. It could be inferred that long ethylene sequences in the copolymer were segregated by the isolated 1-octene units based on the 13C NMR characterization of the copolymer. Moreover, the thermal properties and crystallization of copolymers were determined by DSC and XRD and correlated to the ethylene sequence length distribution. The reactivity ratios calculated by the triad distribution in 13C NMR revealed the random comonomer distribution in the copolymer chain.

研究领域: 高分子化学 · 配位聚合 · 催化化学 · 材料科学 · 高分子物理
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TETRAHEDRON · 2016 · IF 2.645

Chemoselective Claisen–Schmidt bis-substitutional condensation catalyzed by an alkoxy-bridged dinuclear Ti(IV) cluster

Yufei Wu,Jie Hou,Yuliang Liu,Mingfu Zhang,Chen-Ho Tung,Yifeng Wang

The highly efficient and chemoselective α,α′-bis-substitution of alkanones is important in organic synthesis. Herein, a dimeric titanium cluster, Ti 2 Cl 2 (OPr i ) 6 ·2HOPr i ( Ti 2 ), is used in the Claisen–Schmidt condensation reaction, for the selectively activation of symmetrical ketones containing α,α′-methylene groups and production of α,α′-bis-substituted alkanones in high efficiency and chemoselectivity. The high efficiency and chemoselectivity can be extended to a variety of typical alkanones and aromatic aldehydes . Both of the oxo-bridged dimeric motif of Ti 2 and the ionic Ti–Cl bond are responsible for the high efficiency and chemoselectivity.

研究领域: 有机化学 · 催化 · 无机化学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2021 ·Vol. 413 ·期 11 ·2893-2901 · IF 4.157

Facile synthesis of titanium(IV) ion–immobilized arsenate-modified poly(glycidyl methacrylate) microparticles and the application to the specific enrichment of phosphoproteins

Zhang Mengmei,Wang Hao,Bhandari Ramesh,Pan Qiuhui,Sun Fenyong

Selective separation and enrichment of phosphoproteins possess the distinct clinical and biological importance in the diagnosis, treatment, and management of several fatal human diseases. In this study, a facile synthesis of titanium(IV) ion–immobilized arsenate-modified poly(glycidyl methacrylate) microparticles (denoted as Ti 4+ -arsenate-PGMA-MPs) was developed for the efficient enrichment of intact phosphoproteins found in biologically complex protein samples. By virtue of the strong interaction between the titanium ions immobilized on the surface of Ti 4+ -arsenate-PGMA-MPs and phosphate groups of phosphoproteins, Ti 4+ -arsenate-PGMA-MPs had a high saturated adsorption capacity for phosphoproteins (901 mg/g for β-casein), which was much higher than that of non-phosphoproteins (73.5 mg/g for BSA). Ti 4+ -arsenate-PGMA-MPs were characterized by SEM, TEM, and FT-IR, and the average particle diameter was about 2.5 μm with good dispersibility. Besides, the application of Ti 4+ -arsenate-PGMA-MPs in real biological samples was investigated by SDS-PAGE analysis, and the results showed that Ti 4+ -arsenate-PGMA-MPs were able to enrich phosphoproteins efficiently. Graphical abstract

研究领域: 生物化学 · 蛋白质组学 · 材料科学
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JOURNAL OF CHROMATOGRAPHY A · 2021 · IF 4.759

Development of dual-ligand titanium (IV) hydrophilic network sorbent for highly selective enrichment of phosphopeptides

Kaina Zhang,Yun Hao,Dehua Hu,Suimin Deng,Yuhao Jin,Xiangfeng Wang,Hailing Liu,Yuan Liu,Mengxia Xie

A hydrophilic metal-organic network based on Ti 4+ and dual natural ligand, tannic acid (TA) and phytic acid (PA), has been developed to enrich phosphopeptides from complex bio-samples prior to liquid chromatography-mass spectrometric analysis. Due to the strong chelation ability of TA and PA, abundant Ti 4+ can be immobilized in the material, forming hydrophilic network by one-step coordination-driven self-assembly approach. The sorbent, [email protected] 3 O 4 , exhibited satisfactory selectivity for the phosphopeptides in the tryptic digest of β-casein, and can eliminate the interference components in 1000-fold excess of bovine serum albumin. The adsorption capacity of the sorbents for phosphopeptides was up to 35.2 mg g −1 and the adsorbing equilibrium can be reached in 5 min. The adsorbing mechanism has been investigated and the results indicated that the Ti 4+ in forms of [Ti(f-TA)(H 2 O) 4 ] 2+ , [Ti(f-PA)(H 2 O) 4 ] 2+ and Ti(f-PA) 2 (H 2 O) 2 may play an important role in the adsorption process. The sorbent of the [email protected] 3 O 4 has been applied to enrichment of the phosphopeptides in tryptic digest of rat liver lysate, and 3408 phosphopeptides have been identified, while the numbers of the identified phosphopeptides were 2730 and 1217 when the sample was enriched by the commercial TiO 2 and Fe 3+ -IMAC kit, respectively. This work provides a strategy to enrich phosphopeptides from complex samples and shows great potential application in phosphoproteome research.

研究领域: 分析化学 · 生物化学 · 蛋白质组学
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SCIENCE OF THE TOTAL ENVIRONMENT · 2022 · IF 10.753

Efficient oil-water emulsion treatment via novel composite membranes fabricated by CaCO3-based biomineralization and TA-Ti(IV) coating strategy

Hongli Xie,Binghong Chen,Hongjun Lin,Renjie Li,Liguo Shen,Genying Yu,Lining Yang

Continuous increasing discharge of industrial oily wastewater and frequent occurrence of oil spill accidents have taken heavy tolls on global environment and human health. Organic-inorganic modifications can fabricate superhydrophilic/submerged superoleophobic membranes for efficient oil-water separation/treatment though they still suffer from complex operation, non-environmental friendliness, expensive cost or uneven distribution. Herein, a new strategy regarding tannic acid (TA)-Ti(IV) coating and CaCO 3 -based biomineralization through simple inkjet printing processes was proposed to modify polyvinylidene fluoride (PVDF) membrane, endowing the membrane with high hydrophilicity (water contact angle (WCA) decreased from 86.01° to 14.94°) and underwater superoleophobicity (underwater contact angle (UOCA) > 155°). The optimized TA-Ti(IV)-CaCO 3 modified membrane possessed perfect water permeation to various oil/water emulsions (e.g., 355.7 L·m −2 ·h −1 for gasoline emulsion) under gravity with superior separation efficiency (>98.8 %), leading the way in oil/water emulsion separation performance of PVDF membranes modified with polyphenolic surfaces to our knowledge. Moreover, the modified membrane displayed rather high flux recovery after eight cycles of filtration while maintaining the original excellent separation efficiency. The modification process proposed in this study is almost independent of the nature of the substrate, and meets the demand for simple, inexpensive, rapid preparation of highly hydrophilic antifouling membranes, showing abroad application prospect for oil-water emulsion separation/treatment.

CAS / MDL: 1401-55-4
研究领域: 环境工程 · 材料科学 · 化学工程 · 水处理
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ACS Applied Materials & Interfaces · 2015 · IF 6.723

Hydrophilic Carboxyl Cotton Chelator for Titanium(IV) Immobilization and Its Application as Novel Fibrous Sorbent for Rapid Enrichment of Phosphopeptides

Xiao-Mei He,Xi Chen,Gang-Tian Zhu,Qian Wang,Bi-Feng Yuan,Yu-Qi Feng

Sample preparation methods with high selectivity, efficiency, and matrix resistance are essential for phosphoproteomic analysis. In this study, carboxyl cotton chelator-titanium(IV) (CCC-Ti4+) fibers, a novel CCC-based fibrous sorbent with excellent biocompatibility, were successfully synthesized on the basis of the coordination effect between double carboxyl groups on CCC and Ti4+. The synthesis of CCC-Ti4+ fibers was easy, and the incorporated titanium content was high. On the basis of immobilized metal ion affinity chromatography (IMAC), CCC-Ti4+ fibers were used for specific capture of phosphopeptides using a lab-in-syringe solid-phase extraction (SPE) from multiple biological samples, including standard protein digests, nonfat milk digests, human serum, and animal tissue. The proposed sorbent exhibited high selectivity (β-casein/BSA = 1:1000) and good sensitivity (10 fmol) in phosphopeptides analysis. Meanwhile, the lab-in-syringe SPE greatly simplified the entire process of enrichment. Thanks to the good biocompatibility of CCC-based material, CCC-Ti4+ fibers showed excellent performance in phosphopeptide enrichment from protein-rich human serum. Finally, CCC-Ti4+ fibers were applied for selective capture of phosphopeptides from tryptic digests of rat brain lysate followed by LC-MS/MS analysis. Using the proposed method, we identified 3950 unique phosphosites from 1 mg of rat brain in a single experiment, which is much better than previously reported IMAC-based strategies. Taken together, this efficient method will find broad application in large-scale phosphoproteomics analysis because of the rapid (3 min) convenient procedure and excellent performance.

CAS / MDL: 13463-67-7 1314-23-4
研究领域: 分析化学 · 蛋白质组学 · 生物化学
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MACROMOLECULAR CHEMISTRY AND PHYSICS · 2020 ·Vol. 221 ·期 9 ·2000035 · IF 2.335

Surrounding Interactions on Phase Transition Temperature Promoted by Organometallic Complexes in Functionalized Poly(N-isopropylacrylamide-co-dopamine methacrylamide) Copolymers

Yu Wang,Alberto García-Peñas,Santiago Gómez-Ruiz,Florian J. Stadler

The functionalization of different structures with organometallic complexes provides exciting properties in terms of applicability due to its ability to provide multiple benefits for catalysis and biomedicine as well as in other fields. This work reports the direct, facile functionalization of copolymers based on N -isopropylacrylamide and dopamine methacrylamide with bis(cyclopentadienyl)titanium (IV) dichloride (Cp 2 TiCl 2 , Cp = η 5 -C 5 H 5 ), which can offer an easy preparation method in comparison with other functionalization procedures. In addition, the lower critical solution temperature (LCST) is studied through aqueous solutions of new structures, which is affected by the presence of the metallocene moieties. UV–vis spectroscopy shows an average of the LCST-behavior in comparison with rheology that provides essential information about the changes of the phase transition temperature associated with the composition of the polymeric chains and their interactions with the medium. Then, the inclusion of an organometallic complex along the polymeric chain can partially modify the phase transition temperature due to the interactions promoted by the organometallic complex of surroundings over the polymeric sections free of comonomer content.

研究领域: 高分子化学 · 材料科学 · 物理化学
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