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Cyclen
DESALINATION · 2023 · IF 9.9

Nanofiltration membrane comprising structural regulator Cyclen for efficient Li+/Mg2+ separation

Tingyu Li,Xinzhu Zhang,Yu Zhang,Jixiao Wang,Zhi Wang,Song Zhao

Selective lithium recovery from salt lake brine using emerging nanofiltration membranes is expected to solve the insufficient supply of lithium resources. In this work, 1,4,7,10-tetraazacyclododecane (Cyclen) was employed as a novel structural regulator through interfacial polymerization of polyethyleneimine (PEI) and trimesoyl chloride (TMC) to develop polyamide NF membrane with efficient Li + /Mg 2+ separation performance. After the introduction of Cyclen to aqueous phase , the PEI/Cyclen-TMC selective layer was confirmed to possess a higher crosslinking degree and larger d-spacing than PEI-TMC layer, endowing a dedicated channel for Li + transport. The water permeance of PEI/Cyclen-TMC composite membrane reached 14.0 L·m −2 ·h −1 ·bar −1 , about 3.8 times higher than PEI-TMC composite membrane, and meanwhile the separation factor ( S Li,Mg ) could be stabilized as 8.7 to realize a considerable reduction of Mg 2+ /Li + mass ratio from 20 to 2.3. Additionally, PEI/Cyclen-TMC composite membrane was utilized to operate a three-stage nanofiltration treatment procedure of a simulated salt lake brine (Mg 2+ /Li + mass ratio: 40). The results indicated that Li + could be efficiently retracted to obtain a solution with 19.5 mg·L −1 Li + and Mg 2+ /Li + mass ratio of 0.3. After the subsequent precipitation and filtration, the obtained Li 2 CO 3 purity could reach 93 %, indicating the potential application of nanofiltration for lithium recovery.

研究领域: 材料科学 · 环境工程 · 化学工程
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Biomaterials Science · 2025 · IF 5.7

Cyclen-based lipidoids for mRNA delivery and immunotherapy

Lan Zhang,Ping Chen,Xiao-Li Tian,Yue Hu,Rong Wang,Ji Zhang

As mRNA vaccines continue to gain widespread attention, lipid nanoparticles (LNPs), the preferred platform for mRNA delivery, have become a key focus of development. 1, 4, 7, 10-Tetraazacyclododecane (cyclen), with its excellent protonation capability and ease of modification, has emerged as a promising candidate for the ionizable head group of lipid materials. In this study, a series of cyclen-based lipidoids with different linkages and hydrophobic tails were designed and conveniently synthesized. Structure-activity relationship studies were performed to screen out the carriers capable of efficient mRNA delivery and with potential for tumor therapeutic applications. In vivo biodistribution experiments in mice revealed that the lipidoid OEs-K, containing both hydroxyl and ester groups in its linkage, exhibited not only high mRNA delivery efficiency but also lymph node-targeting properties. Using a subcutaneous EG.7-OVA tumor model in mice, the delivery of tumor antigen OVA mRNA by the lipidoid material was evaluated for its antitumor immunotherapeutic potential. The results demonstrated that LNPs formulated with OEs-K promoted dendritic cell uptake in lymph nodes, effectively activated immune responses, and inhibited tumor growth. Hematological and histopathological evaluations indicated no significant toxicity to the body. This study might provide insights into the design and development of carrier materials for mRNA vaccines.

研究领域: 生物医学工程 · 分子生物学 · 免疫学
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EUROPEAN POLYMER JOURNAL · 2022 · IF 5.546

A cyclen-based fluoropolymer as a versatile vector for gene and protein delivery

Zheng Huang,Ya-Ping Xiao,Yu Guo,Hui-Zhen Yang,Rui-Mo Zhao,Ji Zhang,Xiao-Qi Yu

Gene and protein therapy have shown great potential in the treatment of severe human diseases. It’s increasingly necessary for the development of multifunctional vectors that can stabilize the gene / protein and deliver them into cells. Herein, a novel polymer composed of fluorinated linkage and Zn-coordinated macrocyclic polyamine (cyclen) was designed and synthesized via ring-opening polymerization. The Zn-cyclen moiety contributes to the gene transfection efficiency, while the fluorinated backbone might afford the protein delivery ability. Experimental results demonstrated that Zn-coordination could improve the water solubility of the polymer and the stability of the polyplexes formed with DNA. For gene transfection, the target polymer ZnCF4 could give similar to or slightly higher efficiency than the golden standard PEI 25 kDa in various cell lines. Several assays revealed that the improvement of transfection efficiency by the Zn-coordination might come from higher polyplex stability, better cellular uptake, and efficient endosome escape. For protein delivery, the Zn-coordination could also largely enhance the efficiency. β-Galactosidase assay revealed that ZnCF4 could not only effectively transfer protein into cells, but also maintain the protein activity. These results suggest that the title polymer might be a versatile platform for the delivery of various bioactive macromolecules , showing its potential in gene and protein therapy.

CAS / MDL: 106-89-8
研究领域: 生物技术 · 分子生物学 · 药学 · 基因治疗 · 蛋白质治疗
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Matter · 2026 · IF 15.7

Photocontrolling cavity dimension enables sustainable lithium capture and rapid release by cyclen-azobenzene network

Qian Guan,Xu Wu,Yue Zheng,Yilei Fang,Mengyu Tang,Xin Yu,Ranwen Ou,Huanting Wang

Regulating the cavity dimension of crown compounds changes its cation uptake ratio and release efficiency, whereas light-responsive triggers may endow the adsorbent with green regeneration functions. Here, we report a cyclen-azobenzene covalent network (C-azobenzene-4,4′-dicarbonyl dichloride [C-ADC]) supported on graphene oxide (GO) as a light-regenerable lithium-selective adsorbent for sustainable lithium extraction. Under room lighting, C-ADC@GO demonstrated a high adsorption loading of up to 15.27 mmol g −1 and an adsorption rate of 36.58 mmol g −1 h −1 . Under UV light irradiation, cyclen’s cavity is expanded by the pulling of cis -azobenzene, releasing the adsorbed ions within 6 min. The relevant Li + /Mg 2+ and Li + /Na + selectivities reach 11.44 and 31.26. It could extract and purify lithium in synthetic Atacama salt-lake brine from 2.5% to 91.2%. A low energy consumption of 8.84 kWh per ton of Li 2 CO 3 is estimated. This work pioneers a new approach for designing next-generation adsorption materials for energy-efficient and sustainable ion extraction and purification.

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NEW JOURNAL OF CHEMISTRY · 2019 ·Vol. 43 ·期 41 ·16138-16147 · IF 3.069

Zn(II)-cyclen complex-based liposomes for gene delivery: the advantage of Zn coordination

Yu Guo,Qing-Ying Yu,Ji Zhang,Hui-Zhen Yang,Zheng Huang,Xiao-Qi Yu

The unique properties of 1,4,7,10-tetraazacyclododecane (cyclen) make it not only a suitable polyamine headgroup in cationic lipids for gene delivery, but also a good host molecule for metal coordination. In this study, a series of cyclen-based lipids and their Zn(II)-complexes were synthesized to study the effect of Zn-coordination on the gene transfection. Both the Zn-free and Zn-containing lipids could form nano-sized particles with suitable positive potential to condense and protect DNA from degradation by DNase. More importantly, Zn coordination could significantly reduce the cytotoxicity of the liposomes. Meanwhile, the gene transfection efficiency of the cyclen-based lipids could also be distinctly improved by the Zn-coordination. Mechanistic studies reveal that the Zn-free and Zn-containing liposomes showed similar cellular uptake properties. However, confocal microscopy shows that Zn-containing liposomes may induce more efficient endosomal escape than the Zn-free counterpart, which could be attributed to their much higher pH buffering capacity. This study presents an efficient strategy to enhance the gene transfection efficiency and biocompatibility of cyclen-based cationic lipids.

研究领域: 药学 · 分子生物学 · 纳米技术 · 生物医学工程
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Journal of Materials Chemistry C · 2018 ·Vol. 6 ·期 36 ·9636-9641 · IF 5.976

Microwave-assisted synthesis of cyclen functional carbon dots to construct a ratiometric fluorescent probe for tetracycline detection

Zhi Shen,Cheng Zhang,Xinling Yu,Jian Li,Zhenyang Wang,Zhongping Zhang,Bianhua Liu

Carbon dots (CDs) prepared by the crosslinking and carbonization reaction between the carboxyl and amino groups of organic molecules have the characteristics of high fluorescence quantum yield and tunable emission colors, enabling their wide use in chemical sensing and bioimaging. However, straight-chain organic amines are mostly used in the preparation of carbon dots. Here, we chose cyclen that contained an azamacrocyclic ring and citric acid to synthesize bright blue-emitting fluorescent CDs by the microwave method. Under 750 W microwave irradiation, the condensation–crosslinking–carbonization process can be completed within 5 minutes with a quantum yield of up to 27.6%. Taking the advantage of using cyclen, the resulting CDs still have a ring-like structure on the surface, and thus can coordinate with Eu3+ ions to construct a ratiometric fluorescent probe for tetracycline detection. When tetracycline is present in the detection system, a CD–Eu3+–tetracycline ternary complex is formed and generates an intense red emission of Eu3+. Meanwhile, the blue emission of the CDs remains unchanged, realizing accurate tetracycline detection by recording the red to blue emission ratio. Besides, the output color changes from blue to red upon increasing the concentration of tetracycline. Therefore, a smartphone based tetracycline detection technique was successfully developed through the corresponding RGB value analysis.

研究领域: 化学 · 生物传感 · 材料科学
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JOURNAL OF MEMBRANE SCIENCE · 2025 · IF 9

Cyclen-based polyamide thin film composite nanofiltration membranes for humic substances/salts separation from landfill leachate MBR effluent

Fengni Luo,Yalong Liu,Wei Guo,Jiang Li,Juan Zhou,Ke Zheng,Shaoqi Zhou

Nanofiltration (NF) and reverse osmosis (RO) treatment of landfill leachate from MBR effluent will produce refractory leachate concentrates containing high concentrations of humic substances and salts. A NF membrane with the ability to separate organic substances and inorganic salts to prevent the accumulation of humic substances and salts during treatment were prepared through interfacial polymerization (IP), utilizing 1,4,7,10-tetraazacyclododecane (Cyclen) with a large spatial structure as the monomer of aqueous-phase and Trimesoyl chloride (TMC) as the oil-phase monomer. Subsequently, Cyclen/TMC membranes were employed to treat landfill leachate derived from the MBR effluent to separate humic substances and inorganic salts. The resulting Cyclen/TMC membranes exhibited good performance and pure-water permeance (P = 31.73 L m -2 h -1 bar -1 ), low salt rejection (R NaCl = 10.15%, R MgCl2 = 19.60%), and a molecular weight cutoff of 269 g/mol. Moreover, they showed separation properties for humic substances and inorganic salts (R humic substances = 96.36%, R Salts = 9.65%) in landfill leachate MBR effluent. Antifouling and long-term stability tests showed the magnificent operating stability of the Cyclen/TMC membranes. The appropriate negatively charged surface of the membrane contributes to its effective antifouling capability and long-term stability, surpassing those of the NF270 commercial membrane. Cyclen/TMC membranes have the potential for application in landfill leachate treatment, which will promote the advancement of landfill leachate resource management.

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WATER RESEARCH · 2024 · IF 11.4

Supramolecular-coordinated nanofiltration membranes with quaternary-ammonium Cyclen for efficient lithium extraction from high magnesium/lithium ratio brine

Ning Gan,Yuqing Lin,Baolong Wu,Yulong Qiu,Haopan Sun,Jingwen Su,Jianguo Yu,Qian Lin,Hideto Matsuyama

Ion-selective membranes (ISM) with sub-nanosized pore channels hold significant potential for applications in saline wastewater treatment and resource recovery. Herein, novel synergistic ion channels featuring bi-periodic structures were constructed through the coordination of functional Cyclen (quaternary_1,4,7,10-tetraazacyclododecane, Q_Cyclen) and Cu 2+ -m-Phenylenediamine (Cu 2+ -MPD) to develop supramolecular membranes for lithium extraction. The exterior quaternary ammonium-rich sites exhibit a significant Donnan exclusion effect, resulting in tremendous mono/divalent (Li + /Mg 2+ ) ion selectivity; while the interior regular-confined channels of Cyclen yield a fast vehicular pathway, facilitating water molecules and Li + ion-selective transport. The optimized membrane exhibited an increased water permeance of 19.2 L·m -2 ·h -1 ·bar -1 and simultaneously promoted Li + /Mg 2+ selectivity (achieving a selectivity of 18.5 under a Mg 2+ /Li + mass ratio of 30), surpassing the trade-off limit of conventional nanofiltration membranes. Due to the acquired excellent Li + /Mg 2+ selectivity, lithium extraction from simulated salt-lake brines was successfully achieved through a two-stage nanofiltration process, reducing the Mg 2+ /Li + mass ratio from 40 to 1.1. This work validates the applicability of macrocyclic with intrinsic sub-nanosized channels and desired multifunctionality for developing high-performance ISM for efficient lithium separation and beyond.

研究领域: 材料科学 · 环境工程 · 化学工程
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JOURNAL OF MEMBRANE SCIENCE · 2026 · IF 8.8

Negatively Charged Nanofiltration Membranes Containing In-Situ Grown ZIF-L from Cross-Substrate Counter Diffusion Involving Zn(II)/Cyclen Complexes

Mengyao Chen,Tianqi Zheng,Hangqing Xue,Yeqiang Lu,Congjie Gao,Lixin Xue

Cross-substrate counter diffusion (CSCD) between imidazole and Zn(II)-loaded polyamide (PA) layers is carried out to in-situ grow zeolitic imidazole framework-leaf (ZIF-L) particles and improve the nanofiltration (NF) performances of negatively charged NF membranes. To achieve uniform distribution of Zn(II) in the formed PA layer, Cyclen was used to complex Zn(II) precursors during the interface polymerization (IP) between piperazine (PIP) and trimesoyl chloride (TMC) to dissolve the Zn(II)/PIP precipitation in the aqueous phase. Results showed that the addition of Cyclen improved the uniform dispersion and firm combination of ZIF-L particles (PTs) in the PA layers, improving both the water permeance and salt rejection of the formed TFN NF membranes. Under optimal conditions, TFN-PC 0.10-0.15 /ZIF membrane achieves a Na 2 SO 4 rejection of 90.2-96.8%, a pure water permeance of 25.8-32.8 L·m -2 ·h -1 ·bar -1 , a NaCl/Na 2 SO 4 mixed salt separation factor of 9.0-29.8, and good anti-fouling and operational stability.

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JOURNAL OF MEMBRANE SCIENCE · 2022 · IF 10.53

Novel macrocyclic polyamines regulated nanofiltration membranes: Towards efficient micropollutants removal and molecular separation

Ming Wang,Mengxin Li,Zhongyi Ren,Zhaohui Fei,Yingfei Hou,Q. Jason Niu

The discharge of wastewater containing organic micropollutants not only causes severe environmental pollution, but also exacerbates the scarcity of freshwater resources and poses a serious threat to human health. The nanofiltration (NF) membrane has unique advantages and obvious energy-saving effects in the demineralization of organic micropollutants. Poly(piperazine) amide NF membrane exhibits the poor organic micropollutants/salt selectivity and low water permeance. Therefore, developing a novel NF membrane with high water permeance and superior selectivity is of significance. In this study, a loose nanofiltration (LNF) membrane is fabricated by interfacial polymerization with 1, 4, 7, 10-tetraazacyclododecane (Cyclen) as a new aqueous phase monomer to modulate the polyamide microstructure. The steric structure of Cyclen is larger than that of PIP, and the steric hindrance increases, resulting in a low stacking density of the formed polyamide polymer. Compared with the PIP-based NF membrane, the fabricated Cyclen-TMC LNF membrane has a smoother surface, a higher density of carboxyl groups, and a lower degree of cross-linking. The Cyclen-TMC membrane exhibits the considerable water permeance, with the corresponding rejection of 99.9% and 92.7% for methyl blue and tetracycline (pH = 9), respectively, while maintaining a low rejection for monovalent salts (e.g., 4.5% for NaCl). Furthermore, the LNF membrane shows a superior anti-fouling performance with the relatively smooth, highly negatively charged surface and low operation pressure. The novel LNF membrane exhibits a high potential for textile and pharmaceutical wastewater treatment . This study provides a new candidate to regulate the separation performance of NF membranes using new aqueous monomers.

研究领域: 环境科学 · 材料科学 · 水处理 · 化学工程
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HYDROMETALLURGY · 2026 · IF 6.3

Improving Li+/Mg2+ separating performance of polyethylene/polyamide membranes under high Mg(II)/Li(I) ratios: Reverse interface polymerization modulation and Mg(II)-Cyclen interaction

Yangxiang Huang,Mengyao Chen,Lixin Xue,Hangqing Xue,Juexin Wang,Fei Huang,Congjie Gao

To simultaneously increase the Mg 2+ /Li + separating performance under high Mg 2+ /Li + ratios of polyethylene/polyamide (PE/PA) thin film composite (TFC) nanofiltration (NF) membranes, 1,4,7,10-tetraazacyclododecane (Cyclen) was added in the aqueous phase with polyethyleneimine (PEI) monomer. During reverse interface polymerization (RIP) on polyethylene (PE) substrates, phthaloyl chloride (PC) was added to the organic phase with terephthaloyl chloride (TPC) monomer. It was found that the addition of Cyclen and/or PC could both increase the hydrophilicity, surface roughness and average pore sizes of formed virgin PE/PA TFC NF membranes, leading to increased water permeability. The Li + /Mg 2+ separating factor S Li/Mg first increased and then decreased with maximum points at the TPC/PC ratio of 5:1 and Cyclen addition level of 0.02 wt%. Cation absorption, especially Mg(II)-Cyclen interactions in the PA layers under higher Mg 2+ /Li + ratio led to increased surface Zeta potential, decreased average pore diameters μ p, and greatly increased Li + /Mg 2+ separating factor (S Li/Mg ). S Li/Mg value of PEI-TPC/PC 5:1 -Cyclen 0.02 membranes could be increased from 5.0 to 55.47, keeping the water permeability around 6.5 L m −2  h −1  bar −1 when Mg 2+ /Li + ratio increased from 1 to 100 in the brine.

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DESALINATION · 2022 · IF 11.211

Synergistic regulation of macrocyclic polyamine-based polyamide nanofiltration membranes by the interlayer and surfactant for divalent ions rejection and mono-/di-ions sieving

Ming Wang,Mengxin Li,Zhaohui Fei,Jiakun Li,Zhongyi Ren,Yingfei Hou

For nanofiltration membranes, the selective separation of divalent/monovalent cations with high permeance is a desirable yet challenging demand due to the trade-off phenomenon between the perm-selectivity and permeance. In this study, a novel macrocyclic polyamine 1, 4, 7, 10-tetraazacyclododecane (Cyclen) is used as the aqueous phase monomer to construct a nanofiltration (NF) membrane with high permeance without sacrificing the perm-selectivity. The large molecular size of Cyclen greatly limits its interfacial mass transfer across the water/oil interface, resulting in the formation of many defects in the separation layer. Based on the widely applied interlayer technology in literature, a surfactant-assembly regulated interfacial polymerization (SARIP) is adopted to intensify the phase transfer process of the Cyclen. The interlayer accommodates enough Cyclen monomers and the surfactant acts as the phase transfer catalyst, which jointly enhance the monomer's phase transfer rate. The resultant polyamide membrane yields a uniform sub-nanometre pore size, and the combination of reduced pore size and charge distribution within the pores achieves high rejection for divalent ions and low rejection of monovalent ions, with the rejection order of LiCl (18.9 %) < NaCl (24.8 %) < MgSO 4 (96.2 %) < MgCl 2 (96.3 %) < Na 2 SO 4 (97.0 %). The corresponding water permeance for MgCl 2 reaches up to 18.5 L·m −2 ·h −1 ·bar −1 with the desirable Li + /Mg 2+ and Na + /Mg 2+ perm-selectivity of 21.9 and 20.3, respectively.

CAS / MDL: 294-90-6
研究领域: 材料科学 · 环境工程 · 化学工程
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