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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2022 ·Vol. 23 ·期 22 ·14337 · IF 6.208

Coordinative Combination of Nitroamine and Gem-Dinitromethyl with Fused Ring for Enhanced Oxygen Balances and Detonation Properties

Xun Zhang,Yaxi Wang,Xinyuan Zhao,Chunlin He,Siping Pang

Oxygen balance and heat of formation are closely related to the nitrogen and oxygen content in a molecule and have a significant effect on the detonation performance of energetic materials. Here a new family of 1,2,4-triazolo [4,3-b][1,2,4,5]-tetrazine containing gem-dinitromethyl and nitroamine with high nitrogen-oxygen content was synthesized and characterized. Moreover, the structure of the guanidine salt (3) and TATOT salt (4) were confirmed by single-crystal X-ray diffraction. The nitrogen and oxygen content of ammonium salt2reached 82.5%, with a high density (1.805 g cm−3) and high detonation properties (D= 8900 m s−1;P= 32.4 GPa), which were similar to those of RDX.Keywords:nitroamine;gem-dinitromethyl;high nitrogen-oxygen content;triazolo-tetrazine fused ring

研究领域: 化学 · 材料科学
✓ 已验证 DOI PubMed 高影响因子
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FREE RADICAL BIOLOGY AND MEDICINE · 2025 · IF 8.2

A hemicyanine-based dual-modal probe for fluorescence and mass spectrometry imaging of peroxynitrite in biosamples

Yuejie Zhang,Jingfeng Zhang,Weiwei Tang,Bin Li

Peroxynitrite (ONOO - ) is a highly reactive oxidant formed by the reaction of nitric oxide with superoxide. Excessive ONOO - can be produced by the body in response to multiple diseases, resulting in cell death through oxidation and nitration processes. However, technical challenges arise in detection due to its high reactivity and very short lifespan. In this work, we rationally designed and synthesized a novel tetrazine-hemicyanine-based probe (TZN-HCY). This probe demonstrates the ability to capture ONOO - with high selectivity and sensitivity, enabling the detection and imaging of ONOO - in biological samples with both fluorescence and MALDI MS. The 3,6-disubstituted tetrazine moiety could react with ONOO - , and the hemicyanine skeleton with a permanent positive charge could enhance MALDI MS detection. The responsive performances of the TZN-HCY probe were verified on cell models and livers of hepatic ischemia-reperfusion injury (HIRI) model mice. Due to the applicability to dual-mode imaging, the formation of ONOO - and its content change in the liver of living mice were visualized by fluorescence imaging, while the fine-scale spatial distribution of ONOO - in liver tissues was revealed by MALDI MS imaging. This dual-modal probe could serve as a powerful tool for elucidating the diverse and complex roles of biogenic ONOO - in ischemia-reperfusion injury.

CAS / MDL: 1122-58-3
研究领域: 生物化学 · 医学影像学 · 分子生物学
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Research · 2020 · IF 0

S,S-Tetrazine-Based Hydrogels with Visible Light Cleavable Properties for On-Demand Anticancer Drug Delivery

Changping Wang,Chongyi Liu,Qiyao Wei,Lei Yang,Peng Yang,Yiwen Li,Yiyun Cheng

Photocleavable hydrogels are of great importance in the field of controlled drug delivery, stem cell fate regulation, surface patterning, and intelligent devices. However, the development of novel photocleavable gel systems by visible light is usually met with challenges such as the lack of efficient and tunable photocleavable groups and reactions. Herein, we reported the facile fabrication of a new type of photocleavable hydrogels by the direct gelation of 4-arm thiol-terminated polyethylene glycol with 3,6-dichloro-1,2,4,5-tetrazine via the formation of S,S-tetrazine linkages. The prepared hydrogels underwent efficient degradation upon irradiation by ultraviolet or green light, and the degradation kinetics could be significantly promoted by hydrogen peroxide. Correspondingly, the hydrogels loaded with calcium peroxide microparticles or glucose oxidase/catalase enzymes enabled the precise and efficient in vivo photocontrol of gel degradation and drug release for cancer treatment. This work offers a promising and facile strategy towards the fabrication of visible light cleavable hydrogels with tunable and on-demand drug release properties.

研究领域: 生物材料学 · 药剂学 · 肿瘤学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2021 · IF 3.764

Mechanically Robust and Recyclable Styrene–Butadiene Rubber Cross-Linked via Cu2+–Nitrogen Coordination Bond after a Tetrazine Click Reaction

Qiang Wang,Wenchang Wang,Qiuying Li,Chifei Wu

A metal–ligand complex is a useful noncovalent bond to build up a cross-link network. Unfortunately, it is a challenge to construct the coordination cross-link networks in commercial elastomers without ligand groups on their polymer chains. In this study, first, a tetrazine click reaction using 3,6-di(2-pyridyl)-1,2,4,5-tetrazine (DPT) successfully introduced nitrogen-containing groups into styrene–butadiene rubber (SBR) polymer chains with a facile process in the solid status. Then, the introduced groups on SBR could further coordinate with Cu2+ after mixing with CuSO4 and heating under pressure in bulk. Differential scanning calorimetry, Fourier-transform infrared spectroscopy, 1H NMR, X-ray photoelectron spectroscopy, and thermogravimetric analysis proved the modification of SBR by DPT, as well as the coordination between ligand groups on SBR and CuSO4. Elastic torque curves effectively monitored the formation of coordination cross-link networks. Finally, due to the reversible breaking and re-forming nature of metal–ligand bonds, the coordination cross-linked SBR exhibited high strength and toughness. Tensile strength up to 10.52 MPa at a fracture elongation of 695% was obtained when the designed DPT click reaction degree is 2% and the content of CuSO4 is 10 phr. The corresponding composite exhibited some recycling value, and the related fracture energy could sustain 58.9 and 30.7% compared to the virgin sample after being reprocessed once and three times, respectively. Thus, in this work, a simple approach was developed to convert widely used SBR into mechanically robust materials via metal–ligand bonds with some reprocessing and recycling ability without using any conventional vulcanizing agent and accelerator.

研究领域: 材料科学 · 高分子化学
✓ 已验证 DOI 高影响因子
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SENSORS AND ACTUATORS B-CHEMICAL · 2016 · IF 4.758

A fluorescence resonance energy transfer sensor based on quaternized carbon dots and Ellman’s test for ultrasensitive detection of dichlorvos

Juying Hou,Zhengbin Tian,Huizhi Xie,Qingyuan Tian,Shiyun Ai

Here we first reported an ultrasensitive fluorescence resonance energy transfer (FRET) biosensor of dichlorvos based on carbon dots and the traditionally colorimetric Ellman’s test. In Ellman’s test, the absorption intensity of 5-thio-2-nitrobenzoic acid anion (TNB − ) at 412   nm can be used for the determination of acetylcholinesterase (AChE) and its inhibitor. We chose TNB − as energy acceptors to construct a FRET sensing system of AChE and its inhibitor. Quaternized carbon dots (Q-CDs) were chosen as energy donors to form an effective FRET system. By a two-step synthetic method, the Q-CDs with high quantum yield (34.2%) were successfully prepared. Experimental results showed TNB − can quench the fluorescence of Q-CDs to a large extent, which indicated an effective FRET between Q-CDs and TNB − was successfully established. As the inhibitor of AChE and common organophosphorus insecticide, dichlorvos can be detected using this sensing system. Under optimal conditions, the linear range of dichlorvos was 5.0   ×   10 −11 –1.0   ×   10 −7   M. Owing to the high sensitivity and green fluorescent material with high quantum yield, this FRET sensing system was adaptable for automated analyzers using in the rapid determination of a great quantity of samples.

研究领域: 分析化学 · 环境科学 · 毒理学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2025 · IF 3.9

Fabrication of a Nitrogen-Rich Porous Polymer Network with Dense Polytriazine and Polytetrazine for CO2 Capture

Yao Jiang,Dongdong Zheng,Kang Wang,Mingming Xu,Qi Wang,Peng Cui,Lin-Bing Sun

Porous polymer networks are considered potential candidates for CO2 capture, owing to their well-developed porosity and high stability. However, their further application is limited by the relatively low selectivity and unsatisfactory adsorption capacity. In this study, we fabricated a nitrogen-rich porous polymer network, denoted as NRPPN-1, with dense polytriazine and polytetrazine by polymerization of two monomers of melamine and 3,6-dichloro-1,2,4,5-tetrazine. The resulting NRPPN-1 exhibits an abundance of micropores and a high surface area of 668 m2·g–1. Experimental results demonstrate that NRPPN-1 has excellent CO2 adsorption capacity (181.2 mg·g–1) and adsorption selectivity (306.4) at 273 K and 100 kPa for CO2/N2 mixtures, which are corroborated by adsorption potential and breakthrough curve analysis. Moreover, computational simulations reveal that the abundant nitrogen-rich active sites in NRPPN-1 induce strong C···N interactions, which are responsible for the promoted selective capture of CO2 from CO2/N2 mixtures. The novel nitrogen-rich porous polymer network may serve as a promising candidate for the capture of CO2 from flue gas.

CAS / MDL: 108-78-1
研究领域: 材料科学 · 环境科学
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EUROPEAN POLYMER JOURNAL · 2021 · IF 4.598

Toughening, recyclable and healable nitrile rubber based on multi-coordination crosslink networks after “tetrazine click” reaction

Qiang Wang,Yi Shi,Qiuying Li,Chifei Wu

The recycling and self-healing functions of commercial rubber are of great significance in the field of sustainable materials. So far, manufacturing such rubber with excellent strength and toughness was still a huge challenge. Herein, the multi-coordination crosslink networks were designed to achieve this goal. First, the nitrile-butadiene rubber (NBR) was modified through 3,6-di(2-pyridyl)-1,2,4,5-tetrazine (DPT) click reaction to introduce the second ligand group. Next, the blend of modified NBR and metal salt (including ZnCl 2 and CoCl 2 ) was hot-pressed to form the metal-nitrile and metal-pyridine (nitrogen-containing heterocyclic groups) coordination bonds. The designed composite had ultra-high mechanical strength and toughness at the same time. Compared with the NBR/ZnCl 2 composite, the tensile strength of NBR-DPT4-Zn10 composite with multi- coordination bonds was improved by 7.5-fold (from 5.5 MPa to 46.82 MPa), and the corresponding fracture energy was improved by 142% (from 26.2 MJ m −3 to 63.5 MJ m −3 ). At the same time, the high recyclable and heat-healing efficiency were obtained. These achievements are expected to develop commercial rubber’s recyclability and high mechanical properties.

CAS / MDL: 1671-87-0
研究领域: 材料科学 · 可持续材料 · 聚合物化学
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FirePhysChem · 2022 · IF 0

A novel synthetic method of 1,1,4,4-tetramethyl-2-tetrazene (TMTZ) via photocatalytic reaction

Kunkai Wang,Xiangzhi Li,Kaidi Yang,Huan Huo,Qi Xue,Bozhou Wang,Fuqiang Bi

1,1,4,4-Tetramethyl-2-tetrazene (TMTZ), a potential candidate for replacing 1,1-dimethylhydrazine (UDMH), has excellent properties including a high specific impulse, non-toxicity and non-volatility. However, most synthetic methods depicted in the literature use stoichiometric oxidative coupling, and the oxidizing agents are usually heavy metals or halogens, leading to low synthetic efficiency and high environmental pollution. In order to overcome these problems, it is necessary to explore more environmentally friendly and catalytic synthetic methods. In this paper, a method of photocatalytic oxidative coupling for the preparation of TMTZ was reported for the first time. By using an organic photocatalyst Eosin Y, TMTZ was synthesized rapidly and efficiently. The thermal decomposition properties of TMTZ were studied, and different performance characteristics between TMTZ and UDMH were determined and analyzed, which provided a basis for the application of TMTZ based new liquid propellant.

研究领域: 有机化学 · 催化化学 · 能源材料 · 推进剂化学
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ANALYST · 2010 ·Vol. 135 ·期 8 ·2139-2143 · IF 3.272

Determination of formaldehyde in aqueous solutions by a novel fluorescence energy transfer system

Lun Wang,Cai-Ling Zhou,Hong-Qi Chen,Jing-Guo Chen,Jie Fu,Bo Ling

An efficient fluorescence energy transfer (FET) system between CePO4:Tb3+ nanocrystals as donor and 6-mercapto-5-triazole[4,3-b]-S-tetrazine as acceptor was built. CePO4:Tb3+ nanocrystals were synthesized in aqueous solutions, and characterized by transmission electron microscopy, electron diffraction pattern spectroscopy and spectrofluorometry. Under alkaline conditions, 6-mercapto-5-triazole[4,3-b]-S-tetrazine was generated by redox reaction of formaldehyde (HCHO) with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (AHMT) at room temperature. The degree of the overlap was effective for FET between the emission spectrum of CePO4:Tb3+ and the absorption spectrum of 6-mercapto-5-triazole[4,3-b]-S-tetrazine. Based on this system, a simple and sensitive fluorescence method for the selective determination of formaldehyde in aqueous solutions was developed. Under optimal conditions, the quenched fluorescence intensity increased linearly with the concentration of HCHO ranging from 1.03 × 10−9 to 1.03 × 10−5 mg mL−1 with a correlation coefficient of 0.9976. The limit of detection was 1.65 × 10−10 mg mL−1. Compared with several methods, the proposed method had a wider linear range, higher selectivity and sensitivity. Moreover, analytical application of the method was demonstrated by water samples.

研究领域: 分析化学 · 环境监测 · 纳米材料 · 生物传感 · 分子探针
✓ 已验证 DOI 高影响因子
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Journal of Environmental Chemical Engineering · 2025 ·Vol. 13 ·期 6 ·120317 · IF 7.2

Highly selective crystallization of uranium complexes for actinide partitioning in nuclear waste streams

Yarui Li,Guangtao Zhang,Xiaoyuan Zhou,Qing Zou,Jiarui Chen,Yunyi Cui,Peng Lin,Jian Lin

Partitioning actinides from lanthanides is essential for the safe management of nuclear waste and the long-term sustainability of nuclear energy. Here, we report a crystallization-based strategy that leverages the metal-dependent hydrolysis of 3,6-bis-2-pyridyl-1,2,4,5-tetrazine (L1) to generate distinct coordination environments. Specifically, U(VI) hydrolysis produces ( E )-N′-(pyridin-2-ylmethylene) picolinohydrazide (L2), directing the formation of a robust tetranuclear uranyl complex with pentagonal bipyramidal geometry. In contrast, Ln(III) fails to crystallize under the same conditions, and Pd(II) forms crystalline products only under specific solvothermal conditions via L1 hydrolysis, which generates 2-pyridinecarboxylicacid, 2-(2-pyridinylcarbonyl)hydrazide (L3). Systematic evaluation of acidity, ligand stoichiometry, and crystallization kinetics revealed conditions under which U(VI) selectively crystallizes from simulated spent nuclear fuel streams containing 22 competing elements, affording crystalline products with purities up to 99.8 %. High separation factors (SFs) were achieved, with values of 985, 2813, 2536, 1786, 1612, and 6571 for U/Y, U/Ce, U/Pr, U/Eu, U/Gd, and U/Dy, respectively, while ReO 4 – , used as a surrogate for 99 TcO 4 – , exhibited an exceptional SF of 303905. This work demonstrates that crystallization can provide a simple, highly selective, and waste-minimizing pathway for uranium recovery, offering a promising new paradigm for actinide partitioning in spent nuclear fuel reprocessing.

CAS / MDL: 1671-87-0
研究领域: 核化学 · 放射化学 · 分离科学 · 无机化学 · 废物管理
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JOURNAL OF CONTROLLED RELEASE · 2023 · IF 10.8

Targeted delivery of PROTAC-based prodrug activated by bond-cleavage bioorthogonal chemistry for microneedle-assisted cancer therapy

Jing Huang,Zhuo Yao,Bowen Li,Yuan Ping

Proteolysis-targeting chimera (PROTAC) is emerging as a new strategy to degrade target proteins in a precise way by taking advantage of the cellular ubiquitin-proteasome system. However, the potential cytotoxicity of PROTAC should be avoided to mitigate the off-target degradation of proteins in healthy tissues or cells. To address this issue, we herein present a strategy to cage a PROTAC with 4-(vinyloxy) benzyl carbonate ( MZ1-O ), which can be eliminated through a 3,6-dimethyl-1,2,4,5-tetrazine ( Tz )-mediated inverse electron-demand Diels-Alder (iEDDA) reaction to generate a BRD4 (bromodomain-containing protein 4) degrader, MZ1 . We further propose a dissolvable microneedle-assisted strategy for site-specific activation of MZ1-O that is delivered by a targeted delivery vector through systemic route in vivo , and demonstrate such a bioorthogonal strategy is efficient and precise for tumor treatment. Our study suggests that the bioorthogonal activation of PROTAC-based prodrug offers a highly specific and precise approach for cancer therapy.

研究领域: 药理学 · 癌症研究 · 化学 · 生物医学工程
✓ 已验证 产品关联 DOI PubMed 高影响因子
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ADVANCED FUNCTIONAL MATERIALS · 2025 · IF 19

An AB-Type Hydrogel CT Contrast Agent for Precise Localization of Intra-Abdominal Hemorrhage

Kanghua Zeng,Bohong Chen,Qifan Liu,Zheng Zhou,Xiahong Xie,Xiangna Zhang,Xiang Li,Xiuping Zhang,Ben Ma,Mingzhou Ye

Intra-abdominal hemorrhage is a life-threatening condition with high mortality. Rapid localization of the bleeding point is crucial. Conventional computed tomography (CT) imaging is limited by the rapid diffusion and poor retention of small-molecule iodine agents, restricting sensitivity and imaging duration. To overcome these challenges, an “AB-type” hydrogel CT contrast system is developed based on bio-orthogonal click chemistry, designed to enhance both detection sensitivity and spatial precision. The system consists of iodized oil-loaded liposomal nanoparticles (INb NPs) administered intravenously and tetrazine-functionalized hyaluronic acid (HA-Tz) delivered intraperitoneally. At the bleeding site, the two components undergo a rapid click reaction, forming an in situ hydrogel that anchors the contrast agent for prolonged retention and precise localization. This approach demonstrated efficient gelation in vitro and robust performance in vivo, significantly extending the imaging window and sensitivity compared with Iohexol. HA-Tz@INb NPs enhance CT signal intensity and imaging duration by over 60 fold, enabling sensitive detection of occult bleeding. The hydrogel exhibits excellent biosafety, being removable by lavage and fully degradable within days without adverse effects. By integrating nanotechnology, click chemistry, and hydrogel engineering, this strategy provides a clinically translatable diagnostic platform with superior precision and sensitivity for intra-abdominal bleeding.

CAS / MDL: 362596-00-7
研究领域: 纳米医学 · 生物医学成像 · 急诊医学 · 生物材料 · 分子诊断
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