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Green Energy & Environment · 2026 · IF 16.7

Ultrathin c-oriented Cu-TCPP membrane towards shape-selective molecular separation

Xiangyu Guo,Changxue Xie,Xinyao Dong,Han Xiao,Huiye Wei,Kaidi Mao,Tongan Yan,Yunpan Ying,Huina Wang,Chongli Zhong

Highly c-oriented Cu-TCPP ultrathin membrane was prepared through in-situ conversion method. • Green solvents and minimal amount of ligand were used in membrane preparation process. • The membrane can efficiently discriminate linear molecules from non-linear and non-planar molecules. • The shape-based separation mechanism was verified by DFT calculation. Efficient separation of molecules with similar molecular weights is highly demanded in chemical and pharmaceutical industries, yet still hard to achieve with traditional polymer-based membranes. Metal-organic framework (MOF) membranes, especially ultrathin two-dimensional (2D) MOF membranes, offer a good opportunity for realizing these separations. However, current 2D MOF membranes are mainly prepared through the deposition method, which can bring uncertainty to the pore channels, compromising the separation ability. This work reports the preparation of a highly c-oriented ultrathin Cu-TCPP membrane through an electrostatic-assisted in-situ oriented transformation strategy using electrostatically adsorbed copper hydroxide nanostrands as a precursor layer. The resultant membrane has explicit transport channel to be the pores of Cu-TCPP, which enables the efficient discrimination of linear molecules from non-linear and non-planar molecules with similar and even lower molecular weights. Both the experimental work and density functional theory calculations confirm the sieving effect of the Cu-TCPP membrane towards two model molecules (methyl orange and hematoxylin). This work provides a paradigm for fully utilizing the potential of MOF membranes in the precise separation of molecules with similar molecular weights. Effective nanofiltration separation of molecules with similar molecular weights based on steric shape difference is enabled by the ultrathin c-oriented Cu-TCPP membrane prepared through a green and facile electrostatic assisted in-situ conversion strategy Download: Download high-res image (321KB) Download: Download full-size image

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INORGANIC CHEMISTRY COMMUNICATIONS · 2026 · IF 5.9

Single-atom engineering enhanced photodynamic sterilization of 2D In-TCPP MOF nanosheets

Miaoyuan Zhang,Qian Wu,Shaowu Liu,Li Miao,Qi Yang,Ruixue Yu,Xiangqian Li,Huashan Gao,Xinhua Zheng

Atomic layer deposition (ALD) is utilized to precisely construct Pt single atoms and Pt nanoparticles on In-TCPP nanosheets. • The Pt single-atom sites are shown to markedly enhance photodynamic performance by facilitating charge separation and increasing singlet oxygen ( 1 O 2 ) generation compared to Pt nanoparticles. • The resulting Pt SA /In-TCPP composite achieves broad-spectrum photodynamic inactivation against both S. aureus and E. coli via a 1 O 2 -dominated oxidative stress pathway. In the face of the increasingly serious threat of multidrug-resistant bacteria, it is urgent to develop new non-antibiotic antibacterial strategies. Photodynamic therapy (PDT) has attracted much attention due to its advantages of low invasiveness, controllable time and space, and not easy to induce drug resistance, but its efficacy is highly dependent on the photogenerated charge separation efficiency of photosensitizers. In this study, Pt single atoms (Pt SAs) and platinum nanoparticles (Pt NPs) were precisely constructed on the surface of two-dimensional porphyrin metal organic framework (In-TCPP) nanosheets by atomic layer deposition technology. The size effect of platinum species and the enhancement mechanism of single atom construction on photodynamic performance were systematically explored. The evaluation of photodynamic performance shows that Pt single atom modified In-TCPP (Pt SA /In-TCPP) is superior to Pt nanoparticles modified In-TCPP and In-TCPP in the efficiency of generating total reactive oxygen species and singlet oxygen. In vitro antibacterial experiments showed that Pt SA /In-TCPP exhibited excellent broad-spectrum bactericidal performance under 660 nm laser irradiation. This study confirms that the controllable construction of single atom sites by ALD technology is an effective strategy to improve the photodynamic sterilization efficiency of MOF, and provides a new idea for the development of high-performance antibacterial nanomaterials. Multidrug-resistant bacteria pose a severe threat, necessitating antibiotic-free strategies. Herein, Pt single atoms are precisely deposited on 2D In-TCPP MOF nanosheets via atomic layer deposition. Notably, Pt SA /In-TCPP exhibits excellent broad-spectrum photodynamic sterilization against both S. aureus and E. coli under 660 nm laser irradiation, achieving complete bacterial inactivation. Download: Download high-res image (154KB) Download: Download full-size image

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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Simultaneous detection of moxifloxacin and gatifloxacin by Cu-TCPP/rGO electrochemical sensor

Xiao-Zhen Feng,Kun-Zhi Wang,Ke-Hang Song,Guo-Cheng Han,Bing-Lun Li,Heinz-Bernhard Kraatz

Moxifloxacin (MOX) and gatifloxacin (GAT) are structurally similar and possess close oxidation peak potentials, making it difficult for simultaneous detection by electrochemical methods. To address this, an electrochemical sensor was constructed with reduced graphene oxide (rGO) and copper porphyrin complex (Cu-TCPP), achieving signal amplification and simultaneous detection of MOX and GAT. The linear relation range from 5.00 to 600.00 μmol·L −1 for MOX (LOD is 1.34 μmol·L −1 ) and 10 to 300 μmol·L −1 for GAT (LOD is 0.59 μmol·L −1 ). When applied to water samples, it achieved recoveries of 100.09–112.02 % with a relative standard deviation (RSD) of less than 6 % for MOX, and 97.27–110.72 % with an RSD of less than 4 % for GAT. Further calculations indicated that the electro-oxidation of GAT involved two protons and two electrons.

CAS / MDL: 50-81-7 51-61-6
研究领域: 分析化学 · 药物分析 · 电化学
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ACS Applied Materials & Interfaces · 2019 · IF 8.456

Constructing Unique Cross-Sectional Structured Mixed Matrix Membranes by Incorporating Ultrathin Microporous Nanosheets for Efficient CO2 Separation

Xueqin Li,Jinpeng Hou,Ruili Guo,Zhongming Wang,Jianshu Zhang

Ultrathin microporous nanosheets denoted as Zn-tetra-(4-carboxyphenyl)porphyrin (Zn-TCPP) were synthesized and incorporated into a Pebax MH 1657 (Pebax) polymer to fabricate mixed matrix membranes (MMMs) for efficient CO2 separation. The Zn-TCPP nanosheets with a microporous structure provide high-speed channels for fast CO2 transport and shorten the diffusion pathways, both contributing toward high CO2 permeability. Furthermore, scanning electron microscopy results indicate that the ultrathin Zn-TCPP nanosheets with an ultrahigh aspect ratio (>200) tend to arrange horizontally in the Pebax matrix. The obtained unique cross-sectional structure of the MMMs functions as a selective barrier, allowing repeated discrimination of gases due to the tortuous interlayer of horizontal nanosheets, thus improving the selectivity of the MMMs. In addition, the horizontally arranged microporous nanosheets were found to strongly interact with the membrane matrix and endowed the MMMs with excellent interfacial compatibility, which improved the CO2 permeability and eliminated unselective permeation pathways. Significantly, the optimized CO2 separation performance of the MMMs surpassed the 2008 Robeson’s limit.

CAS / MDL: 14609-54-2
研究领域: 材料科学 · 环境工程
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Biomimetic photocatalyst Ce/TCPP-UiO-66-NH2 for NADH regeneration and CO2 activation

Hao Guo,Likun Luan,Jinde Cai,Xiuling Ji,Haijun Yu,Yuhong Huang

CO 2 activation and conversion by enzymes to produce value-added multi-carbon compounds under mild conditions show significant impact on carbon neutrality. However, the enzyme co-factor NADH is expensive and the regeneration is still challenging for the enzyme reaction process. Inspired by natural photosynthesis, this study successfully developed a biomimetic photocatalyst Ce/TCPP-UiO-66-NH 2 (TCPP: meso-tetrakis (4-carboxyphenyl) porphine) for NADH regeneration and CO 2 activation. Structure analysis and spectra showed that the co-doping of Ce and TCPP reduced the band gap width of UiO-66-NH 2 , improved the separation efficiency of photo-generated carriers, and endowed it with excellent photocatalytic performance. The synthesized biomimetic photocatalyst Ce/TCPP-UiO-66-NH 2 was then applied for NADH regeneration. The regeneration efficiency of NADH can reach up to 95 % after 3 h of light reaction, which was about 1.6 times higher than that of the control group. Ultra-fast femtosecond time-resolved transient absorption (fs-TA) showed that Ce/TCPP-UiO-66-NH 2 possessed the shortest average decay time ( τ ¯ τ¯  = 1.12 ps), indicating shorter average life-time of carriers after Ce doping, thus suppressing hole-electron recombination. Finally, the key enzyme formate dehydrogenase (FDHPa) for CO 2 activation was immobilized on the membrane, combining with light regeneration of NADH for CO 2 production to formate. The formate yield (3.1 mM) was 16 times higher than that of the control group (0.19 mM). This work provided an effective strategy and efficient photocatalyst for the biomimetic photocatalytic activation of CO 2 to formate, which is an indispensable bridge for the further high-valuable C n compounds production by biocatalysis.

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Biosensors-Basel · 2024 ·Vol. 14 ·期 6 ·276 · IF 4.9

Construction of Metal–Organic Framework as a Novel Platform for Ratiometric Determination of Cyanide

Zongbao Sun,Zhiwei Wu,Yiran Zong,Chen Li,Wang Guo,Yiqing Guo,Xiaobo Zou

Metal–organic frameworks (MOFs) are frequently utilized as sensing materials. Unfortunately, the low conductivity of MOFs hinder their further application in electrochemical determination. To overcome this limitation, a novel modification strategy for MOFs was proposed, establishing an electrochemical determination method for cyanides in Baijiu. Co and Ni were synergistically used as the metal active centers, with meso−Tetra(4−carboxyphenyl)porphine (TCPP) and Ferrocenecarboxylic acid (Fc−COOH) serving as the main ligands, synthesizing Ni/Co−MOF−TCPP−Fc through a hydrothermal method. The prepared MOF exhibited improved conductivity and stable ratio signals, enabling rapid and sensitive determination of cyanides. The screen−printed carbon electrodes (SPCE) were suitable for in situ and real−time determination of cyanide by electrochemical sensors due to their portability, low cost, and ease of mass production. A logarithmic linear response in the range of 0.196~44 ng/mL was demonstrated by this method, and the limit of detection (LOD) was 0.052 ng/mL. Compared with other methods, the sensor was constructed by a one−step synthesis method, which greatly simplifies the analysis process, and the determination time required was only 4 min. During natural cyanide determinations, recommended readouts match well with GC−MS with less than 5.9% relative error. Moreover, this electrochemical sensor presented a promising method for assessing the safety of cyanides in Baijiu.

研究领域: 分析化学 · 食品科学 · 材料科学
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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

High selectivity, ultra-sensitivity, and ultra-distinguishability of electrochemical sensing platform for simultaneous detection of dopamine, uric acid, and ascorbic acid

Xin Xu,Ximing Guo

Dopamine (DA), uric acid (UA), and ascorbic acid (AA), three similar electroactive biological small molecules, generally coexist in human serum, causing serious interference when detected separately. In order to realize the simultaneous detection of DA, UA, and AA, three similar electroactive biomolecules, through the electrochemical sensing platform based on 2D Cu-TCPP MOFs nanofilms, DA molecules were successfully detected and optimized the detection conditions according to our previous detection methods for UA and AA. The results displayed the perfect electrochemical response signal of DA, excellent linear correlation between current intensity and DA concentration, LODs, repeatability, and stability. The electrochemical potential (E pa ) of UA oxidation peak was intermediate between E pa of AA and DA oxidation peak, the response current intensity of UA oxidation peak continuously decreases with increases of UA concentration. The response current intensity of DA and AA oxidation peak on both sides of UA gradually increases with the increase of DA and AA concentration. On the other hand, there is a significant difference in the oxidation potential difference between adjacent substances DA, UA, and AA (ΔE AA-UA  = 141 mV, ΔE UA-DA  = 167 mV, and ΔE AA-DA = 308 mV), which will play a decisive role in the simultaneous detection of DA, UA, and AA based on 2D Cu-TCPP MOFs/GCE electrochemical sensing platform. Therefore, the electrochemical platform based on 2D Cu-TCPP MOFs nanofilms is more conducive to the simultaneous detection of DA, UA, and AA with high selectivity, ultra-sensitivity, and ultra-distinguishability.

研究领域: 分析化学 · 生物医学工程 · 电化学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Facile synthesis of porphyrin-MOFs with high photo-Fenton activity to efficiently degrade ciprofloxacin

Chang Ping Yang,Cong Yi Hu,Zhong Wei Jiang,Si Yu Xiao,Xiao Yan Wang,Cheng Zhi Huang,Yuan Fang Li,Shu Jun Zhen

The slow conversion of Fe(Ⅱ)/Fe(III) cycle was largely limited the degradation efficiency of many photo-Fenton systems. Herein, four Fe-MOFs nanorods (namely Fe-TCPP-1, Fe-TCPP-2, Fe-TCPP-3, Fe-TCPP-4) with decreasing length-diameter ratios were synthesized in a household microwave oven, using photosensitizer porphyrin and iron ions with Fenton activity as building blocks. Among them, the Fe-TCPP-3 exhibited high photogenerated electron-hole ( e − - h + ) separation efficiency and largest pore structure , endowing Fe-TCPP-3 with superior photo-Fenton property. In addition, Fe-TCPP-3 based photo-Fenton system was applied to efficiently degrade antibiotic ciprofloxacin (CIP) under neutral condition, due to the continuously generated reactive species ( h + , e − , OH · , O 2 ·– , 1 O 2 ) in Fe-TCPP-3 under visible-light irradiation. With irradiation for 30 min, the degradation efficiency of the system could reach about 73 %, which was about 26-fold towards the system without light irradiation . This study paved a way to modulating the photo-Fenton activity of MOF-based catalysts.

研究领域: 材料科学 · 环境化学 · 光化学
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CHEMISTRY OF MATERIALS · 2018 · IF 9.89

Synthesis of Metal–Organic Framework Nanosheets with High Relaxation Rate and Singlet Oxygen Yield

Yuewu Zhao,Ye Kuang,Min Liu,Jine Wang,Renjun Pei

A novel gadolinium–porphyrin metal–organic framework (MOF) nanosheet was synthesized by coordination chelation between gadolinium(III) ions and 4,4,4,4-(porphine-5,10,15,20-tetrayl) tetrakis (benzoic acid) (TCPP). The mechanism and molecular structure of the prepared Gd-TCPP products were analyzed through the comparison of 4,4,4,4-(porphine-5,10,15,20-tetrayl) tetrakis (benzenesulfonic acid) (TPPS) and TCPP. The Gd-TCPP MOF nanosheets exhibit a high relaxation rate of 40.8 mM–1 s–1, which is better than the rates for most reported contrast agents. In addition, the photosensitive activity of the Gd-TCPP nanosheets was enhanced compared to TCPP owing to the special periodic porous structure of the MOF, indicating that the Gd-TCPP nanosheets could produce the singlet oxygen (1O2) more effectively under irradiation by visible light. Performance enhancement was observed for both metal ions and organic ligands in the Gd-TCPP MOF nanosheets. This study presents a new concept in the development bifunctional MOF nanomaterials with enhanced performance in magnetic resonance imaging and photodynamic therapy.

CAS / MDL: 14609-54-2
研究领域: 材料科学 · 医学影像 · 光敏剂研究
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ACS Applied Nano Materials · 2023 · IF 5.9

Ultrathin Cu–TCPP Nanosheet-Based Electrochemical Microsensor for Detecting the Immunosuppressive Drug Mycophenolic Acid

Mingshi Deng,Wei Jin,Wenjuan Yang,Lingling Tian,Xinghua Gao,Xuefeng Wang,Lingyan Feng,Metini Janyasupab,Bingpu Zhou,Yuan Zhang

Mycophenolic acid (MPA), which is a potent immunosuppressant, has been widely used to prevent organ rejection after organ transplantation. In clinical practice, it is essential to monitor the free MPA concentration. Herein, convenient and fast electrochemical microsensing technology is developed for directly detecting the MPA concentration. To implement this method, ultrathin copper-based metal–organic framework (Cu–MOF) nanosheets with a thickness of about 6.6 nm are used to detect MPA. An analysis of electrochemical behavior reveals the direct electrochemical catalytic oxidation mechanism of MPA molecules on a Cu(II) tetrakis(4-carboxyphenyl)porphyrin (Cu–TCPP)-modified electrode. Furthermore, electrochemical testing results show that the ultrathin Cu–TCPP nanosheet-based microsensor exhibits high sensitivity and specificity for MPA in the nano- to micromolar range, with a detection limit of 10 nM. X-ray absorption spectroscopy (XAS) characterization reveals that the unsaturated metal ions in ultrathin nanosheets are the active sites responsible for boosting the catalytic oxidation of MPA molecules. High-performance liquid chromatography–tandem mass spectrometry further shows the catalytic oxidation product of MPA and that the phenolic hydroxyl group in the MPA molecule is the active site where the catalytic reaction occurs. The considerable sensing performance of the Cu–TCPP nanosheet-based microsensor proves that it is possible to develop a fast and convenient method for the direct high-frequency monitoring of immunosuppressive drugs.

研究领域: 分析化学 · 生物医学工程 · 药物分析
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JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY · 2026 · IF 4.4

Er3+-doped in-TCPP accelerates carrier migration to achieve high-efficiency photocatalytic H2 evolution

Qinghong Cai,Chenghua Zhang,Kejie Peng,Yishuang Luo,Youzhou He,Ning Li,Xiaoli Xiong,Xingyan Liu,Min Fu,Bowen Lei

Preparation of upconversion efficient In-TCPP via an “ internally-empowered “ Strategy. • Synergistic enhancement of light absorption and charge carrier migration via the upconversion effect and IEF. • The ITE has highly efficient photocatalytic production capacity of H 2 . The practical application of photocatalytic hydrogen production is primarily constrained by high charge carrier recombination rates and low light utilization efficiency. Herein, upconversion elements Er 3+ was introduced into the In-TCPP framework to prepare In-TCPP-Er-X% (ITE-X%). The ITE-3% demonstrated the optimal photocatalytic hydrogen evolution rate of 183 μmol·g −1 ·h −1 , representing 1.99 times enhancement over In-TCPP. The introduction of Er 3+ not only endows In-TCPP with an upconversion effect but also optimizes its internal charge distribution, generating a strong built-in electric field (IEF) which confirmed by electron paramagnetic resonance (EPR), upconversion fluorescence (UCPL) and DFT. Under the synergistic effect of the upconversion and IEF, ITE-3% can more effectively utilize low-energy near-infrared (NIR) light and promote charge carrier separation, thereby achieving efficient photocatalytic hydrogen production. This work demonstrates the synergistic effect of upconversion and IEF in enhancing photocatalytic hydrogen evolution, thereby paving the way for broader NIR light application. Upconversion elements (Er 3+ ) was doped with In-TCPP. Under the synergistic effect of upconversion and built-in electric field, In-TCPP doped with Er 3+ (ITE-3%) exhibited enhanced light absorption and carrier migration capabilities, demonstrating optimal photocatalytic performance. Download: Download high-res image (140KB) Download: Download full-size image

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JOURNAL OF MEMBRANE SCIENCE · 2020 · IF 7.183

Photothermal responsive ultrathin Cu-TCPP nanosheets/sulfonated polystyrene nanocomposite photo-switch proton conducting membranes

Shabab Hussain,Zheng Deng,Amin Khan,Peipei Li,Zhuoyi Li,Zhou Fang,Xinyi Wan,Xinsheng Peng

Applying different strategies, nanocomposite membranes formation from functionalized polymer(s) and compatible nanofillers is the most renowned way to make the membrane proton conductive without compromising their mechanical strength . Among different types of nanofillers, incorporating photothermal-responsive metal organic frameworks (MOFs) into the ion exchange polymer is the prominent strategy and has achieved advanced attention in smart protonic solids with versatile potential applications. In this work, ultrathin, highly ordered porous photothermal-responsive copper tetrakis(4-carboxyphenyl)porphyrin (Cu-TCPP) nanosheets are incorporated into sulfonated polystyrene (SPS) membranes as novel nanofillers. High loading and well dispersed Cu-TCPP nanosheets incorporated nanocomposite membranes are achieved and demonstrate photo-switchable protonic conductivity due to photothermal response of MOFs nanosheets to visible light. The nanocomposite membrane with highest MOFs content shows a high proton conductivity of 1.42 × 10 −4  S cm −1 at 95 °C at 95% RH. The altered photo-switch proton conductivity of nanocomposite membranes is attributed to the formation and breakage of H-bonding networks with water molecules in the channels of proton transport pathways by the local photothermal heated Cu-TCPP nanosheets. Furthermore, after incorporation of the Cu-TCPP nanosheets into SPS, not only the thermal stability is increased but also almost zero swelling is achieved in water, which reflects the nice durability of nanocomposite membranes. This photo-switchable proton conductivity of polymer proton conducting nanocomposite membranes with nice thermal stability and negligible swelling serves as a new gate for photo-switching proton conductive membranes, photosensors , photoswitches etc .

研究领域: 材料科学 · 化学工程
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