2D Fe/Co-MOF/SOX cascade reactors for fast noninvasive detection of sarcosine level in prostate cancer urine.

Sarcosine plays a key role in screening for early prostate cancer. However, the several already reported peroxidase mimics immobilized with sarcosine oxidase (SOX) utilized to detect uriary sarcosine still have some limitations such as complex synthesis process, using of expensive heavy metals to mimic enzyme activity and long color development time. Herein, an inexpensive peroxidase-like 2D Fe/Co-MOF nanosheet was prepared by a simple solvent modulation method. The resultant 2D Fe/Co-MOF nanosheets have strong peroxidase activity, with its Vmax value for H2O2 of 15.3 × 10-8 M/s, being 1.76 times that of HRP. Then, using the 2D Fe/Co-MOF as a peroxidase model for anchoring natural SOX to construct 2D Fe/Co-MOF/SOX , which can act as a cascade reactor for detection of sarcosine. Considering the above properties, a platform for the detection of sarcosine was built based on a colorimetric method. Because of presence of the high ratio of Fe2+ caused by the electron transfer from Co2+ to Fe3+, large specific surface area and plentiful active sites, 2D Fe/Co-MOF/SOX with TMB (3,3',5,5'-tetramethylbenzidine) colorimetric reagent could have fast color development and can be applied conveniently and fastly in an early screening tool for prostate cancer patients. The sarcosine could be quantified by peroxidase activity with a detection range of 1-400 µM and a limit of detection (LOD) of 0.324 µM. More importantly, the average sarcosine concentration of 21.367 µM and 1.871 µM was detected in patient's and normal urine (n = 5), respectively, which showed an excellent screening effect and a great potential in early prostate cancer.

[Establishment of rabbit knee osteoarthritis model by simple anterior cruciate ligament disruption].

OBJECTIVE: The rabbit knee osteoarthritis(KOA) model was established by simple anterior cruciate ligament disruption. METHODS: The selected 40 adult white rabbits were randomly divided into two groups, blank group with 6 rabbits and model group with 34 rabbits. The rabbits in model group were given the disruption of anterior cruciate ligament of right knee joint. In the fourth, eighth and the twelfth weeks of modeling, different degrees of degenerative changes have been observed on the rabbits articular cartilages from both macroscopic and microscopic aspects. RESULTS: At 4, 8 and 12 weeks after modeling, the articular cartilage of the rabbits in the model group showed degenerative changes in different degrees. At 8 and 12 weeks, the typical pathological manifestations of KOA in the middle and late stages were found in the infrapatellar fat pad and synovium, respectively. There were no changes in articular cartilage, infrapatellar fat pad and synovial membrane in the blank group at the same time. There were significant differences in the gross score between the model group and the blank group at 4 weeks [(1.300±0.674) vs 0.000], 8 weeks [(2.400±0.516) vs 0.000] and 12 weeks [(3.583±0.668) vs 0.000] (P<0.05), the histopathological scores were significantly different, at 4 weeks [(2.900±0.567) vs 0.000], 8 weeks [(7.500±1.178) vs (0.500±0.707)], 12 weeks[(11.833±1.337) vs (1.500±0.707)], (P<0.05). CONCLUSION: The establishment of rabbit knee arthritis model by simply cutting the anterior cruciate ligament is simple and feasible, with good stability, high success rate, small trauma, short modeling cycle and less changes in animal physiological structure. The rabbit knee arthritis model established by simply cutting the anterior cruciate ligament has good modeling effect on different stages and grades of knee osteoarthritis, and the postoperative infection and trauma can be controlled, which can meet the test requirements.

Tannic Acid Selective Modulation Defects to Enhance the Photocatalytic CO2 Reduction Activity of Layered Double Hydroxides.

Recently, layered double hydroxides (LDH) have shown great potential in photoreduction of CO2 owing to its flexible structural adjustability. In this study, the mild acidic property of tannic acid (TA) is exploited to etch the bimetal LDH to create abundant vacancies to gain the coordination unsaturated active centers. Based on the different chelating abilities of TA to various metal ions, the active metals are remained by selective chelation while the inert metals are removed during the etching process of bimetal LDH. Furthermore, selective chelating with metal ions not only increases the percentage of highly active metals but also compensates for the structural damage caused by the etch, which achieves a scalpel-like selective construction of vacancies. The NiAl-LDH etched and functionalized by TA for 3 h exhibits superior photo-reduction of CO2 performance without co-catalysts and photo-sensitizers, which is 14 times that of the pristine NiAl-LDH. The fact that many bimetal LDHs can be functionalized by TA and exhibit significantly improved photocatalytic efficiency is confirmed, suggesting this strategy is generalized to functionalize double- or multi-metal LDH. The method provided in this work opens the door for polyphenol-functionalized LDHs to enhance their ability for light-driven chemical transformations.

Solid-Liquid-Gas Three-Phase Indirect Electrolysis Enabled by Affinity Auxiliary Imparted Covalent Organic Frameworks.

The design of efficient heterogeneous redox mediators with favorable affinity to substrate and electrolyte are much desired yet still challenging for the development of indirect electrolysis system. Herein, for the first time, we have developed a solid-liquid-gas three-phase indirect electrolysis system based on a covalent organic framework (Dha-COF-Cu) as heterogeneous redox mediator for S-S coupling reaction. Dha-COF-Cu with the integration of high porosity, nanorod morphology, abundant hydroxyl groups and active Cu sites is much beneficial for the adsorption/activation of thiols, uniform dispersion and high wettability in electrolyte, and efficient interfacial electron transfer. Notably, Dha-COF-Cu as solid-phase redox mediator exhibits excellent electrocatalytic efficiency for the formation of value-added liquid-phase S-S bond product (yields up to 99 %) coupling with the generation of gas-phase product of H2 (~1.40 mmol g-1 h-1), resulting in a powerful three-phase indirect electrolysis system. This is the first work about COFs that can be applied in three-phase indirect electrolysis system, which might promote the development of porous crystalline materials in this field.

3D Covalent Organic Frameworks with 16-Connectivity for Photocatalytic C(sp3)-C(sp2) Cross-Coupling.

The connectivity (valency) of building blocks for constructing 3D covalent organic frameworks (COFs) has long been limited to 4, 6, 8, and 12. Developing a higher connectivity remains a great challenge in the field of COF structural design. Herein, this work reports a hierarchical expansion strategy for making 16-connected building blocks to construct 3D COFs with sqc topology. The [16 + 2] construction achieved by condensation between a 16-connected carbazolyl dicyanobenzene-based building block (CzTPN) and linear diamino linkers (BD or Bpy) affords two 3D COFs (named CzBD COF and CzBpy COF). Furthermore, attributed to the well-organized donor-acceptor (D-A) heterojunction, the Ni chelated CzBpy COF (Ni@CzBpy COF) exhibits excellent performance for photoredox/Ni dual catalytic C(sp3)-C(sp2) cross-coupling of alkyltrifluoroborates with aryl halides, achieving a maximum 98% conversion and 94% yield for various substrates. This work developed the first case of high-connectivity COFs bearing 16-connected units, which is the highest connectivity reported until now, and achieved efficient photocatalysis applications, thus greatly enriching the possibilities of COFs.

Synthesis of Isotypic Giant Polymolybdate Cages for Efficient Photocatalytic C-C Coupling Reactions.

The construction of isotypic high-nuclearity inorganic cages with identical pristine parent structure and increasing nuclearity is highly important for molecular growth and structure-property relationship study, yet it still remains a great challenge. Here, we provide an in situ growth approach for successfully synthesizing a series of new giant hollow polymolybdate dodecahedral cages, Mo250, Mo260-I, and Mo260-E, whose structures are growth based on giant polymolybdate cage Mo240. Remarkably, they show two pathways of nuclear growth based on Mo240, that is, the growth of 10 and 20 Mo centers on the inner and outer surfaces to afford Mo250 and Mo260-I, respectively, and the growth of 10 Mo centers both on the inner and outer surfaces to give Mo260-E. To the best of our knowledge, this is the first study to display the internal and external nuclear growth of a giant hollow polyoxometalate cage. More importantly, regular variations in structure and nuclearity confer these polymolybdate cages with different optical properties, oxidative activities, and hydrogen atom transfer effect, thus allowing them to exhibit moderate to excellent photocatalytic performance in oxidative cross-coupling reactions between different unactivated alkanes and N-heteroarenes. In particular, Mo240 and Mo260-E with better comprehensive abilities can offer the desired coupling product with yield up to 92% within 1 h.

Constructing Functional Radiation-Resistant Thorium Clusters for Catalytic Redox Reactions.

When catalytic reactions are interfered with by radiation sources, thorium clusters are promising as potential catalysts due to their superior radiation resistance. However, there is currently very little research on the design synthesis and catalytic application of radiation-stable thorium clusters. In this work, we have elaborately engineered and fabricated three high-nuclear thorium cluster catalysts denoted as Th12L3-MA12, Th12L3-MA6-BF6, and Th12L3-Fcc12, which did not undergo any significant alterations in their molecular structures and compositions after irradiation with 690 kGy γ-rays. We systematically investigated the photocatalytic/thermocatalytic properties of these radiation-resistant thorium clusters for the first time and found that γ-rays could not alter their catalytic activities. In addition, it was found that ligand engineering could modulate the catalytic activity of thorium clusters, thus expanding the range of catalytic applications of thorium clusters, including reduction reactions (nitroarene reduction) and some oxidation reactions (N-heterocyclic oxidative dehydrogenation and diphenylmethane oxidation). Meanwhile, all of these organic transformation reactions achieved a >80% conversion and nearly 100% product selectivity. Radiation experiments combined with DFT calculations showed that the synergistic catalysis of thorium-oxo core and ligands led to the generation of specific active species (H+, O2•-, or tBuO/tBuOO•) and activation of substrate molecules, thus achieving superior catalytic performance. This work is not only the first to develop radiation-resistant thorium cluster catalysts to perform efficient redox reactions but also provides design ideas for the construction of high-nuclearity thorium clusters under mild conditions.

Photochromic radical states in 3D covalent organic frameworks with zyg topology for enhanced photocatalysis.

Covalent-organic frameworks (COFs) with photoinduced donor-acceptor (D-A) radical pairs show enhanced photocatalytic activity in principle. However, achieving long-lived charge separation in COFs proves challenging due to the rapid charge recombination. Here, we develop a novel strategy by combining [6 + 4] nodes to construct zyg-type 3D COFs, first reported in COF chemistry. This structure type exhibits a fused Olympic-rings-like shape, which provides a platform for stabilizing the photoinduced D-A radical pairs. The zyg-type COFs containing catalytically active moieties such as triphenylamine and phenothiazine (PTZ) show superior photocatalytic production rates of hydrogen peroxide (H2O2). Significantly, the photochromic radical states of these COFs show up to 400% enhancement in photocatalytic activity compared to the parent states, achieving a remarkable H2O2 synthesis rate of 3324 µmol g-1 h-1, which makes the PTZ-COF one of the best crystalline porous photocatalysts in H2O2 production. This work will shed light on the synthesis of efficient 3D COF photocatalysts built on topologies that can facilitate photogenerating D-A radical pairs for enhanced photocatalysis.

A solvent-free processed low-temperature tolerant adhesive.

Ultra-low temperature resistant adhesive is highly desired yet scarce for material adhesion for the potential usage in Arctic/Antarctic or outer space exploration. Here we develop a solvent-free processed low-temperature tolerant adhesive with excellent adhesion strength and organic solvent stability, wide tolerable temperature range (i.e. -196 to 55 °C), long-lasting adhesion effect ( > 60 days, -196 °C) that exceeds the classic commercial hot melt adhesives. Furthermore, combine experimental results with theoretical calculations, the strong interaction energy between polyoxometalate and polymer is the main factor for the low-temperature tolerant adhesive, possessing enhanced cohesion strength, suppressed polymer crystallization and volumetric contraction. Notably, manufacturing at scale can be easily achieved by the facile scale-up solvent-free processing, showing much potential towards practical application in Arctic/Antarctic or planetary exploration.

Integrated Preparation of Hollow Lignin Nanoparticles as a Drug Carrier and Levulinic Acid from the Poplar Wood Prehydrolysis Liquor.

Prehydrolysis liquid (PHL) from dissolving pulp and biorefinery industries is rich in saccharides and lignin, being considered as a potential source of value-added materials and platform molecules. This study proposed an environmentally friendly and simple method to prepare morphologically controllable hollow lignin nanoparticles (LNPs) and levulinic acid (LA) from PHL. In the first step, after hydrothermal treatment of PHL with p-toluenesulfonic acid (p-TsOH), lignin with a uniform molecular weight was obtained to prepare LNPs. The prepared LNPs have an obvious hollow structure, with an average size of 490-660 nm, and exhibit good stability during 30 days of storage. When the as-obtained LNPs were used as a sustained-release agent for amikacin sulfate, the encapsulation efficiency reached over 70% and the release efficiency within 40 h reached 69.2% in a pH 5.5 buffer. Subsequently, the remaining PHL that contains saccharides was directly used for LA production under the catalysis of p-TsOH. At 150 °C for 1.5 h, the LA yield reached 58.4% and remained at 56% after 5 cycles of p-TsOH. It is worth noting that only p-TsOH was used as a reactive reagent throughout the entire preparation process. Overall, this study provided a novel pathway for the integrated utilization of PHL and showed the immense potential of the preparation and application of LNPs.

Zigzag Hopping Site Embedded Covalent Organic Frameworks Coating for Zn Anode.

Precise design and tuning of Zn hopping/transfer sites with deeper understanding of the dendrite-formation mechanism is vital in artificial anode protective coating for aqueous Zn-ion batteries (AZIBs). Here, we probe into the role of anode-coating interfaces by designing a series of anhydride-based covalent organic frameworks (i.e., PI-DP-COF and PI-DT-COF) with specifically designed zigzag hopping sites and zincophilic anhydride groups that can serve as desired platforms to investigate the related Zn2+ hopping/transfer behaviours as well as the interfacial interaction. Combining theoretical calculations with experiments, the ABC stacking models of these COFs endow the structures with specific zigzag sites along the 1D channel that can accelerate Zn2+ transfer kinetics, lower surface-energy, homogenize ion-distribution or electric-filed. Attributed to these superiorities, thus-obtained optimal PI-DT-COF cells offer excellent cycling lifespan in both symmetric-cell (2000 cycles at 60 mA cm-2) and full-cell (1600 cycles at 2 A g-1), outperforming almost all the reported porous crystalline materials.

Redox Molecular Junction Metal-Covalent Organic Frameworks for Light-assisted CO2 Energy Storage.

Visible-light sensitive and bi-functionally favored CO2 reduction (CRR)/evolution (CER) photocathode catalysts that can get rid of the utilization of ultraviolet light and improve sluggish kinetics is demanded to conquer the current technique-barrier of traditional Li-CO2 battery. Here, a kind of redox molecular junction sp2c metal-covalent organic framework (i.e. Cu3-BTDE-COF) has been prepared through the connection between Cu3 and BTDE and can serve as efficient photocathode catalyst in light-assisted Li-CO2 battery. Cu3-BTDE-COF with redox-ability, visible-light-adsorption region, electron-hole separation ability and endows the photocathode with excellent round-trip efficiency (95.2 %) and an ultralow voltage hysteresis (0.18 V), outperforming the Schiff base COFs (i.e. Cu3-BTDA-COF and Cu3-DT-COF) and majority of the reported photocathode catalysts. Combined theoretical calculations with characterizations, Cu3-BTDE-COF with the integration of Cu3 centers, thiazole and cyano groups possess strong CO2 adsorption/activation and Li+ interaction/diffusion ability to boost the CRR/CER kinetics and related battery property.

Integrated preparation of functional lignin nanoparticles and levulinic acid directly from the pre-hydrolysis liquor of poplar wood.

The pre-hydrolysis liquor (PHL) produced during pulp dissolution and biomass refining is mainly composed of hemicellulose and lignin, and it is a potential source for production of value-added materials and platform chemicals; however, their utilization has been a serious challenge. In this study, we proposed a green and simple strategy to simultaneously prepare size-controlled functional lignin nanoparticles (LNPs) and levulinic acid (LA) from PHL as the raw material. The as-prepared LNPs exhibited remarkable stability thanks to the presence of saccharides with abundant oxygen-containing groups and surface charges, which prevented aggregation and maintained long-term storage stability. Trace amounts of the LNPs (≤ 0.2 wt%) could stabilize various Pickering emulsions, even with oil-to-water ratios as high as 5:5 (v/v). Subsequently, the remaining PHL was directly used to produce LA without adding a catalyst; under optimal conditions (160 °C and 1 h), the yield of LA was 56.3 % based on the dry saccharide content in the raw PHL. More importantly, p-toluenesulfonic acid (p-TsOH), the only reactive reagent used during the entire preparation process, including the two preparation steps of the LNPs and LA, was reusable, and the recovery rate was >70 % after five cycles. Overall, this green and simple strategy effectively and comprehensively utilized the PHL and showed potential for producing biobased nanomaterials and platform chemicals.

ZIFs-Derived Hollow Nanostructures via a Strong/Weak Coetching Strategy for Long-Life Rechargeable Zn-Air Batteries.

Recently, zeolitic imidazolate frameworks (ZIFs) composites have emerged as promising precursors for synthesizing hollow-structured N-doped carbon-based noble-metal materials with diverse structures and compositions. Here, a strong/weak competitive coordination strategy is presented for synthesizing high-performance electrocatalysts with hollow features. During the competitive coordination process, the cubic zeolitic-imidazole framework-8 (Cube-8)@ZIF-67 with core-shell structures are transformed into Cube-8@ZIF-67@PF/POM with yolk-shell nanostructures employing phosphomolybdic acid (POM) and potassium ferricyanide (PF) as the strong chelator and the weak chelator, respectively. After calcination, the hollow Mo/Fe/Co@NC catalyst exhibits superior performance in both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Interestingly, the Mo/Fe/Co@NC catalyst exhibits efficient electrocatalytic performance for Zn-air batteries (ZABs), with a high power density (≈150 mW cm-2) and superior cycling life (≈500 h) compared to commercial platinum/carbon (Pt/C) and ruthenium dioxide (RuO2) mixture benchmarks catalysts. In addition, the density functional theory further proves that after the introduction of Mo and Fe atoms, the adsorption energy with the adsorption intermediates is weakened by adjusting the d-band center, thus weakening the reaction barrier and promoting the reaction kinetics of OER. Undoubtedly, this study presents novel insights into the fabrication of ZIFs-derived hollow structure bifunctional oxygen electrocatalysts for clean-energy diverse applications.

Bridging the Homogeneous and Heterogeneous Catalysis by Supramolecular Metal-Organic Cages with Varied Packing Modes.

Integrating the advantages of homogeneous and heterogeneous catalysis has proved to be an optimal strategy for developing catalytic systems with high efficiency, selectivity, and recoverability. Supramolecular metal-organic cages (MOCs), assembled by the coordination of metal ions with organic linkers into discrete molecules, have performed solvent processability due to their tunable packing modes, endowing them with the potential to act as homogeneous or heterogeneous catalysts in different solvent systems. Here, the design and synthesis of a series of stable {Cu3} cluster-based tetrahedral MOCs with varied packing structures are reported. These MOCs, as homogeneous catalysts, not only show high catalytic activity and selectivity regardless of substrate size during the CO2 cycloaddition reaction, but also can be easily recovered from the reaction media through separating products and co-catalysts by one-step work-up. This is because that these MOCs have varied solubilities in different solvents due to the tunable packing of MOCs in the solid state. Moreover, the entire catalytic reaction system is very clean, and the purity of cyclic carbonates is as high as 97% without further purification. This work provides a unique strategy for developing novel supramolecular catalysts that can be used for homogeneous catalysis and recycled in a heterogeneous manner.

Three-Motif Molecular Junction Type Covalent Organic Frameworks for Efficient Photocatalytic Aerobic Oxidation.

Covalent organic frameworks (COFs), with the features of flexible structure regulation and easy introduction of functional groups, have aroused broad interest in the field of photocatalysis. However, due to the low light absorption intensity, low photoelectron conversion efficiency, and lack of suitable active sites, it remains a great challenge to achieve efficient photocatalytic aerobic oxidation reactions. Herein, based on reticular chemistry, we rationally designed a series of three-motif molecular junction type COFs, which formed dual photosensitizer coupled redox molecular junctions containing multifunctional COF photocatalysts. Significantly, due to the strong light adsorption ability of dual photosensitizer units and integrated oxidation and reduction features, the PY-BT COF exhibited the highest activity for photocatalytic aerobic oxidation. Especially, it achieved a photocatalytic benzylamine conversion efficiency of 99.9% in 2.5 h, which is much higher than that of the two-motif molecular junctions with only one photosensitizer or redox unit lacking COFs. The mechanism of selective aerobic oxidation was studied through comprehensive experiments and density functional theory calculations. The results showed that the photoinduced electron transfer occurred from PY and then through triphenylamine to BT. Furthermore, the thermodynamics energy for benzylamine oxidation on PY-BT COF was much lower than that for others, which confirmed the synergistic effect of dual photosensitizer coupled redox molecular junction COFs. This work provided a new strategy for the design of functional COFs with three-motif molecular junctions and also represented a new insight into the multifunctional COFs for organic catalytic reactions.

Photocatalytic aerobic oxidation of C(sp3)-H bonds.

In modern industries, the aerobic oxidation of C(sp3)-H bonds to achieve the value-added conversion of hydrocarbons requires high temperatures and pressures, which significantly increases energy consumption and capital investment. The development of a light-driven strategy, even under natural sunlight and ambient air, is therefore of great significance. Here we develop a series of hetero-motif molecular junction photocatalysts containing two bifunctional motifs. With these materials, the reduction of O2 and oxidation of C(sp3)-H bonds can be effectively accomplished, thus realizing efficient aerobic oxidation of C(sp3)-H bonds in e.g., toluene and ethylbenzene. Especially for ethylbenzene oxidation reactions, excellent catalytic capacity (861 mmol g cat-1) is observed. In addition to the direct oxidation of C(sp3)-H bonds, CeBTTD-A can also be applied to other types of aerobic oxidation reactions highlighting their potential for industrial applications.

Green synthesis of bifunctional phthalocyanine-porphyrin cofs in water for efficient electrocatalytic CO2 reduction coupled with methanol oxidation.

Electrocatalytic CO2 reduction (ECR) coupled with organic oxidation is a promising strategy to produce high value-added chemicals and improve energy efficiency. However, achieving the efficient redox coupling reaction is still challenging due to the lack of suitable electrocatalysts. Herein, we designed two bifunctional polyimides-linked covalent organic frameworks (PI-COFs) through assembling phthalocyanine (Pc) and porphyrin (Por) by non-toxic hydrothermal methods in pure water to realize the above catalytic reactions. Due to the high conductivity and well-defined active sites with different chemical environments, NiPc-NiPor COF performs efficient ECR coupled with methanol oxidation reaction (MOR) (Faradaic efficiency of CO (FECO) = 98.12%, partial current densities of CO (jCO) = 6.14 mA cm-2 for ECR, FEHCOOH = 93.75%, jHCOOH = 5.81 mA cm-2 for MOR at low cell voltage (2.1 V) and remarkable long-term stability). Furthermore, experimental evidences and density functional theory (DFT) calculations demonstrate that the ECR process mainly conducts on NiPc unit with the assistance of NiPor, meanwhile, the MOR prefers NiPor conjugating with NiPc. The two units of NiPc-NiPor COF collaboratively promote the coupled oxidation-reduction reaction. For the first time, this work achieves the rational design of bifunctional COFs for coupled heterogeneous catalysis, which opens a new area for crystalline material catalysts.

Modulated Connection Modes of Redox Units in Molecular Junction Covalent Organic Frameworks for Artificial Photosynthetic Overall Reaction.

The precise tuning of components, spatial orientations, or connection modes for redox units is vital for gaining deep insight into efficient artificial photosynthetic overall reaction, yet it is still hard achieve for heterojunction photocatalysts. Here, we have developed a series of redox molecular junction covalent organic frameworks (COFs) (M-TTCOF-Zn, M = Bi, Tri, and Tetra) for artificial photosynthetic overall reaction. The covalent connection between TAPP-Zn and multidentate TTF endows various connection modes between water photo-oxidation (multidentate TTF) and CO2 photoreduction (TAPP-Zn) centers that can serve as desired platforms to study the possible interactions between redox centers. Notably, Bi-TTCOF-Zn exhibits a high CO production rate of 11.56 µmol g-1 h-1 (selectivity, ∼100%), which is more than 2 and 6 times higher than those of Tri-TTCOF-Zn and Tetra-TTCOF-Zn, respectively. As revealed by theoretical calculations, Bi-TTCOF-Zn facilitates a more uniform distribution of energy-level orbitals, faster charge transfer, and stronger *OH adsorption/stabilization ability than those of Tri-TTCOF-Zn and Tetra-TTCOF-Zn.