{SeO2(OH)} Bridging Lanthanide-Containing Antimono-Seleno-Tungstates.

A series of new trigonal pyramidal {SeO2(OH)} bridging lanthanide-containing antimono-seleno-tungstates [H2N(CH3)2]8Na8Cs4H9[Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]2·32H2O [Ln = Tb (1), Dy (2), Ho (3), Er (4)] have been prepared by the synthetic strategy of simultaneously using the antimonotungstate precursor and simple material in an acidic aqueous solution and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectrometry, and thermogravimetric analysis. Their molecular structures contain an unprecedented hexameric polyoxoanion [Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]229- constituted by two equivalent trimeric subunits Ln2W4O9(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33) bridged via two µ2-{SeO2(OH)} linkers. Furthermore, the catalytic oxidation of various aromatic sulfides and sulfur mustard simulant 2-chloroethyl ethyl sulfide (CEES) by compound 3 as the heterogeneous catalyst has been investigated, exhibiting high conversion and selectivity as well as good stability and recyclability.

Nanostructured Polyoxometalate-Based Heterogeneous Electrode Materials for Electrochemical Sensing of Glucose.

We exploited a tactic to obtain a low-cost, high-efficiency, pollution-free, and stable nonenzymatic polyoxometalate-based heterogeneous electrode material for electrochemical sensing of glucose. It is first followed by the countercation exchange of K2Na8[Cu4(H2O)2(PW9O34)2] (CuPOM) using cesium chloride to prepare an insoluble CuPOM (Cs-CuPOM), which exhibits a uniform and perfect claviform shape with smooth surface. Further, it was mixed with graphite powder to prepare Cs-CuPOM-modified carbon paste electrode (Cs-CuPOM/CPE) with the Cs-CuPOM content between 15% and 50% in weight. This obtained electrode material Cs-CuPOM shows a better electrochemical sensor activity than Cs-MnPOM, Cs-FePOM, and other reported POM-based electrode materials for glucose oxidation on account of their quicker electron transfer kinetics, which also exhibits conspicuous characteristics with a wide linear range of 5-1500 µM. It also possesses a high sensitivity of 16.3 A M-1 cm-2 and a low limit of detection (LOD) of 0.99 × 10-6 M at the signal-to-noise ratio of 3. The conspicuous sensing feature, low cost, and liable synthetic method can make Cs-CuPOM a promising candidate for the exploitation of a preeminent glucose sensor.

Girth-based administered activity for pediatric 99m Tc-DMSA SPECT.

BACKGROUND: Pediatric molecular imaging requires a balance between administering an activity that will yield sufficient diagnostic image quality while maintaining patient radiation exposure at acceptable levels. In current clinical practice, this balance is arrived at by the current North American Consensus Guidelines in which patient weight is used to recommend the administered activity (AA). PURPOSE: We have previously demonstrated that girth (waist circumference at the level of the kidneys) is better at equalizing image quality than patient weight for pediatric Tc-99m DMSA renal function imaging. However, the correlation between image quality (IQ), AA, and patient girth has not been rigorously and systematically developed. In this work, we generate a series of curves showing the tradeoff between AA and IQ as a function of patient girth, providing the data for standards bodies to develop the next generation of dosing guideline for pediatric DMSA SPECT. METHODS: An anthropomorphic phantom series that included variations in age (5, 10, and 15 years), gender (M, F), local body morphometry (5, 10, 50, 90, and 95th girth percentiles), and kidney size (±15% standard size), was used to generate realistic SPECT projections. A fixed and clinically challenging defect-to-organ volume percentage (0.49% of renal cortex value) was used to model a focal defect with zero uptake (i.e., full local loss of renal function). Task-based IQ assessment methods were used to rigorously measure IQ in terms of renal perfusion defect detectability. This assessment was performed at multiple count levels (corresponding to various AAs) for groups of patients that had similar girths and defect sizes. Receiver-operating characteristics (ROC) analysis was applied; the area under the ROC curve (AUC) was used as a figure-of-merit for task performance. Curves showing the tradeoff between AUC and AA were generated for these groups of phantoms. RESULTS: Overall, the girth-based dosing method suggested different amounts of AA compared to weight-based dosing for the phantoms that had a relatively large body weight but a small girth or phantoms with relatively small bodyweight but large girth. Reductions of AA to 62.9% compared to weight-based dosing guidelines can potentially be realized while maintaining a baseline (AUC = 0.80) IQ for certain 15-year-olds who have a relatively small girth and large defect size. Note that the task-based IQ results are heavily dependent on the simulated defect size for the defect detection task and the appropriate AUC value must be decided by the physicians for this diagnostic task. These results are based purely on simulation and are subject to future clinical validation. CONCLUSIONS: The study provides simulation-based IQ-AA data for a girth-based dosing method for pediatric renal SPECT, suggesting that patient waist circumference at the level of kidneys should be considered in selecting the AA needed to achieve an acceptable IQ. This data may be useful for standards bodies to develop girth-based dosing guidelines.

Metal-Free Selective Ortho-C-H Amidation of Hypervalent(III) Iodobezenes with N-Methoxy Amides under Mild Conditions.

A metal-free selective ortho-C-H amidation of aryl iodines(III) with the use of N-methoxy amides as aminating reagents under mild conditions is described here. In the protocol, excellent chemoselectivity and high regioselectivity were obtained. Notably, the iodine substituent rendered the amidation product suitable to be used for further elaboration.

Vitamin C promotes ACE2 degradation and protects against SARS-CoV-2 infection.

ACE2 is a major receptor for cellular entry of SARS-CoV-2. Despite advances in targeting ACE2 to inhibit SARS-CoV-2 binding, strategies to flexibly and sufficiently reduce ACE2 levels for the prevention of SARS-CoV-2 infection have not been explored. Here, we reveal vitamin C (VitC) administration as a potent strategy to prevent SARS-CoV-2 infection. VitC reduces ACE2 protein levels in a dose-dependent manner, while even a partial reduction in ACE2 levels can greatly inhibit SARS-CoV-2 infection. Further studies reveal that USP50 is a crucial regulator of ACE2 levels. VitC blocks the USP50-ACE2 interaction, thus promoting K48-linked polyubiquitination of ACE2 at Lys788 and subsequent degradation of ACE2 without affecting its transcriptional expression. Importantly, VitC administration reduces host ACE2 levels and greatly blocks SARS-CoV-2 infection in mice. This study reveals that ACE2 protein levels are down-regulated by an essential nutrient, VitC, thereby enhancing protection against infection of SARS-CoV-2 and its variants.

Methotrexate and Triptolide regulate Notch signaling pathway by targeting the Nedd4-Numb axis.

Methotrexate (MTX) is used to treat rheumatoid arthritis, acute leukemia, and psoriasis. MTX can cause certain side effects, such as myelosuppression, while the exact mechanism of myelosuppression caused by MTX is unknown. Notch signaling pathway has been considered to be essential to regulate hematopoietic stem cell (HSC) regeneration and homeostasis, thus contributing to bone marrow hematopoiesis. However, whether MTX affects Notch signaling remains unexplored. Here, our study provides evidence that MTX strongly suppresses the Notch signaling pathway. We found that MTX inhibited the interaction between Nedd4 with Numb, thus restricting K48-linked polyubiquitination of Numb and stabilizing Numb proteins. This in turn inhibited the Notch signaling pathway by reducing Notch1 protein levels. Interestingly, we found that a monomeric drug, Triptolide, is capable of alleviating the inhibitory effect of MTX on Notch signaling pathway. This study promotes our understanding of MTX-mediated regulation of Notch signaling and could provide ideas to alleviate MTX-induced myelosuppression.

Fluorescent Quinoline-Based Supramolecular Gel for Selective and Ratiometric Sensing Zinc Ion with Multi-Modes.

A gelator 1 containing functional quinoline and Schiff base groups that could form organogels in DMF, DMSO, acetone, ethanol and 1,4-dioxane was designed and synthesized. The self-assembly process of geator 1 was characterized by field emission scanning electron microscopy (FESEM), UV-vis absorption spectroscopy, fluorescence emission spectroscopy, Fourier transform infrared spectroscopy(FTIR), X-ray powder diffraction (XRD) and water contact angle. Under non-covalent interactions, gelator 1 self-assembled into microbelts and nanofiber structures with different surface wettability. Weak fluorescence was emitted from the solution and gel state of 1. Interestingly, gelator 1 exhibited good selectivity and sensitivity towards Zn2+ in solution and gel states along with its emission enhancement and change. The emission intensity at 423 nm of solution 1 in 1,4-dioxane was slightly enhanced, and a new emission peak appeared at 545 nm along with its intensity sequentially strengthened in the titration process. The obvious ratiometric detection process was presented with a limit of detection (LOD) of 5.51 µM. The detection mechanism was revealed by a theoretical calculation and NMR titration experiment, which was that Zn2+ induced the transition from trans- to cis- of molecule 1 and further coordinated with 1. This study will introduce a new method for the construction of functional self-assembly gel sensors for the detection of Zn2+.

Photoredox-Catalyzed Acyl Lactonization of Alkenes with Aldehydes: Synthesis of Acyl Lactones.

An acyl lactonization of alkenes with aldehydes under visible-light photoredox catalysis is described. With the protocol, a broad scope of alkenoic acids and aldehydes could be compatible and good functional group tolerance is obtained. A series of acyl lactones are obtained with isolated yields ranging from 50-95%. Mechanistic studies revealed that the transformation should proceed via a radical chain process.

Menthone inhibits type-I interferon signaling by promoting Tyk2 ubiquitination to relieve local inflammation of rheumatoid arthritis.

Rheumatoid arthritis (RA) is an inflammatory autoimmune disease. RA development is mediated by the abnormal activation of multiple signaling pathways. Recent studies have revealed that type-I interferon (IFN-I) signaling plays an essential role in the occurrence and development of RA. However, how to target IFN-I signaling to develop anti-rheumatoid arthritis drugs remains largely unexplored. Here, our study showed that IFN-I signaling was over-activated in articular synovial cells from collagen II-induced arthritis (CIA) mice. Interestingly, we found that a small molecule compound, menthone, strongly inhibited the activation of the IFN-I signaling pathway. Further studies revealed that menthone promoted K48-linked polyubiquitination of Tyk2, thus lowering the protein level and stability of Tyk2. Importantly, menthone administration in the local articulus of CIA mice significantly attenuated the local inflammation in CIA mice. This study could promote our understanding of rheumatoid arthritis, and also suggests a potential strategy to develop anti-RA drugs.

CO2-Driven reversible transfer of amine-functionalized ZIF-90 between organic and aqueous phases.

Phase transfer of metal-organic frameworks is highly desired in many areas, which remains a challenge. Herein, we present for the first time a CO2-driven reversible transfer of amine-functionalized ZIF-90 between organics and water. A mechanistic study showed that the switching is ascribed to the reversible generation of hydrophilic ammonium salts from the reaction of CO2 with the amines on ZIF-90. This unique system has been used for the coupling of trans-esterification reactions, product separation and component recycling for green sustainable processes. This work opens up a new avenue for performing reactions effectively with an easy separation process.

Bis-Pyridine-Based Organogel with AIE Effect and Sensing Performance towards Hg2.

A novel gelator (1) based on a bis-pyridine derivative was designed and synthesized, which could form stable gels in methanol, ethanol, acetonitrile, ethyl acetate, DMF/H2O (4/1, v/v) and DMSO/H2O (4/1, v/v). The self-assembly process of gelator 1 was studied by field emission scanning electron microscopy (FESEM), UV-vis absorption spectroscopy, fluorescence emission spectroscopy, Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction and a water contact angle experiment. Gelator 1 exhibited obvious AIE behavior. On the base of its AIE, the gel of 1 could detect Hg2+, which resulted in fluorescence quenching and a gel-sol transition. 1H NMR titration experiments with Hg2+ revealed that the metal coordination interaction induced the fluorescence quenching and the breakdown of the noncovalent interaction in the gel system. This research provides a new molecular mode for designing a functional self-assembly gel system.

Long non-coding RNA HCG22 inhibits the proliferation, invasion and migration of oral squamous cell carcinoma cells by downregulating miR-425-5p expression.

Long non-coding RNA (lncRNA) HLA complex group 22 (HCG22) is known to be involved in the occurrence and development of cancer; however, its role in oral squamous cell carcinoma (OSCC) remains unclear. Therefore, the main aim of the present study was to investigate the role and mechanisms of action of lncRNA HCG22 in OSCC cells. The expression levels of lncRNA HCG22 and microRNA (miR)-425-5p in OSCC cells were assessed using reverse transcription-quantitative PCR analysis. Cell proliferation was detected using Cell Counting Kit-8 and colony formation assays. In addition, the expression levels of cell proliferation-related proteins, p27, cyclin E and cyclin-dependent kinase 2, were detected by western blot analysis. The cell invasive ability was detected by Transwell assay, while the cell migratory ability was detected via a wound healing assay. The expression levels of the invasion- and migration-related proteins, MMP2 and MMP9, were measured by western blot analysis. The targeted association between lncRNA HCG22 and miR-425-5p was verified by RNA immunoprecipitation and dual-luciferase reporter assays. The results revealed that lncRNA LCG22 was expressed at low levels, while miR-425-5p was highly expressed in OSCC cell lines, based on bioinformatics analysis. The overexpression of lncRNA HCG22 inhibited the proliferation, invasion and migration of OSCC cells. Moreover, lncRNA HCG22 and miR-425-5p were found to have a direct targeted association, and lncRNA HCG22 inhibited cell proliferation, invasion and migration by targeting miR-425-5p. Collectively, the findings of the present study demonstrated that lncRNA HCG22 may inhibit the proliferation, invasion and migration of OSCC cells by downregulating miR-425-5p expression.

Double Trigonal Pyramidal {SeO3} Groups Bridged 2-Picolinic Acid Modified Cerium-Inlaid Polyoxometalate Including Mixed Selenotungstate Subunits for Electrochemically Sensing Ochratoxin A.

An organic-inorganic hybrid trigonal pyramidal {SeO3} group, bridged cerium-inlaid polyoxometalate (POM) Na16[Se2Ce4(H2O)8W4(HPIC)4O10][B-ß-SeW8O30]2[Se2W12O46]2·60H2O (1) (HPIC = 2-picolinic acid), containing two disparate selenotungstate (ST) building blocks was synthesized by a one-step assembly strategy, which is established by two asymmetric sandwich-type {[Ce2(H2O)4W2(HPIC)2O4][B-ß-SeW8O30][Se2W12O46]}10- moieties joined by double trigonal pyramidal {SeO3} groups. Its outstanding structural trait is that it contains two types of ST building blocks, Keggin-type [B-ß-SeW8O30]8- and Dawson-like [Se2W12O46]12-, which are extremely rare in ST chemistry. Remarkably, [Se2W12O46]12- is first obtained in lanthanide-inlaid STs. Furthermore, 1@PPy conductive film (PPy = polypyrrole) was prepared by electrochemical polymerization and served as the electrode material, and then nano-gold particles (NGPs) were deposited on the surface of 1@PPy conductive film by an electrochemical deposition method in order to immobilize the aptamer of ochratoxin A. With the help of exonuclease I (EN I), the oxidation peak of the metalized Ag works as the detection signal to achieve the detection of ochratoxin A (OTXA). This study offers an available approach for creating organic-inorganic hybrid heteroatom-bridged lanthanide-inlaid POMs and reveals the likelihood of extending heteroatom-bridged lanthanide-inlaid POMs into electrochemical biosensing applications.

Development and autoregulation of kidney function in children: a retrospective study using 99mTc-MAG3 renography.

BACKGROUND: Both the development of kidney function in healthy children and autoregulation ability of kidney function in patients with asymmetric kidneys are important in clinical diagnosis and treatment of kidney-related diseases, but there are however only limited studies. This study aimed to investigate development of kidney function in normal children with healthy symmetric kidneys and autoregulation of the healthy kidney compensating the functional loss of a diseased one in children with asymmetric kidneys. METHODS: Two hundred thirty-seven children (156 male, 81 female) from 0 to 20y (average 4.6y ± 5.1) undergoing 99mTc-MAG3 renography were included, comprising 134 with healthy symmetrically functioning kidneys and 103 with asymmetric kidneys. Clearance was calculated from kidney uptakes at 1-2 min. A developmental model between MAG3 clearance (CL) and patient age in normal group was identified (CL = 84.39Age0.395 ml/min, r = 0.957, p < 0.001). The clearance autoregulation rate in abnormal group with asymmetric kidneys was defined as the ratio of the measured MAG3 clearance and the normal value predicted from the renal developmental model of normal group. RESULTS: No significant difference of MAG3 clearance (p = 0.723) was found between independent abnormal group and normal group. The autoregulation rate of kidney clearance in abnormal group was 94.2% on average, and no significant differences were found between two age groups (p = 0.49), male and female (p = 0.39), and left kidney and right kidney (p = 0.92) but two different grades of asymmetric kidneys (p = 0.02). CONCLUSIONS: The healthy kidney of two asymmetric kidneys can automatically regulate total kidney function up to 94% of two symmetric kidneys in normal children.

Switchable Supramolecular Configurations of Al3+/LysTPY Coordination Polymers in a Hydrogel Network Controlled by Ultrasound and Heat.

Coordination-driven self-assembly with controllable properties has attracted increasing interest because of its potential in biological events and material science. Herein, we report on the remote, instant, and switchable control of competitive coordination interactions via ultrasound and heat stimuli in a hydrogel network. Configurational coordination changes result in the transformation of blue-emissive and opaque Al3+-amide aggregations to yellow-green-emissive and transparent Al3+-terpyridine aggregations. Interestingly, circularly polarized luminescence "off-on" switches of the metallo-supramolecular assembly are also created by these configuration changes. Additionally, the impact of the stoichiometric ratio of Al3+ and LysTPY on the assembly is also studied in detail. With a higher content of Al3+, the hydrogel with branched and abundant junctions exhibited robust, self-healing, and self-supporting properties. This in-depth understanding of the coordination interaction adjustment will afford new insights into the preparation of stimuli-responsive metallogels.

Visible-Light Photoredox-Catalyzed Sulfonyl Lactonization of Alkenoic Acids with Sulfonyl Chlorides for Sulfonyl Lactone Synthesis.

A visible-light photoredox-catalyzed sulfonyl lactonization of unsaturated carboxylic acids with sulfonyl chlorides is described. This reaction features good functional group tolerance and a broad substrate scope, providing a simple and efficient protocol to access a wide range of sulfonyl lactones in high to excellent yields. Preliminary mechanistic investigations suggested that a free-radical pathway should be involved in the process.

Renal 99mTc-DMSA pharmacokinetics in pediatric patients.

99mTc-DMSA is one of the most commonly used pediatric nuclear medicine imaging agents. Nevertheless, there are no pharmacokinetic (PK) models for 99mTc-DMSA in children, and currently available pediatric dose estimates for 99mTc-DMSA use pediatric S values with PK data derived from adults. Furthermore, the adult PK data were collected in the mid-70's using quantification techniques and instrumentation available at the time. Using pediatric imaging data for DMSA, we have obtained kinetic parameters for DMSA that differ from those applicable to adults. METHODS: We obtained patient data from a retrospective re-evaluation of clinically collected pediatric SPECT images of 99mTc-DMSA in 54 pediatric patients from Boston's Children Hospital (BCH), ranging in age from 1 to 16 years old. These were supplemented by prospective data from twenty-three pediatric patients (age range: 4 months to 6 years old). RESULTS: In pediatric patients, the plateau phase in fractional kidney uptake occurs at a fractional uptake value closer to 0.3 than the value of 0.5 reported by the International Commission on Radiological Protection (ICRP) for adult patients. This leads to a 27% lower time-integrated activity coefficient in pediatric patients than in adults. Over the age range examined, no age dependency in uptake fraction at the clinical imaging time was observed. Female pediatric patients had a 17% higher fractional kidney uptake at the clinical imaging time than males (P < 0.001). CONCLUSIONS: Pediatric 99mTc-DMSA kinetics differ from those reported for adults and should be considered in pediatric patient dosimetry. Alternatively, the differences obtained in this study could reflect improved quantification methods and the need to re-examine DMSA kinetics in adults.

Detecting lumbar lesions in 99m Tc-MDP SPECT by deep learning: Comparison with physicians.

PURPOSE: 99m Tc-MDP single-photon emission computed tomography (SPECT) is an established tool for diagnosing lumbar stress, a common cause of low back pain (LBP) in pediatric patients. However, detection of small stress lesions is complicated by the low quality of SPECT, leading to significant interreader variability. The study objectives were to develop an approach based on a deep convolutional neural network (CNN) for detecting lumbar lesions in 99m Tc-MDP scans and to compare its performance to that of physicians in a localization receiver operating characteristic (LROC) study. METHODS: Sixty-five lesion-absent (LA) 99m Tc-MDP studies performed in pediatric patients for evaluating LBP were retrospectively identified. Projections for an artificial focal lesion were acquired separately by imaging a 99m Tc capillary tube at multiple distances from the collimator. An approach was developed to automatically insert lesions into LA scans to obtain realistic lesion-present (LP) 99m Tc-MDP images while ensuring knowledge of the ground truth. A deep CNN was trained using 2.5D views extracted in LP and LA 99m Tc-MDP image sets. During testing, the CNN was applied in a sliding-window fashion to compute a 3D "heatmap" reporting the probability of a lesion being present at each lumbar location. The algorithm was evaluated using cross-validation on a 99m Tc-MDP test dataset which was also studied by five physicians in a LROC study. LP images in the test set were obtained by incorporating lesions at sites selected by a physician based on clinical likelihood of injury in this population. RESULTS: The deep learning (DL) system slightly outperformed human observers, achieving an area under the LROC curve (AUCLROC ) of 0.830 (95% confidence interval [CI]: [0.758, 0.924]) compared with 0.785 (95% CI: [0.738, 0.830]) for physicians. The AUCLROC for the DL system was higher than that of two readers (difference in AUCLROC [ΔAUCLROC ] = 0.049 and 0.053) who participated to the study and slightly lower than that of two other readers (ΔAUCLROC  = -0.006 and -0.012). Another reader outperformed DL by a more substantial margin (ΔAUCLROC  = -0.053). CONCLUSION: The DL system provides comparable or superior performance than physicians in localizing small 99m Tc-MDP positive lumbar lesions.

DeepAMO: a multi-slice, multi-view anthropomorphic model observer for visual detection tasks performed on volume images.

Purpose: We propose a deep learning-based anthropomorphic model observer (DeepAMO) for image quality evaluation of multi-orientation, multi-slice image sets with respect to a clinically realistic 3D defect detection task. Approach: The DeepAMO is developed based on a hypothetical model of the decision process of a human reader performing a detection task using a 3D volume. The DeepAMO is comprised of three sequential stages: defect segmentation, defect confirmation (DC), and rating value inference. The input to the DeepAMO is a composite image, typical of that used to view 3D volumes in clinical practice. The output is a rating value designed to reproduce a human observer's defect detection performance. In stages 2 and 3, we propose: (1) a projection-based DC block that confirms defect presence in two 2D orthogonal orientations and (2) a calibration method that "learns" the mapping from the features of stage 2 to the distribution of observer ratings from the human observer rating data (thus modeling inter- or intraobserver variability) using a mixture density network. We implemented and evaluated the DeepAMO in the context of Tc 99 m -DMSA SPECT imaging. A human observer study was conducted, with two medical imaging physics graduate students serving as observers. A 5 × 2 -fold cross-validation experiment was conducted to test the statistical equivalence in defect detection performance between the DeepAMO and the human observer. We also compared the performance of the DeepAMO to an unoptimized implementation of a scanning linear discriminant observer (SLDO). Results: The results show that the DeepAMO's and human observer's performances on unseen images were statistically equivalent with a margin of difference ( Δ AUC ) of 0.0426 at p < 0.05 , using 288 training images. A limited implementation of an SLDO had a substantially higher AUC (0.99) compared to the DeepAMO and human observer. Conclusion: The results show that the DeepAMO has the potential to reproduce the absolute performance, and not just the relative ranking of human observers on a clinically realistic defect detection task, and that building conceptual components of the human reading process into deep learning-based models can allow training of these models in settings where limited training images are available.

Electric-Field-Mediated Electron Tunneling of Supramolecular Naphthalimide Nanostructures for Biomimetic H2 Production.

The design and synthesis of two semiconducting bis (4-ethynyl-bridging 1, 8-naphthalimide) bolaamphiphiles (BENI-COO- and BENI-NH3+ ) to fabricate supramolecular metal-insulator-semiconductor (MIS) nanostructures for biomimetic hydrogen evolution under visible light irradiation is presented. A H2 evolution rate of ca. 3.12 mmol g-1 ⋅h-1 and an apparent quantum efficiency (AQE) of ca. 1.63 % at 400 nm were achieved over the BENI-COO- -NH3+ -Ni MIS photosystem prepared by electrostatic self-assembly of BENI-COO- with the opposite-charged DuBois-Ni catalysts. The hot electrons of photoexcited BENI-COO- nanofibers were tunneled to the molecular Ni collectors across a salt bridge and an alkyl region of 2.2-2.5 nm length at a rate of 6.10×108  s-1 , which is five times larger than the BENI-NH3+ nanoribbons (1.17×108  s-1 ). The electric field benefited significantly the electron tunneling dynamics and compensated the charge-separated states insufficient in the BENI-COO- nanofibers.