Stereoselective Synthesis of Complex Polyenes through Sequential α-/ß-C-H Functionalization of trans-Styrenes.

Sequential C-H functionalization of molecules containing multiple C-H bonds can efficiently lead to structural diversity. Herein we present the first chelation-assisted sequential α-/ß-C-H functionalization of E-styrenes with simple alkenes and alkynes in excellent regio- and stereo-selectivity. The process involves α C-H functionalization by six-membered exo-cyclopalladation to result in tri- and tetrasubstituted 1,3-dienes and ß C-H functionalization through seven-membered endo-cyclopalladation to produce tetra- and pentasubstituted 1,3,5-trienes in up to 97 % yield with up to >99/1 E/Z selectivity, both enabled by the chelation assistance of pyrazinamide. The protocol is demonstrated to be widely applicable, tolerant to a wide range of functional groups and bioactive fragments, and suitable for gram-scale synthesis as well as one-pot and two step preparation of trienes. Mechanistic experiments and density functional theory (DFT) calculations were performed to elucidate the selectivity and reactivity.

A ternary nucleotide-lanthanide coordination nanoprobe for ratiometric fluorescence detection of ciprofloxacin.

Ciprofloxacin (CIP) is a widely used broad-spectrum antibiotic and has been associated with various side effects, making its accurate detection crucial for patient safety, drug quality compliance, and environmental and food safety. This study presents the development of a ternary nucleotide-lanthanide coordination nanoprobe, GMP-Tb-BDC (GMP: guanosine 5'-monophosphate, BDC: 2-amino-1,4-benzenedicarboxylic acid), for the sensitive and ratiometric detection of CIP. The GMP-Tb-BDC nanoprobe was constructed by incorporating the blue-emissive ligand BDC into the Tb/GMP coordination polymers. Upon the addition of CIP, the fluorescence of terbium ion (Tb3+ ) was significantly enhanced due to the coordination and fluorescence sensitization properties of CIP, while the emission of the BDC ligand remained unchanged. The nanoprobe demonstrated good linearity in the concentration range of 0-10 µM CIP. By leveraging mobile phone software to analyze the color signals, rapid on-site analysis of CIP was achieved. Furthermore, the nanoprobe exhibited accurate analysis of CIP in actual drug and milk samples. This study showcases the potential of the GMP-Tb-BDC nanoprobe for practical applications in CIP detection.

Knockdown of LINC01087 inhibits gastric cancer malignant behavior by regulating the miR-135a-5p/CAAP1 axis.

Long noncoding RNAs play important roles in the occurrence and development of many malignant cancers. This study focuses on the effects of LINC01087 on gastric cancer and its underlying mechanism. In the present study, LINC01087 and CAAP1 were found to be upregulated, and miR-135a-5p was diminished in gastric cancer specimens and cells. Inhibition of LINC01087 resulted in cell proliferation inhibition and induced cell apoptosis through the intrinsic apoptosis signaling pathway, as evidenced by the activation of caspase-3 and caspase-9. An investigation of the signaling pathway revealed that the effects on proliferation and apoptosis following LINC01087 knockdown were mediated by suppression of CAAP1. Furthermore, application of a miR-135a-5p inhibitor or overexpression of CAAP1 could attenuate the apoptotic effect achieved by LINC01087 inhibition, confirming the involvement of miR-135a-5p/CAAP1 signaling in the occurrence of gastric cancer. In conclusion, the LINC01087/miR-135a-5p/CAAP1 axis modulates gastric cancer tumorigenesis and pathogenesis and presents new insight into gastric cancer targeted therapy.

Comparative analysis of clinical efficacy between laparoscopic and open pancreaticoduodenectomy.

Laparoscopic pancreaticoduodenectomy (LPD) is a technically demanding procedure but is gradually gaining acceptance in clinical practice. This study was performed to compare the short-term outcomes of LPD with open pancreaticoduodenectomy (OPD). The perioperative data of the patients who underwent LPD (n = 25) and OPD (n = 40) from January 1, 2017 to December 31, 2021 at Zhangjiagang Hospital Affiliated to Soochow University were collected and retrospectively analyzed. All patients received R0 resection, and none of the patients died within the perioperative period. The preoperative data (gender, age, body mass index [BMI], and preoperative bilirubin), the intraoperative data (operative time, number of retrieved lymph nodes), and postoperative data (level 1 monitoring time, postoperative fluid diet time, postoperative fluid feeding time, and hospitalization cost) were comparable between the 2 groups (P > .05). The estimated blood loss, abdominal drainage tube removal time, postoperative hospital stay, catheter removal time, and analgesic drug use were significantly lesser in the LPD group, when compared to the OPD group (P < .05). LPD is safe and feasible. Compared to OPD, LPD has less surgical trauma, less intraoperative bleeding, and faster postoperative recovery.

Risk factor analysis and construction of prediction models of gallbladder carcinoma in patients with gallstones.

Background: Gallbladder carcinoma (GBC) is a biliary tract tumor with a high mortality rate. The objectives of this study were to explore the risk factors of GBC in patients with gallstones and to establish effective screening indicators. Methods: A total of 588 patients from medical centers in two different regions of China were included in this study and defined as the internal test samples and the external validation samples, respectively. We retrospectively reviewed the differences in clinicopathologic data of the internal test samples to find the independent risk factors that affect the occurrence of GBC. Then, we constructed three different combined predictive factors (CPFs) through the weighting method, integral system, and nomogram, respectively, and named them CPF-A, CPF-B, and CPF-C sequentially. Furthermore, we evaluated these indicators through calibration and DCA curves. The ROC curve was used to analyze their diagnostic efficiency. Finally, their diagnostic capabilities were validated in the external validation samples. Results: In the internal test samples, the results showed that five factors, namely, age (RR = 3.077, 95% CI: 1.731-5.496), size of gallstones (RR = 13.732, 95% CI: 5.937-31.762), course of gallstones (RR = 2.438, 95% CI: 1.350-4.403), CEA (RR = 9.464, 95% CI: 3.394-26.392), and CA199 (RR = 9.605, 95% CI: 4.512-20.446), were independent risk factors for GBC in patients with gallstones. Then, we established three predictive indicators: CPF-A, CPF-B, and CPF-C. These models were further validated using bootstrapping with 1,000 repetitions. Calibration and decision curve analysis showed that the three models fit well. Meanwhile, multivariate analysis showed that CPF-B and CPF-C were independent risk factors for GBC in patients with gallstones. In addition, the validation results of the external validation samples are essentially consistent with the internal test samples. Conclusion: Age (≤58.5 vs. >58.5 years), size of gallstones (≤1.95 vs. >1.95cm), course of gallstones (≤10 vs. >10 years), CEA (≤5 vs. >5 ng/ml), and CA199 (≤37 vs. >37 U/ml) are independent risk factors for GBC in patients with gallstones. When positive indicators were ≥2 among the five independent risk factors or the score of the nomogram was >82.64, the risk of GBC was high in gallstone patients.

New Staging Model for Radiation-based Hepatocellular Carcinoma Treatment: A National Multicenter Study.

Background and Aims: The study aimed to create a new staging model for radiotherapy-based treatment for prognostic hepatocellular carcinoma (HCC) classification. Methods: The training cohort comprised 658 patients receiving stereotactic body radiotherapy and external validation cohort comprised 533 patients receiving three-dimensional conformal radiotherapy and intensity-modulated radiotherapy. We established a modified staging system as follows: stage I, solitary nodule without macrovascular invasion, or 2-3 nodules no more than 3.0 cm apart, and performance status (PS) 0-2 (Ia: ALBI-1 grade; Ib: ALBI-2 or 3 grade); stage II: 2-3 nodules with any one nodule more than 3.0-cm apart, or ≥4 nodules, and performance status 0-2 (IIa: ALBI-1 grade; IIb: ALBI-2 grade); stage III: macrovascular invasion, regional lymph node metastasis or distant metastasis, and performance status 0-2 (IIIa: ALBI-1 grade; IIIb: ALBI-2 grade); stage IV: performance status 3-4, or performance status 0-2 with ALBI-3 grade. We analyzed long-term overall survival based on different stages. Results: The staging model showed an excellent ability to discriminate patients according to four stages and seven substages with notably different curves in the training and validation cohort. The median survival decreased from stages I to IV with 63.0 months in stage I (not reached in Ia, and 53.0 months in Ib), 24.0 months in stage II (28.0 months in IIa, and 22.0 months in IIb), 11.0 months in stage III (18.0 months in IIIa, and 9.0 months in IIIb), and less than 9.0 months in stage IV in the training cohort. Conclusions: The modified staging model may provide an alternative for clinical radiation oncologists.

Porous materials formed by four self-construction processes.

Multiple self-construction behavior of cyclic oligoesters is described. Rigid braces and elastic hinges are periodically incorporated into these cyclomers, which enables these rings to form various topological frameworks, such as holes, caves or cages with different sizes and shapes, through self-folding. Among them, the cave-type cyclomer self-assembles into nanotunnels and then forms porous materials via self-packing of these tunnels. This discovery provides a new perspective for the construction of novel materials aided by multiple supramolecular effects. In this work, the simplest rigid brace components and ones with soft hinges were chosen to construct cyclomers to confirm the supramolecular strategy.

RhoGDI2 induced malignant phenotypes of pancreatic cancer cells via regulating Snail expression.

BACKGROUND: Rho GDP dissociation inhibitor 2 (RhoGDI2) has been shown to contribute to the aggressive phenotypes of human cancers, such as tumor metastasis and chemoresistance. OBJECTIVE: This study aimed to assess the effects of RhoGDI2 on tumor progression and chemoresistance in pancreatic cancer cells. METHODS: The expression of RhoGDI2 in pancreatic cancer cells was detected by Western blot analysis. Gain-of-function and loss-of-function approaches were done to examine the malignant phenotypes of the RhoGDI2-expressing or RhoGDI2-depleting cells. The correlation between RhoGDI2 and Snail was also analyzed. RESULTS: Differential expression of RhoGDI2 protein in pancreatic cancer cell lines was identified. Gain-of-function and loss-of-function experiments showed that RhoGDI2 induced the malignant phenotypes of pancreatic cancer cells, including proliferation, migration, invasion, and gemcitabine (GEM) chemoresistance. The upregulation of RhoGDI2 stimulated the expression of Snail, resulting in the altered expression of epithelial marker E-cadherin and mesenchymal marker Vimentin, which were characteristics of the tumorigenic activity of epithelial-mesenchymal transition. The expression of RhoGDI2 and Snail was upregulated in clinical tumor samples, and higher expression of RhoGDI2 or Snail was significantly associated with poor patient survival in pancreatic ductal adenocarcinoma (PDAC). CONCLUSION: The findings indicated that RhoGDI2 promoted GEM resistance and tumor progression in pancreatic cancer and that RhoGDI2 might be a potential therapeutic target in patients with PDAC.

d-Orbital Reconstructions Forced by Double Bow-Shaped Deformations and Second Coordination Sphere Effects of Cu(II) Heme Analogs in HER.

Both geometric architecture and electronic configurations of heme proteins contribute to its activity. In this work we designed and synthesized a series of four copper(II) porphyrin complexes (4-, 3-, 2- and 1-Cu) where the molecular conformations are modulated by a pair of stepwise shortened straps on the same porphyrin side (cis-ortho) to give double bow-shaped skeletons. Single crystal structures demonstrate that the straps gradually increase the saddle deformation and the deviation of the metal centers, which is in accordance with two, unusual d-orbital reconstructions of two different ground states, as revealed by 4 K EPR and DFT calculations. In the study of the electrocatalytic hydrogen evolution reaction (HER), 1-Cu, with the shortest straps, showed the most apparent improvement of activity. Second coordination sphere (SCS) effects created by the double bow-shaped architecture and the strong saddle porphyrin core in 1-Cu are found to play key roles in proton trapping during the catalytic process. The work contributes a novel strategy to improve the catalytic performance of heme analogs through ligand geometric modulation.

Optimal stereotactic body radiotherapy dosage for hepatocellular carcinoma: a multicenter study.

BACKGROUND: The optimal dose and fractionation scheme of stereotactic body radiation therapy (SBRT) for hepatocellular carcinoma (HCC) remains unclear due to different tolerated liver volumes and degrees of cirrhosis. In this study, we aimed to verify the dose-survival relationship to optimize dose selection for treatment of HCC. METHODS: This multicenter retrospective study included 602 patients with HCC, treated with SBRT between January 2011 and March 2017. The SBRT dosage was classified into high dose, moderate dose, and low dose levels: SaRT (BED10 ≥ 100 Gy), SbRT (EQD2 > 74 Gy to BED10 < 100 Gy), and ScRT (EQD2 < 74 Gy). Overall survival (OS), progression-free survival (PFS), local control (LC), and intrahepatic control (IC) were evaluated in univariable and multivariable analyses. RESULTS: The median tumor size was 5.6 cm (interquartile range [IQR] 1.1-21.0 cm). The median follow-up time was 50.0 months (IQR 6-100 months). High radiotherapy dose correlated with better outcomes. After classifying into the SaRT, SbRT, and ScRT groups, three notably different curves were obtained for long-term post-SBRT survival and intrahepatic control. On multivariate analysis, higher radiation dose was associated with improved OS, PFS, and intrahepatic control. CONCLUSIONS: If tolerated by normal tissue, we recommend SaRT (BED10 ≥ 100 Gy) as a first-line ablative dose or SbRT (EQD2 ≥ 74 Gy) as a second-line radical dose. Otherwise, ScRT (EQD2 < 74 Gy) is recommended as palliative irradiation.

Application of encapsulated algae into MBR for high-ammonia nitrogen wastewater treatment and biofouling control.

Low microbial activity and serious membrane biofouling are still critical problems that hinder the extensive application of membrane bioreactor (MBR) for industrial wastewater treatment. To address these bottlenecks, we report a new specialized microorganism encapsulation strategy for constructing a highly efficient MBR system. In our study, the algae-entrapping fiber macrospheres with polymeric coating were first coupled with membrane separation for treating refractory high-ammonia nitrogen wastewater. In comparison with traditional alginate beads, the developed macrocapsule (~0.5 cm) exhibited higher biomass harvesting and lower microbial leakage because of the confined micro-aerobic environment created by dual encapsulation of rigid inorganic macrosphere and porous polymeric layers. Application of algae-encapsulating macrocapsule to MBR presented excellent chemical oxygen demand (COD) and ammonia nitrogen (NH3-N) removal efficiency of 62.23 and 97.38 %, respectively, which were higher than the corresponding values for algae/SA beads and free algae. The biodegradation performance of NH3-N by encapsulated microalgae was similar or superior to that by free cells when the initial content of ammonia nitrogen ranged from 50 to 100 mg/L. The results well demonstrated that the GFS@polymer macrocapsule as a physical barrier reduced the inhibitory effect of higher concentration ammonia nitrogen on the bioactivity of living cells. Importantly, the encapsulated core-shell macrocapsules showed superior anti-biofouling capacity, which had a membrane resistance of 3-5 times lower than that of cell/alginate beads and free cells. This work will open a new avenue to develop a novel encapsulated MBR for various non-degradable wastewater treatments as an energy-saving and sustainable way.

Superelastic, Sensitive, and Low Hysteresis Flexible Strain Sensor Based on Wave-Patterned Liquid Metal for Human Activity Monitoring.

Flexible strain sensors have been widely used in wearable electronic devices for body physical parameter capturing. However, regardless of the stretchability of the sensing material, the resolution of small strain changes or the hysteresis between loading/unloading states has always limited the various applications of these sensors. In this paper, a microfluidic flexible strain sensor was achieved by introducing liquid metal eutectic gallium indium (EGaIn) embedded into a wave-shaped microchannel elastomeric matrix (300 µm width × 70 µm height). The microfluidic sensor can withstand a strain of up to 320%, and the hysteresis performance was also improved from 6.79 to 1.02% by the wave-patterned structure which can restrain the viscoelasticity of the elastomer effectively. Moreover, an enhanced wave-shaped strain sensor was fabricated by increasing the length of the microfluidic channel; it has high sensitivity (GF = 4.91) and resolution, and even as low as 0.09% strain change could be detected, which is capable of resolving microdeformation; besides, the enhanced wave-shaped strain sensor exhibits quick response time (t = 116 ms), long-term stability, and durability under periodic dynamic load. As an example of potential applications, the enhanced flexible sensor showed excellent mechanical compliance and was successfully applied as a conceptual wearable device for distinctively monitoring various kinds of human body and robot activities, such as the different states of the finger, neck, breathing chest, robot's joint, and so forth. The flexible wave-shaped strain sensor has great promising applications for wearable electronics, motion recognition, healthcare, and soft robotics.

Gait Rhythm Dynamics for Neuro-Degenerative Disease Classification via Persistence Landscape- Based Topological Representation.

Neuro-degenerative disease is a common progressive nervous system disorder that leads to serious clinical consequences. Gait rhythm dynamics analysis is essential for evaluating clinical states and improving quality of life for neuro-degenerative patients. The magnitude of stride-to-stride fluctuations and corresponding changes over time-gait dynamics-reflects the physiology of gait, in quantifying the pathologic alterations in the locomotor control system of health subjects and patients with neuro-degenerative diseases. Motivated by algebra topology theory, a topological data analysis-inspired nonlinear framework was adopted in the study of the gait dynamics. Meanwhile, the topological representation-persistence landscapes were used as input of classifiers in order to distinguish different neuro-degenerative disease type from healthy. In this work, stride-to-stride time series from healthy control (HC) subjects are compared with the gait dynamics from patients with amyotrophic lateral sclerosis (ALS), Huntington's disease (HD), and Parkinson's disease (PD). The obtained results show that the proposed methodology discriminates healthy subjects from subjects with other neuro-degenerative diseases with relatively high accuracy. In summary, our study is the first attempt to provide a topological representation-based method into the disease classification with gait rhythms measured from the stride intervals to visualize gait dynamics and classify neuro-degenerative diseases. The proposed method could be potentially used in earlier interventions and state monitoring.

A Supersensitive, Multidimensional Flexible Strain Gauge Sensor Based on Ag/PDMS for Human Activities Monitoring.

For more comprehensive monitoring human state of motion, it is necessary to sense multidimensional stimulus information. In this paper, we reported a supersensitive flexible sensor based on Ag/PDMS composites with sensing abilities of strain and force. The fabrication method is simple and rapid, which only need physically grinding the silver particles and mixing with liquid PDMS. The flexible sensor has excellent performances in multidimensional detection. The strain gauge factor can reach as high as 939 when it was stretched to 36%, and the minimum resolution for force detection is 0.02 N. The sensing characteristic of the sensors with different filling fraction and thickness were analyzed from the microscopic point of view. Multidimensional sensing abilities of flexible sensor have greatly expands its applications. We experimentally verified the Ag/PDMS based sensor in human body dynamic monitoring and sound detecting in real-time, which has shown great potential in motion recognition, haptic perception and soft robotics.

Horizontal and Vertical Push Effects in Saddled Zinc Porphyrin Complexes: Implications for Heme Distortion.

A heme oxygen binding behavior was described through a unique geometric and electronic comparison of zinc porphyrin complexes. In this work, a charge transfer model for saddled metalloporphyrin complexes outlined the push effects of the ring nonplanarity and axial imidazole, and the pull effect of the axial dioxygen. The origin and role of the horizontal (ring nonplanarity) push effect and its relationship to the vertical (axial ligand) push/pull effect and its contribution to dioxygen binding were considered from the perspectives of crystal structures, theoretical calculations, and bathochromic shifts. Single-point energy and molecular orbital calculations starting from crystal structures were used to obtain the electronic structures of zinc porphyrin complexes. This study not only revealed that the electronic behavior of metalloporphyrins is driven by ring nonplanarity and axial ligation but also afforded new insight into the oxygen carrier mechanism in heme.

Upregulation of musashi1 increases malignancy of hepatocellular carcinoma via the Wnt/ß-catenin signaling pathway and predicts a poor prognosis.

BACKGROUND: Hepatocellular carcinoma (HCC) is a common human malignant cancer due to a high metastatic capacity and the recurrence rate is also high. This study is aim to investigate the role of musashi1 as a potential biomarker for therapy of HCC. METHODS: The mRNA and protein expression levels of musashi1 were detected in HCC samples and cell lines. The malignant properties of HCC cells, including proliferation, invasion and migration were measured by overexpressing or knocking down expression of musashi1. Additionally, the correlation between musashi1 and clinicopathological indexes and prognosis were analyzed. The expression of CD44 was measured and the correlation between CD44 and musashi1 was analyzed. RESULTS: In vitro cytological experiments demonstrated that musashi1 was elevated in HCC samples and cell lines and this increased expression affected cancer cell viability, migration and invasive capacity by activating of the Wnt/ß-catenin signaling pathway. Analysis of clinicopathological characteristics suggested that up-regulation of musashi1 was related to metastasis potential and a poor prognosis. Besides, there was a positive correlation between CD44 and musashi1 expression. Upregulation of musashi1 in malignant liver tumors may have contributed to the maintenance of stem-cell like characteristics of HCC cells. CONCLUSIONS: Upregulation of musashi1 could enhance malignant development of HCC cells and thus might be a novel marker for HCC therapy.

Geometric deconstruction of core and electron activation of a π-system in a series of deformed porphyrins: mimics of heme.

The predominant distortion of heme is responsible for its electronic activity, catalytic ability and spectral properties. In this work, altogether 12 new X-ray structures of saddled, waved and ruffled porphyrins are reported. Three types of deformed porphyrins as mimics of heme were evaluated and analyzed by geometric deconstruction, spectral comparison, and electrochemical tracking, which shows a unique relationship of deformation fashions and distortion degree to the geometry of the core and electron transfer ability of rings in these enzyme containing porphyrins. These mimics can adjust their core geometry for changing the structures of potential metals; while for rings themselves, they can also regulate the electron activity by switching the HOMO of the large π systems. These deformed porphyrins can be used as ideal mimics for heme. These findings help us to understand the principle and contribution of these deformations to electron transfer in catalytic oxidation and photoreactions. The nonplanar mimics have been synthesized through a modular synthetic approach under Adler-Longo or Lindsey condensation conditions.

Donor-Acceptor Fluorophores for Energy-Transfer-Mediated Photocatalysis.

Triplet-triplet energy transfer (EnT) is a fundamental activation pathway in photocatalysis. In this work, we report the mechanistic origins of the triplet excited state of carbazole-cyanobenzene donor-acceptor (D-A) fluorophores in EnT-based photocatalytic reactions and demonstrate the key factors that control the accessibility of the 3LE (locally excited triplet state) and 3CT (charge-transfer triplet state) via a combined photochemical and transient absorption spectroscopic study. We found that the energy order between 1CT (charge transfer singlet state) and 3LE dictates the accessibility of 3LE/3CT for EnT, which can be effectively engineered by varying solvent polarity and D-A character to depopulate 3LE and facilitate EnT from the chemically more tunable 3CT state for photosensitization. Following the above design principle, a new D-A fluorophore with strong D-A character and weak redox potential is identified, which exhibits high efficiency for Ni(II)-catalyzed cross-coupling of carboxylic acids and aryl halides with a wide substrate scope and high selectivity. Our results not only provide key fundamental insight on the EnT mechanism of D-A fluorophores but also establish its wide utility in EnT-mediated photocatalytic reactions.

Hierarchical combinatorial deep learning architecture for pancreas segmentation of medical computed tomography cancer images.

BACKGROUND: Efficient computational recognition and segmentation of target organ from medical images are foundational in diagnosis and treatment, especially about pancreas cancer. In practice, the diversity in appearance of pancreas and organs in abdomen, makes detailed texture information of objects important in segmentation algorithm. According to our observations, however, the structures of previous networks, such as the Richer Feature Convolutional Network (RCF), are too coarse to segment the object (pancreas) accurately, especially the edge. METHOD: In this paper, we extend the RCF, proposed to the field of edge detection, for the challenging pancreas segmentation, and put forward a novel pancreas segmentation network. By employing multi-layer up-sampling structure replacing the simple up-sampling operation in all stages, the proposed network fully considers the multi-scale detailed contexture information of object (pancreas) to perform per-pixel segmentation. Additionally, using the CT scans, we supply and train our network, thus get an effective pipeline. RESULT: Working with our pipeline with multi-layer up-sampling model, we achieve better performance than RCF in the task of single object (pancreas) segmentation. Besides, combining with multi scale input, we achieve the 76.36% DSC (Dice Similarity Coefficient) value in testing data. CONCLUSION: The results of our experiments show that our advanced model works better than previous networks in our dataset. On the other words, it has better ability in catching detailed contexture information. Therefore, our new single object segmentation model has practical meaning in computational automatic diagnosis.

Electron Transfer and Geometric Conversion of Co-NO Moiety in Saddled Porphyrins: Implications for Trigger Role of Tetrapyrrole Distortion.

The electrons of NO and Co are strongly delocalized in normal {Co-NO}8 species. In this work, {Co-NO}8 complexes are induced to convert from (CoII)+•-NO• to CoIII-NO- by a core contraction of 0.06 Šin saddled cobalt(II) porphyrins. This intramolecular electron transfer mechanism indicates that nonplanarity of porphyrin is involved in driving conversion of the NO units from electrophilic NO• as a bent geometry to nucleophilic NO- as a linear geometry. This implies that distortion acts as a trigger in enzymes containing tetrapyrrole. The electronic behaviors of the CoII ions and Co-NO moieties were confirmed by X-ray crystallography, EPR spectroscopy, theoretical calculation, UV-vis and IR spectroscopy, and electrochemistry.