HOO• as the Chain Carrier for the Autocatalytic Photooxidation of Benzylic Alcohols.

The oxidation of benzylic alcohols is an important transformation in modern organic synthesis. A plethora of photoredox protocols have been developed to achieve the aerobic oxidation of alcohols into carbonyls. Recently, several groups described that ultraviolet (UV) or purple light can initiate the aerobic oxidation of benzylic alcohols in the absence of an external catalyst, and depicted different mechanisms involving the photoinduction of •O2- as a critical reactive oxygen species (ROS). However, based on comprehensive mechanistic investigations, including control experiments, radical quenching experiments, EPR studies, UV-vis spectroscopy, kinetics studies, and density functional theory calculations (DFT), we elucidate here that HOO•, which is released via the H2O2 elimination of α-hydroxyl peroxyl radicals [ArCR(OH)OO•], serves as the real chain carrier for the autocatalytic photooxidation of benzylic alcohols. The mechanistic ambiguities depicted in the precedent literature are clarified, in terms of the crucial ROS and its evolution, the rate-limiting step, and the primary radical cascade. This work highlights the necessity of stricter mechanistic analyses on UV-driven oxidative reactions that involve aldehydes' (or ketones) generation.

Effects of extracorporeal diaphragm pacing combined with inspiratory muscle training on respiratory function in people with stroke: a randomized controlled trial.

OBJECTIVES: To evaluate the effect of external diaphragmatic pacing (EDP) combined with inspiratory muscle training on respiratory function in post-stroke patients. METHODS: Patients with stroke were enrolled from the First Affiliated Hospital of Soochow University in China between 2021 and 2022. The patients were randomized into an EDP treatment group (control group) or an EDP treatment plus inspiratory muscle training group (experimental group). Each therapy was administered once a day for 6 days per week. The peak inspiratory flow (PIF), maximal inspiratory pressure (MIP), forced expiratory volume in 1 s (FEV1), forced vital capacity (FVC), FEV1/FVC% ratio, and diaphragm thickness and mobility were measured and compared between the two groups after 4 weeks. RESULTS: After 4 weeks of intervention, respiratory muscle function indicators including PIF (95% CI: 0.21-1.28, p = 0.008) and MIP (95% CI: 6.92-25.44, p = 0.001) significantly improved in the experimental group. Diaphragmatic thickness also significantly increased in the experimental group (p < 0.05), while diaphragmatic excursion showed no significant difference between the two groups. Additionally, FVC (95% CI: 0.14-1.14, p = 0.013) and FEV1 (95% CI: 0.20-1.06, p = 0.005) demonstrated a significant increase in the experimental group, whereas FEV1/FVC% (95% CI: -0.84 to 9.36, p = 0.099) exhibited no significant group difference. CONCLUSION: EDP combined with inspiratory muscle training in individuals with stroke provides greater benefits than EDP alone in terms of respiratory function recovery, except for the parameters of diaphragmatic excursion and FEV1/FVC%.

Graph modeling of relational structures among functioning variables with low back pain: an exploratory analysis based on International Classification of Functioning, Disability and Health.

BACKGROUND: Given the complex etiology, multidimensional impact, and widespread prevalence of low back pain (LBP), it is crucial to prioritize intervention targets based on understanding the relationships between functional impairments in patients. This prioritization maximizes the physical and psychological benefits for patients, and graph modeling holds promise in achieving these objectives. AIM: The aim of this study was establishing a graphical model of functioning variables for LBP based on the International Classification of Functioning, Disability, and Health (ICF) to identify the most influential items (i.e., functioning variables) on the physical and mental well-being of patients. Exploring feasible intervention measures by understanding the dysfunction correlations among these variables. DESIGN: Cross-sectional survey. SETTING: Nine hospitals in Jiangsu Province, China. POPULATION: Three hundred and six persons with LBP aged ≥18 years. METHODS: All patients were assessed using the Comprehensive ICF Core Sets for LBP. The scoring system was converted to dichotomous data, with 1 indicating dysfunction and 0 indicating no dysfunction. In the graphical model, network parameters and the results of Item Response Theory modeling (as detailed in our other article) were used to determine the importance of items, while partial correlations were utilized to estimate the dysfunction correlations between functioning variables. RESULTS: 1) A total of 56 ICF items were located in the backbone structure of LBP, among which d430 (Lifting and carrying objects) occupied the most central position, followed by b126 (Temperament and personality functions). 2) In the main component of backbone structure, d430 has moderate dysfunction correlation with looking after one's health (0.6027), social norms, practices and ideologies (0.597), stability of joint functions (0.5759), and emotional functions (0.4078). b126 has moderate dysfunction correlation with basic interpersonal interactions (0.6595). CONCLUSIONS: d430 and b126 significantly impact the physical and mental well-being of LBP patients. To improve d430, maintaining exercise habits, reducing working hours, enhancing lumbar stability, and overcoming fear-related emotions are recommended. Similarly, improving b126 can be achieved through enhancing interpersonal relationships. CLINICAL REHABILITATION IMPACT: Through the identification of crucial functioning variables and the associated dysfunctional correlation relationships, graphical model of Comprehensive ICF Core Set for LBP can offer healthcare decision-makers valuable insights into potential treatment targets and pathways aimed at improving the condition of LBP patients.

Establishment and evaluation of a nomogram prediction model for recurrence risk of atrial fibrillation patients after radiofrequency ablation.

OBJECTIVE: To explore the risk factors for recurrence of atrial fibrillation (AF) in patients after radiofrequency ablation and construction of a targeted nomogram prediction model. METHODS: A prospective cohort study design was used to select 312 patients who were separated into two groups; a recurrence group (n = 79) and a non-recurrence group (n = 233) with or without AF, who underwent radiofrequency ablation for the first time between January 2017 and December 2017, with a completed a 12-month follow-up after surgery. The recurrence of AF within 12 months after follow-up was recorded. The nomogram prediction model was established. The original data were resampled using the Bootstrap method. The recurrence risk after resampling was predicted using a nomogram model. The calibration curve and ROC curve of the nomogram model were established. The predicted calibration degree and discrimination degree of the nomogram model were evaluated with the Hosmer-Lemeshow deviation test and area under the curve. RESULTS: The 12-month follow-up showed that a total of 79 patients (25.32%) had recurrence of AF. The type of AF, sex, gender, disease course, left atrial anteroposterior diameter, left atrial volume, and cardiac function classification were independent risk factors for the recurrence of AF (P < 0.05). After the nomogram prediction model passed the Bootstrap self-sampling 1000 times, Hosmer-Lemeshow deviation test: χ2 = 8.070, P = 0.427; the area under ROC curve was 0.852 (95% CI: 0.806-0.898), the sensitivity was 78.48%, and the specificity was 81.12%, suggesting that the nomogram model has better predictive calibration and discrimination. CONCLUSION: The recurrence rate in patients with AF after radiofrequency ablation is high. The nomogram model based on the risk factors of AF recurrence has high prediction accuracy and can be used to predict the recurrence risk of AF in patients after radiofrequency ablation.

Structure-based bioisosterism design, synthesis, insecticidal activity and structure-activity relationship (SAR) of anthranilic diamide analogues containing 1,2,4-oxadiazole rings.

BACKGROUND: Anthranilic diamide derivatives are among the most important classes of synthetic insecticides. Moreover, the 1,2,4-oxadiazole heterocycle, a bioisostere of amide, has been extensively used in pesticides. In order to discover novel molecules with high insecticidal activities, a series of anthranilic diamide analogues containing 1,2,4-oxadiazole rings were designed and synthesised. RESULTS: A series of novel anthranilic diamide derivatives containing 1,2,4-oxadiazole were obtained, and confirmed by 1 H and 13 C nuclear magnetic resonance and high-resolution mass spectrometry. The structure of 3-bromo-N-(4-chloro-2-methyl-6-{3-[(methylsulphonyl)methyl]-1,2,4-oxadiazol-5-yl}phenyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide was further characterised by X-ray diffraction analysis. In addition, bioassays showed that most of the newly synthesised compounds displayed 100% mortality against Plutella xylostella at 100 mg L-1 , and compound 3IIl showed 90% larvicidal activities at a concentration of 0.5 mg L-1 . The LC50 value of 3IIl was 0.20 mg L-1 , which indicated that it may be used as a potential leading compound for further structural optimisation. Furthermore, brief comparative molecular field analysis (CoMFA) models were established to study the structure-activity relationships (SARs) of the title compounds. CONCLUSION: Compound 3IIl may be used as a potential leading compound for further structural optimisation, and SARs and CoMFA models could provide reliable clues for further structural optimisation. © 2016 Society of Chemical Industry.

Treatment of detrusor external sphincter dyssynergia using ultrasound-guided trocar catheter transurethral botulinum toxin a injection in men with spinal cord injury.

OBJECTIVE: To evaluate the effects of transrectal ultrasound-guided trocar catheter transurethral botulinum toxin A (BTX-A) injection into the external urethral sphincter (EUS) for treating detrusor external sphincter dyssynergia (DESD) in men with spinal cord injury (SCI). DESIGN: Descriptive study. SETTING: Hospital rehabilitation department. PARTICIPANTS: Patients (N=15; mean age, 40.5y; range, 22-64y) with suprasacral SCI with confirmed DESD determined by urodynamic study. INTERVENTIONS: A single dose of 100U BTX-A was injected into the EUS via transrectal ultrasound-guided trocar catheter transurethral injection. MAIN OUTCOME MEASURES: Maximal detrusor pressure, detrusor leak point pressure, maximal pressure on static urethral pressure profilometry, postvoid residual volume, and maximal flow rate. RESULTS: After BTX-A transurethral injection, 4 (28.5%) patients showed an excellent result and 7 (46.7%) patients showed an improved result, whereas 4 (28.5%) patients experienced treatment failure. The overall success rate was 75.2%. We observed a significant decrease in static urethral pressure (P<.05) and detrusor leak point pressure after treatment (P<.05), but not in detrusor pressure. The postvoid residual volume were significantly decreased in the fourth week after treatment (P<.05). CONCLUSIONS: Transrectal ultrasound-guided trocar catheter transurethral BTX-A injection into the EUS effectively suppresses or ameliorates DESD. A potential advantage of the method is that ultrasound guidance may not be necessary in the next injection.

Synthesis, insecticidal activities and structure-activity relationship studies of novel anthranilic diamides containing pyridylpyrazole-4-carboxamide.

BACKGROUND: Anthranilic diamide insecticides containing pyridylpyrazole-5-carboxamide are extremely important in modern agriculture. New structurally modified compounds with high insecticidal activity were discovered by designing a series of novel pyridylpyrazole-4-carboxamides (9I to 9IV) and pyridylpyrazole-4-carboxamides (10I to 10IV), the latter designed by the cyclisation of two amides. The structure-activity relationship (SAR) between the two series is of interest. RESULTS: Two series of novel anthranilic diamides containing pyridylpyrazole-4-carboxamide were synthesised and characterised via melting point, (1)H NMR, (13)C NMR, MS and elemental analyses. The insecticidal activities of these compounds against Plutella xylostella were evaluated. At a concentration of 100 mg L(-1), the compounds with unmodified amide moieties (9I to 9IV) exhibited much better larvicidal activities than the other derivative compounds (10I to 10IV). Most of the compounds 9I to 9IV showed over 90% larvicidal activity at 100 mg L(-1). Furthermore, compounds 9IIIa, 9IIIc, 9IIId and 9IVd displayed significant insecticidal activity at 10 mg L(-1). Density functional theory (DFT) calculation was carried out to provide more information regarding SAR. CONCLUSION: Thirty-two new anthranlic diamides containing pyridylpyrazole-4-carboxamide were designed and obtained. SAR analysis and DFT calculation results revealed that the amide moiety had a very important effect on bioactivity. This work has provided information that could aid investigations of novel insecticides.

Up-regulation of microRNA-135a protects against myocardial ischemia/reperfusion injury by decreasing TXNIP expression in diabetic mice.

BACKGROUND AND AIMS: The heart in diabetic state is sensitive to myocardial ischemia reperfusion (mI/R) injury. In the present study, we investigated the potential mechanisms of modulating mI/R injury in diabetic state. METHODS: Diabetic db/db mice and control non-diabetic mice were administrated with mI/R injury or sham operation. Mouse atrial-derived cardiac cell line HL-1 subjected to hypoxia-reoxygenation (H/R) was used as in vitro model of I/R injury to the heart. RESULTS: Compared with normal mice, mI/R elevated the levels of myocardial infarct size, apoptosis and TXNIP expression (in mRNA and protein) in diabetic mice. Myocardial miR-135a expression level was reduced in diabetic mice regardless of mI/R treatment or not. MiR-135a overexpression protected myocardial cells from mI/R injury in diabetic mice. In vitro, high glucose incubation contributed to a significant down-regulation of miR-135a and up-regulation of TXNIP in cells with or without H/R treatment. Luciferase reporter assay showed that TXNIP was a target gene of miR-135a. MiR-135a overexpression protected HL-1 cells from H/R injury in high glucose condition, while this effect was reversed by up-regulated TXNIP. CONCLUSION: miR-135a protects against mI/R injury by decreasing TXNIP expression in diabetic state.

Effects of doxycycline on cx43 distribution and cardiac arrhythmia susceptibility of rats after myocardial infarction.

This study aims to observe the effects of doxycycline (DOX) on gap junction remodeling after MI and the susceptibility of rats to cardiac arrhythmia. The proximal left anterior descending coronary artery of rats was ligated to establish a myocardial infarction animal model. DOX, methylprednisolone (MP), or vehicle was intraperitoneally injected into the animals for two weeks. Then, the heart size and heart function of all animals were determined through echocardiography. The experimental animals were sacrificed after the electrophysiologic study. Myocardial tissues were sampled to analyze the distribution of Cx43 using immunofluorescence; the Cx43 content was analyzed using western blot analysis; and the MMP-2 and MMP-9 activity in the myocardium was analyzed using gelatin zymography. The distribution of Cx43 in the border of the infarcted myocardia in the MI and MP groups was clearly disrupted and the Cx43 content was significantly reduced. In addition, the distribution of Cx43 in the border of the infarct in the DOX group was relatively regular, whereas two weeks of DOX treatment significantly inhibited MMP activity. Meanwhile, the induction rate of arrhythmia in the rats after DOX treatment was lower than those in the MI and MP groups. The results show that DOX treatment after myocardial infarction improves gap junction remodeling in the myocardial tissue near the infarcted area by inhibiting MMP activity and reducing susceptibility to cardiac arrhythmia.

Cx43 in mesenchymal stem cells promotes angiogenesis of the infarcted heart independent of gap junctions.

Mesenchymal stem cells (MSCs) with elevated levels of connexin 43 (Cx43) have been shown to exhibit improved protection for ischemic hearts. However, it remains unclear whether Cx43 is involved in the paracrine actions of angiogenesis, the major mechanism of cell therapy. In the present study, an in vitro model with deprivation of oxygen and a murine myocardial infarction model with permanent ligation of the left anterior­descending (LAD) coronary artery were used to determine whether gap junctions in MSCs promote angiogenesis. It was observed that MSCs that overexpressed Cx43 (MSCs­Cx43), improve the cardiac function of infarcted myocardium as compared with control MSCs (MSCs­vector) and MSCs with Cx43 knocked down by small interfering RNA (MSCs­siCx43), accompanied with a reduction of infarct size and an increase in the vascular density and maturity. Increased levels of representative angiogenic factors [vascular endothelial growth factor (VEGF) and basic fibroblast growth factor (bFGF)] were produced by MSCs­Cx43 compared with MSCs­siCx43 in vivo and in vitro. However, neither Cx43 formed gap junction specific inhibitor (Cx43 mimetic peptide) or gap junction opener (antiarrhythmic peptide) affected the production of VEGF and bFGF in MSCs under hypoxic stress. These data support the hypothesis that Cx43 in MSCs promotes angiogenesis in the infarcted heart, independent of gap junction formation.

4-Di-phenyl-phosphanyl-8-methyl-1,5-naphthyridine.

In the title compound, C21H17N2P, the dihedral angles between the 1,5-naphthyridine ring system (r.m.s. deviation = 0.005 Å) and the phenyl rings are 89.18 (8) and 77.39 (8)°. The phenyl rings are almost perpendicular, making a dihedral angle of 88.12 (8)°. The only possible inter-molecular inter-action is a very weak aromatic π-π stacking inter-action [centroid-centroid separation = 3.898 (2) Å].

1,4-Di-bromo-2,5-di-p-toluoyl-benzene.

In the title compound, C22H16Br2O2, which has approximate non-crystallographic inversion symmetry, the dihedral angles between the central ring and the pendant rings are 89.1 (4) and 82.4 (3)°; the dihedral angle between the pendant rings is 12.1 (4)°. In the crystal, the packing is influenced by van der Waals forces and no aromatic π-π stacking is observed.

Novel multifunctional organic semiconductor materials based on 4,8-substituted 1,5-naphthyridine: synthesis, single crystal structures, opto-electrical properties and quantum chemistry calculation.

A series of 4,8-substituted 1,5-naphthyridines (1a-1h) have been successfully synthesised by a Suzuki cross-coupling between 4,8-dibromo-1,5-naphthyridine (4) and the corresponding boronic acids (2a-2h) in the presence of catalytic palladium acetate in yields of 41.4-75.8% and have ben well characterized. They are thermally robust with high phase transition temperatures (above 186 °C). Compounds 1b, 1e and 1f crystallized in the monoclinic crystal system with the space groups P2(1)/c, P2(1)/c and P2(1)/n, respectively. All of them show the lowest energy absorption bands (λ(max)(Abs): 294-320 nm), revealing low optical band gaps (2.77-3.79 eV). These materials emit blue fluorescence with λ(max)(Em) ranging from 434-521 nm in dilute solution in dichloromethane and 400-501 nm in the solid state. 4,8-Substituted 1,5-naphthyridines 1a-1h have estimated electron affinities (EA) of (2.38-2.72 eV) suitable for electron-transport materials and ionization potentials (IP) of 4.85-5.04 eV facilitate excellent hole-injecting/hole-transport materials properties. Quantum chemical calculations using DFT B3LYP/6-31G* showed nearly identical the lowest unoccupied molecular orbitals (LUMO) of -2.39 to -2.19 eV and the highest occupied molecular orbitals (HOMO) of -5.33 to -6.84 eV. These results demonstrate the 4,8-substituted 1,5-naphthyridines 1a-1h with a simple architecture might be promising blue-emitting (or blue-green-emitting) materials, electron-transport materials and hole-injecting/hole-transport materials for applications for developing high-efficiency OLEDs.

9,9-Dibutyl-9H-fluorene-2-carbonitrile.

The fluorene fragment of the title compound, C(22)H(25)N, is essentially planar, with an r.m.s deviation of the five-membered ring of 0.005 (2) Å. The dihedral angle between this ring and the outer benzene rings are 1.5 (2) and 0.7 (2)° while that between the benzene rings is 2.1 (2)°. The cyano group makes an angle of 0.3 (2)° with the attached benzene ring.

Blue-light-emitting multifunctional triphenylamine-centered starburst quinolines: synthesis, electrochemical and photophysical properties.

A series of triphenylamine-centered starburst quinolines (1a-1g) have been synthesized by Friedländer condensation of the 4,4',4''-triacetyltriphenylamine (2) and 2-aminophenyl ketones (3a-3g) in the presence of catalytic sulfuric acid and characterized well. They are thermally robust with high glass transition temperatures (above 176.4 °C) and decomposition temperatures (above 406 °C). These compounds emit blue fluorescence with λ(max)(Em) ranging from 433 to 446 nm in dilute toluene solution and 461 to 502 nm in the solid-state and have a relatively high efficiency (Φ(u) = 0.98-0.57). 1a-1g have estimated ionization potentials (IP) of 4.54 to 6.45 eV which are significantly near or higher than those of well-known electron transport materials (ETMs), including tris(8-hydroxyquinoline)aluminium (Alq(3)) (IP = 5.7-5.9 eV), and previously reported oligoquinolines (IP = 5.53-5.81 eV). Quantum chemical calculations using DFT B3LYP/6-31G* showed the highest occupied molecular orbital (HOMO) of -5.05 to -4.81 eV, which is close to the work function of indium tin oxide (ITO). These results demonstrate the potential of 1a-1g as hole-transporting/light-emitting/electron-transport materials and the host-materials of a dopant for hole-injecting for applications in organic light-emitting devices.

Design, synthesis, insecticidal activity and structure-activity relationship of 3,3-dichloro-2-propenyloxy-containing phthalic acid diamide structures.

BACKGROUND: Phthalic acid diamide derivatives are among the most important classes of synthetic insecticides. In this study, a 3,3-dichloro-2-propenyloxy group, the essential active group of pyridalyl derivatives, was incorporated into phthalic acid diamide derivatives with the aim of combining the active groups to generate more potent insecticides. RESULTS: Thirty-one new phthalic acid diamides were obtained, and these were characterised by (1) H and (13) C NMR. The structure of N(2) -[1,1-dimethyl-2-(methoxy)ethyl]-3-iodo-N(1) -[4-(3,3-dichloro-2-propenyloxy)-3-(trifluoromethyl)phenyl]-1,2-benzenedicarboxamide was determined by X-ray diffraction crystallography. The insecticidal activities of the compounds against Plutella xylostella were evaluated. The title compounds exhibited excellent larvicidal activities against P. xylostella. Structure-activity relationships revealed that varying the combination of aliphatic amide and aromatic amide moieties, or the nature and position of substituent Y on the aniline ring, could aid the design of structures with superior performance. CONCLUSION: A series of novel phthalic acid diamides containing a 3,3-dichloro-2-propenyloxy group at the 4-position of the aniline ring were designed and synthesised. Structure-activity relationships with the parent structure provided information that could direct further investigation on structure modification.

1,5-Bis[(2-meth-oxy-eth-oxy)meth-yl]-1,5-naphthyridine-4,8(1H,5H)-dione.

The complete mol-ecule of the title compound, C(16)H(22)N(2)O(6), is generated by crystallographic inversion symmetry. The conformation of the N-C-O-C fragment of the side chain is approximately gauche [torsion angle = -74.84 (17)°]. In the crystal, weak C-H⋯O inter-actions link the mol-ecules.

2-Cyano-N,N-dimethyl-acetamide.

In the crystal structure of the title compound, C(5)H(8)N(2)O, mol-ecules are linked by weak C-H⋯O hydrogen bonds, forming a three-dimensional network.

2-(2-Nitro-anilino)benzoic acid.

In the title compound, C(13)H(10)N(2)O(4), the nitro N atom deviates by 0.031 (2) Šfrom the plane of the benzene ring to which it is attached. The aromatic rings are oriented at a dihedral angle of 50.6 (1)°. An intra-molecular N-H⋯O hydrogen bond occurs. In the crystal, inversion dimers are formed by pairs of O-H⋯O inter-actions.

8-Thia-1,6-diaza-bicyclo-[4.3.0]nonane-7,9-dione.

There are two independent mol-ecules, A and B, in the asymmetric unit of the title compound, C(6)H(8)N(2)O(2)S. In the crystal, pairs of inter-molecular S⋯O contacts [3.286 (1) Å] link the B mol-ecules into inversion dimers.