The association between serum copper concentration and prevalence of diabetes among US adults with hypertension (NHANES 2011-2016).

The objective of this study was to examine the association between the serum copper concentration and the prevalence of diabetes among US adults with hypertension using the data from the National Health and Nutrition Examination Survey (NHANES). The study population was selected from adults aged over 20 years old in the three survey cycles of NHANES from 2011 to 2016. Logistic regression model analyses were applied to determine the independent risky effect of copper to the prevalence of diabetes. Also, a restricted cubic spline (RCS) model was performed to explore the potential nonlinear association between serum copper concentration and the prevalence of diabetes. A total of 1786 subjects (742 cases and 1044 controls) were included, and 924 were men (51.7%), and 742 (41.5%) were diabetic. Compared with non-diabetic individuals, the concentration of serum copper in diabetic patients with hypertension was higher. After adjusting for age, sex, race, education, marital status, body mass index (BMI), family poverty income ratio (PIR), smoking, alcohol drinking, physical activity, systolic blood pressure (SBP), diastolic blood pressure (DBP), and hyperlipidemia, the highest quartile of serum copper concentration significantly increased the risk of diabetes as compared with the lowest quartile (OR: 1.38, 95% CI: 1.01-1.92, ptrend = 0.036). The results of RCS analysis showed significant non-linear relationship between serum copper concentration and prevalence of diabetes (p-non-linear = 0.010). This study finds that serum copper concentration are significantly associated with risk of diabetes in hypertensive patients, which suggests copper as an important risk factor of diabetes development.

Polar covalent apex-base bonding in borapyramidanes probed by solid-state NMR and DFT calculations.

Pyramidane molecules have attracted chemists for many decades due to their regular shape, high symmetry and their correspondence in the macroscopic world. Recently, experimental access to a number of examples has been reported, in particular the rarely reported square pyramidal bora[4]pyramidanes. To describe the bonding situation of the nonclassical structure of pyramidanes, we present solid-state Nuclear Magnetic Resonance (NMR) as a versatile tool for deciphering such bonding properties for three now accessible bora[4]pyramidane and dibora[5]pyramidane molecules. 11 B solid-state NMR spectra indicate that the apical boron nuclei in these compounds are strongly shielded (around -50 ppm vs. BF3 -Et2 O complex) and possess quadrupolar coupling constants of less than 0.9 MHz pointing to a rather high local symmetry. 13 C-11 B spin-spin coupling constants have been explored as a measure of the bond covalency in the borapyramidanes. While the carbon-boron bond to the -B(C6 F5 )2 substituents of the base serves as an example for a classical covalent 2-center-2-electron (2c-2e) sp2 -carbon-sp2 -boron σ-bond with 1 J(13 C-11 B) coupling constants in the order of 75 Hz, those of the boron(apical)-carbon(basal) bonds in the pyramid are too small to measure. These results suggest that these bonds have a strongly ionic character, which is also supported by quantum-chemical calculations.

Whole-tumor histogram analysis of postcontrast T1-weighted and apparent diffusion coefficient in predicting the grade and proliferative activity of adult intracranial ependymomas.

PURPOSE: To investigate the value of histogram analysis of postcontrast T1-weighted (T1C) and apparent diffusion coefficient (ADC) images in predicting the grade and proliferative activity of adult intracranial ependymomas. METHODS: Forty-seven adult intracranial ependymomas were enrolled and underwent histogram parameters extraction (including minimum, maximum, mean, 1st percentile (Perc.01), Perc.05, Perc.10, Perc.25, Perc.50, Perc.75, Perc.90, Perc.95, Perc.99, standard deviation (SD), variance, coefficient of variation (CV), skewness, kurtosis, and entropy of T1C and ADC) using FireVoxel software. Differences in histogram parameters between grade 2 and grade 3 adult intracranial ependymomas were compared. Receiver operating characteristic curves and logistic regression analyses were conducted to evaluate the diagnostic performance. Spearman's correlation analysis was used to evaluate the relationship between histogram parameters and Ki-67 proliferation index. RESULTS: Grade 3 intracranial ependymomas group showed significantly higher Perc.95, Perc.99, SD, variance, CV, and entropy of T1C; lower minimum, mean, Perc.01, Perc.05, Perc.10, Perc.25, Perc.50 of ADC; and higher CV and entropy of ADC than grade 2 intracranial ependymomas group (all p < 0.05). Entropy (T1C) and Perc.10 (ADC) had a higher diagnostic performance with AUCs of 0.805 and 0.827 among the histogram parameters of T1C and ADC, respectively. The diagnostic performance was improved by combining entropy (T1C) and Perc.10 (ADC), with an AUC of 0.857. Significant correlations were observed between significant histogram parameters of T1C (r = 0.296-0.417, p = 0.001-0.044) and ADC (r = -0.428-0.395, p = 0.003-0.038). CONCLUSION: Whole-tumor histogram analysis of T1C and ADC may be a promising approach for predicting the grade and proliferative activity of adult intracranial ependymomas.

Superoxide dismutases: marker in predicting reduced left ventricular ejection fraction in patients with type 2 diabetes and acute coronary syndrome.

AIM: To examine the prognostic value of superoxide dismutase (SOD) activity for monitoring reduced left ventricular ejection fraction(LVEF)in the patients with type 2 diabetes and acute coronary syndrome (ACS). METHODS: The population of this cross-sectional study included 2377 inpatients with type 2 diabetes who had an ACS admitted to the Shandong Provincial Hospital Affiliated to Shandong First Medical University from January 2016 to January 2021. RESULTS: Diabetic patients with ACS were divided into 2 subgroups based on LVEF. The mean SOD activity was significantly lower in patients with an LVEF ≤ 45% than in those with an LVEF > 45% (149.1 (146.4, 151.9) versus 161.9 (160.8, 163.0)). Using ROC statistic, a cut-off value of 148.8 U/ml indicated an LVEF ≤ 45% with a sensitivity of 51.6% and a specificity of 73.7%. SODs activity were found to be correlated with the levels of NT-proBNP, hs-cTnT, the inflammatory marker CRP and fibrinogen. Despite taking the lowest quartile as a reference (OR 0.368, 95% CI 0.493-0.825, P = 0.001) or examining 1 normalized unit increase (OR 0.651, 95% CI 0.482-0.880, P = 0.005), SOD activity was found to be a stronger predictor of reduced LVEF than CRP and fibrinogen, independent of confounding factors. CONCLUSIONS: Our cross-sectional study suggests that SOD activity might be a valuable and easily accessible tool for assessing and monitoring reduced LVEF in the diabetic patients with ACS.

Pyridinium-Derived Mesoionic N-Heterocyclic Olefins (py-mNHOs).

Mesoionic polarization allows access to electron-rich olefins that have found application as organocatalysts, ligands, or nucleophiles. Herein, we report the synthesis and characterization of a series of 3-methylpyridinium-derived mesoionic olefins (py-mNHOs). We used a DFT-supported design concept, which showed that the introduction of aryl groups in the 1-, 2-, 4-, and 6-positions of the heterocyclic core allowed the kinetic stabilization of the novel mesoionic compounds. Tolman electronic parameters indicate that py-mNHOs are remarkably strong σ-donor ligands toward transition metals and main group Lewis acids. Additionally, they are among the strongest nucleophiles on the Mayr reactivity scale. In reactions of py-mNHOs with electron-poor π-systems, a gradual transition from the formation of zwitterionic adducts via stepwise to concerted 1,3-dipolar cycloadditions was observed experimentally and analyzed by quantum-chemical calculations.

Convenient Synthetic Protocols for Diverse Functionalized Dihydrobenzofuran-Fused Spiro-indanedione-oxindole Scaffolds.

Diverse functionalized dihydrobenzofuran spiro-indanedione-oxindole scaffolds were conveniently synthesized by base-promoted cyclization reaction of Morita-Baylis-Hillman (MBH) carbonates of isatins and 2-(o-hydroxybenzylidene)-1,3-indanediones. The two diastereomeric dispiro[indene-2,1'-cyclopenta[b]benzofuran-2',3″'-indolines] could be selectively synthesized by using DABCO or DMAP as a base promoter. More importantly, DABCO or DMAP facilitated the annulation reaction of MBH formates of isatins and 2-(o-hydroxybenzylidene)-1,3-indanediones selectively, resulting in spiro[cyclopropa[c]chromene-1,2'-indene]-1',3'-diones or dispiro[indene-2,1'-cyclopenta[b]benzofuran-2',3″'-indolines]. Additionally, a similar reaction with MBH maleimides of isatins afforded dispiro[indene-2,5'-benzofuro[2',3':1,5]cyclopenta[1,2-c]pyrrole-4',3″'-indolines] in high yields and with high diastereoselectivity.

Acid-Modulated Construction of Cyclopenta[b]indole and Cyclohepta[b]indole via Unprecedented C3/C2 Carbocation Rearrangement.

p-TsOH-catalyzed cycloaddition of various 3-vinylindoles and (indol-2-yl)diphenylmethanols in acetonitrile gave the functionalized cyclopenta[b]indoles in good yields and with high diastereoselectivity via [3 + 2] cycloaddition reaction. More importantly, FeCl3-catalyzed annulation reaction afforded unexpected functionalized cyclohepta[1,2-b:4,5-b']diindoles in satisfactory yields, in which a formal [4 + 3] cycloaddition and an unprecedented C3/C2 carbocation rearrangement were first confirmed by the determination of single-crystal structure.

Effects of additives on the performance of a laser-induced graphene sensor modified with ZrO2 nanoparticles for OP detection.

In this study, a simple and portable electrochemical sensor based on laser-induced graphene (LIG) has been developed to systematically investigate the feasibility of LIG as an electrode to detect organophosphorus pesticides (OPs). It proves that the LIG-based electrode has a relatively high electrochemically active surface area (ECSA) and heterogeneous electron transfer (HET) of 0.100 cm2 and 0.000825 cm s-1, respectively. In addition, zirconium dioxide nanoparticles (ZrO2 NPs) have been modified on the electrode with three different binders, ß-cyclodextrin (ß-CD), chitosan (CS) and Nafion, to improve the adsorption capacity of the electrode toward OPs, and the effect of the binders on the performance of the as-fabricated sensor has been investigated in detail. The results show that ß-CD increases not only the electrochemically active surface area of the electrode but also the redox peak current of methyl parathion (MP). To evaluate the sensitivity of the sensor, differential pulse voltammetry (DPV) curves have been tested in solutions containing different concentrations of MP using ZrO2-ß-CD/LIG as an electrode, which shows a detection range of 5-200 ng ml-1 and a detection limit of 0.89 ng ml-1. In summary, the LIG-based sensor has a low detection limit, high sensitivity and good interference resistance, and thus has tremendous potential for the detection of pesticides in the environment.

Tandem ring-opening and formal [3 + 2] cycloaddition of furo[2,3-d]pyrimidine-2,4-diones.

The base promoted tandem annulation reaction of activated cyclic 1,3-dipolarophiles such as 2-arylidene-1,3-indanediones, 2-(o-hydroxybenzylidene)-1,3-indanediones and 3-methyleneoxindoles with functionalized furo[2,3-d]pyrimidine-2,4-diones was systematically investigated. This reaction provided efficient synthetic protocols for complex dispiro/dispiro fused tricyclic compounds including dispiro[indene-2,3'-cyclopentane-1',5''-pyrimidines], dispiro[indoline-3,3'-cyclopentane-1',5''-pyrimidines] and spiro[cyclopenta[c]indeno[1,2-b]chromene-3,5'-pyrimidines] in good yields and with high diastereoselectivity. The reaction was believed to proceed via sequential ring-opening of the furyl ring, formal [3 + 2] cycloaddition and annulation of the o-hydroxyphenyl group.

Discovery of berberine analogs as potent and highly selective p300/CBP HAT inhibitors.

The protein p300 is a positive regulator of cancer progression and is related to many human pathological conditions. To find effective p300/CBP HAT inhibitors, we screened an internal compound library and identified berberine as a lead compound. Next, we designed, synthesized, and screened a series of novel berberine analogs, and discovered that analog 5d was a potent and highly selective p300/CBP HAT inhibitor with IC50 values of 0.070 µM and 1.755 µM for p300 and CBP, respectively. Western blotting further proved that 5d specifically decreased H3K18Ac and interfere with the function of histone acetyltransferase. Although 5d had only a moderate inhibitory effect on the MDA-MB-231 cell line, 5d suppressed the growth of 4T1 tumor growth in mice with a tumor weight inhibition ratio (TWI) of 39.7%. Further, liposomes-encapsulated 5d increased its inhibition of tumor growth to 57.8 % TWI. In addition, 5d has no obvious toxicity to the main organ of mice and the pharmacokinetic study confirmed that 5d has good absorption properties in vivo.

Cardiometabolic Index (CMI), Lipid Accumulation Products (LAP), Waist Triglyceride Index (WTI) and the risk of acute pancreatitis: a prospective study in adults of North China.

OBJECTIVE: To investigate the correlation between anthropometric indexes [cardiometabolic index (CMI), lipid accumulation products (LAP), waist triglyceride index (WTI), and body mass index (BMI)] and acute pancreatitis (AP) in a Chinese adult population. METHODOLOGY: The present investigation consisted of a prospective group including 117,326 subjects who were enrolled in the Kailuan investigation. The individuals were categorized into quartiles based on their baseline levels of CMI, LAP, and WIT. BMI was categorized into three distinctive groups: normal weight group (BMI < 24 kg/m2), overweight group (BMI 24-28 kg /m2), and obesity group (BMI ≥ 28 kg/m2). The data were subjected to analysis in order to investigate the correlation between these anthropometric indexes and the incidence of AP. Cox regression models were employed to assess the relative risk of AP while accounting for known risk factors through appropriate adjustments. OUTCOMES: Over the course of a median follow-up duration of 12.59 ± 0.98 years, we documented 401 incident AP cases. Incidence density and cumulative incidence rates of AP increased with the increase of CMI, LAP, and WTI. After multivariate adjustment, the fourth quartile of CMI, LAP, and WTI exhibited the greatest risk of AP [CMI: hazard ratio (HR) 1.93, 95% confidential interval (CI) (1.45-2.57); LAP: HR 2.00, 95% CI(1.49-2.68); WTI: HR 2.13,95% CI (1.59-2.83)]. In comparison to the normal weight group, the obesity group (BMI ≥ 28 kg/m2) had an elevated risk of AP (HR = 1.58, 95% CI: 1.21-2.05). Furthermore, the incremental effect of BMI combined with CMI on the prognostic value of AP was greater than that of BMI alone (the C statistics demonstrated a result of 0.607 versus 0.546; the integrated discrimination improvement revealed a result of 0.321%; net reclassification improvement was 1.975%). CONCLUSION: We found that CMI, LAP, and WTI were positively and independently connected to the risk of AP. Additionally, CMI demonstrates a superior prognostic capacity than other indexes in anticipating AP.

Betaine prevents cognitive dysfunction by suppressing hippocampal microglial activation in chronic social isolated male mice.

Chronic social isolation (SI) stress, which became more prevalent during the COVID-19 pandemic, contributes to abnormal behavior, including mood changes and cognitive impairment. Known as a functional nutrient, betaine has potent antioxidant and anti-inflammatory properties in vivo. However, whether betaine can alleviate the abnormal behavior induced by chronic SI in mice remains unknown. In this study, we investigated the efficacy of betaine in the treatment of behavioral changes and its underlying mechanism. Three-week-old male mice were randomly housed for 8 weeks in either group housing (GH) or SI. The animals were divided into normal saline-treated GH, normal saline-treated SI, and betaine-treated SI groups in the sixth week. The cognitive and depression-like behavior was determined in the eighth week. We found that long-term betaine administration improved cognitive behavior in SI mice but failed to prevent depression-like behavior. Moreover, long-term betaine administration inhibited hippocampal microglia over-activation and polarized microglia toward the M2 phenotype, which effectively inhibited the expression of inflammatory factors in SI mice. Finally, the protective effect of betaine treatment in SI mice might not be due to altered activity of the hypothalamic-pituitary-adrenal axis. Collectively, our findings reveal that betaine can improve SI-induced cognitive impairment, thus providing an alternative natural source for the prevention of memory loss caused by SI or loneliness.

A Laser-Induced Graphene-Based Sensor Modified with CeO2 for Determination of Organophosphorus Pesticides with Improved Performance.

In this work, a flexible electrochemical sensor was developed for the detection of organophosphorus pesticides (OPs). To fabricate the sensor, graphene was generated in situ by laser-induced graphene (LIG) technology on a flexible substrate of polyimide (PI) film to form a three-electrode array, and pralidoxime (PAM) chloride was used as the probe molecule. CeO2 was used to modify the working electrode to improve the sensitivity of the sensor because of its electrocatalytic effect on the oxidation of PAM, and the Ag/AgCl reference electrode was prepared by the drop coating method. The effects of the laser power, laser scanning speed, and CeO2 modification on the electrochemical properties of the sensor were studied in detail. The results prove that the sensor has good repeatability, stability, and anti-interference ability, and it shows an excellent linear response in the chlorpyrifos concentration range from 1.4 × 10-8 M to 1.12 × 10-7 M with the detection limit of 7.01 × 10-10 M.

Borole/Borapyramidane Relationship.

Boroles and borapyramidanes are classical and nonclassical constitutional isomers, respectively. It is here shown that they can indeed be interconverted. Treatment of the bis(alkynyl)B(C6F5) SMe2 adduct 3·SMe2 with HB(C6F5)2 gave borole 1·SMe2, featuring trimethylsilyl substituents in both α positions to boron, by means of a 1,1-hydroboration/alkenylboration sequence. Photolysis of the classical borole adduct 1·SMe2 resulted in rearrangement to its nonclassical structural isomer, borapyramidane 2, in high yield, which exhibits a vicinal pair of trimethylsilyl substituents at the square pyramidane base. Neutral borapyramidane 2 is a rare example of an isoster of the (CH)5+ pyramidane cation. Thermolysis of borapyramidane 2 in the presence of SMe2 at 60 °C re-formed borole 1·SMe2, which converted at 100 °C to 2,3-bis-silyl-substituted borole isomer 8·SMe2. Its photolysis also gave borapyramidane 2. Prolonged photolysis of 2 at elevated temperatures converted this to borapyramidane isomer 10 containing a pair of trimethylsilyl groups in 1,3-position at its square C4-pyramidal base. The borole and borapyramidane isomers were characterized by X-ray diffraction, and the system was analyzed by density functional theory (DFT) calculations.

Metabolomic Analysis Reveals that SPHK1 Promotes Oral Squamous Cell Carcinoma Progression through NF-κB Activation.

BACKGROUND: Metabolic disorders are significant in the occurrence and development of malignant tumors. Changes of specific metabolites and metabolic pathways are molecular therapeutic targets. This study aims to determine the metabolic differences between oral squamous cell carcinoma (OSCC) tissues and paired adjacent noncancerous tissues (ANT) through liquid chromatography-mass spectrometry (LC-MS). SPHK1 is a key enzyme in sphingolipid metabolism. This study also investigates the potential role of SPHK1 in OSCC. MATERIALS AND METHODS: This study used LC-MS to analyze metabolic differences between OSCC tissues and paired ANT. Principal component analysis (PCA) and partial least-squares discriminant analysis (PLS-DA) were applied to explain the significance of phospholipid metabolism pathways in the occurrence and development of OSCC. Through further experiments, we confirmed the oncogenic phenotypes of SPHK1 in vitro and in vivo, including proliferation, migration, and invasion. RESULTS: The sphingolipid metabolic pathway was significantly activated in OSCC, and the key enzyme SPHK1 was significantly upregulated in oral cancer tissues, predicting poor OSCC prognosis. In this study, SPHK1 overexpression was associated with high-grade malignancy and poor OSCC prognosis. SPHK1 targeted NF-κB by facilitating p65 expression to regulate OSCC tumor progression and promote metastasis. CONCLUSIONS: This study identified metabolic differences between OSCC and paired ANT, explored the carcinogenic role of overexpressed SPHK1, and revealed the association of SPHK1 with poor OSCC prognosis. SPHK1 targets NF-κB signaling by facilitating p65 expression to regulate tumor progression and promote tumor metastasis, providing potential therapeutic targets for diagnosing and treating oral tumors.

Effects of rifampicin on antineoplastic drug pyrotinib maleate pharmacokinetics in healthy subjects.

PURPOSE: Pyrotinib (PTN), an irreversible EGFR/HER2 dual tyrosine kinase inhibitor used for treating HER2-positive breast cancer, is primarily metabolized by cytochrome P450 (CYP)3A4 isozyme. Rifampicin (RIF) is a strong index CYP3A4 inducer. Therefore, the study aimed to elucidate the effect of RIF on PTN pharmacokinetics (PK) in Chinese healthy volunteers. METHODS: This phase I, open-label study investigated the effects of steady-state RIF administration on single-dose PK of PTN. 18 healthy participants were enrolled in this trial, who received a single oral dose of 400 mg of PTN on days 1 and 13, and were administrated with RIF 600 mg qd on days 6 through 16. RIF was administrated on an empty stomach, PTN were administrated orally in the morning 30 min after the start of the standard meal. Serial PK samples for PTN were collected on days 1 and days 13. Safety assessments were performed via clinical laboratory tests throughout the study. RESULTS: 18 subjects were enrolled and 16 completed the study. RIF significantly reduced PTN exposure: Geometric least-squares mean ratios (90% CI) for PTN + RIF versus PTN alone were 0.04 (0.034,0.049), 0.04 (0.037,0.054), and 0.11 (0.09,0.124) for area under the curve from time zero to time of last quantifiable concentration (AUC0 - t), area under the curve from time zero to infinity (AUC0-∞ ), and maximum observed plasma concentration(Cmax), respectively. PTN alone and co-administered with RIF was well tolerated. CONCLUSION: The exposure of PTN was significantly affected by the action of RIF. The findings suggest that concomitant strong CYP3A4 inducers should be avoided during PTN treatment. Concurrent administration of PTN and RIF was well tolerated.

Proton-phosphorous connectivities revealed by high-resolution proton-detected solid-state NMR.

Proton-detected solid-state NMR enables atomic-level insight in solid-state reactions, for instance in heterogeneous catalysis, which is fundamental for deciphering chemical reaction mechanisms. We herein introduce a phosphorus-31 radiofrequency channel in proton-detected solid-state NMR at fast magic-angle spinning. We demonstrate our approach using solid-state 1H/31P and 1H/13C correlation experiments at high magnetic fields (850 and 1200 MHz) and high spinning frequencies (100 kHz) to characterize four selected PH-containing compounds from the chemistry of phosphane-borane frustrated Lewis pairs. Frustrated Lewis pairs have gained high interest in the past years, particularly due to their capabilities of activating and binding small molecules, such as di-hydrogen, however, their analytical characterization especially in the solid state is still limited. Our approach reveals proton-phosphorus connectivities providing important information on spatial proximity and chemical bonding within such compounds. We also identify protons that show strongly different chemical-shift values compared to the solution state, which we attribute to intermolecular ring-current effects. The most challenging example presented herein is a cyclotrimeric frustrate Lewis pair-associate comprising three crystallographically distinct phosphonium entities that are unambiguously distinguished by our approach. Such 31P spin-filtered proton-detected NMR can be easily extended to other material classes and can strongly impact the structural characterization of reaction products of hydrogen-activated phosphane/borane FLPs, heterogeneous catalysts and solid-state reactions in general.

Differentiation of intracranial solitary fibrous tumor/hemangiopericytoma from atypical meningioma using apparent diffusion coefficient histogram analysis.

This study aimed to investigate the value of apparent diffusion coefficient (ADC) histogram analysis in differentiating intracranial solitary fibrous tumor/hemangiopericytoma (SFT/HPC) from atypical meningioma (ATM). Retrospective analyzed the clinical, magnetic resonance imaging, and pathological data of 20 and 25 patients with SFT/HPC and ATM, respectively. Histogram analysis was performed on the axial ADC images using MaZda software, and nine histogram parameters were obtained, including mean, variance, skewness, kurtosis, and the 1st (ADC1), 10th (ADC10), 50th (ADC50), 90th (ADC90), and 99th (ADC99) percentile ADC. Differences in ADC histogram parameters between SFT/HPC and ATM were compared by an independent t test or Mann-Whitney U test, while the statistically significant histogram parameters were further analyzed by drawing receiver operating characteristic (ROC) curves to evaluate the differential diagnostic performance. Among the nine ADC histogram parameters we extracted, the mean, ADC1, ADC10, ADC50, and ADC90 in the SFT/HPC group were greater than those of ATM, and significant differences were observed (all P < 0.05). ROC analysis showed that the ADC1 generated the highest area under the curve (AUC) value of 0.920 in distinguishing the two tumors, when using 91.00 as the optimal threshold. The sensitivity, specificity, accuracy, positive predictive value, and negative predictive value in distinguishing between SFT/HPC and ATM were 84.00%, 85.00%, 84.44%, 87.50%, and 81.00%, respectively. ADC histogram analysis can be a reliable tool to differentiate between SFT/HPC and ATM, with the ADC1 being the most promising potential parameter.

Formation of a Hybrid 1-Bora-3-boratabenzene Heteroarene Anion Derivative.

The B(C6 F5 )2 -substituted borole 2⋅SMe2 was obtained from the phenyl bis(trimethylsilylethynyl) borane SMe2 adduct (1⋅SMe2 ) by a synthetic sequence containing a rare 1,1-hydroboration reaction. Subsequent thermolysis at 50 °C converted it to the bicyclic borenium/borate zwitterion 3⋅SMe2 . Photolysis of 3⋅SMe2 gave the diboracyclohexadiene derivative 4⋅SMe2 , which after ligand exchange with N,N-dimesitylimidazolylidene and deprotonation gave the 1-bora-3-boratabenzene anion derivative as its potassium salt 6. Some unique follow-up reactions of the unsaturated diboron containing six-membered heterocycles were investigated.

Carbon Monoxide Coupling Reactions via a Frustrated Lewis Pair-Derived η2-Formyl Borane.

The η2-formyl borane system 3 is readily available by carbonylation of the vicinal P/BH frustrated Lewis pair (FLP) 1. It serves as a frustrated C/B Lewis pair toward carbon dioxide or phenylisocyanate. In the presence of B(C6F5)3, it forms the coupling product between two CO-derived units. The resulting compound 13 rearranged to a doubly O-borylated endiolate, with both of the central carbon atoms originating from carbon monoxide. The subsequent treatment with a silane gave a rare macrocyclic silicon endiolate.