Bispidine (3,7-diazabicyclo[3.3.1]nonane, C7H14N2) analogues of cisplatin, carboplatin, and oxaliplatin have been prepared. (C7H14N2)PtCl2·DMF (1b), obtained from (1,5-hexadiene)PtCl2 and bispidine in DMF, is dimeric in the solid state. Dissolving 1b in hot N-methylformamide allows crystallization of the solvent-free polymeric (C7H14N2)PtCl2 (1a). Recrystallization of 1a,b from hot water yields the trihydrate (C7H14N2)PtCl2·3H2O (1c). Reaction of 1 with Ag2(cbdca) (cbdca = 1,1-cyclobutanedicarboxylate) in water affords the pentahydrate (C7H14N2)Pt{C4H6(CO2)2}·5H2O (2b), which loses water in vacuo to give (C7H14N2)Pt{C4H6(CO2)2} (2a). Reaction of 1 with AgNO3 in water, followed by addition of Na2C2O4, affords the water-free polymeric (C7H14N2)Pt(C2O4) (3). All complexes have been structurally characterized, revealing various patterns of N-H···Cl and N-H···O hydrogen bonds. In the hydrates 1c and 2b the complexes are embedded in intricate three-dimensional water networks. Complexes 1a, 2a, and 3 have been tested for their cytotoxicity against human cancer cell lines K562 (chronic myeloid leukemia), A2780 (ovarian cancer), and its platinum-resistant subline A2780 CisR and are compared to their parent analogues. The new complexes show significant cytotoxic activity along with a low platinum resistance factor.

Background Previous studies has shown a significant relationship between baseline triglyceride-glucose (TyG) index and cardiovascular disease (CVD). However, the long-term effect of TyG index and incident CVD remains uncertain. This study aimed to investigate the association between cumulative TyG index and the risk of CVD. Method In this study, we recruited individuals participating in Kailuan Study from 2006 to 2013 without stroke, myocardial infarction, and cancer in the four consecutive examinations. Cumulative TyG index was calculated by multiplying the average TyG index and the time between the two consecutive examinations. Cumulative TyG index levels were categorized into four quartile groups: Q1 group, ≤ 50.65 (as reference group), Q2 group, 50.65–53.86, Q3 group, 53.86–57.44, Q4 group, > 57.44. The association between cumulative TyG index and the risk of CVD was estimated by multivariable Cox proportional hazard models. Result A total of 44,064 individuals participated in the final analysis. After a mean follow-up of 6.52 ± 1.14 years, incident CVD, MI and stroke occurred in 2057, 395 and 1695, respectively. The risk of developing CVD increased with the quartile of cumulative in TyG index, after adjustment for multiple potential confounders, the HR for CVD events were 1.25 (1.08–1.44) in Q2, 1.22 (1.05–1.40) in Q3 and 1.39 (1.21–1.61) in Q4, compared to Q1 group. The longer duration of higher TyG index exposure was significantly associated with increased CVD risk. Similar results were obtained in the subgroup and sensitivity analysis. Conclusion Cumulative TyG index was associated with increased risk of CVD. Maintaining an appropriate level of TG and FBG within the desirable range and better control of cumulative TyG index are important for prevention of CVD.

An effective degradation reaction of CH2Cl2 by bispidine (3,7‐diazabicyclo[3.3.1]nonane, C7H12(NH)2, 1) is reported. The reaction starts as low as −20 °C and is quantitative with respect to 1. The overall reaction implies nucleophilic substitution of chloride, followed by a series of cascading acid–base reactions, ending with the formation of two easily separable products, one being soluble and the other insoluble. The starting 1, the intermediates, and the products show a variety of interesting solid‐state structures, associated with plasticity, N–H⋯N and N–H⋯Cl⋯H–N hydrogen bonding, and polymorphism. Copyright © 2012 John Wiley & Sons, Ltd.

Purpose: Triglyceride-glucose index (TyG) index, as a marker of insulin resistance, have been associated with risk of cardiovascular disease (CVD) in older adults. Nevertheless, it is unclear to whether TyG index affects risk of CVD and the subtypes of CVD in general Chinese population. Methods: A total of 96541 participants who met the criteria were included from the Kailuan Study. The TyG index was calculated as ln (fasting triglyceride [mg/dL] × fasting glucose [mg/dL]/2). The study participants were divided into 4 groups (Q1, Q2, Q3 and Q4) by quartiles of the TyG index. Incident of CVD events (myocardial infarction and stroke) during 2006-2017 were con rmed by review of medical records.The Cox proportional hazard regression models were used to assess the association TyG index with the risk of CVD and the subtypes of CVD by calculating the hazard ratios (HR) and 95% con dence interval (CI).Results: During a median 10.33 years of follow-up, we documented 6421 CVD events including 1493 myocardial infarction events and 5083 stroke events. Multivariate Cox regression analysis showed that compared with the participants in Q1 group, HR (95% CI) for CVD events were for Q2 group 1.12 (95%, 1.03-1.21), Q3 groups 1.28 (95%, 1.18-1.38), and Q4 groups 1.34 (95%, 1.23-1.45). We conducted timedependent TyG index found compared with Q1 group, HR (95% CI) for CVD events were for Q2 group 1.09(95%, 1.02-1.18), Q3 groups 1.17(95%, 1.09-1.27), and Q4 groups 1.20 (95%, 1.11-1.30). We found similar results in myocardial infarction and stroke.Conclusions: The TyG index is an independent risk factor for CVD. The TyG index may be useful identifying individuals at high risk of developing CVD at an early stage, it can contribution to prevent and control of CVD.

3,7-Diallyl-bispidin-9-one (6) (bispidin-9-one = 3,7-diazabicyclo[3.3.1]nonan-9-one) is converted to N-unsubstituted spiro[bispidin-9,2'-[1,3]dioxolane] (12; 35%). The ketal crystallizes in the forms of anhydrous 12a and the dihydrate 12b. The molecules in anhydrous 12a are linked to each other, forming N1-H1···N2-H2···N1* hydrogen-bond chiral helices of alternating chirality. In the dihydrate 12b, the ketal molecules are connected to a central string of water molecules by O3-H···O1 and O4-H···N1 hydrogen bonds, but not to themselves. Reaction of 12 with (1,5-hexadiene)PtCl2 affords almost quantitatively spiro[bispidin-9,2'-[1,3]dioxolane]PtCl2 (13). Cleavage of the ketal to retrieve the ketone produces the geminal diol (bispidin-9,9-diol)PtCl2 (14; 85%). Compound 14 reacts with Ag2cbdca (cbdca = 1,1-cyclobutanedicarboxylate) to give the dihydrate (bispidin-9,9-diol)Pt(cbdca)·2H2O (15b), which can be dehydrated to obtain anhydrous (bispidin-9,9-diol)Pt(cbdca) (15a). Similarly, anhydrous (bispidin-9,9-diol)Pt(oxalate) (16) is obtained. Crystal structures of 14 and 15b reveal association by various forms of O-H···O, O-H···Cl, N-H···Cl, and N-H···O hydrogen bonds. Biological studies showed a moderate cytotoxic activity of the bispidin-9,9-diol complexes 14-16, compared to the 9,9-unsubstituted bispidine complexes. No unspecific cytotoxicity of 14-16 up to 316 μM was found against the noncancer cell line HEK293.

The synthesis of 3,7-diallyl-3,7-diazabicyclo-[3.3.1]nonane (C 7 H 12 N 2 allyl 2 , 3) has been revisited, and several hitherto undetected byproducts have been identified. Pure 3 and these byproducts were isolated by both prep-GC and column chromatography. Monoprotonated 3 in the form of the PF 6 salt [(C 7 H 13 N 2 allyl 2 ]PF 6 (9) and the addition complexes of 3 to Ni(acac) 2 and CuI, (C 7 H 12 N 2 allyl 2 )Ni-(acac) 2 (10) and {(C 7 H 12 N 2 allyl 2 )Cu(μ-I)} 2 (11), have been prepared. From the reactions of {(η 3 -C 3 H 5 )M(μ-X)} 2 (M = Ni, Pd, Pt; X = Cl, Br) with 3 and TlPF 6 the complexes [(C 7 H 12 N 2 allyl 2 )M(η 3 -C 3 H 5 )]PF 6 (M = Ni (12a), Pd (12b), Pt (12c)) were obtained. Compounds 9−11 and 12b were characterized by X-ray crystallography. The reaction of (1,5-hexadiene)PtCl 2 with 3 gave, after HCl elimination, monomeric {C 7 H 12 N 2 (C 3 H 5 )CHCHCH 2 }PtCl (13a), and the presence of MeOH afforded {C 7 H 12 N 2 (C 3 H 5 )CH 2 CH(OMe)CH 2 }PtCl (13b), both compounds featuring novel anionic tridentate ligands. Furthermore, chiral N,N′-bis((R)-1-phenylethyl)-1,7octadiene-(S,S)-4,5-diamine (15) reacts with CuI to give [{(C 3 H 5 ) 2 C 2 H 4 N 2 (CHMePh) 2 }Cu(μ-I)] 2 ( 16). The unbound N-allyl functions on the ligands in the product complexes allow for immobilization of the transition metal complexes on polyester fibers.

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A series of mixed alkoxyalkoxo chloro complexes of vanadium(V), [VOCl2(OCH2CH2OR)]2 (R = Me, Et, iPr, Bz), [VOCl2(OCMe2CH2OMe)]2 and [VOCl2(OCH2(cyclo-C4H7O)]2, were synthesised and characterised. The title compounds can be obtained either from VOCl3 and the alkoxyalcohols by HCl elimination or from the corresponding lithium alkoxides and VOCl3 by salt metathesis reaction. X-Ray diffraction studies revealed the title compounds to be dimers with chloride bridging ligands and intramolecular ether coordination. Electrochemical results obtained by cyclic voltammetry indicate irreversible, reductive behaviour. The interactions of the title compounds with oxygen, nitrogen and phosphorus donor ligands were examined. Phosphorus and nitrogen donors lead to reduction products whereas tetrahydrofuran coordinates to the vanadium(V) centre by breaking the chloride bridge. All tetrahydrofuran complexes, [VOCl2(OCH2CH2OR)(thf)] (R = Me, Et, iPr) and [VOCl2(OCMe2CH2OMe)(thf)], have been characterised by single-crystal X-ray diffraction. The solid-state structures of these complexes show that they consist of six-coordinate monomers. Reaction of [VOCl2(OCH2CH(2)OMe)]2 with Me3SiCH2MgCl gave [VO(CH2SiMe3)3], which has been structurally characterised. The compounds were tested as catalysts for epoxidation and polymerisation reactions. They convert unfunctionalised olefins into the corresponding epoxides with moderate activity. They are good pre-catalysts for the polymerisation of ethene and oligomerise 1-hexene.