The syntheses of a new class of potentially biomimetic, tripodal, mixed functionality ligands, (2-hydroxyphenyl)bis(pyrazolyl)methane (L1), (2-hydroxyphenyl)bis(3,5-dimethylpyrazolyl)methane (L2), and (2-hydroxyphenyl)bis(3-isopropylpyrazolyl)methane (L3), are described. These ligands have been used to prepare the cobalt(II)4. X-ray structural analysis of 1-4 gave the following structural parameters: 1, C 30 H 34 N 8 CoO 6 , triclinic, a ) 8.286(2) Å, b ) 10.053(3) Å, c ) 10.562(2) Å, R ) 109.66(2)°, β ) 96.57(1)°, γ ) 91.11(3)°, space group P1 h, Z ) 1; 2, C 38 H 38 N 8 CoO 6 , triclinic, a ) 8.746(5) Å, b ) 10.900(5) Å, c ) 11.399(8) Å, R ) 70.82(4)°, β ) 75.13(5)°, γ ) 81.46(4)°, space group P1 h, Z ) 1; 3, C 20 H 26 N 4 Cl 4 CoO, monoclinic, a ) 10.934(2) Å, b ) 12.404(2) Å, c ) 19.267(3) Å, β ) 98.33(1)°, space group P2 1 /n, Z ) 4; 4, C 58 H 70 N 12 BCo 3 F 4 O 9 , monoclinic, a ) 14.798(5) Å, b ) 23.657(8) Å, c ) 20.614(7) Å, β ) 97.75(2)°, space group P2 1 /n, Z ) 4.

Background: Glycemic control in hospital intensive care units (ICU) has been the subject of numerous research publications and debate over the past 2 decades. There have been multiple studies showing the benefit of ICU glucose control in reducing both morbidity and mortality. GlySure Ltd has developed a glucose monitor based on a diboronic acid receptor that can continuously measure plasma glucose concentrations directly in a patient’s vascular system. The goal of this study was to validate the performance of the GlySure CIGM system in different patient populations. Methods: The GlySure Continuous Intravascular Glucose Monitoring (CIGM) System was evaluated in both the Cardiac ICU (33 patients) and MICU setting (14 patients). The sensor was placed through a custom CVC and measured the patients’ blood glucose concentration every 15 seconds. Comparison blood samples were taken at 2 hourly then 4 hourly intervals and measured on a YSI 2300 STAT Plus or an i-STAT. Results: Consensus error grid analysis of the data shows that the majority of the data (88.2% Cardiac, and 95.0% MICU) fell within zone A, which is considered to be clinically accurate and all data points fell within zones A and B. The MARD of the Cardiac trial was 9.90% and the MICU trial had a MARD of 7.95%. Data analysis showed no significant differences between data generated from Cardiac and MICU patients or by time or glucose concentration. Conclusions: The GlySure CIGM System has met the design challenges of measuring intravascular glucose concentrations in critically ill patients with acceptable safety and performance criteria and without disrupting current clinical practice. The accuracy of the data is not affected by the patients’ condition.

The preparation of a new class of mixed functionality biomimetic ligand, (2-hydroxyphenyl)bis(pyrazolyl)methane, L1, (2-hydroxyphenyl)bis(3,5-dimethylpyrazolyl)methane, L2, and (2-hydroxyphenyl)bis(3-isopropylpyrazolyl)methane, L3, is described. These ligands were used to synthesize the nickel(II) complexes, [Ni(L1)2], 1·MeCN; [Ni(L2)2], 2·0.5MeOH and 2·2H2O; [Ni(μ-L2)2NiCl2], 3·2H2O and 3·2CH2Cl2; [Ni3(μ3-Cl)2(μ-L3)2(L3)(MeOH)]Cl, 4·MeOH·4H2O and 4·MeOH·1.42iPr2O; and [Ni3(μ3-OH)2(μ-L3)3][BF4], 5 and 5·2Me2CO. X-ray crystal analysis of 1−5 gave the following structural parameters:  1·MeCN, C28H25N9NiO2, triclinic, a = 10.600(3) Å, b = 11.371(3) Å, c = 12.194(3) Å, α = 71.17(2)°, β = 94.69(2)°, γ = 83.04(2)°, space group P1̄, Z = 2; 2·2H2O, C34H42N8NiO4, monoclinic, a = 9.037(2) Å, b = 19.272(3) Å, c = 19.643(3) Å, β = 94.69(2)°, space group C2/c, Z = 4; 3·2CH2Cl2, C36H42N8Cl6Ni2O2, monoclinic, a = 13.891(4) Å, b = 18.188(7) Å, c = 15.012(4) Å, β = 92.70(2)°, space group C2/c, Z = 4; 4·MeOH·1.42iPr2O, C67.52H96.88Cl3N12Ni3O6.42, monoclinic, a = 12.400(2) Å, b = 13.520(1) Å, c = 24.616(3) Å, β = 102.04(1)°, space group Pn, Z = 2; 5·2Me2CO, C63H83N12BF4Ni3O7, monoclinic, a = 14.521(3) Å, b = 18.827(3) Å, c = 26.283(4) Å, β = 105.85(2)°, space group:  P21/c, Z = 4. The effects on the type of complex formed with varying steric hindrance on the pyrazole rings is discussed.

The synthesis and characterization of the tridentate “heteroscorpionate” mixed functionality ligand, (2-thiophenyl)bis(pyrazolyl)methane, L1, is reported. This ligand was used to synthesize the complexes, [Fe(L1)2][ClO4], [Co(L1)2][BPh4], and [V(L1)2][BPh4]. X-ray crystallographic analysis of the latter two complexes gave the following structural parameters:  [V(L1)2][BPh4]·MeCN· i Pr2O, C58H57N9B1O1S2V1, monoclinic, a = 16.197(2) Å, b = 19.281(2) Å, c = 17.985(2) Å, β = 102.343(9)°, space group P21/c; [Co(L1)2][BPh4]·CH2Cl2, C51H42N8B1Cl2Co1S2, triclinic, a = 12.751(1) Å, b = 12.830(1) Å, c = 14.740(1) Å, α = 98.351(7)°, β = 98.122(6)°, γ = 97.023(8)°, space group P1̄. An example of the use of this new class of “heteroscorpionate” ligands for systematic comparisons of electronic properties of metal complexes with identical topology that vary only in the nature of one of the donor atoms is given.

The mixed functionality pyrazole/phenol ligand (2-hydroxyphenyl)bis(pyrazolyl)methane, L1OH, has been used to prepare a series of linear trimetallic systems with the general structural motif [M(3)(L1O)(4)](2+), where M = Mn(2+), Co(2+), Ni(2+), Cu(2+), and Zn(2+). Each of these complexes has been structurally characterized by X-ray crystallography giving the following structural parameters: [Zn(3)(L1O)(4)][BF(4)](2).H(2)O, C(52)H(44)N(16)B(2)F(8)O(5)Zn(3), monoclinic, a = 18.572(4) Å, b = 22.400(5) Å, c = 15.921(3), beta = 112.439(8) degrees, space group C2/c, Z = 4; [Cu(3)(L1O)(4)] [BF(4)](2).2MeCN, C(56)H(44)N(18)B(2)Cu(3)F(8)O(4), monoclinic, a = 40.574(2) Å, b = 16.701(1) Å, c = 19.841(2) Å, beta = 111.388(5) degrees, space group C2/c, Z = 8; [Ni(3)(L1O)(4)][ClO(4)](2).MeCN.0.5H(2)O, C(54)H(44)N(17)Cl(2)Ni(3)O(12.5), monoclinic, a = 12.324(4) Å, b = 26.537(2) Å, c = 18.829(3) Å, beta = 102.78(1) degrees, space group C2/c, Z = 4; [Co(3)(L1O)(4)][BF(4)](2).MeCN, C(54)H(44)N(17)B(2)Co(3)F(8)O(4), monoclinic, a = 12.395(2) Å, b = 26.483(3) Å, c = 18.703(4) Å, beta = 103.22(2) degrees, space group C2/c, Z = 4; [Mn(3)(L1O)(4)(MeCN)][ClO(4)](2).1.4MeCN, C(56.68)H(44)N(18.34)Cl(2)Mn(3)O(12), orthorhombic, a = 15.471(2) Å, b = 17.364(2) Å, c = 24.216(2) Å, space group Pbcn, Z = 4. For Zn(2+), Cu(2+), Ni(2+), and Co(2+) the central metal atom of the linear trimetallic [M(3)(L1O)(4)](2+) unit is four coordinate and has a pseudotetrahedral geometry with a dihedral angle, omega, between the two M(central)O(2)M(terminal) planes of 79.9 degrees (Zn), 61.2 degrees (Co), 60.4 degrees (Ni), and 46.8 degrees (Cu). The central Mn(2+) atom of [Mn(3)(L1O)(4)(MeCN)][ClO(4)](2).1.4MeCN is five-coordinate, with a trigonal bipyramidal stereochemistry, the result of an equatorially coordinated MeCN solvent molecule. Variable-temperature magnetic data indicate that the Ni, Cu, and Mn complexes display modest antiferromagnetic coupling between the metal centers, while the Co derivative is strongly ferromagnetically coupled.