Systematic Tuning of Electronic Ground and Excited States in Donor-Acceptor Dyes; Steps toward Designer Compounds for Modern Technologies.

The vibrational and electronic properties of six systematically altered donor-acceptor dyes were investigated with density functional theory (DFT), spectroscopy, and electrochemical techniques. The dyes incorporated a carbazole donor connected to a dithieno[3,2-b:2',3'-d]thiophene linker at either the C2 (m) or C3 (p) position. Indane-based acceptors contained either dimalononitrile (IndCN), ketone and malononitrile (InOCN) or diketone (IndO) electron accepting groups. Molecular geometries modeled by DFT using the BLYP functional and def2-TZVP basis set showed planar geometries containing large, extended π-systems and produced Raman spectra consistent with the experimental data. Electronic absorption spectra had transitions with π-π* character at wavelengths below 325 nm and a charge transfer (CT) transition region from 500 to 700 nm. The peak wavelength was dependent on the donor and acceptor architecture, with each modulating the HOMO and LUMO levels, respectively, supported by TD-DFT estimates using the LC-ωPBE* functional and 6-31g(d) basis set. The compounds showed emission in solution with quantum yields ranging from 0.004 to 0.6 and lifetimes of less than 2 ns. These were assigned to either π-π* or CT emissive states. Signals attributed to CT states exhibited positive solvatochromism and thermochromism. The spectral emission behavior of each compound trended with the acceptor unit moieties, where malononitrile units lead to greater π-π* character and ketones exhibited greater CT character.

Syntheses and crystal structure of a (2,6-diiso-propyldi-naphtho-[2,1-d:1',2'-f][1,3]dithiepin-4-yl)(phen-yl)methanol atropisomer.

The racemic title compound, C34H32OS2, comprises an atropisomeric binaphthyl di-thio-acetal substituted at the methyl-ene carbon atom with a chiral benzyl alcohol. The two naphthalene ring systems are additionally substituted at the 3,3'-position with isopropyl groups. The overall stereochemistry is defined as aS,R and aR,S. The hydroxyl group forms an intra-molecular O-H⋯S hydrogen bond to one of the sulfur atoms. The crystal structure contains weak C-H⋯π inter-actions that link the mol-ecules into extended arrays.

Syntheses and crystal structures of two di-naph-tho[2,1-d:1',2'-f][1,3]dithiepine atropisomers.

The closely related title compounds, 1-(di-naphtho-[2,1-d:1',2'-f][1,3]dithiepin-4-yl)-2,2-di-methyl-propan-1-ol, C26H24OS2, 1 and 2-(di-naphtho-[2,1-d:1',2'-f][1,3]dithiepin-4-yl)-3,3-di-methyl-butan-2-ol, C27H26OS2, 2, both comprise an atrop-isomeric binaphthyl di-thio-acetal unit substituted at the methyl-ene carbon atom with a chiral neopentyl alcohol grouping. The overall stereochemistry of the racemate in each case is defined as aS,R and aR,S. In 1, the hydroxyl group generates inversion dimers via pairwise inter-molecular O-H⋯S hydrogen bonds whereas in 2, the O-H⋯S link is intra-molecular. Weak C-H⋯π inter-actions link the mol-ecules into extended arrays in both structures.

O-Acylated Flavones in the Alpine Daisy Celmisia viscosa: Intraspecific Variation.

Flavonoids acylated on their core phenolic groups are rare. The Aotearoa New Zealand endemic alpine daisy Celmisia viscosa is widespread, but its flavonoids have not previously been identified. Leaf extracts yielded a series of 8-O-acylated flavones with combinations of 3-methylbutanoate, 2-methylbutanoate, and 2-methylpropanoate groups and one, two, or three O-methyls, all previously unreported. Regiochemistries of 8-(3″-methylbutanoyl)-5-hydroxy-6,7,4'-trimethoxyflavone (5) and 8-(2″-methylbutanoyl)-5,7,4'-trihydroxy-6-methoxyflavone (10) were defined by X-ray crystallography. LC analyses of leaf extracts from the full geographic range of C. viscosa showed intraspecific variation of these flavones: most had high concentrations of trimethoxy 8-O-acylated flavones, but dimethoxy 8-O-acylated flavones were the most abundant flavonoids in two individuals. Three other viscid (sticky leaved) Celmisa species also contained these rare flavones, but four nonviscid Celmisa had none detectable.

Efficacy and Safety of Novel Beta-Chitin Patches as Haemostat in Rat Vascular and Neurosurgical Model.

Background: Intraoperative hemorrhage is a major cause of poor post-operative outcome. Beta-chitin patch has previously been found to be an effective haemostat, but whether modifying the patch can improve its efficacy and safety, remains unknown. In this study, beta-chitin patches were modified using polyethylene oxide, Pluronic-F127 (Chi/F127), calcium (Chi/20%Ca), increased thickness (Chi/Thick) or polyphosphate (Chi/PP). Objective: Using rat (Wistar Albino; 8-10 weeks old) vascular and neurosurgical models, this project investigated and compared the efficacy and safety of beta-chitin patches with gauze, Surgicel and FloSeal. Methods: Ninety rats underwent a standardized femoral artery injury and were randomized to receive either beta-chitin patches, gauze, Surgicel or FloSeal. The bleeding time and total blood loss was measured. For the neurosurgical model, forty-four rats underwent a standardized cortical injury and randomization to a treatment group. Following a 48 h recovery period, their brains were collected for histopathological examination. Results: The mean bleeding time with Chitin (120.8 s) and Chi/PP (117.3 s) was ~60 s lower than Chi/F127, Chi/20%Ca and Chi/Thick (p < 0.05). Chitin and Chi/PP had a significantly lower bleeding time than FloSeal (174.2 s) (p < 0.05), but not Surgicel (172.7 s). Gauze (400 s) had a significantly higher bleeding time compared to all other groups (p < 0.05). There were no significant differences in the total blood loss between the groups. Histopathological examination of brains found no adverse inflammatory reaction to any of the haemostatic compounds. Conclusion: Chi/PP had superior haemostatic efficacy compared to Surgicel and FloSeal, but not compared to non-modified beta-chitin patch. All of the haemostats were equally safe.

Heterotrimetallic Double Cavity Cages: Syntheses and Selective Guest Binding.

A strategy for the generation of heterotrimetallic double cavity (DC) cages [Pdn Ptm L4 ]6+ (DC1: n=1, m=2; and DC2: n=2, m=1) is reported. The DC cages were generated by combining an inert platinum(II) tetrapyridylaldehyde complex with a suitably substituted pyridylamine and PdII ions. 1 H and DOSY nuclear magnetic resonance spectroscopy (NMR) and electrospray ionization mass spectrometry (ESIMS) data were consistent with the formation of the DC architectures. DC1 and DC2 were shown to interact with several different guest molecules. The structure of DC1, which features two identical cavities, binding two 2,6-diaminoanthraquinone (DAQ) guest molecules was determined by single-crystal X-ray crystallography. In addition, DC1 was shown to bind two molecules of 5-fluorouracil (5-FU) in a statistical (non-cooperative) manner. In contrast, DC2, which features two different cage cavities, was found to interact with two different guests, 5-FU and cisplatin, selectively.

Synthesis, crystal structure and Hirshfeld surface analysis of 1-ferrocenylundecane-1,11-diol.

The racemic title compound, [Fe(C5H5)(C16H27O2)], comprises an α,ω-diol-substituted undecyl chain with a ferrocenyl substituent at at one terminus. The alkane chain is inclined to the substituted ring of the ferrocene grouping by 84.22 (13)°. The ferrocene rings are almost eclipsed and parallel. The crystal structure features O-H⋯O and C-H⋯O hydrogen bonds and C-H⋯π contacts that stack the mol-ecules along the c-axis direction. A Hirshfeld surface analysis reveals that H⋯H inter-actions (83.2%) dominate the surface contacts.

The effect of chemical and structural modifiers on the haemostatic process and cytotoxicity of the beta-chitin patch.

Beta-chitin patch has previously been proven to be an effective haemostat, but whether modifying the patch affects its efficacy and safety, remains unanswered. In this study, the patch was modified using polyethylene oxide, Pluronic-F127, calcium, increased thickness or polyphosphate, and their effect on the process of haemostasis and cytotoxicity was tested and compared with standard-of-care, Surgicel and FloSeal. Whole blood collected from volunteers was applied to the patches to test their whole blood clotting and thrombin generation capacities, whilst platelet isolates were used to test their platelet aggregation ability. The fluid absorption capacity of the patches was tested using simulated body fluid. Cytotoxicity of the patches was tested using AlamarBlue assays and PC12 cells and the results were compared with the standard-of-care. In this study, beta-chitin patch modifications failed to improve its whole blood clotting, platelet aggregation and thrombin generation capacity. Compared to non-modified patch, modifications with polyethylene oxide or calcium reduced platelet aggregation and thrombin generation capacity, while increasing the thickness or adding polyphosphate decreased platelet aggregation capacity. The cytotoxicity assays demonstrated that the beta-chitin patches were non-toxic to cells. In vivo research is required to evaluate the safety and efficacy of the beta-chitin patches in a clinical setting.

6,6'-Ditriphenylamine-2,2'-bipyridine: Coordination Chemistry and Electrochemical and Photophysical Properties.

A 2,2'-bipyridine with bulky triphenylamine substituents in the 6 and 6' positions of the ligand (6,6'-ditriphenylamine-2,2'-bipyridine, 6,6'-diTPAbpy) was generated. Despite the steric bulk, the ligand readily formed bis(homoleptic) complexes with copper(I) and silver(I) ions. Unfortunately, efforts to use the 6,6'-diTPAbpy system to generate heteroleptic [Cu(6,6'-diTPAbpy)(bpy)]+ complexes were unsuccessful with only the [Cu(6,6'-diTPAbpy)2](PF6) complex observed. The 6,6'-diTPAbpy ligand could also be reacted with 6-coordinate metal ions that featured small ancillary ligands, namely, the [Re(CO)3Cl] and [Ru(CO)2Cl2] fragments. While the complexes could be formed in good yields, the steric bulk of the TPA units does alter the coordination geometry. This is most readily seen in the [(6,6'-diTPAbpy)Re(CO)3Cl] complex where the Re(I) ion is forced to sit 23° out of the plane formed by the bpy unit. The electrochemical and photophysical properties of the family of compounds were also examined. 6,6'-diTPAbpy exhibits a strong ILCT absorption band (356 nm, 50 mM-1 cm-1) which displays a small increase in intensity for the homoleptic complexes ([Cu(6,6'-diTPAbpy)2]+; 353 nm, 72 mM-1 cm-1, [Ag(6,6'-diTPAbpy)2]+; 353 nm, 75 mM-1 cm-1), despite containing 2 equiv of the ligand, attributed to an increased dihedral angle between the TPA and bpy moieties. For the 6-coordinate complexes the ILCT band is further decreased in intensity and overlaps with MLCT bands, consistent with a further increased TPA-bpy dihedral angle. Emission from the 1ILCT state is observed at 436 nm (τ = 4.4 ns) for 6,6'-diTPAbpy and does not shift for the Cu, Ag, and Re complexes, although an additional 3MLCT emission is observed for [Re(6,6'-diTPAbpy)(CO)3Cl] (640 nm, τ = 13.8 ns). No emission was observed for [Ru(6,6'-diTPAbpy)(CO)2Cl2]. Transient absorption measurements revealed the population of a 3ILCT state for the Cu and Ag complexes (τ = 80 ns). All assignments were supported by TD-DFT calculations and resonance Raman spectroscopic measurements.

Peptide Chitosan/Dextran Core/Shell Vascularized 3D Constructs for Wound Healing.

Three-dimensional (3D) bioprinting has emerged to create novel cell-based therapies for regenerative medicine applications. Vascularized networks within engineered constructs are required, and toward this end, we report a promising strategy using core-shell (c/s) extrusion 3D-bioprinting technology that employs biomimetic biomaterials to construct regenerative, prevascularized scaffolds for wound care. A custom-designed cell-responsive bioink consisting of a 13% (w/v) cell-laden gelatin methacryloyl (GelMA) shell surrounding a peptide-functionalized, succinylated chitosan (C)/dextran aldehyde (D) cell-laden core was successfully bioprinted resulting in organized microdesigns exhibiting excellent cell viability and subsequent vessel formation. Our templating strategy takes advantage of GelMA's intrinsic thermoreversible properties of low degree of acryloyl functionalization used in combination with a lightly, chemically cross-linked peptide-CD core to serve as temporal structural supports that stabilize during extrusion onto a cooled platform. Mechanical integrity was further strengthened layer-by-layer via GelMA UV photo-cross-linking. We report the first example of GelMA used in combination with a peptide-CD bioink to c/s 3D-bioprint regenerative, prevascularized constructs for wound care. Particular cell adhesion and proteolytic peptide-CD functionalized pair combinations, P15/MMP-2 and P15/cRGD, were found to significantly increase growth of human bone-marrow-derived mesenchymal stems cells (hBMSCs) and human umbilical vein endothelial cells (HUVECs). The constructs delivered two cell types: hBMSCs in the shell bioink and HUVECs within the core bioink. Cord-like, natural microvascularization was shown with endothelial cell marker expression as confirmed by immunofluorescence (IF) staining exhibiting tubelike structures. In addition, in vitro skin wound healing activity of the construct showed a ∼twofold rate of wound closure. Overall, c/s 3D-bioprinted, peptide-CD/GelMA constructs provided the appropriate microenvironment for in vitro stem and endothelial cell viability, delivery, and differentiation. We foresee these custom constructs as representing a fundamental step toward engineering larger scale regenerative, prevascularized tissues.

Excited-State Switching Frustrates the Tuning of Properties in Triphenylamine-Donor-Ligand Rhenium(I) and Platinum(II) Complexes.

The photophysical properties of a series of rhenium(I) tricarbonyl and platinum(II) bis(acetylide) complexes containing a triphenylamine (TPA)-substituted 1,10-phenanthroline ligand have been examined. The complexes possess both metal-to-ligand charge-transfer (MLCT) and intraligand charge-transfer (ILCT) transitions that absorb in the visible region. The relative energies and ordering of the absorbing CT states have been successfully controlled by changing the metal center and modulating the donating ability of the TPA group through the addition of electron-donating methoxy and electron-withdrawing cyano groups. The ground-state properties behave in a predictable manner as a function of the TPA substituent and are characterized with a suite of techniques including electronic absorption spectroscopy, resonance Raman spectroscopy, electrochemistry, and time-dependent density functional theory calculations. However, systematic control over the ground-state properties of the complexes does not extend to their excited-state behavior. Unexpectedly, despite variation of both the MLCT and ILCT state energies, all of the luminescent complexes displayed near-isoenergetic emission at 298 K, yet the emissive lifetimes of the complexes vary from 290 ns to 3.9 µs. Excited-state techniques including transient absorption and transient resonance Raman, combined with a suite of quantum-chemical calculations, including scalar relativistic effects to elucidate competitive excited-state relaxation pathways, have been utilized to aid in assignment of the long-lived state in the complexes, which was shown to possess differing 3MLCT and 3ILCT contributions across the series.

Tough polymeric hydrogels using ion-pair comonomers.

Hydrogels with excellent mechanical properties were synthesized by radical photo-polymerization of three different types of ion-pair comonomers (IPC), without requiring any chemical cross-linking agent. Insoluble gels formed only at a specific solution concentration range, which was unique to the particular salt. The gels changed properties after one day soaking in water, becoming less stiff and more extendible, but remained stable after that. Strains of up to 4000% were measured for one salt pair and ultimate stresses of up to 2.53 MPa for another. Self-healing properties were noted along with some recovery of creep, due to the non-covalent nature of the gel. These properties arise through a combination of electrostatic and hydrophobic interactions of the polymer chains. Immersion of the gels in salt solution screened the electrostatic interactions, resulting in dissolution of the gel.

The structure and Hirshfeld surface analysis of the salt 3-methacryl-amido-N,N,N-tri-methyl-propan-1-aminium 2-acryl-amido-2-methyl-propane-1-sulfonate.

The title salt, C10H21N2O+·C7H12NO4S-, comprises a 3-methacryl-amido-N,N,N-tri-methyl-propan-1-aminium cation and a 2-acryl-amido-2-methyl-propane-1-sulfonate anion. The salt crystallizes with two unique cation-anion pairs in the asymmetric unit of the ortho-rhom-bic unit cell. The crystal studied was an inversion twin with a 0.52 (4):0.48 (4) domain ratio. In the crystal, the cations and anions stack along the b-axis direction and are linked by an extensive series of N-H⋯O and C-H⋯O hydrogen bonds, forming a three-dimensional network. Hirshfeld surface analysis was carried out on both the asymmetric unit and the two individual salts. The contribution of inter-atomic contacts to the surfaces of the individual cations and anions are also compared.

Structure and Hirshfeld surface analysis of the salt N,N,N-trimethyl-1-(4-vinyl-phen-yl)methanaminium 4-vinyl-benzene-sulfonate.

In the title compound, the asymmetric unit comprises an N,N,N-trimethyl-1-(4-vinyl-phen-yl)methanaminium cation and a 4-vinyl-benzene-sulfonate anion, C12H18N+·C8H7O3S-. The salt has a polymerizable vinyl group attached to both the cation and the anion. The methanaminium and vinyl substituents on the benzene ring of the cation subtend angles of 86.6 (3) and 10.5 (9)° to the ring plane, while the anion is planar excluding the sulfonate O atoms. The vinyl substituent on the benzene ring of the cation is disordered over two sites with a refined occupancy ratio of 0.542 (11):0.458 (11). In the crystal, C-H⋯O hydrogen bonds dominate the packing and combine with a C-H⋯π(ring) contact to stack the cations and anions along the a-axis direction. Hirshfeld surface analysis of the salt and of the individual cation and anion components is also reported.

Gel actuators based on polymeric radicals.

Low-voltage electrochemical actuation of radical polymer gels has been demonstrated in an organic electrolyte. Polymer gels were prepared by post-modification of active-ester precursor gels with an amine-functionalised radical. A combination of few-layer graphene and multiwall carbon nanotubes gave high conductivity and improved actuation in the gels, with 32% linear actuation. The actuator system showed good stability over at least 10 cycles, showing its promise. The cycle time was several hours due to mass-transport limited transport of ions and solvent into the device.

Metallosupramolecular Architectures Formed with Ferrocene-Linked Bis-Bidentate Ligands: Synthesis, Structures, and Electrochemical Studies.

The self-assembly of ligands of different geometries with metal ions gives rise to metallosupramolecular architectures of differing structural types. The rotational flexibility of ferrocene allows for conformational diversity, and, as such, self-assembly processes with 1,1'-disubstituted ferrocene ligands could lead to a variety of interesting architectures. Herein, we report a small family of three bis-bidentate 1,1'-disubstituted ferrocene ligands, functionalized with either 2,2'-bipyridine or 2-pyridyl-1,2,3-triazole chelating units. The self-assembly of these ligands with the (usually) four-coordinate, diamagnetic metal ions Cu(I), Ag(I), and Pd(II) was examined using a range of techniques including 1H and DOSY NMR spectroscopies, high-resolution electrospray ionization mass spectrometry, X-ray crystallography, and density functional theory calculations. Additionally, the electrochemical properties of these redox-active metallosupramolecular assemblies were examined using cyclic voltammetry and differential pulse voltammetry. The copper(I) complexes of the 1,1'-disubstituted ferrocene ligands were found to be coordination polymers, while the silver(I) and palladium(II) complexes formed discrete [1 + 1] or [2 + 2] metallomacrocyclic architectures.

A mechanically strengthened polyacrylamide gel matrix fully compatible with electrophoresis of proteins and nucleic acids.

Polyacrylamide gel electrophoresis is a universal tool in a biochemist's toolkit for protein and nucleic acid separation and subsequent visualisation and analysis. The standard formulation of polyacrylamide gels consists of acrylamide (ACM) monomer crosslinked with bisacrylamide (MBA) which creates a gel with excellent sieving properties but which is mechanically fragile and prone to tearing during post-electrophoresis manipulations involved in visualisation and analysis. By adding a poly(ethylene oxide) macro-crosslinker to the standard gel formulation, we have created a tough gel matrix that can be used to fractionate proteins and nucleic acids by polyacrylamide gel electrophoresis. The protein and nucleic acid resolving capabilities and performance during staining and electroblotting of the tough gel matrix rivals that of conventional acrylamide/bisacrylamide gels. The tough gel matrix is resistant to tear and remarkably elastic, capable of stretching to over four times its original length before breaking, and represents a significant improvement over standard polyacrylamide gel formulations.

A ferrocene based switchable molecular folding ruler.

A 2,2'-bipyridine-appended bis(ferrocene) three tiered molecular folding ruler, can be switched from a folded conformation to an extended conformation by the addition of [Cu(CH3CN)4](PF6) and 6,6'-dimesityl-2,2'-bipyridine. This extension and contraction process could be triggered either chemically or electrochemically and was reversible.

Crystal structures of the polymer precursors 3-(2,5-dimeth-oxy-3,4,6-tri-methyl-phen-yl)propyl methacrylate and 3-(2,4,5-trimethyl-3,6-dioxo-cyclo-hexa-1,4-dien-yl)propyl methacrylate.

The closely related title compounds, 3-(2,5-dimeth-oxy-3,4,6-tri-methyl-phen-yl)propyl methacrylate, C18H26O4 (I), and 3-(2,4,5-trimethyl-3,6-dioxo-cyclo-hexa-1,4-dien-yl)propyl methacrylate, C16H20O4 (II), are monomers suitable for the preparation of redox polymers. They consist of a propyl-methacrylate group and three methyl substituents on di-meth-oxy-benzene and quinone cores, respectively. Both crystal structures feature weak C-H⋯O hydrogen bonds and C-H⋯π(ring) contacts between methyl groups and the six-membered rings.

Excited States of Triphenylamine-Substituted 2-Pyridyl-1,2,3-triazole Complexes.

A new 2-pyridyl-1,2,3-triazole (pytri) ligand, TPA-pytri, substituted with a triphenylamine (TPA) donor group on the 5 position of the pyridyl unit was synthesized and characterized. Dichloroplatinum(II), bis(phenylacetylide)platinum(II), bromotricarbonylrhenium(I), and bis(bipyridyl)ruthenium(II) complexes of this ligand were synthesized and compared to complexes of pytri ligands without the TPA substituent. The complexes of unsubstituted pytri ligands show metal-to-ligand charge-transfer (MLCT) absorption bands involving the pytri ligand in the near-UV region. These transitions are complemented by intraligand charge-transfer (ILCT) bands in the TPA-pytri complexes, resulting in greatly improved visible absorption (λmax = 421 nm and ϵ = 19800 M-1 cm-1 for [Pt(TPA-pytri)Cl2]). The resonance Raman enhancement patterns allow for assignment of these absorption bands. The [Re(TPA-pytri)(CO)3Br] and [Pt(TPA-pytri)(CCPh)2] complexes were examined with time-resolved infrared spectroscopy. Shifts in the C≡C and C≡O stretching bands revealed that the complexes form states with increased electron density about their metal centers. [Pt(TPA-pytri)Cl2] is unusual in that it is emissive despite the presence of deactivating d-d states, which prevents emission from the unsubstituted pytri complex.