Characterization of dimethacrylate polymeric networks: a study of the crosslinked structure formed by monomers used in dental composites

The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol–gel composition was determined by extraction with dichloromethane followed by ¹H NMR analysis. Results show that, as expected, volumetric shrinkage increases with TEGDMA concentration and monomer conversion. Extraction/¹H NMR studies show increasing participation of the more flexible TEGDMA towards the limiting stages of conversion/crosslinking development. As the conversion progresses, either based on longer irradiation times or greater TEGDMA concentrations, the network becomes more dense, which is evidenced by the decrease in free volume and weight loss after extraction in these situations. For the same composition (BisGMA/TEGDMA 60–40 mol%) light-cured for increasing periods of time (from 10 to 600 s), free volume decreased and volumetric shrinkage increased, in a linear relationship with conversion. However, the correlation between free volume and macroscopic volumetric shrinkage was shown to be rather complex for variable compositions exposed for the same time (600 s). The addition of TEGDMA decreases free-volume up to 40 mol% (due to increased conversion), but above that concentration, in spite of the increase in conversion/crosslinking, free volume pore size increases due to the high concentration of the more flexible monomer. In those cases, the increase in volumetric shrinkage was due to higher functional group concentration, in spite of the greater free volume. Therefore, through the application of the PALS model, this study elucidates the network formation in dimethacrylates commonly used in dental materials.     

Synthesis of NanoQ, a copper-based contrast agent for high-resolution magnetic resonance imaging characterization of human thrombus

A new site-targeted molecular imaging contrast agent based on a nanocolloidal suspension of lipid-encapsulated, organically soluble divalent copper has been developed. Concentrating a high payload of divalent copper ions per nanoparticle, this agent provides a high per-particle r1 relaxivity, allowing sensitive detection in T1-weighted magnetic resonance imaging when targeted to fibrin clots in vitro. The particle also exhibits a defined clearance and safety profile in vivo.     

Controllable three-component luminescence from a 1,8-naphthalimide/Eu(III) complex: white light emission from a single molecule

A macrocycle-appended naphthalimide derivative and its Eu(III) complex show triple luminescence from isolated naphthalimide (blue), aggregated naphthalimide excimers (green) and Eu centres (red) with the balance being sensitive to the degree of aggregation, allowing white light emission to be obtained from a single molecule.     

Quantifying dithiothreitol displacement of functional ligands from gold nanoparticles

Dithiothreitol (DTT)-based displacement is widely utilized for separating ligands from their gold nanoparticle (AuNP) conjugates, a critical step for differentiating and quantifying surface-bound functional ligands and therefore the effective surface density of these species on nanoparticle-based therapeutics and other functional constructs. The underlying assumption is that DTT is smaller and much more reactive toward gold compared with most ligands of interest, and as a result will reactively displace the ligands from surface sites thereby enabling their quantification. In this study, we use complementary dimensional and spectroscopic methods to characterize the efficiency of DTT displacement. Thiolated methoxypolyethylene glycol (SH-PEG) and bovine serum albumin (BSA) were chosen as representative ligands. Results clearly show that (1) DTT does not completely displace bound SH-PEG or BSA from AuNPs, and (2) the displacement efficiency is dependent on the binding affinity between the ligands and the AuNP surface. Additionally, the displacement efficiency for conjugated SH-PEG is moderately dependent on the molecular mass (yielding efficiencies ranging from 60 to 80?% measured by ATR-FTIR and ≈90?% by ES-DMA), indicating that the displacement efficiency for SH-PEG is predominantly determined by the S–Au bond. BSA is particularly difficult to displace with DTT (i.e., the displacement efficiency is nearly zero) when it is in the so-called normal form. The displacement efficiency for BSA improves to 80?% when it undergoes a conformational change to the expanded form through a process of pH change or treatment with a surfactant. An analysis of the three-component system (SH-PEG?+?BSA?+?AuNP) indicates that the presence of SH-PEG decreases the displacement efficiency for BSA, whereas the displacement efficiency for SH-PEG is less impacted by the presence of BSA.

Long range dipole-dipole correlations in nitrobenzene-benzene solutions

Hyper-Rayleigh scattering (HRS) from liquid nitrobenzene-benzene solutions with nitrobenzene mole fraction in the range 0.001 < x(NB) < 1 was measured for several combinations of linear polarized incident and scattered light, for scattering angles near 90°. Polar collective modes are identified by their distinctive HRS polarization dependence. At all concentrations the nitrobenzene HRS intensity is dominated by the transverse polar collective mode contribution and the longitudinal collective mode contribution is near zero. The transverse polar mode HRS is due to long range dipole-dipole orientation correlations between the nitrobenzene molecules, such that the molecular dipoles are oriented transverse to the wave vector for each spatial Fourier component of the orientation distribution.     

Upper critical fields of superconducting superconducting rare-earth molybdenum selenides

Upper critical fields, H_c2(T), for superconducting LaMo₆Se₈, La_0.8Eu_0.2Mo₆Se₈, La_0.8Ce_0.2Mo₆Se₈ and PrMo₆Se₈ were measured. For the best material, LaMo₆Se₈, T_c = 11.3 K, (dH_c²/dT)_T=Tc=70 kG/K and and H_c² (4.2 K) = 370 kG. These selenide compounds show promise as very high field superconductors.     

Superconductivity in the ternary borides CeOs3B2 and CeRu3B2: Magnetic susceptibility and specific heat measurements

The compounds CeOs₃B₂ and CeRu₃B₂ show superconductivity with T_c's of 3.5 and 1.1 K respectively. The magnetic susceptibility of both these compounds may be described as the sum of a Curie-Weiss term dominating at low temperature and a large temperature independent term. The heat capacity measurements yield the value of electronic specific heat coefficient γ of 40.1 and 15.6 mJ/mol K² for Os and Ru compounds, respectively. These compounds appear to be conventional bulk superconductors in which Ce is in a strongly mixed valent state.     

Superconducting transition temperature,its pressure dependence and structural transformation in (La,Ce)Ru2 alloys

The superconducting transition temperature and its dependence on hydrostatic pressure to 22 kbar have been determined for a series of (La, Ce)Ru₂ alloys. The variations of these quantities with composition are found to be generally related; however, specific irregularities in the curve of dT_c/dp versus composition are not reflected in the smooth variation of the transition temperature T_c. Some features of dT_c/dp may be correlated with the occurrence of a cubic-tetragonal transformation at low temperatures.     

Superconductivity and ferromagnetism in the orthorhombic system (TbxLu1−x)RuB2

The pseudoternary orthorhombic system Tb_xLu_1?xRuB₂) (0 ? x ? 0.1 andx = 1.0) has been investigated by static magnetization, ac susceptibility and resistivity measurements down to 1.5 K. Superconductivity occurs for 0 ? x ? 0.1, while ferromagnetic order occurs for x = 1.0. For each sample studied, the Tb ion maintains a configurationally stable trivalent state. The initial linear depression of the superconducting transition temperature yields a coupling constant value N(0)Γ² between conduction electrons and magnetic Tb³⁺ moments of 3.5 x 10^-4 ev-atom-states/spin-direction.     

LaAg under hydrostatic pressure: Superconductivity and phase transformation

The electrical resistivity of LaAg has been measured from 1–300 K at hydrostatic pressures to 12.4 kbar and the superconducting transition temperature T_c determined inductively to 23 kbar. For P ? 6.2 kbar a lattice transformation is observed at a temperature T_M which increases rapidly with pressure. T_c shows an oscillatory pressure dependence, increasing initially from T_c (0) = 1.062 K. There is no obvious correlation between the pressure dependence of T_M and T_c.