Fuzzy distribution fitting energy-based active contours for image segmentation

This paper presents an unsupervised fuzzy energy-based active contour model for image segmentation, based on techniques of curve evolution. The paper proposes a fuzzy energy functional which involves intensity distributions in regions of image to segment and value of fuzzy membership functions. The intensity distributions are derived using a Gaussian mixture model (GMM)-based intensity distribution estimator. Meanwhile, the fuzzy membership functions valued in [0,1] is used to measure the association degree of each image pixel to the region outside and inside the curve. The proposed energy functional is then incorporated into a pseudo-level set formulation. To minimize the energy functional, instead of solving Euler?CLagrange equation of underlying problem, we utilize a direct method to calculate the alterations of the fuzzy energy. In addition, since the parameters of intensity distributions are preestimated, the proposed model avoids the step of updating them at each iteration of curve evolution. The proposed model therefore overcomes the initialization problem of common gradient-descent-based active contour models and converges quickly. Besides, it can work with images with blurred object boundaries. In addition, the extension of the model for the more general case of local space-varying intensities enables dealing with images with intensity inhomogeneity. Experimental results for synthetic and real images validate the desired performances of the proposed model.     

ESI‐MS/MS of expanded porphyrins: a look into their structure and aromaticity

Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd.     

Mössbauer spectra and electric conductivities of bidentate base bridged iron(II) phthalocyanine

Bidentate bridging base polymer complexes of iron(II) phthalocyanine FePcL, where L = pyrazine (pyz), 4,4′-bipyridine (bpy), trans-1,2-bis(4-pyridyl)ethylene (bpe), 1,2-bis(4-pyridyl)ethane (bpa) and 4,4′-trimethylene bipyridine (tmbpy), have been prepared, characterized and oxidized by iodine to give a range of iron(II) and iron(III) complexes (FePcL)_n · I_x. The electrical conductivities and Mössbauer parameters both change with respect to the kinds of bidentate bridging bases. The conjugation of bridged ligand markedly effects the conductivity of the complexes.     

Structures and Mössbauer spectra of phosphido-bridged heterobimetallic complexes CpFe(CO)2(μ-PPh2)W(CO)5 and CpFe(CO)(μ-CO)(μ-PPh2)W(CO)4

Structures of non metal-metal bonded phosphido-bridged heterobimetallic complexes, including CpFe(CO)₂(μ-PPh₂)W(CO)₅ (1-W) and metal-metal bonded CpFe(CO)(μ-CO)(μ-PPh₂)W(CO)₄ (2), were determined by a single crystal X-ray diffraction study. In 1-W, the long distance between Fe and W indicates no metal-metal bond to exist. In 2, a Fe---W bond with bond length 2.851 Å and a semibridging carbonyl with W---C---O angle 153° were observed. Mössbauer spectra of 1-W and 2 were taken at 77 K. Isomer shifts of 1-W and 2 were − 0.0203 mm s⁻¹ and 0. 1917 mm s⁻¹ respectively.     

Immobilization of Tyrosinase on Chitosan — An Optimal Approach to Enhance the Productivity of L‐DOPA from L‐Tyrosine

Tyrosinase was immobilized on Chitosan (CTS) beads to produce 3,4‐dihydroxy‐L‐phenylalanine (L ‐DOPA) from L ‐tyrosine. Epichlorohydrin (ECH), ethylene glycol diglycidyl ether (EGDE), and glutaraldehyde (GLU) were used as coupling agents, respectively. Ultraviolet/visible measurements on CTS films showed that the reaction intermediate (L ‐dopaquinone) attacked the amino groups on CTS, so the amine residues on chitosan were capped by acetic acid anhydride (Ac) or formaldehyde (Fm) to avoid the deactivation of the immobilized tyrosinase. The pH and temperature of the maximal rate to produce L‐DOPA were investigated. GLU (coupling agent) and Ac (capping agent) were selected for practical utility. A 7.5% (w/v) concentration of GLU was found to attain maximal activity of the immobilized enzyme. The thermal stability of tyrosinase immobilized on CTS‐GLU‐Ac, and after treatment with sodium borohydride, was enhanced to a great extent. The L ‐DOPA converting efficiency in the environmental conditions of this study decreased from 45.1% to 39.9% (between 1^st and 30^th batch). This immobilized tyrosinase can be used practically in the production of L‐DOPA from L‐tyrosine.     

Development of biodegradable co-poly( -lactic/glycolic acid) microspheres for the controlled release of 5-FU by the spray drying method

The water-soluble anti-cancer drug, 5-fluorouracil (5-fluoro-2,4-pyrimidinedione) (5-FU) is encapsulated into biodegradable co-poly ( -lactic/glycolic acid) (PLGA) using the spray drying method for the development of long-lasting controlled release systems. In this study, the effects of both polymeric composition and technological parameters on release profiles of 5-FU were investigated. The degradation of various microspheres was also investigated. The mixture of dichloromethane/chloroform/methanol (1:1:2 v/v) instead of dichloromethane/chloroform (1:1 v/v) resulted in the modification of morphology, while the physical structure of the microsphere varied from a porous PLGA microsphere to a dense PLGA microsphere. The results show that the average diameter was 2 μm and the anti-cancer drug loading of microspheres approached approximately 8% (w/w). In addition, the lactide/glycolide ratio of the polymer is an important parameter for controlling the release profile of the entrapped anticancer drug. Our results indicate that the mixture solvent using the spray drying method was more efficient than emulsification solvent diffusion.     

Natural Bond Orbital Rationalizations of NMR Observations for Metal‐Ligand Bonding (II): Rehybridization of Phosphorus Arising from Coordination of Methyl‐Phenyl‐Phosphines

Carbonyls' 2π orbital populations, [2π], in W(CO)₅L {L = PPh₃, PPh₂Me, PPhMe₂} have been determined by NMR spin‐lattice relaxation techniques. Experimental values of axial [2π], compared with those reported for PMe₃ and P(OMe)₃, reveal that PMe₃ is a slightly better π‐acid than PPh₃. Through space interactions between carbonyl and phenyl groups are insignificant since values of [2π] do not vary significantly in the series of phosphines, going from PMep₃ to PPh₃. Natural bond orbital (NBO) studies indicate that π‐accepting capabilities for these phosphines are primarily governed by the nature of P‐C anti‐bonding, σ*_P‐C. Compared with PPh₃, the better π‐accepting σ*_P‐C, as well as the better s‐donating lone‐pair LP(P), in PMe₃ can both be explained by the higher extents of rehybridization of the coordinated phosphorus atom. Based on this rehybridization argument, the NBO predicted order of increasing π‐acidic strengths PPh₃ < PPh₂Me < PPhMe₂ < PMe₃, which cannot be clearly distinguished by NMR experiments, is ascribed to the same NBO trend of σ‐donating capabilities in a synergistic manner. Effects of coordination on P‐Y (Y = C, O, F) bonding strengths in phosphines (or phosphites) are depending on two conflicting effects: rehybridization of LP(P) and the hyperconjugative‐like d_π → σ*_P‐Y back‐donation.