Hydrogels containing silver nanoparticles for burn wounds show antimicrobial activity without cytotoxicity

This research introduces a novel dressing for burn wounds, containing silver nanoparticles in hydrogels for infected burn care. The 2-acrylamido-2-methylpropane sulfonic acid sodium salt hydrogels containing silver nanoparticles have been prepared via ultraviolet radiation. The formation of silver nanoparticles was monitored by surface plasmon bands and transmission electron microscopy. The concentration of silver nitrate loaded in the solutions slightly affected the physical properties and mechanical properties of the neat hydrogel. An indirect cytotoxicity study found that none of the hydrogels were toxic to tested cell lines. The measurement of cumulative release of silver indicated that 70%–82% of silver was released within 72 hr. The antibacterial activities of the hydrogels against common burn pathogens were studied and the results showed that 5 mM silver hydrogel had the greatest inhibitory activity. The results support its use as a potential burn wound dressing.

Multidirectional effects of Sr, Mg and Si-containing bioceramic coatings with high bonding strength on inflammation, osteoclastogenesis and osteogenesis

Ideal coating materials for implants should be able to induce excellent osseointegration, which requires several important parameters, such as good bonding strength, limited inflammatory reaction, balanced osteoclastogenesis and osteogenesis, to gain well-functioning coated implants with long-term life span after implantation. Bioactive elements, like Sr, Mg and Si, have been found to play important roles in regulating the biological responses. It is of great interest to combine bioactive elements for developing bioactive coatings on Ti-6Al-4V orthopedic implants to elicit multidirectional effects on the osseointegration. In this study, Sr, Mg and Si-containing bioactive Sr2MgSi2O7 (SMS) ceramic coatings on Ti-6Al-4V were successfully prepared by plasma-spray coating method. The prepared SMS coatings have significantly higher bonding strength (~37MPa) than conventional pure hydroxyapatite (HA) coatings (mostly in the range of 15-25 MPa). It was also found that the prepared SMS coatings switch the macrophage phenotype into M2 extreme, inhibiting the inflammatory reaction via the inhibition of Wnt5A/Ca2+ and Toll-like receptor (TLR) pathways of macrophages. In addition, the osteoclastic activities were also inhibited by SMS coatings. The expression of osteoclastogenesis related genes (RANKL and MCSF) in bone marrow derived mesenchymal cells (BMSCs) with the involvement of macrophages was decreased, while OPG expression was enhanced on SMS coatings compared to HA coatings, indicating that SMS coatings also downregulated the osteoclastogenesis. However, the osteogenic differentiation of BMSCs with the involvement of macrophages was comparable between SMS and HA coatings. Therefore, the prepared SMS coatings showed multidirectional effects, such as improving bonding strength, reducing inflammatory reaction and downregulating osteoclastic activities, but maintaining a comparable osteogenesis, as compared with HA coatings. The combination of bioactive elements of Sr, Mg and Si into bioceramic coatings can be a promising method to develop bioactive implants with multifunctional properties for orthopaedic application.

Voltage quality improvement in distribution networks containing DERs using UPQC

Single phase distributed energy resources (DERs) can cause voltage rise along distribution feeder and power imbalance among the phases. Usually transformer tap setting are used to mitigate voltage drop along feeders. However this can aggravate the voltage rise problem when DERs are connected. Moreover if the power generation in a phase is more than its load demand, the excess power in that phase will be fed back to the transmission network. In this paper, a unified power quality compensator (UPQC) has been utilized to alleviate the voltage quality excess power circulation problems. Through analysis and simulation results, the mode of operation of UPQC is highlighted. The proposals are validated through extensive digital computer simulation studies using PSCAD and MATLAB.

Interstellar molecules : Conversion or C3O-. to C3O in the gas phase

Neutral C3O has been prepared by collision induced neutralisation of the precursor radical anion formed by the reaction C-=C-CO-OEt --> C3O-. +EtO. . The similar neutralisaaion reionisation (-NR+) and charge reversal (CR) spectra of C3O-. indicate that the potential surfaces of C3O and C3O+. show favourable vertical Franck-Condon overlap, This suggests that the bond connectivities of anion, neutral and cation C3O are the same. Copyright (C) 1999 John Wiley & Sons, Ltd.

Potential interstellar molecules : Formation of neutral C6CO from C6CO- in the gas phase

Computations at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G* level of theory indicate that neutral C6CO is a stable species. The ground state of this neutral is the singlet cumulene oxide :C=C=C=C=C=C=C=O. The adiabatic electron affinity and dipole moment of singlet C6CO are 2.47 eV and 4.13 D, respectively, at this level of theory. The anion (C6CO)(-.) should be a possible precursor to this neutral. It has been formed by an unequivocal synthesis in the ion source of a mass spectrometer by the S(N)2(Si) reaction between (CH3)(3)Si-C=C-C=C-C=C-CO-CMe3 and F- to form C-=C-C=C-C=C-CO-CMe3 which loses Me3C in the source to form C6CO-.. Charge stripping of this anion by vertical Franck-Condon oxidation forms C6CO, characterised by the neutralisation-reionisation spectrum (-NR+) of C6CO-., which is stable during the timeframe of this experiment (10(-6) s), Copyright (C) 2000 John Wiley & Sons, Ltd.

Generation of two isomers of C5H from the corresponding anions. A theoretically motivated mass spectrometric study

Molecular orbital calculations have predicted the stability of a range of connectivities for the radical C5H potential surface. The most energetically favorable of these include the linear C4CH geometry and two ring-chain structures HC2C3 and C2C3H The corresponding anions are also shown to be theoretically stable, and furthermore, a fourth isomer, C2CHC2, is predicted to be the most stable anion connectivity. These results have motivated experimental efforts. Methodologies for the generation of the non-ring-containing isomeric anions C4CH and C2CHC2 have been developed utilizing negative ion mass spectrometry. The absolute connectivities of the anions have been established using deuterium labeling, charge reversal, and neutralization reionization techniques. The success of the latter experiment confirms theoretical predictions of stability of the corresponding neutral species. This is the first reported observation of the neutral C2CHC2 species that calculations predict to be substantially less stable than the C4CH connectivity but still bound relative to isomerization processes.

Interstellar molecules. Conversion or C3O-. to C3O in the gas phase

Neutral C3O has been prepared by collision induced neutralisation of the precursor radical anion formed by the reaction C-=C-CO-OEt --> C3O-. +EtO. The similar neutralisaaion reionisation (-NR+) and charge reversal (CR) spectra of C3O-. indicate that the potential surfaces of C3O and C3O+. show favourable vertical Franck-Condon overlap, This suggests that the bond connectivities of anion, neutral and cation C3O are the same. Copyright (C) 1999 John Wiley & Sons, Ltd.

Bond dissociation energies of organic molecules

In this Account we have compiled a list of reliable bond energies that are based on a set of critically evaluated experiments. A brief description of the three most important experimental techniques for measuring bond energies is provided. We demonstrate how these experimental data can be applied to yield the heats of formation of organic radicals and the bond enthalpies of more than 100 representative organic molecules.

Conversion of neutral C2COC2 to C4CO. potential interstellar molecules

Both [C4CO]−· and [C2COC2]−· are formed in the ion source of a VG ZAB 2HF mass spectrometer by the respective processes HO− + Me3Si–CC–CC–CO–CMe3 → [C4CO]−· + Me3SiOH + Me3C·, and Me3Si–CC–CO–CC–SiMe3 + SF6 + e → [C2COC2]−· + 2Me3SiF + SF4. The second synthetic pathway involves a double desilylation reaction similar to that first reported by Squires. The two radical anion isomers produce different and characteristic charge reversal spectra upon collisional activation. In contrast, following collision induced charge stripping, both radical anions produce neutral C4CO as evidenced by the identical neutralisation reionisation (−NR+) spectra. The exclusive rearrangement of C213COC2 to C413CO indicates that 12C–O bond formation is not involved in the reaction. Ab initio calculations (at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G∗ level of theory) have been used to investigate the reaction coordinates on the potential surfaces for both singlet and triplet rearrangements of neutral C2COC2. Singlet C2COC2 is less stable than singlet C4CO by 78.8 kcal mol−1 and requires only 8.5 kcal mol−1 of additional energy to effect conversion to C4CO by a rearrangement sequence involving three C–C ring opening/cyclisation steps.

Clinical dyslipidaemia is associated with changes in the lipid composition and inflammatory properties of apolipoprotein-B-containing lipoproteins from women with type 2 diabetes

The aim of this study was to use lipidomics to determine if the lipid composition of apolipoprotein-B-containing lipoproteins is modified by dyslipidaemia in type 2 diabetes and if any of the identified changes potentially have biological relevance in the pathophysiology of type 2 diabetes. VLDL and LDL from normolipidaemic and dyslipidaemic type 2 diabetic women and controls were isolated and quantified with HPLC and mass spectrometry. A detailed molecular characterisation of VLDL triacylglycerols (TAG) was also performed using the novel ozone-induced dissociation method, which allowed us to distinguish vaccenic acid (C18:1 n-7) from oleic acid (C18:1 n-9) in specific TAG species. Lipid class composition was very similar in VLDL and LDL from normolipidaemic type 2 diabetic and control participants. By contrast, dyslipidaemia was associated with significant changes in both lipid classes (e.g. increased diacylglycerols) and lipid species (e.g. increased C16:1 and C20:3 in phosphatidylcholine and cholesteryl ester and increased C16:0 [palmitic acid] and vaccenic acid in TAG). Levels of palmitic acid in VLDL and LDL TAG correlated with insulin resistance, and VLDL TAG enriched in palmitic acid promoted increased secretion of proinflammatory mediators from human smooth muscle cells. We showed that dyslipidaemia is associated with major changes in both lipid class and lipid species composition in VLDL and LDL from women with type 2 diabetes. In addition, we identified specific molecular lipid species that both correlate with clinical variables and are proinflammatory. Our study thus shows the potential of advanced lipidomic methods to further understand the pathophysiology of type 2 diabetes.

Formation of two isomeric C3HO radicals from charged precursors in the gas phase. Potential interstellar molecules

Theoretical calculations of the C3HO potential surface at the CCSD(T)/aug-cc-pVDu/B3LYP/6-31G* level indicate that the three radicals HCCCO, CCCHO, and (cyclo-C3H)=O are stable, with HCCCO being the most stable of the three. A fourth isomer, CCHCO, is unstable with respect to cyclization to (cyclo-C3H)=O. Two isomers have been prepared by neutralization of charged precursors, formed as follows: (i) HCCCO, by HC drop C-C(O)-O+(H)(Me) --> HC3O+ + MeOH, and (ii) C2CHO, by (a) Me3SiC drop C-CHO + HO- --> C- drop C-CHO + Me3SiOH and (b) C- drop C-CH(OH)-C drop CH --> C- drop C-CHO + C2H2. A comparison of the CR and -NR+ spectra of -C2CHO indicate that C2CHO is (partially) rearranging to an isomer that shows significant formation of CO.(+) in the -NR+ spectrum of the anion. Ab initio calculations indicate that HCCCO is the product of the isomerism and that a proportion of these isomerized neutrals dissociate to CO and C2H. The neutral HCCCO may be formed by (i) synchronous rearrangement of C2CHO and/or (ii) stepwise rearrangement of C2CHO through (cyclo-C3H)=O. The second of these processes should have the higher rate, as it has the lower barrier in the rate-determining step and the higher Arrhenius pre-exponential A factor.

Generation of two isomers of C5H from the corresponding anions. A theoretically motivated mass spectrometric study

Molecular orbital calculations have predicted the stability of a range of connectivities for the radical C5H potential surface. The most energetically favorable of these include the linear C4CH geometry and two ring-chain structures HC2C3 and C2C3H The corresponding anions are also shown to be theoretically stable, and furthermore, a fourth isomer, C2CHC2, is predicted to be the most stable anion connectivity. These results have motivated experimental efforts. Methodologies for the generation of the non-ring-containing isomeric anions C4CH and C2CHC2 have been developed utilizing negative ion mass spectrometry. The absolute connectivities of the anions have been established using deuterium labeling, charge reversal, and neutralization reionization techniques. The success of the latter experiment confirms theoretical predictions of stability of the corresponding neutral species. This is the first reported observation of the neutral C2CHC2 species that calculations predict to be substantially less stable than the C4CH connectivity but still bound relative to isomerization processes.

Chemotaxis and chemokinesis of human prostate tumor cell lines in response to human prostate stromal cell secretory proteins containing a nerve growth factor-like protein

The migration of three human prostate tumor epithelial cell lines (TSU-pr1, PC-3, DU-145) in response to secreted protein from a human prostate stromal cell line was investigated by using the modified blind-well Boyden chamber assay. Migrated cells were quantified by spectrophotometrically measuring the concentration of crystal violet stain extracted from their nuclei. Cell number was correlated linearly with the concentration of extracted crystal violet stain. All three tumor cell lines showed intrinsic migratory ability in the absence of chemoattractants, such that approximately 1-7% of plated cells migrated across the filter of the Boyden chambers during a 5-h incubation period. Prostate tumor cell migration was significantly enhanced (3-13-fold) in response to stromal cell secretory protein in a dose-dependent manner, whereas bovine serum albumin had no effect on stimulating tumor cell migration. Immunoprecipitation of the stromal cell secreted protein with a nerve growth factor antibody partially and significantly reduced its stimulatory activity for tumor cell migration. A Zigmond-Hirsch matrix assay of tumor cell migration in response to various concentration gradients of stromal cell secreted protein demonstrated both chemotaxis and chemokinesis by all three cell lines. These results are consistent with the stromal cell secretory protein stimulation of chemokinetic tumor cell migration through the capsule of the prostate. Outside of the prostate gland metastasis of tumor cells may occur by chemotaxis to preferential sites containing chemoattractants similar to or related to maintenance factors that can substitute for components of stromal cell secretory protein.

Anionic migration in aromatic systems effected by collisional activation. Unusual fragmentations of deprotonated anilides containing methoxyl and ethoxyl substituents

Long-range cross-ring reactions occur when (M - H)(-) ions of methoxy- and ethoxy-C6H4-(-)NCOR (R = H, CH3, C6H5 and CH3O) are subjected to collisional activation, These reactions are generally minor processes: a particular example is the cross-ring elimination p-C2H5O-C6H4-(NCOCH3)-N-- --> [CH3-(p-C2H5O-C6H4-NCO)] --> p-(O--)-C6H4-NCO + C2H4 + CH4. Major processes of these (M - H)(-) ions involve (i) losses of radicals to form stabilised radical anions, e.g. (a) loss of a ring H-. or (b) CH3. (or C2H5.) from the alkoxy group, and (ii) proximity effects when the two substituents are ortho, e.g. loss of CH3OH from o-CH3O-C6H4-(NCHO)-N-- yields deprotonated benzoxazole. Another fragmentation of an arylmethoxyl anion involves loss of CH2O. It is proposed that losses of CH2O are initiated by anionic centres but the actual mechanisms in the cases studied depend upon the substitution pattern of the methoxyanilide: o- and p-methoxyanilides may undergo ipso proton transfer/elimination reactions, whereas the in-analogues undergo proton transfer reactions to yield an o-CH3O substituted aryl carbanion followed by proton transfer from CH3O to the carbanion site with concomitant loss of CH2O.

Formation of neutral molecules of potential stellar interest by neutralisation of negative ions in a mass spectrometer - The application of experiment and molecular modelling in concert

This paper is a modified version of a lecture which describes the synthesis, structure and reactivity of some neutral molecules of stellar significance. The neutrals are formed in the collision cell of a mass spectrometer following vertical Franck-Condon one electron oxidation of anions of known bond connectivity. Neutrals are characterised by conversion to positive ions and by extensive theoretical studies at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory. Four systems are considered in detail, viz (i) the formation of linear C-4 and its conversion to the rhombus C-4, (ii) linear C-5 and the atom scrambling of this system when energised, (iii) the stable cumulene oxide CCCCCO, and (iv) the elusive species O2C-CO. This paper is not intended to be a review of interstellar chemistry: examples are selected from our own work in this area. (C) 2002 Elsevier Science Inc. All rights reserved.