Formation of Concentrated Nanoemulsion by W/O Microemulsion Dilution Method: Biodiesel, Tween 80, and Water System

In this work, we show the formation of concentrated green O/W nanoemulsion (dispersed phase mass fraction was up to 0.5) by diluting W/O microemulsion in the water/Tween 80/biodiesel system. The mechanism of the formation of nanoemulsions was examined and illustrated by small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM). At high temperature, nanosized droplets formed spontaneously due to the surfactant migration and inversion upon dilution of W/O microemulsions, but these droplets were highly unstable. When cooled to room temperature, their stability was highly enhanced due to the decrease of collision frequency rate and the enhancement of stabilization of the oil/water interface. Even though, the Ostwald ripening still results in growth of droplets of the nanoemulsions after long-term storage, which limits the practical applications of nanoemulsions. W/O microemulsions are thermodynamic systems. Hence, W/O microemulsions that can form nanoemulsions by simple dilution of water can be used as an alternative to O/W nanoemulsion during storage and transport. Furthermore, biodiesel nanoemulsions could meet the requirements of green chemistry and engineering and be used as new green lubricants in water-based drilling fluid

Computational Study of Methane C–H Activation by Diiminopyridine Nitride/Nitridyl Complexes of 3d Transition Metals and Main-Group Elements

The C–H bond activation of methane using ^Ph,MePDI–M≡N [^Ph,MePDI = 2,6-(PhNCMe)₂C₅H₃N] (M = V, Mn, Fe, Co, Ni, Al, or P) has been studied via three reaction pathways: [2_σ + 2_π] addition, hydrogen atom abstraction (HAA), and direct insertion. The activating ligand is a nitride/nitridyl (N), with diiminopyridine (PDI) as the supporting ligand. Calculations show reasonable C–H activation barriers for Co, Ni, Al, and P ^Ph,MePDI nitrides, complexes that favor an HAA pathway. Electrophilic ^Ph,MePDI nitride complexes of the earlier metals with a nucleophilic actor ligandV, Mn, Fefollow a [2_σ + 2_π] addition pathway for methane activation. Free energy barriers for methyl migration, ^Ph,MePDI–M­(CH₃)NH → ^Ph,MePDI–M–N­(H)­CH₃, are also interesting in the context of alkane functionalization; discriminating factors in this mechanistic step include the strengths of the σ-bond and metal-actor ligand π-bond that are broken and the electrophilicity of the actor ligand to which methyl migrates

Computational Study of Methane C–H Activation by Diiminopyridine Nitride/Nitridyl Complexes of 3d Transition Metals and Main-Group Elements

The C–H bond activation of methane using ^Ph,MePDI–M≡N [^Ph,MePDI = 2,6-(PhNCMe)₂C₅H₃N] (M = V, Mn, Fe, Co, Ni, Al, or P) has been studied via three reaction pathways: [2_σ + 2_π] addition, hydrogen atom abstraction (HAA), and direct insertion. The activating ligand is a nitride/nitridyl (N), with diiminopyridine (PDI) as the supporting ligand. Calculations show reasonable C–H activation barriers for Co, Ni, Al, and P ^Ph,MePDI nitrides, complexes that favor an HAA pathway. Electrophilic ^Ph,MePDI nitride complexes of the earlier metals with a nucleophilic actor ligandV, Mn, Fefollow a [2_σ + 2_π] addition pathway for methane activation. Free energy barriers for methyl migration, ^Ph,MePDI–M­(CH₃)NH → ^Ph,MePDI–M–N­(H)­CH₃, are also interesting in the context of alkane functionalization; discriminating factors in this mechanistic step include the strengths of the σ-bond and metal-actor ligand π-bond that are broken and the electrophilicity of the actor ligand to which methyl migrates

mRNA expression of Slug in HS and normal skin tissues.

<p>mRNA expression of Slug was increased in HS ( = 0.76, <i>s</i> = 0.13, <i>n</i> = 4) compared to normal skin ( = 0.38, <i>s</i> = 0.04, <i>n</i> = 5) (A) and (B). Similar to the change of Slug mRNA level, western blot (C) and graphic analysis (D) showed that Slug was significantly increased in HS ( = 0.84, <i>s</i> = 0.22, <i>n</i> = 4) than that in normal skin ( = 0.42, <i>s</i> = 0.18, <i>n</i> = 5). * <i>P</i><0.01.</p

Quantitative RT-PCR analysis of COL1 and COL3 mRNA expressions

<p>. The mRNA levels of COL1 (A) and COL3 (B) in normal skin fibroblasts ( = 0.24, <i>s</i> = 0.06;  = 0.28, <i>s</i> = 0.05, respectively) were significantly lower, compared with other three groups. However, there is no significant difference in mRNA levels of COL1 (A) and COL3 (B) in HSFBs transfected with Slug shRNA ( = 0.82, <i>s</i> = 0.08;  = 0.78, <i>s</i> = 0.12, respectively), compared with non-transfected HSFBs ( = 0.95, <i>s</i> = 0.17;  = 0.85, <i>s</i> = 0.08, respectively) and HSFBs transfected with control shRNA ( = 0.80, <i>s</i> = 0.11;  = 0.92, <i>s</i> = 0.14, respectively), suggesting Slug shRNA had no effect on the collagen proteins synthesis in HS formation. *: <i>P</i><0.01 versus Slug shRNA; ^†: <i>P</i><0.01 versus Control shRNA; ^‡: <i>P</i><0.01 versus HSFBs.</p

Expression of Slug in HSFBs and normal skin fibroblasts.

<p>Nuclear positive Slug was significantly higher in HSFBs (B,  = 51.73, <i>s</i> = 3.74, <i>n</i> = 38) than that in normal skin fibroblasts (A,  = 22.91, <i>s</i> = 3.33, <i>n</i> = 22). (C) Staining analysis of Slug in HS and normal skin. Scale bar: 20 µm (A and B). * <i>P</i><0.01.</p

Effects of Slug shRNA on the expression of apoptosis-relative genes in HSFBs.

<p>The mRNA expression of Bcl-2 is decreased in HSFBs transfected with Slug shRNA ( = 0.23, <i>s</i> = 0.03) than those in other groups. HSFBs transfected with control shRNA ( = 0.68, <i>s</i> = 0.10) and non-transfected HSFBs ( = 0.70, <i>s</i> = 0.06) expressed the most increased level of Bcl-2 than that in normal skin fibroblasts ( = 0.38, <i>s</i> = 0.05) and HSFBs transfected with Slug shRNA ( = 0.23, <i>s</i> = 0.03) (A and B). Similar with mRNA expression level, the protein expression of Bcl-2 is most decreased in Slug shRNA group ( = 0.24, <i>s</i> = 0.06) and most increased in control shRNA ( = 0.96, <i>s</i> = 0.07) and non-transfected group ( = 0.90, <i>s</i> = 0.15) (C and D). Expression of Bax and PUMA at mRNA and protein level was detected in all groups. The mRNA level of Bax and PUMA was similar among the four groups (A and B). Similarly, western blot (C) and graphic analysis (D) showed that Bax and PUMA were similar in all groups.*: <i>P</i><0.01 versus Normal skin fibroblast; ^†: <i>P</i><0.01 versus Control shRNA; ^‡: <i>P</i><0.01 versus HSFBs.</p

Effects of SFRP2 shRNA on the protein expression of SFRP2 and Slug in HSFBs.

<p>The SFRP2 protein level was significantly increased and decreased in the non- transfected HSFBs ( = 1.06, <i>s</i> = 0.15) and the SFRP2 shRNA group ( = 0.14, <i>s</i> = 0.02), respectively, compared with the normal skin fibroblasts ( = 0.36, <i>s</i> = 0.05). And the protein expression of SFRP2 in HSFBs transfected with control shRNA ( = 0.90, <i>s</i> = 0.06) was not significantly decreased than that in non-transfected HSFBs. After the treatments of the shRNAs, the SFRP2 protein level was significantly lower than that in the HSFBs and the HSFBs transfected with control shRNA (A and B). Similar to the effects on the expression of SFRP2, Slug expression was significantly higher in the non- transfected HSFBs and HSFBs transfected with control shRNA than that in normal skin fibroblasts both in mRNA ( = 0.70, <i>s</i> = 0.08;  = 0.63, <i>s</i> = 0.10;  = 0.37, <i>s</i> = 0.05, respectively) and protein levels ( = 0.90, <i>s</i> = 0.04;  = 0.84, <i>s</i> = 0.11;  = 0.43, <i>s</i> = 0.04, respectively). Moreover, both the Slug mRNA and protein levels were significantly decreased in HSFBs transfected with SFRP2 shRNA ( = 0.20, <i>s</i> = 0.06;  = 0.25, <i>s</i> = 0.05, respectively) compared with the non- transfected HSFBs and HSFBs transfected with control shRNA (B- F). *: <i>P</i><0.01 versus Normal skin fibroblast; ^†: <i>P</i><0.01 versus Control shRNA; ^‡: <i>P</i><0.01 versus HSFBs.</p

Effects of Slug shRNA on the protein expression of Slug in HSFBs.

<p>The Slug protein level was significantly decreased in the HSFBs of the Slug shRNA group ( = 0.26, <i>s</i> = 0.05), compared with the normal skin fibroblasts ( = 0.46, <i>s</i> = 0.04), HSFBs transfected with control shRNA ( = 0.86, <i>s</i> = 0.10) and non-transfected HSFBs ( = 0.92, <i>s</i> = 0.04). And the protein expression of Slug in HSFBs transfected with control shRNA was not significantly decreased than that in non-transfected HSFBs. And the Slug protein level was significantly lower in normal skin fibroblast than that in non-transfected HSFBs and HSFBs transfected with control shRNA (A and B). *: <i>P</i><0.01 versus Normal skin fibroblast; ^†: <i>P</i><0.01 versus Control shRNA; ^‡: <i>P</i><0.01 versus HSFBs.</p

Patient characteristics.

*<p>Tissues for semi-quantitative RT-PCR and Western blot.</p