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Wednesday, June 29, 2011
An Agent's Inbox #15
While running with scissors, seventh-grader, Lucienne trips and loses her eye. By age sixteen, Lucienne feels like a freak despite having a prosthetic eye, and wonders if the sloth Jeremy tripped her on purpose. She wished she knew the truth.
One morning Lucienne can not only see through her prosthetic eye, but sees her mother's lies. Losing the dad she loved to cook with was bad enough but being stuck with her workaholic mother who lies isintolerable. The eye reveals the secrets she's always suspected her mother is hiding about her missing dad. Lucienne must decide whom to trust when everyone she loves harbors secrets. And she must decide to dig for untruths that may upset the house of cards she lives in. The truth will put Lucienne in danger, and she'll have to use the magic that created her eye to save lives.
Readers of Far from You by Lisa Schroeder will connect with Lucienne's grief over her father and strained relationship with her mother, while readers of Divergent by Veronica Roth will be swept up in the plot twists. This manuscript is written in the first person from Lucienne's point of view. It alternates chapters between Lucienne's past and present. These mosaic tiles culminate to reveal several betrayals and one deadly secret.
Thank you for your consideration of my 66k-word YA fantasy Naked Eye. A synopsis and complete manuscript are available upon request. This is a multiple submission.
I'm a member of SCBWI. My short story "Daisy" was included in the 100 Stories for Queensland anthology and my vampire short story "Allured"will appear in the upcoming YA Fangtales anthology. I'm a substitute teacher in the Cambridge Public Schools, which gives me ample opportunity to observe teenagers in their natural habitat. Thank you for your consideration of this manuscript.
You know how adults always warn children not to run with scissors because they could lose an eye and to stop tipping back their chairs because they could crack open their skulls? I've never cracked open my skull from tipping back a desk chair, but in 7th-grade, I ran with scissors and lost an eye.
Three years later, my prosthetic eye looks and works almost like my old eye. The unusual amber hue of the left eye has been recreated to an amazing degree. If my left eye moves to the left or right or up or down, so does my fake one, though not as well. At this point, most people have forgotten I'd lost an eye. I didn't forget. For one, it doesn't feel like my old eye and I know if I step into sunlight, my left pupil dilates while my right one does not because it's always set for "moderate light" as Doctor Ocular calls it.
I also haven't forgotten how the other kids at school treated me for the year I'd refused to get the glass eye. Only Orion and Morgan have stuck with me.
Sitting in the rustic kitchen eating yogurt, I watch my mother blab into her cell phone at the other end of the table. "Yes, if there's anything really wrong after the inspection, you can walk away without penalty…. Yes,the inspector will be very thorough. Don't worry, I'm here for you."
I smirk because at least she's there for someone.
10 comments:
I'm not sold on the premise. But this might be subjective. Your comparables need to be more in the same genre. Divergent, especially, shouldn't be used because it's Dystopian. Recheck your own genre too--fantasies are set in other worlds.
Sample Page: Your transition between backstory and current action is jarring, a device to convey information then move on with the story. An agent might continue reading but they'd be wary.
- June 29, 2011 at 1:56 PM
- Melodie Wright said...
Concept aside (how does a glass eye get magic?) I think your query needs a little tightening. Here is what I mean w/ my edits (this is just an idea, you'll obviously write it much better!) :
One morning Lucienne can not only see through her prosthetic eye, but sees her workaholic mother's lies. The eye reveals the secrets her mother hides about her missing dad. Lucienne discovers everyone has a secret and digging for the truth grows a danger that threatens those she loves.
I suggest giving an idea as to what ths secret re: dad is - is he a secret agent? either narrow this down or tell us this to give an idea of the stakes.
Good luck!
- June 29, 2011 at 3:40 PM
- Unknown said...
At first I didn't think it had anything to do with magic and that she just discovered a lie her mom told. So that could be more clear.
You could also include more about what happens after that. What does she do about this new knowledge? What happens in the story? Where do Lucienne's actions take her? What are the consequences of her actions?
You could cut paragraph 3 and the line about being a teacher.
also change the other part to:
NAKED EYE is a 66,000-word urban fantasy. (or contemporary fantasy) Thank you for your consideration.
sample page: I like the idea for the first paragraph but you might get better impact if you reword it.
When I was in 7th-grade I ran with scissors and lost an eye. Laugh all you want but it really happened. I should have listened to my dad.
I don't know if that's exactly what you want. Play around with a few versions and get friends to tell you what they like better.
I like the last line. Snarky.
- June 29, 2011 at 9:07 PM
- Sharon Bayliss said...
This sounds like a creative premise. I am confused about how the eye works. How can she "see" a lie? I know you don't want to add too many details, I think it would help the reader to know a little more about how the magic works. I suggest removing the entire third paragraph.
Good luck!
- June 30, 2011 at 12:06 AM
- Dorothy Dreyer said...
I get the premise with the magical eye, but as the others mentioned, this sounds like urban fantasy or paranormal to me. Otherwise, I would read on to see where this is going.
- June 30, 2011 at 3:54 AM
- Nick Sanford said...
Hey there! I love the idea of a magical prosthetic. Like others, I'm a little confused on how the eye "works," but I'm sure that can all be fixed with a line or two in the query. I imagine it comes across clearer in the manuscript.
Perhaps the most perplexing part is the "seeing" a lie. Does she see something specific on a liar, a certain something that she can't see on people who aren't lying?
Also, this sounds more like an Urban Fantasy because it appears to be set in our own world.
Thanks so much for sharing your work with us! Good luck with everything!
- June 30, 2011 at 2:21 PM
- Melinda said...
I think you need to focus more on the interesting part. Like others have said...what's the deal with this eye, what changed, and how does it work?
Also cut the chair tipping back make the eye losing part more banging. :) Nice job on the sample page.
- June 30, 2011 at 11:34 PM
- Jennifer Pickrell said...
The premise definitely caught my attention.
With the query:
In the first paragraph - will Jeremy have anything to do with the story? Seems like you could remove that part and have the hook of the magical eye sooner.
Like the other commenters, I'm confused over how the eye works. Think the part about her missing dad could be reworded, because when I read "losing," I thought at first that he'd died. And when did he disappear?
"House of cards" sounds cliche, so would remove that. Also, third paragraph isn't really necessary - it's telling, rather than showing, and reader will figure out quickly the story is in 1st person and alternates between past/present.
Sample page:
Would take out the leaning back in chairs part to give first paragraph more "umph." Transition between the narrative and action is somewhat jarring. Like MC's last line b/c it shows right away there's tension b/t her and mom.
- July 1, 2011 at 9:19 AM
- Theresa Milstein said...
Thanks for the feedback, everyone.
There seems to be a big question about genre. I've been told urban fantasy is gritty and takes place in a city. High fantasy takes place in other worlds.
I did some research after reading your comments and realized that contemporary fantasy is the correct sub genre.
I've worked on transition as well.
- July 3, 2011 at 12:29 PM
- Nicole Zoltack said...
I don't think the first paragraph of your query is necessary, especially since Jeremy is never mentioned again.
Other than that, I think the query is fairly good. I would like to know how the eye works exactly, and what changes so that now she can see lies when before she couldn't.
As others said, this is YA urban (or contemporary) fantasy.
I enjoyed the voice of the excerpt, although I don't think all of the details in the second paragraph are needed, or at least not right in the beginning of the story. Other than that, I enjoyed it.
- July 3, 2011 at 5:59 PM


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Blackcurrant Ribes negrum
Familiar to many gardeners, the blackcurrant is a shrub that grows up to 1.5m tall.
Every part of it is strongly aromatic - simply pick a leaf from a bush the next time you are near one and wonder at the power of the scent from its leaves.
Blackcurrant is known as a particularly rich source of Vitamin C. During the 1940s when oranges became scarce in the UK, blackcurrant syrup was handed out free to school children - probably giving rise to the UK's love affair with blackcurrant as a flavour to this day.


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|Southeast Spotlight
New Exhibit opens at the Silverbow
Published: 08/05/2010 14:00:00
A photography exhibit opening this week at the Silverbow features images from award winning nature photographer Amy Gulick's book, "Salmon in the Trees," an intimate glimpse into the rare ecosystem of Southeast Alaska. When we spoke with Amy about the exhibit, we found that there's a whole lot more to the book and the exhibit than just the astounding photography. She related to us the story behind it all.
VIDEO: A photography exhibit opening this week at the Silverbow features images from award winning nature photographer Amy Gulick's book, "Salmon in the Trees". (Image: Amy Gulick)
"Well salmon in the trees tells the story of this remarkable connection, between salmon and trees in Southeast Alaska. This part of the world is a place where the forest and the sea are so intertwined that you can't separate the two and probably no other species relies on both the forest and the sea more than salmon do. So salmon bring the ocean nutrients with them in their bodies into the spawning stream, the bears then deliver them to the forest floor, and the trees absorb these nutrients through their roots. And scientists have actually been able to trace a particular form of marine nitrogen that comes from the ocean, in trees, near salmon streams, that they can link directly back to the fish. So that's where the book gets its title, and when I read about that connection between salmon and trees here, I just knew I had to come here and photograph it and tell this unique story. I mean the salmon are in the trees, the salmon are in the berries, the salmon are in the bears, the salmon are in the people, they're really everywhere, they really define what Southeast Alaska is all about."
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Amy's feelings about Southeast Alaska and her work were readily apparent in the enthusiasm which bubbled freely from her during the interview, she finished by saying "And so when I come here, I get goose bumps just when I think about what is still here and how special it is and how rare it is and I hope that it's always going to be a place where there's salmon in the trees."
By: Rik Pruett - firstname.lastname@example.com


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Boletín de la Sociedad Chilena de Química
versión impresa ISSN 0366-1644
Bol. Soc. Chil. Quím. v.47 n.4 Concepción dic. 2002
Crotonaldehyde Hydrogenation on Rh/TiO2 catalysts.
In situ DRIFTS studies.
P. Reyes *1, M del C Aguirre 1, I. Melián-Cabrera 2,
M. López Granados 2 and J. L. G. Fierro2
1Facultad de Ciencias Químicas, Universidad de Concepción,
Casilla 160-C, Concepción, Chile.
2Instituto de Catálisis y Petroloeoquímica, CSIC,
Campus UAM, Cantoblanco, 28049 Madrid, España
(Recieved: October 29, 2001) - (Accepted: October 24, 2002)
The surface and catalytic properties in the vapor-phase hydrogenation of crotonaldehyde on Rh/TiO2 has been studied. It was found that a partial reduction of the support produces a surface decoration of the metal component. Thus, interfacial sites are created, which are responsible of an increase in the selectivity to crotyl alcohol, via enhancement of the polarization of the C=O bond. Photoelectron spectra revelead that rhodium is in different oxidation states, with a contribution of ca. 20 % Rhd + and 80 % Rhº species for LTR catalyst and only a slight increase of Rhd + for HTR catalyst. TEM studies revelead that Rh has metal particle size close 3 nm with small increases in the catalyst reduced at high temperature. DRIFTS essayed carried out under reaction conditions allowed to identify crotonaldehyde species strongly adsorbed through the C=C bond and weakly coordinated through both the C=C and C=O bonds. After reduction at 723 K an increase in the peak at 1660 cm-1 ascribed to an interaction between the carbonyl group and the surface, was observed. This peak seems to be stabilized at interfacial Rh/TiOx sites The deactivation in crotyl alcohol formation can be ascribed to the generation of strongly chemisorbed asymmetric carboxylate species detected by band at 1740 cm-1. This band grows at expense of crotonaldehyde O s - bonded intermediate chemisorbed on coordinatively unsaturated sites (Lewis acid sites) responsible of the crotyl alcohol obtaintion (detected by a band at 1653 cm-1). Additionally, a small band at 2068 cm-1 assigned to CO adsorbed on transition metals, which increases with time on-stream may explain the deactivation of the catalysts in flow systems.
Keywords : Rh/TiO2 , crotonaldehyde hydrogenation , DRIFTS
Se estudiaron las propiedades superficiales y catalíticas en la hidrogenación de crotonaldehído en fase vapor de catalizadores Rh/TiO2. Se encontró que una parcial reducción del soporte, inducida por una reducción a alta temperatura produce una decoración superficial del componente metálico. Los sitios interfaciales creados son los responsables de un incremento en la selectividad hacia el alcohol crotílico a través de un aumento en la polarización del enlace C=O. La espectroscopía fotoelectrónica de rayos X, XPS, reveló que el rodio se encontraba en diferentes estados de oxidación, con una contribución cercana a 20% de especies Rhd + y 80 % de especies Rhº para catalizadores reducido a a baja temperatura, LTR, y sólo un ligero aumento adicional de la proporción de Rhd + para catalizadores reducidos a alta temperatura, HTR. Estudios por microscopía electrónica de transmisión,TEM, mostraron que los cristalitos de Rh tenían un tamaño cercano a 3 nm , detectandosé sólo un ligero incremento en el tamaño de cristal en el catalizador HTR. Los estudios mediante DRIFTS se efectuaron en condiciones de reacción y permitieron identificar especies crotonaldehído fuertemente adsorbidas a través del enlace C=C y débilmente coordinada a través de ambos enlaces C=C y C=O. El catalizador reducido a alta temperatura, 723 K, muestró un incremento en la banda a 1660 cm-1 atribuído a interacción entre el grupo carbonílico y la superficie. Esta banda parece ser estabilizada en los sitios interfaciales Rh/TiOx .La desactivación observada en la hidrogenación del alcohol crotílico puede atribuírse a la generación de especies carboxilato asimétricas fuertemente quimisorbidas, que aparece como una banda a 1740 cm-1. Esta banda crece a expensas del intermediario de crotonaldehído con enlace O s - quimisorbido coordinativamente sobre sitios insaturados (sitios ácidos Lewis) responsables de la formación del alcohol crotílico (detectado por una banda a 1653 cm-1). Adicionalmente, se observa una pequeña banda a 2068 cm-1, la cual es asignada a CO adsorbido sobre metales de transición, la cual crece con el tiempo de reacción, puede explicar la desactivación observada en los catalizadores que operan en reactores de flujo contínuo.
Palabras claves : Rh/TiO2 , crotonaldehído, hidrogenación , DRIFTS.
There is an increased interest in the use of heterogeneous catalysts for the synthesis of fine chemicals. Hydrogenation reactions of a , b unsaturated aldehydes to produce unsaturated alcohol are of great importance in the field of fine chemistry. One kind of reactions lead to two primary reaction products, the saturated aldehyde and the unsaturated alcohol (see Fig. 1). For small molecules, like acrolein and crotonaldehyde the hydrogenation of C=C bond is favored both by kinetics and thermodynamics considerations 1-3, while for larger a ,b -unsaturated aldehydes, steric restrictions imposed by the substituents on the C=C double bond might influence the products selectivity. Therefore, it is desirable to find catalysts, which may control the intramolecular selectivity by preferentially hydrogenation of the C=O group while keeping the olefinic double bond intact (Fig. 1, reaction 1 vs 2). Additionally, in order to prevent consecutive hydrogenation towards the saturated alcohol (reaction 3 and 4) and the isomerization of the allylic alcohol (reaction 5), the catalyst has to suppress these reaction pathways. Different metals and supports have been used to study the selective hydrogenation of these kind of unsaturated compounds.
|Fig. 1. Reaction network of the hydrogenation of crotonaldehyde.
Catalysts used in this type reaction contain a group VIII hydrogenation component( Pt, Rh, Co, Ru, Ir etc.) showing great differences in activity and selectivity. Catalysts modified by the addition of a second metal have been prepared by different ways: alloying 1,2, by adding promoters 3,4, by using strong interactive support 5-8, by inducing electronic effects and by providing appropriate morphologies to the active sites9-10. Eventhough the number of investigations carried out in this field, there is not an agreement in which effect may have a more significant impact on the selectivity towards the unsaturated alcohol, because usually two or more effects are acting simultaneously.
Particularly important seems to be the catalytic behavior exhibited by catalysts supported on reducible oxides, responsible of the strong metal support interaction (SMSI) effect. Vannice et.al 11 have reported significant differences in both activity and selectivity to crotyl alcohol during hydrogenation of crotonaldehyde on Pt supported catalysts. In fact, catalysts in which little or not metal-support interactions should exist, specific activities show similar values. Conversely, Pt/TiO2 catalysts reduced at high temperature, HTR, which exhibit the SMSI effect, show much higher selectivities to the crotyl alcohol. Due to the characteristics of this state, a decrease in H2 chemisorption capacity produced by physical blockage of the metal surface caused by the migration of TiOx species during the HTR step 12-14. Besides the differences in activity even more critical is the change in selectivity. Thus, the selectivity to crotyl alcohol increases from zero over Pt/SiO2 and Pt/h -Al2O3 to 37 % over Pt/TiO2. In all of these samples, the metal was highly dispersed. If the reaction is performed on poorly disperse catalysts, the selectivity to the unsaturated alcohol may reach higher values 8,15.
The aim of the present work, is to study the hydrogenation of crotonaldehyde over Rh/TiO2 catalysts, after high and low temperature reduction (LTR and HTR) in order to change the surface decoration. The catalysts have been characterized by nitrogen adsorption at 77 K, H2 chemisorption measurements, TEM studies for particle size evaluation, XPS experiments to estimate surface composition and in situ DRIFTS studies during of adsorbed crotonaldehyde hydrogenation to add further information dealing with possible reaction intermediates were also performed. Additionally, catalytic hydrogenation of crotonaldehyde was also carried out by pulse method at 373 K.
Rh/TiO2 catalysts were prepared by impregnation of TiO2 (P25 -DEGUSSA, SBET =72 m2/g) at 398 K with the appropriate amount of aqueous solution of RhCl3 to get 0.5 wt % of the metal. Then, the samples were dried at 383 K for 24 h and calcined at 673 K for 4 h. Prior to their characterization or catalytic use the solids were reduced in situ in flowing H2 at 473 K (LTR) or 723 K (HTR) for 2 h. These samples were labelled as Rh/TiO2 LTR or HTR respectively. To evaluate specific surface area, pore volume and average pore diameter, nitrogen adsorption isotherms at 77 K in the relative pressure range 0.05 to 0.0995 were carried out in a Micromeritics Gemini 2370 apparatus. Hydrogen chemisorption at 298 K was carried out in a volumetric system to evaluate the H2 uptake and H/Rh ratio. Prior the chemisorption experiments, the samples were reduced in situ at 723 K (HTR) or 473 K (LTR) for 2 h and then outgassed for 4 h at 773 K.
Transmission electron microscopy (TEM) was used for the observation of supported rhodium particles these experiment were performed in JEOL JEM-1200 EX II System. the samples were prepared by the extractive replica procedure. Powder X-ray diffraction (XRD patterns ) were performed in a Rigaku diffractometer using a Nickel filtered CuKa radiation.
Diffuse-reflectance infrared spectra, DRIFTS, (256 scans) were collected on a Nicolet-510 FTIR spectrophotometer working at a resolution of 4 cm-1 using a Harrick HVC-DRP environmentally-controlled cell. About 50 mg of the powdered sample was packed in a sample holder and different gases were passed through the sample . First of all sample was reduced in 50 mL min-1 of pure H2 at 723 K (HTR) or 473 K (LTR) for 2 h (heating rate 5 K/min). Then, it was cooled down in H2 a 373 K. Subsequently, He flow was switched to 50 mL.min-1and DRIFT spectrum of sample was recorded as background. All the following recorded spectra were referred to this background. Then, flow is switched to the reaction mixture and DRIFT spectrum of sample under reaction conditions and after different time on-stream was recorded. Reaction mixture was obtained by bubbling H2 through a saturator containing crotonaldehyde and maintained in an ice bath 273 K. A number of spectra were recorded after different time under reaction conditions. After some time on-stream, reaction mixture was switched again and He flowed through the sample. Several spectra at different time and temperature under He flow were then collected.
Photoelectron spectra (XPS) were recorded using an Escalab 200R spectrometer provided with a hemispherical analyzer, operated in a constant pass energy mode and unmonochromatized Mg Ka , X- ray radiation (hn =1253.6 eV), working at 120 watts. The surface Rh/Ti were estimated from the integrated intensities of Rh 3 d 5/2 and Ti 2 p 3/2 lines after background subtraction and corrected by the atomic sensitivity factors 16 . The C1s line at 284.9 e V was used as an internal standard . Rhodium were decomposed into several components assuming that the peaks had Gaussian -Lorentzian shapes.
Catalytic experiments were carried out in a pulse reactor with an on line GC. This procedure was chosen because steady-state measurements could not be reached due to the strong catalyst deactivation. This deactivation process has been observed in other catalysts as it has been well documented17. In each experiments, 50 mg of catalyst was reduced in situ in flowing of hydrogen (20 mL.min-1) in a programmed mode at 10 K.min-1 up to 723 K (HTR) or 573 K (LTR) for 2 h. Then, the sample was cooled down till the reaction temperature. The catalytic activity was measured by injecting 1.0 m L of the organic reactant . Blank experiment showed no catalytic activity due to the support in these conditions.
Table I summarizes the H/Rh atomic ratio and metal particle size obtained from TEM. The H/Rh values are higher for the catalysts reduced at lower temperatures (LTR), which indicates a higher metal exposure and it is not related to changes in metal dispersion. The particle size values of the LTR catalysts are close to those reported previously for Rh/TiO2 catalysts prepared under comparable conditions 18. However , TEM analysis revealed only a slight increase in the catalysts reduced at higher temperature. This apparent discrepancy is explained on the basis of the significant decrease in the hydrogen uptake observed in the catalysts reduced at higher temperature (HTR). This fact, first identified by Tauster at al 19 is a distinctive feature of the so called SMSI catalysts. Nowadays, it is well established that the chemisorption suppression after high temperature reduction, is a common feature of all group VIII metals supported catalysts on partial reducible support such as TiO2. The extent of suppression is usually taken as an indication of the extent of metal-support interaction and described as decoration of metal particles by TiOx species generated upon reduction process. Obviously, it is expected that this process will occur in a higher extension as temperature increases. The presence of chlorine ions may also produce a slight suppression in the hydrogen uptake. Similar behavior reported previously by Van der Boogert et al 20and Orita et al21, responsible of decrease in CO hydrogenation activity on Rh/TiO2 and it has been ascribed in terms of a chloride-assisted TiOx migration.
X-ray diffractogram of Degussa P25 TiO2 used as support, shows the expected lines attributed to rutile and anatase, having approximately 85 % of anatase and 15 % of rutile . This latter is the most stable and the complete transformation anatase to rutile takes place at about 1300 K. However, in the presence of foreign atoms which can catalize this transformation, it may occur at lower temperatures 18,22. Both rhodium HTR and LTR catalysts shown no changes in crystallinity in agreement with previous findings which have shown that for Rh/TiO2 a 2 wt % Rh is the minimum required to enhance the anatase to rutile transformation 22.
Table I.H/Rh ratio obtained from chemisorption data, particle size evaluated by chemisorption and TEM, binding energies (eV) of Rh 3 d 5/2 core level, Rh/Ti atomic ratios evaluated from XPS for 0.5wt % Rh/TiO2 catalysts.
Rh 3d5/2B.E(eV)
307.1 (78)
307.3 (80)
The chemical state of rhodium for both catalysts has been studied by XPS. Fig. 2 displays Rh 3d core level for Rh/TiO2 catalysts. Table I also gives the Rh/Ti surface ratio obtained from XPS. The B.E of the Rh 3d5/2 peak are ca. 307.2 and 308.7 by Rhº and Rh d +, respectively. For the reduced samples the XP spectra of Rh 3d core levels showed the 3d doublet having a broadening indicative of Rh in different oxidation states. After curves deconvolution, a contribution of approximately 80 and 20 % of Rhº and Rhd + species respectively were found. Only a slight increase in the extent of Rhd + species were found in those catalysts reduced at higher temperatures (HTR). At low temperatures, the small metal particles are in intimate contact with the TiO2 being possible to produce electronic transfer between the support and the metal, generating Md + species. These species seems to be responsible in the increase in selectivity to crotyl alcohol discussed below, due to an enhancement in the polarization of the carbonyl group.
|Fig. 2. XP spectra by reduced Rh/TiO2 catalysts , Rh 3d core level .
Hydrogenation crotonaldehyde was carried out in a pulse reactor at 373 K. This procedure is extremely useful in reaction in which deactivation takes place, avoiding interference due to the deactivation process. The obtained products were mainly crotyl alcohol (CROL), butyraldehyde (BUHO), butylalcohol (BUOH), CO and products of hydrogenolysis and polymerization. Table II summarizes the activity and selectivity of the Rh/TiO2 catalysts. It can be seen that the activity, expressed as m mole converted per second per gram of catalyst, in LTR catalyst was approximately half of that observed for the HTR counterpart. Selectivity to different products expressed, as % does not change significantely. Converserly, activity per site, TOF, displays values 10 times higher for the catalyst reduced at high temperature (values between brackets in table II). This behavior may be understood considering that, in spite of a low extent of metal surface is expossed to the reactant molecules, Rh/TiOx interfacial sites having improved characteristic are involved. As Vannice has pointed out23, the creation of the new active sites in the interfacial region may explain not only the change in activity, but also the change in selectivity. In fact, these sites, which implies partially reduced TiOx species (or oxygen vacancies) decorating Rh crystallites, can coordinate the oxygen atom in the C=O group to account a more selective activation of these organic molecule8,23. Further support to this theory is supplied by the DRIFT experiments showed below. Only small changes in selectivity (mole %) were observed. However, considering that the activity, expressed as m mole of crotonaldehyde converted per second per gram of catalysts, exhibit by HTR catalyst is almost twice to that of LTR state, the yield to CROL is larger in the former state. This indicates that a higher proportion of sites for selective hydrogenation of C=O bond are present at HTR state. Eventhough the selectivity towards crotyl alcohol is low -close to 10 %- it is considerable better than Rh metal catalysts supported on non-SMSI catalysts for which the selectivity to the unsaturated alcohol is almost zero. In all rhodium catalysts, the saturated aldehyde is the main product (selectivity higher than 50 %) indicating that the reaction path 2 in fig.1 is more favorable.
Table II. Catalytic activity (m mole/s gcat) and TOF (S-1) at 373 K and selectivity (mole%) in brackets as (m mole/s gcat) to products in crotonaldehyde hydrogenation.
Selectivity,mole% (umole/s gcat)
|54 (1.67)
|34 (1.05)
Figure 3, shows the DRIFT spectra obtained under reaction and after switching to He flow by Rh/TiO2-HTR. Figure 4, displays the result of subtracting the DRIFT spectrum of the sample after 5 min under reaction mixture to the spectra of sample after more than 5 min on-stream. This figure is very helpful in order to see new intermittent bands under reaction mixture. At the C-H stretching vibration region, bands at 2959, 2930, 2876, 2718, 1695, 1653, 1541, 1458 and 1400 cm-1 were clearly visible. The 2718 cm-1 bands is assigned to n (C-H) of aldehydic group, which suggests that adsorbate containing aldehyde functional group is present at the surface of the catalysts. They can not be assigned neither to reaction intermediate at the catalysts surface nor to reaction product at the gas phase since bands intensity remains when reaction mixture is swichted to He flow. They must arise from side-products or spectators of the reaction which are strongly chemisorbed at the catalyst surface (their intensity is not much altered after flowing He at 473 K). Actually, their concentration at the catalyst surface increase with time on-stream. This means that the surface is progressively covered by such compounds. The 2805 cm-1 bands can also be assigned to C-H aldehydic groups 24.
|Fig. 3. DRIFT spectra of Rh/TiO2 HT during crotonaldehyde hydrogenation at 373 K after 5 min on stream. b) 15 min. c) 30 min. d) 60 min. e) 90min. f) after 15 min under helium flow at 373 K. g ) 30 min under helium flow at 373 K. h) after 15 min under helium flow at 473 k.
|Fig. 4. DRIFT spectra of Rh/TiO2 HT during crotonaldehyde hydrogenation at 373 K after subtraction of 5 min on stream spectrum to a) 15 min, b) 30 min, 60min, d) 90min.
CO displacement by adsorption of products on the Rh particles was also evidenced by feature at 1977 cm-1 band. Among the more remarkable complexes detected by the DRIFT spectra are: O s bonded aldehyde to cationic sites (1653 cm-1), carbonyl group interacting with OH forming asymmetric and symmetric carboxylates (1541 and 1458 cm-1). The strong band at 1653 cm-1 is believed to arise from crotonaldehyde O s -bonded to coordinatively unsaturated metal cations in metal oxide surfaces. The s complex is formed between the unshared electron pair on the antibonding n(s ) orbital localized on the oxygen atom of the carbonyl group and the metal cation25 . This adsorption mode has also been described a donating -on-top h 1 adsorbed species26, 27 . Such interaction results in a 50-70 cm-1 red shift of n (C=O) frequency with respect to gas phase crotonaldehyde. This band has been observed in crotonaldehyde interacting with Ni/TiO2 and Pt/TiO2 reduced at high temperature 11. TiOx moities covering the metal particles and originated while reduction at high temperature supplies the cationic metal sites for the s bond. The same phenomenon was also observed for the other a ,b unsaturated aldehydes contacting Co/SiO2 28. Cationic cobalt species, remaining due to an incomplete reduction of Co oxide supplies the Lewis acid sites for the C=O donating-on -top h 1 crotonaldehyde adsorption. Figure 4, shows that as the catalysts is under reaction conditions, the 1653 cm-1 band is weakened as a band at 1740 cm-1, no clearly visible in figure 3 develops. This effect, explained by the formation of asymmetric carboxylate at expenses of the active intermediate (O -s bonded aldehyde). Several authors have reported similar results: The O -s bonded of carbonyl group is transformed to an asymmetric surface carboxylate complex when heated or increasing the aldehyde-metal oxide surface contact time25, 29. Therefore, it can be proposed that the drops in the yield to crotyl alcohol must be related with the transformation of the active intermediate into inactive and strongly chemisorbed surface asymmetric carboxylate spectator, while catalysts is under reaction conditions. When reaction mixture flow swichted to He flow, after 5min of inert gas flush, the band at 1653 cm-1 has almost disappeared which demonstrates that this adsorbate is only present when crotonaldehyde is flowing. This fact gives additional support to the assumption that the s complex is an intermediate of crotyl alcohol formation.
The band at 1720 cm-1 is in the region of carbonyl frequency, which indicates that it arises from a carbonyl group containing compound. It is strongly adsorbed at the surface because it also remains adsorbed after He flow at 474 K. A band 1725 cm-1 was detected by Trifiro at al 30 after adsorbing acrolein on silica at high temperatures and they suggest that it arises from acrolein oligomerization leading to polymeric acrolein. It is reasonable that the carbonyl group are weakly affected by the surface and the vibration frequency is close to 1720 cm-1, frequency at which C=O group of gas phase acrolein vibrates. Falconer et al.31 showed that acetaldehyde undergoes aldol condensation on TiO2 producing crotonaldehyde which again oligomerizes leading to heavier products containing carbonyl group with conjugated C=C bonds only removable by H2 reduction or oxidation and higher temperatures. Crotonaldehyde can undergoes similar aldol condensation and oligomerization processes on the Rh/TiO2 surface catalysts, leaving heavy residues containing C=O and C=C functional groups on the catalysts surface, which must be taken into account also as a source of deactivation.
The 1545 and 1454 cm-1 bands can be ascribed to carboxylate (crotonoates or butanoates) complexes (n asym. and n sym. of CO2- carboxylate group)25,29,32. They are definitively different in nature to the species described above as asymmetric carboxylate complexes even if they are related with the metal oxide support: The former are bonded to metal cations to lattice oxygen. However, it must be taken into account that symmetric carboxylates have been shown to arise from the conversion of asymmetric carboxylates complexes25,29. It has been suggested that symmetric complexes are related with the lack of crotyl alcohol formation while on-stream 28, but since the observed weakening of the 1653 cm-1 band is not related with any change in the n as and n s of CO2- carboxylate group frequencies such involvement can be discarded. Other features suggest a non involvement of the symmetric carboxylate complexes in the reaction, such as: i) their intensities do not change significantly with time on stream and ii) these species are strongly chemisorbed to surface and they remain on He flow and even after heating under He at 473 K, the intensities are maintained.
Spectra features in figure 5. DRIFT spectrum by Rh/TiO2-LTR after 5 min on-stream (bands at 2950 , 2932, 2882, 2802, 2706, 1722, 1656, 1535, 1464, 1381 and 1255 cm-1 ) can also be discussed according to the assignation already presented for previous spectra. It is noteworthy that 1535 and 1464 cm-1, ascribable to symmetric carboxylate complexes are rather weak as compared with the intensity in HTR Rh catalyst. The 1656 cm-1 band (O s bonded to cationic sites ) is quite weak after 5 min on-stream. Considering that it has been proposed to be the intermediate of the crotyl alcohol formation, its low intensity explains the lower yield to crotyl alcohol of these catalysts. The removal of CO adsorbed on Rh particles by new crotonaldehdye derived adsorbates explains the negative peaks at 2056 cm-1 and positive peak at 2006 cm-1. A new peak at ca. 1800 cm-1 never seen in previous experiments, are due to bridged CO chemisorbed on Rh particles 33. It is unlikely that it comes from displacement of initially adsorbed CO. It is reasonable to assign this band to the decarbonylation of crotonaldehydewhich supplies additional CO that ends up chemisorbed on Rh-TiOx patches. The more remarkable changes in the spectra when catalyst is maintained under reaction stream is that the intensity of the bands at 1722 and 1656 cm-1 decrease significantly. After switching to He flow the band at 1690 cm-1 dominate in n (C=O) frequency region, whereas the 1722 cm-1 band significantly faded and 1653 cm-1 peak vanished.
|Fig. 5. DRIFT spectra of Rh/TiO2 LT during crotonaldehyde hydrogenation at 373 K after 5min on stream , b) 15 min, c) 30 min , d) 60 min , e) 90 min , f) after 15 min under helium flow at 373 K, g) 30 min under helium flow at K , h) after 15 min under helium flow at 473 K.
A kinetic and DRIFTS study of crotonaldehyde hydrogenation was carried out over Rh/TiO2 catalysts. The influence of the reduction temperature on the surface and catalytic properties was also analyzed. It was found that partial reduction of the support produce a surface decoration of the metal component, generating interfacial sites responsible of an increase in the selectivity to crotyl alcohol, allowing an enhancement in the polarization of the C=O bond as a result of surface decoration of the metal component. The presence of chlorine ions in the metal-support interfacial region also allows, in a certain extension, a polarization of the carbonyl bond. DRIFT studies carried out under reaction condition allowed to identify an adsorbed species responsible to the obtaintion of crotyl alcohol. This characteristic band appears at 1653 cm-1 and it is ascribed to an interaction between the carbonyl group and the surface, which is likely to be, stabilized at interfacial Rh/TiO2 sites. Additionally, a small band at 2068 cm-1 assigned to a CO adsorbed on transition metals, which increase with time on stream may also explain the deactivation of the catalysts in flow systems.
The authors thank CONICYT (Chile FONDECYT Grants 2990065 and 1980345 and CSIC-CONICYT Collaboration Programme) for their financial support.
1.- G.C.Raab, J.A.Lercher, J.Mol. Catal. 75,71(1992). [ Links ]
2.- J.M. Bonnier, J.O. Damori and J.Masson, Appl. Catal. 42, 285(1988). [ Links ]
3.- T.B.L.Marinelli, S.Nabuurs ,V.Ponec , J.Catal. 151,431 (1995). [ Links ]
4.- A. Sepúlveda-Escribano, F.Coloma,F. Rodriguez-Reinoso, J. Catal. 178, 649 (1998). [ Links ]
5.- S. Galvagno, C. Milone, G. Neri, A. Donato, R. Pietropaolo, Stud. Surf. Sci. Catal. 78, 163(1993). [ Links ]
6.- H.Yoshitake, Y. Iwasawa , J.Catal. 125, 227(1990). [ Links ]
7.- B.Coq, P.S. Kumbhar, C. Moreau, P. Moreau, F. Figueras, J. Phys. Chem. 98, 1080 (1994). [ Links ]
8.- A.Vannice, B. Sen , J. Catal. 115, 65 (1989). [ Links ]
9.- M.English, A. Jentys, J. A. Lercher, J. Catal. 166, 25 (1997). [ Links ]
10.- S. Galvagno, C. Milone, A. Donato, G. Neri, R. Pietropaolo, Catal. Lett. 18, 211 (1993). [ Links ]
11.- A.Dandekar, M. A. Vannice, J. Catal. 183, 344 (1999). [ Links ]
12.- M. A. Vannice, Catal. Today 12, 255 (1992). [ Links ]
13.- G. L. Haller, D. E. Resasco, Adv. Catal. 36, 173 (1989). [ Links ]
14.- G. Munuera, A. R. González-Elipe, J. P. Espinós, J. C. Conesa, J. J. Sanz, Phys.Chem.91, 6625(1987). [ Links ]
15.- M. A. Vannice, Topics in Catalysis 4, 241(1997). [ Links ]
16.- C. D. Wagner, L. E. Davis, M. V. Zeller, J. A. Taylor, R. H. Raymond and L. H. Gale, Surf. Interf. Anal. 3, 211(1981). [ Links ]
17.- G. C. Raab, J. A. Lercher, Catal. Lett. 18, 99(1993). [ Links ]
19.- S. J. Tauster, S. C. Fung, R. L. Garten, J. Am. Chem.Soc. 100, 170 (1978). [ Links ]
20.- W. J. Van der Boogert, G. Van der Lee, H. Luo,V. Ponec, Appl. Catal, 29, 243 (1987). [ Links ]
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21.- T. Huizinga, J. C. Vis, H. F. Van´t Blik, R. Prins, Trav.Chim. Pay-Bas. 102,496 (1983). [ Links ]
22.- D. E. Resasco, Ph.D. Thesis,Yale Univ. New Haven , Connecticut, USA, 1983. [ Links ]
23.- M.A.Vannice, J. Mol. Catal. 59, 165 (1990). [ Links ]
24.- N. Sheppard, C. De la Cruz, Advan. Catal. 41, 1 (1996). [ Links ]
25.- G. Ya Popova, A. A. Davydov, T. V Andruschkevich and I. I Zakharov, Kinet. Catal. 36, 125 (1995). [ Links ]
26.- V. Ponec, Appl. Catal. A:General 149, 27 ( 1997). [ Links ]
27.- S. Nishiyama, T. Hara , S. Tsuruya, M. Masai, J. Phys. Chem. 103, 4431(1999). [ Links ]
28.- J. E. Bailie, C. H. Rochester and G. J. Hutchings, J. Chem. Soc. Faraday Trans. 93,4389 (1997). [ Links ]
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*Corresponding author FAX. 56-41-245974 . E mail : firstname.lastname@example.com


text:
A couple of weeks ago I took my very first photos ever of a baby. Good photos...well, I think they are good photos anyways. ;) Braylon's dad works with my husband Josh, and they gave me the chance to photograph him! I was very excited for the opportunity. I took tons of photos, and these ones happen to be my favorites. How cute is it when he holds his fists under his chin like he is in deep thought...so darling! Loved capturing that in photographs!
I took a ton more, but those ones are my very favorites. Feel free to let me know what you think of the shots!
I will have some crafty stuff to share later in the week! Hope you enjoyed my photography post tonight!
Until later,
16 comments
Great photos, Lea. He is an adorable cutie.ReplyDelete
Wow Lea, these are absolutely gorgeous! What sweet, sweet pictures that perfectly capture all the love and tenderness of the moment! If these are anything to go by you are going to breeze through photography school and be in great demand!ReplyDelete
Hugs Mrs Jx
FABulous Photography Lea...you really captured some sweet moments!ReplyDelete
Lovely, precious photos Lea! You're going to be such an amazing professional photographer! I'm glad you had fun shooting the wedding! ♥♥ KayReplyDelete
These are totally fantastic. This baby is heartwrenchingly cute. :)ReplyDelete
Awesome photograhs! You go girl!ReplyDelete
GORGEOUS photo's Lea!! What a little doll baby!! :DReplyDelete
Your photographs are so beautiful Lea! I wish I had some like these of my little guys! What a talent you are!ReplyDelete
(-: Heidi
Beautiful photos!ReplyDelete
These are great Lea! Fabulous work!ReplyDelete
- AnonymousApril 21, 2009 at 7:00 PM
Hi Lea .......Gorgeous baby...aw ....ReplyDelete
You can tell you enjoy your photography with a passion it shows in these such beautful photo`s Lea...
Absolute fab...
Glad you enjoyed the Wedding..
Enjoy the rest of your week:)♥
well, they are great lea!! that first one is AWESOME!! and the second one - how hilarious!!ReplyDelete
What sweet photos!!! You did an awesome job my friend!!!! What a sweetie!!! I sspecially love the daddy kissing Braylon and the focus being on Braylon holding dad's thumb!!! So sweet!!! Wish I would have know about scrapping when my kids were young!! I would have soooo many more photos!!! Hope you have a great day my friend!!ReplyDelete
Absolutely gorgeous Lea!!! Both the baby and the photos!! What a talent!ReplyDelete
So beautiful. Soft and precious. What a beautiful family.ReplyDelete
Lea, these pics are just so beautiful. Nothing as beautiful as the innocence of a child. Hugs from DesireReplyDelete


text:
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Good evening all, I am a new member to this forum, it seems like a great place for beginners like me!
I am at the very beginning of my Java education and I am having a little trouble with an exercise involving Static Methods.
This exercise is designed to introduce me to invoking static methods inside a class without instantiating an object. Basically; I am just trying to print out the value of a returned calculation, but I am getting a compile error. I'll paste me code below. Thanks in advance for any guidance
public class MyMath {
public static long square(int a){
long b = (long) (a*a);
return b;
public class Squares {
public static void main(String[] args) {


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text:
Who gets to hire workers for city construction projects?
In San Diego, voters will now have a say.
A petition drive sponsored by non-union contractors has gathered enough signatures to qualify it for next year's primary election ballot.
U.S. & World
News from around the country and around the globe
The measure, following in the political footsteps of others throughout California and the country, would ban so-called "project labor agreements," known as PLAs, that favor contractors who do their hiring through union halls.
It's not often that the city of San Diego goes the PLA route to build facilities.
Next June, however, voters could mandate that it never does again.
But such a move could come at a high price exacted by the Legislature.
Within a couple blocks of each other in downtown San Diego's East Village are two major projects fitting each profile.
A $185 million central library venture, due for completion in 2013, is not covered by a PLA.
By contrast, PETCO Park, home of the San Diego Padres since it opened in 2004, was completed under a project labor agreement. That happened at a time when collective bargaining rates actually were lower than some of the prevailing wage rates that both union and non-union contractors otherwise have to pay.
Passage of a PLA ban would raise questions about the hiring of 4,000 workers needed for the proposed expansion of the Convention Center.
"If you don't hire from a labor pool, then you've got to hire everybody individually," said Jai Ghorpade, emeritus professor of management and labor issues at San Diego State University.
"Where are they going to go -- to Home Depot?" Ghorpade said. "Are they going to go to a private employment agency?"
Project managers who have handled both approaches point out that even on most major construction endeavors that aren't under PLAs, the majority of the workforce tends to be union labor.
"Unions, in general, have done a much better job of apprenticeship training," said Charles Black, manager of San Diego's proposed $550 million Convention Center expansion project.
"Some of the non-union contractors have, but most have not," Black said. "And so when you have 'contract qualifications' that are imposed on a contract, many non-union contractors can't qualify."
Also, Black points out, big national and regional contractors that land major public works projects tend to be unionized.
Unions seem to hold a certain sway over decisions by the California Coastal Commission -- whose approval would be needed to green-light the Convention Center expansion.
So the anti-PLA measure shapes up as high-stakes politics, indeed.
"It's not a rational issue," Ghorpade said. "It's an ideological issue."
Black sees it in terms more political than economic.
"I think the worst thing that could happen in this ongoing dialogue is for either side to pursue a 'scorched-earth' policy," he said. "That is to say, either side would rather kill a project if they don't get everything they want out of that project."
That's happened often enough in California and elsewhere that anti-PLA measures are popping up and passing in a lot of places.
But there's legislation on Gov. Brown's desk, Senate Bill 922, that would withhold state funding for public works projects by agencies that ban PLAs -- including redevelopment and Mello-Roos special tax proceeds.
Let us know what you think. Comment below, send us your thoughts via Twitter @PropZero or add your comment to our Facebook page.


text: In fact, camera-guided missile needs a wire too (fiber optics), to transfer control and video image from the camera. An old/common approach solution of wire-guide missile is a control by the launcher movements (2 axis). The missile steer towards to the crosshair.What'd be the control/implementation for wire-guided though? That's a bit more broad category, so I'm not sure the exact setup you had in mind. Being able to lock onto a target and have the missile steer towards it?


text:
House Air Waybill(redirected from AWB)
Also found in: Acronyms, Wikipedia.
House Air Waybill (AWB)
An air waybill issued by an air freight consolidator.
House Air Waybill
A receipt issued by an air freight consolidator. A house air waybill indicates to the customer that his/her goods have been received by the company and have been passed on for freight by air. They often include tracking numbers so that the customer can check the status of the shipment.


text:
I understand there are more simplified ways of doing what I am making now, but for the time being I am just using my current knowledge of Java to expand on what I already know. So right now I am making a script to convert between binary and text and vice versa. One issue I am having is that the decimal answer is coming out all wrong when I test the binary to text (decimal for now) part. I keep getting this 4-5 digit answer whenever I enter a 8-bit binary number. I've rechecked my code and broke it down to parts, printed each value through the loop but for some reason I get these bizarre numbers. Here's what I have, but keep in mind that THIS IS INCOMPLETE:
import java.lang.*; import java.io.*; import java.util.Scanner; public class BinaryOrText { public static void main(String[] args) throws IOException { int method; int iter = 0; int binary; int power = 0; int decimal; char binaryDigit = 0; String strBinary; String text = ""; Scanner in = new Scanner(System.in); System.out.print("Pick a Conversion Method; Enter [1] to Binary | [2] to Text: "); method = in.nextInt(); //text to binary if (method == 1){ System.out.print("Enter text: "); text = in.next(); char charT = text.charAt(0); System.out.println((int)charT); // ...Incomplete } //binary to text else if (method == 2){ decimal = 0; //declare System.out.print("Enter Binary: "); //prompt binary = in.nextInt(); //assign original input strBinary = Integer.toString(binary); //make a string version power = strBinary.length() - 1; //sets the starting power by length of binary code for (int i = 0; i < strBinary.length(); i++){ binaryDigit = strBinary.charAt(iter); //Takes binary digit from char position. decimal += binaryDigit*Math.pow(2,power); // digit * 2^pow. System.out.println(decimal); iter++; //Goes to next binary digit. power--; //Goes to power on next digit } } } }


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This is a tale of two surveys…one innovation focused, the other supply chain focused. What both have in common is how the reports focused on define the traits and qualities of those who lead and those who follow in their respective business spaces. Those who innovate tend to lead while those who follow…well, often play catch up. That's not too efficient and can lead to wasteful use of resources. Trust me-as I learned last fall (see photo), it's better to be the lead horse rider in a dusty trail ride.
The Leaders vs. Laggards Survey
In 2010, as part of its Innovation Survey Series, Cap Gemini Consulting performed a "Leader versus Laggard" study. The goal of the study was understand the "current state of affairs regarding innovation, and … to identify what drives the success of companies that view themselves as successful". Over 375 companies responded to the survey. Those reporting 'over 75%' of innovation efforts having a positive material impact on the company's business results were considered "leaders" (slightly more than 11%). The 'less than 25%' category represents the innovation "laggard" group (nearly 25% of the respondents). The remaining 65% percent were somewhere in the middle, innovation-wise. The primary drivers of innovation were: evolving customer needs, technological advances and changes, executive direction/internal demands, macroeconomic/external factors, globalization, and changing supplier capabilities. Innovation efforts were generally wrapped into the following five categories: customer focused innovation, new product development, incremental product improvement, business process innovation, and, business model innovation.
Innovation was considered a top-three strategic priority by more than 76 percent of the respondents to the Capgemini survey. Further, over half of the respondents indicated they have developed relationships with third parties to support their innovation efforts on an ongoing basis. The key study takeaways were:
- Innovation leaders have advanced beyond other innovators by having an accountable innovation executive or other form of formal innovation governance structure that deals with this kind of decision-making.
- Laggard companies hadn't mastered collaborating effectively with external partners to improve their innovation results. Leaders however had been able to successfully leverage suppliers, customers and other third parties in the innovation process, including filling in missing capabilities or resources – such as technology and talent.
- Business model innovation will be the next big differentiator for companies aspiring to innovation leadership. Innovation leaders are allocating increasingly more resources to business model innovation.
Why is this study valuable in terms of supply chain sustainability? Read on.
The Sustainable Supply Chain Survey
A revealing and promising study was released by the Aberdeen Research Group a couple of months ago. The Sustainable Supply Chain surveyed 360 companies and found that sustainable supply chain management and supply chain risk management are among the top three areas for improvement in their organization for one third of the respondents. While that isn't a stellar number there are some positive trends. For instance, the survey showed that 76% of the overall survey respondents have incorporated sustainability criteria into some or all of their supply chain management processes. The results provide further proof that in 2010 more companies viewed sustainable supply chain and greening as a foundational aspect of their business operations.
This survey fared compared well with another survey conducted by eyefortransport (EFT) that I reported on in a prior post). In the EFT survey, well over 60 percent of those companies surveyed had implemented or were initiating sustainability focused efforts in 2010- ranking around 10th out of nearly 40 supply chain management project categories. In the logistics survey, most respondents noted a far higher level of positive environmental performance in 2010 compared with 2009.
The Aberdeen survey found that two primary drivers for sustainability revolved around achieving "competitive advantage" and assurance that companies were compliant "with current and future regulations". Additional drivers noted by about a third of the respondents included interest in positive impacts to bottom line financials and responding to consumer demands for 'eco friendly' products. These drivers, according to the reports highlighted perspectives of five different stakeholders along the end-to-end supply network: customers, suppliers, regulators, competitors and shareholders.
What makes the Aberdeen survey unique was how it distinguished business pattern between "leaders" and "laggards" (like the Capgemini report). Two key take-aways were:
1) Best-in-Class companies were twice as likely to incorporate sustainability principles throughout all supply chain management (SCM) processes and
2) a principal characteristic of "laggards" was their lack of focus on incorporating sustainability into their SCM processes.
For example, the Aberdeen study identified a 29% spread between leaders who've achieved 12% emission reductions versus laggards corresponding 17% increase in emissions. Similar polar opposite movement was found in areas related to energy consumption and operating margin containment. And like the Capgemini study, best in class (leaders) companies were 70% more likely to establish corporate governance teams, making technology investment to collect and report metrics, and engaging their suppliers. Think of the potential savings that leaders have realized compared to their laggard counterparts.
Logistics Providers Leading the Way
As one example, two logistics giants, FedEx and UPS have done deep dives in their business practices and implemented industry leading solutions to bake supply chain sustainability into their operations and supplier networks. UPS has deployed "package-flow" software to map out its most efficient delivery routes. Besides limiting left-hand turns, UPS estimates it shaved nearly 30 million miles off its delivery routes, saved 3 million gallons of gas and reduced CO2 emissions by 32,000 metric tons. FedEx has deployed cleaner vehicles, sourced alternative power sources for its facilities and engaged its supply chain to promote recycling, product reuse and greener packaging to support FedEx's operations. The company reports that they've improved total fleet miles per gallon within the U.S. by 14.1 percent since 2005, saving over 53 million gallons of fuel or approximately 472,700 metric tons of carbon dioxide emissions, with a goal of improving by 20 percent by 2020. And like UPS, FedEx is (according to its web site) redesigning its "physical distribution models to maximize the density of … ground and air shipments. This reduces the amount of fuel it takes to ship each package…."
The Aberdeen study also mentioned how the UK based non-profit Supplier Ethical Data Exchange (Sedex) has developed a secure online platform for companies to share and monitor sustainability data across supply chain. Sedex's mission is "connecting businesses and their global suppliers to share ethical data and enabling continuous improvement in ethical performance". Currently used in over 160 countries, the membership driven initiative focuses on metrics capture across four "key pillars": Labor standards, health and safety, business integrity and environment. Being on Sedex does not mean that a company has met any ethical standards or is in compliance with any code but it does mean that suppliers have made a commitment to continuous improvement. Suppliers to major retailers and brand owners continue to own the data and manage its use, and keep it updated on a semiannual basis. Suppliers' customers then have the option to run a "risk profile" which can allow them in turn to prioritize suppliers for additional collaboration to manage the sustainability footprint of their products or practices.
The Work's Not Done
The Aberdeen study did uncover several challenges that companies face, especially those with wide supply chain networks. The study found that about 40% of companies outsourcing at least some of their manufacturing struggle to establish operational capabilities that yield measurable results (less than 10% efficiency). This underscores the difficulties that many manufacturers have in effectively controlling or influencing supply chain behavior. And while sustainability initiatives focused on improved energy use efficiency and practices to reduce environmental footprints are highly relevant in improving operations efficiencies, execution still remains challenging.
"The focus on sustainability has changed from being a philanthropic, 'nice to have' initiative, to the one that is core to the success of organization…Consistently adhering to the sustainability mandates established by clients as well as establishing mandates for your suppliers is an important strategy to gain incremental business value in the current environment" – Nari Viswanathan, Vice President and Principal Analyst of Supply Chain Management at Aberdeen.
Pushing the Supply Chain Envelop Requires Innovation and Leadership
Many of my prior posts have suggested that "supply chain successes are driven by those who lead through innovation and don't procrastinate. These organizations have vision– for the short term and long-term". The Aberdeen and Capgemini surveys are proof that 'first mover' companies are changing the way business gets done, sometimes in marked, 'greener' ways.
I believe that innovative companies are those who consider business operations through a "sustainability lens" by 1) developing key performance goals and metrics to make supply chain sustainability initiatives thoughtful, effective and believable; 2) implementing sustainability initiatives that create environmental and social benefit and that are aligned with the company's financial strategies and business vision; and 3) identifying and developing value-added transparency and proactive collaboration throughout the supply chain.
Who is up to pushing the supply chain envelope, be a sustainability leader and reap the benefits?


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8 Steps to write Effective MBA Essays
With so many applications to B-schools, there is no doubt that there might be many others with a profile similar to yours. Of course you might have unique experiences to show in your application, you would want to present it in way so that the admissions committee member reviewing your essay should not be bored. Considering that he's reading essays all day long, you want to capture his concentration when it comes to your application.
www.essaycom.com gives some tips which can make your essays effective and polish your application. Not to mention the fact that these are generic tips about the most commonly asked questions and seeing the application as a whole. All these points should be covered in the application. It is at your discretion to include what portion in each specify.
1. List your achievements. This is the first task in your homework. Make a list of your achievements however big or small they are. They may be prioritized later. I have felt that at times, while straightaway getting down to the essay, without proper homework, the low priority achievements get unnecessary highlight.
2. Classify your achievements. After the list of achievements is done, you can classify them in the following four broad categories:
3. Give importance to each category. Ensure that each category has something substantial to talk about you. This way your all-round abilities would come to the forefront. But if your abilities in area are not competitive enough, make sure to compensate with achievements in another area. For example, if your under-graduate score is low, you can compensate that by highlighting your GMAT score, or if you have taken any other course outside of the scheduled courses, do mention that.
4. Write the Career Progression Essay first. Almost all MBA schools expect this essay in their application. I remember for class of 2007 application, ISB had this essay. If this essay is present in the applicartion, make it a point to write this essay first. This would help you in your resume walk through and you can chalk down your professional achievements in a chronological manner, without leaving any significant event out. Who knows, you may get some ideas for other essays in the application.
5. Research the school you are applying. Find out if the courses offered are relevant to your aspirations or not. It would be better if you have the knowledge about the companies visiting the campus. It shows off in your application and improves your admit chances as it shows genuine interest in the school. Another aspect could be if there are some extra curricular initiatives taken by the school which match your interest, do not hesitate to highlight in the application, and use that as a platform to highlight your skills. The benefit would be two fold.
6. Answer "Why MBA?". Undoubtedly the most important question of the application. Do answer the question with proper homework and supplement it with your post MBA long term and short term plans.
7. Be specific. Do make it a point to stick to the question asked in the application and do not add extra information just for the sake of highlighting it. Make full use of the word limit provided and highlight yourself well within the constraints of the question asked.
8. Get your essays reviewed. There will be some aspects which you might not notice. A third person review would certainly help. Ask opinions about the coverage of the topic, how you are perceived as a third person. Do not get it reviewed by your friends or family as the opinion might be biased. Get hold of some alumni or an expert who knows the importance of the essay. Discuss the changes with him/her and include them if required in your own style.


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And the answers is very simple: some transactions in the payments domain are only possible with a card and or a sixteen digit (with CVV) number.
It is very complex and difficult to perform a payment transactions at a traditional merchant (with a POS) or to withdraw cash at an ATM without a plastic card. To really get the benefit of these huge traditional payment networks it is essential to offer plastic cards in conjunction of mobile money accounts.


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By Lady Mary of Montevale
Features Reporter, Pennsic Independent
Wednesday's 11th annual Pennsic Children's Fete in the Barn was a resounding success. Like Mary Poppins, it was practically perfect in every way.
From improved traffic flow which had no one waiting in line to register for more than 20 minutes to the estimated 500 balloon animals created on the spot by three balloon artists to the hot, sweaty parents who trudged out of there, laden down with booty and goodies at 4 p.m., it was simply a wonderful afternoon.
First and foremost, it was a wonderful afternoon for the 351 children who attended the festivities. They were streaming in all afternoon, almost right up to the last minutes, according to Baroness Cairistiona (Atlantia) who was in charge of registration.
If you were Madeline (4), it was wonderful to have a purple, pink, and silver sparkly butterfly painted on your left cheek that matched your very special pink and purple dragon friend that you brought to the party. The dragon is a very new friend—no name yet, although Madeline confided that she knows this is a girl dragon.
If you were Justin (9), it was wonderful to be handed what you immediately declared to be "the best balloon snake I have ever seen."
If you were Rebecca (7), it was wonderful to take three pairs of balloons and some rice and find they could be turned into three juggling balls of your own.
And if you were any number of young lords (and even some young ladies), it was wonderful to use a foam boffer sword to rush an armored adult fighter (who is also armed with a boffer or pool noodle), bring him to his knees with a cry of "Surrender to me now!"… And then find that you have just "killed" His Majesty Conrad, King of Caid. Even better, His Majesty also gives you suggestions to improve your fighting technique so you can try to "kill" him again.
For the 115+ adult volunteers, some of whom had been working for a year to bring this day about, the big payoff was seeing the smiles on the children's faces and hearing their expressions of delight as they completed a picture, a necklace, or a figure in clay.
But there was something else perhaps just as important. All one had to do was look at the many pink gowns worn by the women working at the Fete, notice how many large, burly men were wearing pink tunics or baldrics, see the pink name tags of the volunteers which were embellished with the familiar twist of pink ribbon representing the fight against breast cancer. The Pennsic Children's Fete, for the adults who work to make it happen, is a memorial to its founder, Duchess Arielle of Atlantia, who lost her fight against breast cancer just two weeks before last year's Pennsic. The continuing success of the Children's Fete and the pleasure it brings to the children of Pennsic are Her Grace's legacy to Pennsic and to all of us.
Countess Rowan of Atlantia had high praise for this year's director of the children's party, Herrin Emeludt Hansler, who is also the Chancellor of Youth Activities for Atlantia. Her Excellency mentioned the year of organizational meetings, the email list, the solicitation of donations of time and supplies from other groups and from the royalty of other kingdoms, and many other tasks that were part of what she deemed "an excellent job" by this year's director.
Parents and children saw some of the results of improved traffic flow (just one entrance point and just one exit point) and improved security measures for the fete this year. Large tables blocked most of the open side of the Barn to keep anxious children from just rushing in to join the fun before they'd been registered. Parents wore pin-on tickets for each child in their care, and a 6-foot-plus muscular door "dragon" kept on eye on the exit spot so children would not leave in the company of anyone other than a parent.
Countess Rowan also praised HRH Princess Brianna of Atlantia and the other members of her household who hold fundraisers every year to finance the refreshments served at the fete and then handle the serving of those refreshments at the party. This year, the liquid refreshment was a choice of lemonade or water—both very welcome in Wednesday's heat and humidity.
The inflated jumping castle was just as popular this year as it was when it was first introduced last year. Andreas (Atlantia), who has been involved with the children's party since its very first year, was keeping admirable order at the castle, where there were weight and number limits on how many could jump at a time, and where Andreas made sure that each set of jumpers kept to their limit of exactly 3 minutes. Just like last year, the castle was one of the first places the children formed lines as they entered.
Many youngsters left proudly clutching the muslin tote bags on which they had creatively and colorfully painted iron-on transfers of heraldic images. This very popular all-in-one activity and souvenir was the work of Baronessa AnnaBella di Cherubino and Baroness Elsbeth Donofrey, both of the East. Her Excellency AnnaBella donated the plain muslin tote bags and ironed on the transfers of the heraldic images that Her Excellency Elsbeth had drawn. Older children received slightly plainer totes so that they could create their own heraldry.
Not every volunteer at the party was a veteran. Evelyn (14, Atlantia) is attending her very first Pennsic. While her mother was part of the band of bardic performers who performed both as a group and individually as they roamed the party, Evelyn was a "fan girl" for Countess Rowan and other noble volunteers.
Thanks to the heat and humidity, and the closed nature of the barn, there were many other adults fanning themselves as well, whether with proper fans, straw hats, or even just sheets of paper. The kids were having too good a time to care about the weather.
After all the children had departed, some rather reluctantly and some of the youngest ones dozing in their strollers or wagons, Herrin Emeludt summed up the afternoon with these words: "We had a lot of fun and we will do it again next year." Her Grace Duchess Arielle would most certainly approve.


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Many things happened in 1978. The third generation Chevy Monte Carlo was downsized from the larger body due to the Arab Oil Embargo. Gas was 63 cents a gallon, the first cellular telephone was introduced; and in Oahu, the most populous island in the State of Hawaii, Keoni Teixeira was born. On the islands, family is regarded as the most important thing, and the Teixeira clan is no different.
Passing down traditions would come to be a recurring theme in Keoni's life. His father, Gerald, was an avid car builder, who would spend most of his days in the garage building hot rods and traveling to local car shows. Only a child then, Keoni started picking up on custom cars, too; even lending a hand to his father on occasion. Once he turned ten, his father bought him a paint gun and guided him through his first custom paint job. The experience became life changing, as painting seemed to be second nature for him and was all he wanted to do.
At 23, Keoni and his family left the islands and moved to Sunrise, Florida, just outside of Ft. Lauderdale. Looking for employment, he found a local shop that specialized in custom cars and offered his painting expertise. He got even more than he bargained for as he found a stock 1978 Chevy Monte Carlo for sale at the shop and jumped on it, making it his first car in the States. What was initially a small project became an obsession and before long, Keoni was going all out on the build. The Monte's frame was removed and Keoni laid down a Purple Pearl over the entire body. Testing out his pinstripe knowledge, he added gold leaf throughout the frame while patterns were dropped on the roof to add to the appeal.
In 2002, Keoni's son Kanoa Teixeira was born and the circle of life in the Texeira family would repeat itself. The building tradition carried on as Keoni would spend late nights in his garage with his son by his side. Now six years old, Kanoa has already learned about hydraulic suspensions and in another four years, he might even take the paint gun away from his father. A dedicated member of 25th Street Riders out of Hollywood, Florida, Keoni has brought all the right ingredients to the Lowrider culture. Rest assured, "Island Stylin" will always be a family tradition.


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It seems like a glitch, something not caught in quality testing for Timeline, but Facebook's once again let a privacy concern slip into a universal feature, according to The Next Web.
Friends can go into a photo in Timeline and change the location of that photo --even if they are not tagged. Just parachute in, change the location to PERDITION or whatever and wait to see how your friend reacts.
Drew Olanoff did the heavy lifting of finding the privacy setting that needs changed to turn this "feature" off. Of course, it also turns off location tags, overall.
U.S. & World
Another note on Timeline is that the mobile version is not available on iOS -- only Android and m.facebook.com. From Facebook:
Mobile timeline starts with your unique cover photo. As you scroll down, you'll see your posts, photos and life events as they happened, back to the day you were born. Photo albums and other posts are horizontally swipeable, so you can quickly view multiple photos or posts inline without leaving timeline. You can also swipe through the views at the top of your timeline to navigate to your map, photos, subscribers and more.
There's no further comment on iOS or why they went Android-first.


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Dancing With The Stars Maks Chmerkovsky And Kirstie Alley Attend Zang Toi Spring 2013 Fashion Show
Aren't these some sweet takes of Maks Chmerkovsky and Kirstie Alley?!! Yesterday, the dancing pair of Dancing With The Stars Season 13 attended the Zang Toi Spring 2013 fashion show at The Stage at Lincoln Center in New York City, New York. Other celebrities to attend were Abigail Spencer, Nick Hisson, Julie Macklowe, and Ramona Singer. You can see a whole slew of new photos of them and this event at Getty Images and Zimbio Pictures. Gorgeous! "Black" is Kirstie's color!! Cue Maks!!


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Where are all the people taking walks on Gorham Street's new sidewalks? We don't have any children going past on their way to school. We don't have any walkers coming into Morenci from the city or county lines trying to get to downtown shopping. We don't even have walkers who drive to Gorham Street, park their cars, and just enjoy the fresh new place to take a walk in the great outdoors. We do have occasional Gorham Street residents going for a walk, but overall the foot traffic is low.
If you drive down Gorham Street you will see that the contractors did a really great job on the projects. The residents spent a lot of money to have these walks put in and the City of Morenci paid $7.00 a linear foot in reimbursements, too.
With Morenci citizens struggling with the current economic hardships, why has so much money been spent on this street for a sidewalk that goes nowhere anyone wants to go? I'm real sure this was not one of the City's better ideas. The problem now is we already put the sidewalks in and need a good use for them.
A few ideas come to mind. Why not let the school busses drop the children off on Gorham and let them walk to school from here. The police chief could take all the traffic violators to Gorham Street, park their cars and say, "there is the edge of town walk yourself towards it and out of here." Or the best yet, why not have the parades in town walk down Gorham Street and back to town just for some extra steps.
Failing these ideas, here is an open invitation to use our sidewalks. For all the residents in Morenci who don't have a nice sidewalk to walk on or just want to help us out, there is always Gorham Street available for a stroll. I look forward to seeing you walk by, after all, you helped pay for it, enjoy.
– Ernie & Sharon Cardinal
Gorham Street residents


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Welcome, Zones!
"Glad you made it to the page! It looks like League would be a great fit for Zones. Feel free to get in touch to learn more!"
Morgan Aycox
Sr. Business Development Representative
There's a Better Way to do Health Benefits
Big changes happen when you make the switch to League. HR teams spend less time on admin, companies see lower costs and less turnover, and employees pick up healthy habits.
Why League would be a great fit for Zones
Zones clearly values the employee experience, and in particular adding value to your employees' lives through rewards such as comprehensive health benefits, professional development programs and flexible work environment.
However, with a comprehensive health and wellness package for your employees, it is difficult to manage the administrative burden. As well, this can decrease the amount of time your HR team can spend on priority projects.
Similar organizations, like OMERS and Shopify are already using League to not only demonstrate an increased commitment to the well-being of their employees, but also to decrease the time your HR team spends on administrative tasks.
Finally—Employee Benefits That Are Easy and Engaging
An Engaging Employee Experience
Members are empowered to manage their health with a digital platform that looks and feels like their favorite apps.
Effortless Benefits Administration
HR teams get the most out of their investment with automated admin work, simple integration and real-time usage reports.
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Why do benefits have so many different systems that can't seem to get along? (It's a rhetorical question—we don't have the answer either.) The League platform plays well with any existing HRIS or HCM systems, integrating seamlessly into the software you're already using.
What Our Clients Are Saying
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