text:
Investigation of chemical transformations of thiophenylglycoside of muramyl dipeptide on the fumed silica surface using TPD-MS, FTIR spectroscopy and ES IT MS
- Liana R Azizova†1Email author,
- Tetiana V Kulik†1Email author,
- Borys B Palianytsia1,
- Aleksandr E Zemlyakov2,
- Viktoriya N Tsikalova2 and
- Vasiliy Ya Chirva2
© Azizova et al.; licensee Springer. 2014
Received: 10 December 2013
Accepted: 23 April 2014
Published: 13 May 2014
In this study, chemical transformations of benzyl ester of О-(phenyl-2-acetamido-2,3-dideoxy-1-thio-β-d-glucopyranoside-3-yl)-d-lactoyl-l-alanyl-d-isoglutamine (SPhMDPOBn) on the fumed silica surface were examined, and the surface complex structure was characterized by temperature-programmed desorption mass spectrometry (TPD-MS), infrared spectroscopy (FTIR) and electrospray ion trap mass spectrometry (ES IT MS). Stages of pyrolysis of SPhMDPOBn in pristine state and on the silica surface have been determined. Probably, hydrogen-bonded complex forms between silanol surface groups and the C = O group of the acetamide moiety NH-(CH3)-C = O…H-O-Si≡. The thermal transformations of such hydrogen-bonded complex result in pyrolysis of SPhMDPOBn immobilized on the silica surface under TPD-MS conditions. The shifts ∆ν of amide I band (measured from 1,626 to 1,639 cm−l for SPhMDPOBn in pristine state) of 33 and 35 cm−l which occurred when SPhMDPOBn was immobilized on the silica surface may be caused by a weakening of the intramolecular hydrogen bonding of the SPhMDPOBn because the interaction with the silica surface as hydrogen bond with silanol groups is weaker than that in associates.
Muramyl dipeptide Temperature-programmed desorption mass spectrometry (TPD-MS) Pyrolysis Thioglycosides Electrospray ion trap mass spectrometry (ESI IT MS) Fourier transform infrared spectroscopy (FTIR)Background
It has long been known that non-specific stimulation of the immune system can be brought about by exposure to bacteria or components extracted from bacterial cells [1]. The minimum effective structure responsible for the immunoadjuvant activities of the bacterial cell wall was identified as a sugar-containing peptide of the peptidoglycan component [2, 3]. The smallest effective synthetic molecule was found to be an N-acetylmuramyl-l-alanyl-d-isoglutamine (MDP) [2, 3]. MDP was found to exert numerous immunomodulatory activities. However, the administration of MDP into different hosts was always associated with serious toxicity that hampered its use in man [4]. Therefore, in an effort to generate MDP analogues with reduced toxicity and enhanced biological activities, several hundred derivatives were synthesized by chemical modification of the parent molecule [5–8].
Sulfur-containing compounds play an important role in living organisms in energy metabolism (energy production), blood clotting, and synthesis of collagen (the main protein of connective tissue in animals which is the major constituent of bones, fibrous tissues of the skin, hair, and nails) and also participate in enzyme formation. Thioglycosides are less investigated in contrast to O-glycosides. It is known that O-glycosidase is able to split O-glycosides, including of O-arylglycosides, in biological systems. Enzymes capable of cleaving the thioglycosidic bond are less common in nature and occur mainly in plants [9, 10]. While O-glycosidases are ubiquitous, plant myrosinase is the only known S-glycosidase [11]. Thioglycosides possess significantly lower susceptibility to enzymatic hydrolysis than the corresponding oxygen glycosides [12]. Also, thioglycosides have gained widespread use in carbohydrate chemistry as inhibitors of O-glycosidase and O-glycosyltransferase inhibitors [13]. Nevertheless, unlike intensively investigated O-glycosides of MDP, S-glycosides have received relatively little attention. Currently, only three S-alkyl glycosides of MDP, namely, methyl and butyl β-glycosides and hexadecyl S-glycoside, have been obtained [8], although 1-thiomuramyl dipeptide itself was found to possess the adjuvant effect close to the action of muramyl dipeptide [8]. For this reason, we synthesized the thioglycosides of MDP.
Fumed silica with controlled particle size, morphology and surface area, along with its chemical, thermal and easy functionalization properties, is suitable for application in adsorption, catalysis, chemical separation, drug delivery and biosensors [14–20]. Silica nanoparticle-MDP thioglycoside complexes' synthesis is a way of structure modification that results in enhanced bioavailability of MDP thioglycosides and prolonged action and simplifies delivery in biological systems [21]. Parfenyuk et al. [21] have demonstrated the possibility of the application of silica nanoparticles for topical delivery of the immunomodulatory drug glucosaminylmuramyl dipeptide (GMDP; the chemically synthesized natural equivalent of peptidoglycan) to the peritoneal macrophages of women with endometriosis. Researchers have shown that the immunomodulatory effect of GMDP can be increased by its immobilization on silica nanoparticles.
The aim of this study was to examine chemical transformations of thiophenylglycoside of MDP with silica surface and to characterize the structure of the adsorbed films on silica by temperature-programmed desorption mass spectrometry (TPD-MS) and Fourier transform infrared spectroscopy (FTIR).
Powdery fumed silica (pilot plant at the Institute of the Surface Chemistry, Kalush, Ukraine; with a specific surface area of 270 m2/g) was used in this work. Fumed silica was previously heated on air for 2 h at 400°С to remove adsorbed organic substances.
The details of the synthesis procedure of SPhMDPOBn have been previously reported [22].
Loading of MDP arylthioglycosides on the fumed silica surface
The sample of SPhMDPOBn with a concentration of 0.6 mmol/g on the silica surface was obtained by impregnation. It is known that the concentration of free silanol groups (isolated ≡ Si-OH groups), the main active sites, on the silica surface is equal to 0.6 mmol/g of silica [23]. The weight of the MDP thioglycoside batch was such as to ensure a ratio of the concentration of modifier to that of silica surface silanol groups of 1:1. A 0.0121 g of SPhMDPOBn dissolved in 0.8 mL of 96% ethanol was added to 0.03 g of fumed silica in a Petri dish. The components were mixed and left on air at approximately 20°C till the solvent is evaporated (approximately 12 h). In the experiment, the air-dried sample was under investigation.
Instrument and procedures
Electrospray ionization ion trap mass spectrometry analysis
Mass spectra were obtained with the ion trap mass spectrometer Bruker HCT Plus (Bruker Daltonics, Bremen, Germany) equipped with an electrospray ionization source. Ionization was performed under electrospray conditions (flow rate 1.0 μL/min, spray voltage 4.8 kV, sheath gas 40 arb). All spectra were acquired at a capillary temperature of 25°C, and all ion guide voltages were tuned to maximize the abundance of the total ion current.
The analyte solutions (250 pmol/μL) were prepared in methanol. Methanol was of HPLC grade (Sigma, St. Louis, MO, USA).
Fourier transform infrared spectroscopy
FTIR spectra were recorded using a FT IR NEXUS spectrometer (Thermo Fisher Scientific Inc., Madison, WI, USA) at room temperature in the frequency range of 4,000 to 400 сm−1 in diffuse reflection mode at a resolution of 4 сm−1, a scan rate of 0.5 сm/s and number of scans of 150. In diffuse reflectance mode, the powdered samples were mixed with freshly calcined and milled KBr (1:100).
Method of temperature-programmed desorption mass spectrometry
TPD-MS experiments were performed in a MKh-7304A monopole mass spectrometer (Electron, Sumy, Ukraine) with electron impact ionization, adapted for thermodesorption measurements. A typical test comprised placing a 20-mg sample on the bottom of a molybdenum-quartz ampoule, evacuating to approximately 5 × 10−5 Pa at approximately 20°C and then heating at 0.15°C/s from room temperature to approximately 750°C. For all the samples, the sample vials were filled approximately 1/16 full, which helped limit interparticle diffusion effects [24–28]. Limiting the sample volume along with the high vacuum should further limit readsorption and diffusion resistance as described elsewhere [24–33]. The volatile pyrolysis products was passed through a high-vacuum valve (5.4 mm in diameter, a length of 20 cm and a volume of 12 mL) into the ionization chamber of the mass spectrometer where they were ionized and fragmented by electron impact. After mass separation in the mass analyzer, the ion current due to desorption and pyrolysis was amplified with a VEU-6 secondary-electron multiplier ("Gran" Federal State Unitary Enterprise, Vladikavkaz, Russia). The mass spectra and the P-T curves (where P is the pressure of volatile pyrolysis products, and T is the temperature of the samples) were recorded and analyzed using a computer-based data acquisition and processing setup. The mass spectra were recorded within 1 to 210 amu. During each TPD-MS experiment, approximately 240 mass spectra were recorded and averaged. During the thermodesorption experiment, the samples were heated slowly while keeping a high rate of evacuation of the volatile pyrolysis products. The diffusion effects can thus be neglected, and the intensity of the ion current can be considered proportional to the desorption rate.
Results and discussion
Electrospray ionization ion trap mass spectrometry analysis of О-(phenyl-2-acetamido-2,3-dideoxy-1-thio-β-d-glucopyranoside-3-yl)-d-lactoyl-l-alanyl-d-isoglutamine
TPD-MS analysis of О-(phenyl-2-acetamido-2,3-dideoxy-1-thio-β-d-glucopyranoside-3-yl)-d-lactoyl-l-alanyl-d-isoglutamine
Probably, a hydrogen-bonded complex forms between the silanol surface groups and the C = O group of the acetamide moiety: NH-(CH3)-C = O…H-O-Si≡. The thermal transformations of such hydrogen-bonded complex results in the pyrolysis of SPhMDPOBn immobilized on the silica surface under TPD-MS conditions.
FTIR spectroscopy
Assignments of the main silica bands in the 700- to 4,000 cm −1 region
Band maximum (KBr powder, cm−1) | Assignmenta | Reference |
3,745 | ν (isolated silanol groups) Si-OH | |
3,700 to 3,000 | ν hydrogen-bonded silanols (overlapping of the stretching modes in hydrogen-bonded hydroxyl bands produced by O-H bonds in adsorbed water and Si-OH) | |
1,867 and 1,980 | Si-O-Si stretching modes | |
Approximately 1,628 to 1,630 | Proton-containing components σOH (silanol groups and the deformation vibrations of the O-H groups in physically adsorbed molecular water at the silica surface) | |
Approximately 1,083 | Si-O-Si stretching | |
1,000 to 1,300 | νas, anti-symmetric stretching of Si-O-Si bonds | [38] |
932 to 939 | Si-OH stretching | |
Approximately 809 | Bending vibration of Si-O-Si bonds | |
Approximately 790 | Bending modes in Si-OH bonds |
The Si-O-Si and Si-O vibration bands appeared, respectively, at 1,083 and 809 cm−1 for the silica sample. The symmetric vibrations of the silicon atoms in a siloxane bond occur at approximately 809 cm−1 (νas-Si-O-Si). The largest peak observed in the silica spectrum is present at approximately 1,197 cm−1 and is dominated by antisymmetric motion of silicon atoms in siloxane bonds (νas-Si-O-Si).
The infrared spectra of SPhMDPOBn can be divided into several spectral regions. The IR spectra of SPhMDPOBn in the range 4,000 to 3,100 cm−1 are dominated by absorption arising from the symmetric and asymmetric N-H stretching modes. The IR spectrum of SPhMDPOBn adsorbed on the silica surface in the range 4,000 to 3,100 cm−1 shows a widened band near 3,313 cm−1 representing the N-H stretching mode, which is partially overlapped by the bands of the silica matrix (Figure 9). The maximum at 3,313 cm−1 is assigned to the N-H groups which were involved in hydrogen bonding interactions with the surface hydroxyl groups.
The bands in the IR spectra of SPhMDPOBn in the pristine state and adsorbed on the silica surface in the region 3,100 to 2,800 cm−1 are assigned as the symmetric and antisymmetric stretching vibrations of the С-Н bonds in a methylene group (in pristine state: νs = 2,850 cm−1 and νas = 2,925 cm−1; on the silica surface: νs = 2,850 cm−1 and νas = 2,931 cm−1).
The 1,800- to 1,700-cm−l region involves bands due to the C = O stretching modes of benzyl ester-protected carboxylic group of isoglutamine fragment. The bands at 1,724 cm−l in the spectrum of SPhMDPOBn in pristine state and at 1,728 cm−l on the silica surface referred to the ester C = O stretch mode.
Absorption frequencies of amide I and amide II bands and N-H stretching modes of SPhMDPOBn
Аmide I ( ν(сm−1)) | Аmide II ( ν(сm−1)) | νN-H((сm−1)) | ||||
Pr | Аd | Pr | Аd | Pr | Ad | |
SPhMDPOBn | 1,626 | 1,659 | 1,535 | 1,547 | 3,275 | 3,313 |
1,639 | 1,674 | 1,568 | 3,291 | |||
3,319 |
Assignments of amide bands to the secondary structure of peptides and proteins (literature data)
Assignment | Amide I, ν(сm−1) | Amide II, ν(сm−1) | Reference |
α-helix | 1,649; 1,653 to 1,657; 1,655 | 1,545 | [45] |
1,648 to 1,660 | - | [46] | |
1,650 to 1,652 | 1,540 to 1,546; 1,516 | [47] | |
β-sheet | 1,621 to 1,623; 1,630; 1,634 to 1,639; 1,647 to 1,648 | 1,530 | [45] |
1,620 to 1,640; 1,670 to 1,695 | - | [46] | |
1,633 | 1,530 | [47] | |
β-turn | 1,661; 1,667; 1,673; 1,677 | 1,528; 1,577 | [45] |
1,620 to 1,640; 1,650 to 1,695 | - | [46] | |
1,663; 1,670; 1,683; 1,688; 1,694 | [47] | ||
Random coil | 1,648; 1,654; 1,642 to 1,657 | - | [45] |
1,640 to 1,657; 1,660 to 1,670 | - | [46] |
The spectral region 1,400 to 1,200 сm−1 is characterized by overlapping deformation vibrations of the C-H bond in methyl and methylene groups of peptide fragment, stretching vibrations of the С-О bond in carbonyl group and amide III vibrations (stretching vibrations of С-N bond and N-H bend in plane) and the Si-O-Si, Si-O and O-Si-O vibration bands of the silica matrix.
The stages of pyrolysis of aglycone, peptide fragment and carbohydrate residue of thiophenylglycoside of muramyl dipeptide in the pristine state and adsorbed on the silica surface have been determined. Decomposition of thiophenylglycoside of muramyl dipeptide in pristine state occurs within the narrow temperature range from 150°C to 250°C. The decomposition of thiophenylglycoside of muramyl dipeptide adsorbed on the silica surface undergoes certain reactions to produce pyrolysis products such as thiophenol, benzyl alcohol and carbohydrate fragment with m/z 125 in the temperature range from 50°C to 450°C. Probably, the hydrogen-bonded complex forms between silanol surface groups and the C = O group of the acetamide moiety NH-(CH3)-C = O…H-O-Si≡. The thermal transformations of such hydrogen-bonded complex result in the pyrolysis of SPhMDPOBn immobilized on the silica surface under TPD-MS conditions.
The intensity of the infrared band at 3,745 cm−l assigned to the OH stretching vibrations of isolated silanol groups on silica decreased after the immobilization of SPhMDPOBn. This indicated the hydrogen-bonding of SPhMDPOBn molecule with silanol groups.
The shifts ∆ν of the amide I band (measured from 1,626 to 1,639 cm−l for SPhMDPOBn in the pristine state) of 33 and 35 cm−l which occurred when SPhMDPOBn was immobilized on the silica surface may be caused by a weakening of the intramolecular hydrogen bonding of the SPhMDPOBn because the interaction with the silica surface as hydrogen bond with silanol groups is weaker than that in the associates.
Authors' information
LRA is a Ph.D. degree holder and a Junior Research Fellow. TVK is a Ph.D. degree holder, a Senior Researcher, Head of the Laboratory of the Kinetics and Mechanisms of Chemical Transformations on Solid Surfaces. BBP is a Junior Research Fellow. VNT is a Ph.D. degree holder and a Senior Laboratory Assistant. AEZ is a Dr. Sci. holder and a Professor of the Department of Organic and Biological Chemistry, the Faculty of Biology and Chemistry. VYC is Dr. Sci. holder and a Professor and the Head of the Department of Organic and Biological Chemistry, Faculty of Biology and Chemistry.
electrospray ion trap mass spectrometry
Fourier transform infrared spectroscopy
muramyl dipeptide
nuclear magnetic resonance
- SPhMDPOBn:
temperature-programmed desorption mass spectrometry.
This work was partially supported by the grant UKC2-7072-KV-12 from the U.S. Civilian Research & Development Foundation (CRDF Global) with funding from the United States Department of State and by the grant M/299-2013 from the State Agency of Ukraine for Science, Innovation and Information.
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New York Explorer 23-26 June 2009
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Im doing this tour and then heading off on the North by North East!! So excited even with the saving money stress! - 0 people like this
14 Feb 2009 bengal_77 said
Hi Emma, I'll be on this tour with you as well before heading off on the Grand Northern …
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subset: commoncrawl


text: Why You Should Always Insist on a Written Job OfferDave Greenbaum7/20/14 11:00amFiled to: jobsinterviewsworkcareers341EditPromoteShare to KinjaToggle Conversation toolsGo to permalinkWhen you get that call or email offering a new job, your first instinct may be to say yes. You might want to reconsider and make sure all the details are in writing before you accept that offer.AdvertisementThe Muse advises that after you say yes based on just salary, it may be too late to discuss other matters:That said, you'll also put yourself in a poor position to negotiate if you find out later that your job offer doesn't include, say, basic short-term disability insurance. (In case you're wondering, insurance is not generally something companies are willing to negotiate on, but if you're not offered it, you can use it as a point to ask for a higher base salary.) Saying yes and then going back and pretending like you're reconsidering unless they meet you in the middle is the equivalent of showing your hand in a poker game.The Muse has some other tips on how to politely ask for this important tool for deciding whether to accept a job offer.AdvertisementGet it in Writing: Why You Absolutely Must Have a Written Job Offer | The MusePhoto by Bruno Covas.Reply34 repliesLeave a reply


text: Real Madrid Player Makes No-Look Buzzer-BeaterSamer Kalaf11/10/13 3:45pmFiled to: basketballreal madridfelipe reyes19EditPromoteShare to KinjaToggle Conversation toolsGo to permalink No, not the soccer club. With 0.4 on the clock, Real Madrid Baloncesto's Felipe Reyes caught a full-court inbounds pass and blindly tossed it up. It somehow hit nothing but net. Advertisement Via Tas MelasReply19 repliesLeave a reply


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WATCH: Luke Maye Hits Game Winner To Send UNC To Final FourThe Tar Heels exorcised some of last year's demons with a last second game winner to punch their ticker to Phoenix.
2017 ACC Basketball Tournament PreviewFrom UNC and FSU to Notre Dame and Louisville, the ACC has a logjam of talented teams vying for the conference title come tip off Tuesday.
CBS Sports' Seth Davis Breaks Down UNC-Miami ACC MatchupCBS Sports college basketball analyst Seth Davis discusses the ACC matchup between #9 North Carolina and Miami.
Answering College Basketball's Biggest Questions Ahead Of TipoffCBS Sports Network's Steve Lappas gives a preview of the college basketball season, including Friday's Veterans Classic featuring UNC-Temple and Florida-Navy.
No. 1 DU Lacrosse Team Travels East To Face No. 4 Tar HeelsThe Denver Pioneers lacrosse team was out practicing with big piles of snow next to their field on Wednesday.
Top 10 Random College Football Bowl Names For 2014College bowl season is here, and this year marks the debut of the new College Football Playoff and "New Year's Six."
Musicians + Sports: Chase Rice On NFL Dreams And NASCAR Victories With Jimmie Johnson"The NFL was a very, very attainable goal," the country music star and former North Carolina Tar Heels linebacker revealed during the exclusive video interview.
DU Lacrosse Ready To Quiet East Coast Fans With Win Over DrexelThe University of Denver Pioneers are in the NCAA lacrosse tournament for the fifth straight year, proving that they are now a powerhouse in the sport.
DU Lacrosse Wins Opening Round Of NCAA Tourney, Advances To Play DrexelUniversity of Denver's lacrosse team dominated North Carolina on Saturday in the opening round of the NCAA tournament.
Top 5 Greatest Team Rivalries In SportsIsn't it better when the teams hate each other? Here are the top 5 team rivalries in sports.


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Last night in the "Big Brother 15" house, after the excitement of the engagement died down, the hamsters got together to (naturally) talk smack about each ohter. But first, there was a pretty good prank pulled in the house.
Sign up for the live feeds because later today, we'll find out who America voted onto the block after Elissa (and maybe Aaryn and/or Kaitlin).
So, Judd decided to put on Nick's hat and towel and run through the house, with ELissa shouting that the "twist" is that Nick is back! It made GinaMarie start to cry. Seriously, folks. Pictures above. She is not a well person.
Then later, she was slamming Candice (again, what else is new?) when the houseguests were talking about who walks around the house in an annoying way:
Spencer: "Candice drags her feet too."
GinaMarie: "Real bad, it's f***ing annoying actually. She's too fat she can't pick up her f***ing feet. I can't stand her f***ing voice, drives me f***ing bananas. Never in my life have I heard anybody like that. … Can't a f***ing house just fall on her?"
The irony that Candice's voice annoys GM is too delicious.
Later, GM continues her craziness by saying, "I'm gonna marry [Nick], you'll see. Mark my words. I'm gonna marry him. I'll have Candice make my dress."
Run, Nick. RUN.
Kaitlin pipes up, "If Jeremy and I ever got married, the majority of these people would be invited to the wedding. Candice would not be invited, Amanda would not b einvited, McCrae would not be invited."
Then GinaMarie shouts, "Know what [Candice] could do? She can be the valet to park my motherf***ing cars, that's what she can do."
Can someone please tell us — what did Candice ever do to GinaMarie? Seriously, her hatred is ugly and kind of mind-boggling.
Stay tuned for the latest, including the replacement nominee after today's POV ceremony.


text: A time back a correspondent suggested it must be hard obtaining sufficient material for a daily post. Quite the opposite. The Sundance Channel's Action Poetry featuring the poems of Billy Collins provides a wealth of starting off points with different styles of movies. Today's movie therefore is 31 year old Brady Baltezore's The Country (20mb) made in 2006. Collins explores the little anxieties that plague us, in this instance, the rural householder who locks away his matches in case a mouse takes one into the floorboards and sets the house on fire. Initially sceptical, even amused, the narrator, a city dweller, is nevertheless himself disturbed as he ponders that little grey figure scurrying about beneath his bed, lighting the match and igniting the building. He leaps into fantasy as the "brown Druid" raises his torch to his grey followers and burns the house down. Anxieties: what if a mouse found a match, did I actually lock the front door before setting off to another continent, what if what I said to her was interpreted as….The neuroses of modern man sprinkled with a dry humour. Brady treats the story in linear fashion - the guy lecturing on the dangers of matches, the restless night, the rodent weaving its way through the innards of the house, striking the match and captivating his thrilled followers to a backdrop of blazing house. The piece is drawn in 2D with lots of close-ups of matches, mouse and man. Into this world are added rendered photographic images of keys, pipework or kitchen table. The mix complements a poem in which fear and fun are intertwined. Formally working for San Francisco's Radium Brady is now freelance. More of his work, as I am wont to say, later. In the meantime Brady's website is Pistols Loaded and terrific.


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The Brazilian has impressed for Lazio this season, aiding their cause with nine league goals, and reports suggest that John Guidetti could be involved should any deal be struck
4/1 | Sergio Aguero is 4/1 with William Hill to score in a Manchester City win over Tottenham |
Lazio are enjoying a good campaign this season, currently sixth in the Serie A table, with Hernanes's nine goals helping their cause but his agent, Joseph Lee, admits that a move to the Premier League would interest the 27-year-old.
"These are rumours and for now I do not wish to comment on them," Lee told LaLazioSiamoNoi.it. "City are a top club at world level and Hernanes loves the Premier League but I have too much respect for Lazio to say any more.
"We discussed many things with president Claudio Lotito in September, including his contract, but the situation has remained unchanged since then. There are no other meetings planned.
"What would happen if an offer came in from Manchester City? I repeat, for now we are talking about rumours, but if it did arrive then Lotito would be forced to call us."


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10 Celebrity Instagrams You Have To Follow
Looking at blurry pics of some indiscernible band your friend saw in concert the other night and the "best pizza" they've "ever had" is great and all, but sometimes celebs' lives are just more interesting. Here's some accounts the Kia Soul thinks you shouldn't miss.
1. Ludacris (itsludacris)
Ludacris's Instagram is—pardon the pun, but it's totally necessary—ludicrous. His feed features everything you'd expect…
2. Taylor Swift (taylorswift)
You've probably underestimated how good Taylor Swift's Instagram would be. Or even that it WOULD be good, at all. It is, though—she posts plenty of good pics of her SCOTTISH FOLD cat, not to mention backstage concert photos and her just hangin' out.
3. Zooey Deschanel (zooeydeschanel)
Zooey's Instagram often features pictures of herself with any number of people (including her mom), as well as posed with strange objects. Everyone should be fine with that.
4. Oprah Winfrey (oprah)
Oprah is one of the richest women in the world. By far. So it's awesome that her Instagram is full of chill pics of her just livin' her life, tending her garden, feeding fish. Gotta do what you gotta do.
5. Jenna Marbles (jennamarbles)
Jenna Marbles is best-known for her hysterically funny "tutorial" videos on YouTube, and that humor has no trouble translating onto Instagram.
6. Jamie Oliver (jamieoliver)
The star of Naked Chef lives up to at least the second part of his name—his Instagram is perfect for foodies who also like a bit of sass.
7. Snoop Dogg (snoopdogg)
Obviously. Snoop's (Lion?) Instagram is nuts, in the best way possible. He puts up pics of everything from his family to his blue-faced Avatar costume, to, of course, his after-hours self. And it's all perfect.
8. Hailee Steinfeld (HaileeSteinfeld)
It can't be any surprise that one of the youngest actresses to ever be nominated for an Oscar has an amazing Instagram. Sure, it's a bit less glamorous than some of the others here, but it's cute and Hailee hangs out with Jeff Bridges, so.
9. Ian Somerhalder (IanJSomerhalder)
Ian's more than just a super-attractive vampire and somewhat-overprotective brother stranded on an island in the South Pacific. He also chills hard and loves animals. And he's still super-attractive.
10. Rob Kardashian (robkardashian)
Sure, you don't want to follow Rob Kardashian, but you really should. Most of his photos are so inexplicable that you have to just go: ¯\_(ツ)_/¯ and laugh.


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Babymetal to play Sonisphere 2014 Knebworth show
PUBLISHED: 11:59 08 April 2014 | UPDATED: 11:59 08 April 2014
Japanese YouTube sensation Babymetal has been added to this year's Sonisphere line-up.
Since uploading their song Gimme Chocolate!! online in February, the band has received over 5 million hits on the video sharing site.
They join current headliners The Prodigy, Iron Maiden and Metallica.
Early Bird Weekend tickets for Sonisphere 2014 are on sale now priced at £170.
For further information please visit www.sonisphere.co.uk


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The Electronic Low Frequency Massager – a bioelectric neuromuscular stimulating device, presents the user with an effective relief of pain through unique massage and acupuncture delivered by effective application of low frequency waves via self-adhesive skin electrodes.
The unit has been designed to provide an enjoyable and relaxing massage or deliver non-invasive acupuncture resulting in a relief of musculoskeletal pain and discomfort any time and anywhere.
- Gold-hand adopts the profound Chinese traditional medical theory
- Features 2 connectors with 2 electrodes each – works on 4 areas simultaneously
- Improve blood circulation and release of fatigue
- Pushing, tapping, Kneading and rhythmical vibration options make the massage more effective and more enjoyable
- Work-out anytime and anywhere
- Brand New
- 30 Day Warranty
- New


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Skip to Content
Home > Wellness Resources > Health Library > Gestational Diabetes: Counting Carbs
Carbohydrate counting helps you to control your blood sugar when you have gestational diabetes.
Here are some ways to help you count carbohydrate and spread carbohydrate throughout the day.
Eat at least three meals a day to spread your intake of food, especially carbohydrate, throughout the day.
It is a great idea to get out your cookbooks and plan several main meals(What is a PDF document?) at the same time. You can double some recipes and freeze the leftovers to use for other meals.
The following suggestions can help you count carbohydrate and balance your meals and snacks:
ByHealthwise StaffPrimary Medical ReviewerKathleen Romito, MD - Family MedicineAdam Husney, MD - Family MedicineSpecialist Medical ReviewerRhonda O'Brien, MS, RD, CDE - Certified Diabetes EducatorColleen O'Connor, PhD, RD - Registered Dietitian
Current as ofJuly 5, 2016
Current as of: July 5, 2016
Author: Healthwise Staff
Medical Review: Kathleen Romito, MD - Family Medicine & Adam Husney, MD - Family Medicine & Rhonda O'Brien, MS, RD, CDE - Certified Diabetes Educator & Colleen O'Connor, PhD, RD - Registered Dietitian
This information does not replace the advice of a doctor. Healthwise, Incorporated, disclaims any warranty or liability for your use of this information. Your use of this information means that you agree to the Terms of Use. Learn how we develop our content.
To learn more about Healthwise, visit Healthwise.org.
© 1995-2016 Healthwise, Incorporated. Healthwise, Healthwise for every health decision, and the Healthwise logo are trademarks of Healthwise, Incorporated.


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The couple, who entertained the audiences and the judges for almost four weeks, will be voted out this weekend
This weekend, Nach Baliye 5 will be filled with loads of interesting stuff. And we've already talked about that, remember? But guess it won't we happy-happy all the way and a tear or two will be shed this time around too. That's 'coz apart from witnessing Ajay Devgn, Kajal Aggarwal and Akshay Kumar's pagalpanti on the sets, we will also be privy to the elimination of one of the most entertaining couples on the show – Dimpy Mahajan and Rahul Mahajan. Sniff, sniff.
Now while Rahul's two left feet could well be blamed for this one, we can't help but wonder if it's Dimpy who grew weary of reality shows – Nach Baliye 5 and Welcome: Baazi Mehmaan Nawaazi Ki – had prayed fervently for a way out. Possible, isn't it?
Whatever the reason, this news suddenly makes us feel nostalgic about the way this jodi made us smile during the last four weeks. While we remember Dimpy being one of the most earnest dancers covering up for her pati parmeshwar's awkward style, we also remember how the couple's bizarre get-ups had made us – and the judges Shilpa Shetty, Sajid Khan and Terence Lewis – ROFL. Then, of course, there was a heart breaking performance that Mr and Mrs Mahajan dedicated to the late Pramod Mahajan.
So as Rahul and Dimpy's elimination inches closer, take some time out to shuffle through the memories that the two created on the sets of Nach Baliye 5. And while you do that, don't forget to tell us – Do you think Dimpy and Rahul Mahajan's should have been voted out of the show?
Photos: Yogen Shah


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As soon as Moffat County Fair organizers decided to add chicken roping to the 2006 fair events, they called Mary Martinez to reserve the chickens.
Martinez has chickens. And ducks. And geese and turkeys. Along with goats, pigs, steers, lambs, horses and llamas.
"I love my animals," Martinez said. "One year we took nine animals to the county fair."
The Craig native met her husband, Stan, in 1996 at a 4-H event. When they leased 100 acres four years ago, she decided to fill the place with animals.
As a youngster, Mary only entered 4-H crocheting and knitting events. However, her children are more involved in the fair's animal events.
Her son, 19-year-old Tony Webb, has been in 4-H for eight years.
"He shows steers and pigs and was in the catch-a-calf at the stock show," Mary said. "He caught and raised a Hereford."
Mary's daughter, 17-year-old Bailee Porter, shows steers, lambs and pigs.
"She also entered crochet and leather items during her seven years in 4-H," Mary said.
Martinez doesn't only look after animals for her own children to enter in the fair.
She also supplies baby animals to other children for projects, sometimes boarding them for kids that live in town.
"I like to help the kids that don't have money for their projects," Martinez said. "I tell them just to pay me later when they sell the animal."
When boarding animals for town children, Martinez expects them to care for the animals. She makes sure the children clean the pens and walk the animals each afternoon. She makes sure that all the animals have hay, feed and shelter.
Sun up 'til sun down
Preparing animals for county fair projects is not a short-term commitment.
Martinez puts the Billy goat in with the females on the first Sunday in August, so that babies will be ready for selection by the children as 4-H projects in April.
In the fall, Martinez helps the children prepare their animals for showing at the fair, sometimes driving to Maybell to sheer lambs with the youngsters.
"It's neat to help the kids," she said. "I really love that."
Feeding the animals is a big event at the Martinez ranch. A lot of lives depend on Mary.
Her animals eat once a day, always in the evening, and it takes time to feed them all.
"I have five pigs that eat pellets. Eight 80-pound bags last about a month when they're little," she said. "Now they're eating two to three bags a week. They all eat better than I do."
The goats get cracked corn and rolled oats, and go through a 5-gallon-bucket of feed each day. The birds eat a diet of cracked corn and poultry mix.
The Martinez property is irrigated and the hay crop goes toward feeding the four-legged animals in the winter.
Inside the Martinez home are many clues that give away the owners' love of animals.
A laptop computer keeps track of important dates for vaccinations and listing the ear-tag that match mother and baby goats.
A veterinarian book on the table helps Martinez diagnose health problems, and a set of scales stands nearby, ready to weigh the next baby.
The Martinez menagerie is not only for 4-H projects.
Each year Mary helps the Horizons organization by supplying animals for a petting zoo during its Special Olympics dinner. She brings her animals to Sheep Wagon Days, as well.
She purchases turkeys at Murdoch's each year to grow for Thanksgiving and Christmas dinners, although they frequently won't fit in the fryer because they have grown too large.
She presently has 15 geese, and often won't accept payments when people want a goose for their yard or for dinner.
The geese make good watchdogs she said, making a lot of noise if someone enters the yard.
Martinez will often share pig pens with neighbors, butchering the swine when the time is right.
It's all worth it
Her involvement with animals keeps her and her husband in demand at times.
"When people need help moving animals, me and my husband are there," she said. "He does the horseback part, and I stay on foot. I like that better."
A 4-H leader for the past four years, Martinez has passed on the job this year to pursue other interests.
She's currently busy building pens for the next batch of goats, expected at the end of the month.
Winter takes much more work when tending to the animals, and it takes more money for heating bills.
"You need heat lamps when you are kidding out," Martinez said about her goats. "Birds are also tougher to raise in the winter. The turkeys will fight, and their little feet freeze."
There's a propane heater on the horses' water-tank, and electric heaters for the goats' water on the Martinez ranch.
The birds get fresh water every day.
"I'm out there at night with headlights and flashlights praying the hoses are thawed," she said "If they're frozen I put them in the washing machine."
Besides farm animals, Martinez has a couple of cats, and dogs, including two Corgis and a Jack Russell Terrier. She expects to get a border collie before New Years.
A visitor unfamiliar with Martinez might ask, "Is it worth all the trouble?"
Martinez has to smile at that question.
"Sometimes my mom and dad, (Bill and Dorothy Webb) come out just to look at the animals," she said. "If you can give back to the community, that's important. People did it for me as a kid when I lived in town."
Dan Olsen can be reached at 824-7031, ext. 207, or firstname.lastname@example.com.


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Month: February 2008
I just realized that gmail had been filtering my blog comments into my spam folder, so I apologize for those of you who I haven't responded to yet.
SXSW "featured" my podcast last week (I was like the second person to actually do it) so here it is, for your listening pleasure.
I'm headed to LA tomorrow for the iConference, where I'm participating in the Doctoral Colloquium, presenting a poster on the MySpace moral panic and sitting on an SNS panel with Fred, danah and Cliff, which I'm very happy about.
Otherwise, I plan on enjoying the 70 degree weather in LA and going to the Getty and maybe the La Brea Tar pits and definitely Aardvark's on Melrose.
In completely different news, I am disgusted with Vista. I really enjoyed it for the first three months I used it, but now I'm seeing the cracks in the facade. The wireless networking is buggy. Explorer crashes not infrequently. There are well-known device driver conflicts that nobody's figured out how to deal with, and it's a terrible resource hog.
Worse, I hate Windows Genuine Advantage with a passion. I have no interest in having Microsoft "validate" whatever applications I choose to run. I am very suspicious of this as it smacks of Trustworthy Computing (which I worked on for 9 months or so): e.g. when Microsoft decides uTorrent cannot run simultaneously with WGA and blocks it, then there's nothing you can do. The problem is that even with my totally 100% legal copy of Vista, I can't install patches without installing WGA.
For example: there's this bug where when I put my laptop into hibernate, about 60% of the time it crashes. This is, according to Microsoft, a "known issue" (thanks guys). On the MS support website, they claim a fix. So I go to Windows Update to get the fix. Of course, Windows Update doesn't work in Firefox (which is exactly the kind of shit which got them under investigation for anti-trust and you would think that they would have stopped pulling it). So I open up Internet Explorer, which immediately tries to set itself as my default browser for everything (no thank you), navigate to Windows Update.. it won't work without installing WGA. I find an alternative patch, but after it unpacks itself, it crashes. Hibernate bug still in full effect.
SO: what I'm going to do is call Sony, get them to send me a copy of my Vista disk (a) which should have come automatically with the laptop and b) which I can't use to reinstall Vista b/c Sony packed literally like 40GB of bloatware on this laptop, including full, DRM versions of Spiderman 1 and 2), torrent Vista + SP1 (which has been released but not in an over-the-air update, wtf) + WGA crack, and use Vista to my heart's content. I've said it before, I'll say it again: When using legal software is MORE DIFFICULT than using illegal software, you have a problem.
Technorati Tags: windows genuine advantage
Oh my god, I just recorded the dorkiest podcast for my "I'm Internet Famous: Status in Social Media" core conversation session at SXSW Interactive (It's SUNDAY MORNING at 11:30, people! You know you don't have anything better to do than show up!). I've never done my own podcast before, and I think I should have gone FUNNER and SPARKIER. But I wrote a script and read it, using my best "enthusiastic lecturer voice." I did loop in the backing track of "You Know I'm No Good" by Ms. Amy Winehouse in the intro.
I should have said on the podcast that I would give everyone bagels if they showed up. 11:30 on Sunday at SXSW, everyone is going to be hung over and mourning the day they were born, or at least the night before. But I'll be up early and bright-eyed sitting expectantly at my table hoping people come give me free data for my dissertation topic.
Anyway, I used Audacity to record the podcast (my VAIO has a built in microphone, which I didn't know, which probably means I can record directly to YouTube– ugh, the possibilities) and, like most open-source projects, the software is great but the Help files are atrocious. Someday when I am long tenured and have a lot of time on my hands, I will donate my tech writing services to my favorite open-source/free software. It's a shame that lesser-than geeky types don't contribute to F/OS projects as much as hardcore geeks, because UI, documentation and other non-coding efforts are just as important.
EBay bans negative feedback for buyers.
EBay is finally confronting the "revenge problem" of negative feedback: almost nobody leaves negative feedback for sellers in fear of being retaliated against. I know I've bought from sellers who were terribly late or uncommunicative, who deserved at best neutral feedback. Instead, I just didn't leave any feedback at all. Unsurprisingly, sellers are super pissed and are organizing a mass boycott against this and other new policies (including some shady sounding PayPal holds).
This edges up against two common themes of online communities: ownership and transparency. Who "owns" a community? Is it the company who runs it, and who invests in infrastructure, personnel, server costs, and maintenance, or is it the users, who make the community economically viable? LiveJournal and Digg have both seen very nasty fights over this issue in the last year, with users arguing that they should have a say in community policy-making, bringing us to transparency. Like it or not, online communities are usually supported by commercial structures, which replace democracy or constitutional politics with Terms of Service. These ToS can encompass everything from limiting political discourse to copyright infringement liability, and they are always tipped in favor of the company that writes them.
This is why making claims about the internet as "democratic" space are always problematic.
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I saw an excellent talk by Joseph Reagle today. Joe's dissertation is on Wikipedia, and he presented a chapter called "Encyclopedic Anxiety," in which he argues that reference works "often serve as a flashpoint for larger social anxieties." This was very timely as I am half-way through David Foster Wallace's essay "Authority and American Usage" from Consider the Lobster, in which Wallace riffs on class and power issues in American lexicography and grammar in general.
To make a very long story very short, Wallace outlines the debate between proponents of descriptive dictionary building (dictionaries should describe how people use the language, including terms considered non-standard or "wrong" like ain't and irregardless) and prescriptive dictionary building (dictionaries should codify and enforce the rules of standard grammar). Clearly, what's "right" and "wrong" are social judgments that usually reflect the interests of the class of people building the dictionary. Wallace calls these people SMOOTS; they are the copy editors of the world, often disparaged as "grammar Nazis."
Reading this essay proved two things to me.
1) I was never formally taught grammar at any of the many educational institutions I attended, and therefore am woefully ignorant AND
2) Contentious debates about participatory culture, Web 2.0, content contribution etc. are just part of a very long struggle over Who Decides the Rules, Who Decides Whether Or Not There Should Be Rules and Who Is Allowed to Bend the Rules.
Joe places Wikipedia at the end of a long debate over reference works ranging from the first edition of Britannica (which encountered controversy for its entry on midwifery, which included illustrations of a fetus and the female pelvis), to the French Enlightenment text the Encyclopedie (which caused no end of trouble including censure, confiscation, imprisonment, and the torture and execution of a young nobleman purportedly under its influence), to Webster's Third, a version of the unabridged dictionary seen as overly permissive and dismissed as "dogma that far transcends the limits of lexicography" (source: Wikipedia's page on Webster's Third). But what fascinates me is this idea of descriptive vs. prescriptive.
Descriptive vs. prescriptive is a debate that extends far beyond reference works. Any time a point of view is taken, there is a normative stance associated with it. For instance, if I write for a magazine for teenage girls that includes long articles explaining plastic surgery and bikini waxing, it is very likely that I will be seen as endorsing those practices, even if the articles themselves are neutral.
In my status project, I am examining what I'm calling status affordances: software mechanisms that enable users to be ranked or placed in some sort of social hierarchy or order. These include features like MySpace's Top 8, Yelp's Elite status and LiveJournal's public Friends list. Reputation mechanisms, like eBay Feedback, Amazon reviewer rankings, and Digg's "made popular" attribution often function as status affordances as well. Most of these mechanisms aim to be descriptive: They show which reviewer has written the most reviews, or how many friends a person has. But they are also prescriptive, in that they define what a user must do to improve his or her reputation or social status. These mechanisms operationalize whatever they're measuring, whether it's "trustworthiness," "usefulness" or "coolness,", which in turn creates a metric for that feature that makes it clear what must be done to increase one's rank.
This means that status affordances both define and prescribe intended behavior. They create a determination of "quality" for a site's users or contributions and determine what is appropriate or inappropriate behavior. For instance, the rank and order built into Amazon's review system encourages people to submit thousands of reviews. Shay David and Trevor Pinch (I know I've cited this study before, but it's so interesting) used custom-built software to parse existing reviews and found that hundreds were exact duplicates, modified slightly for different products. This explains how top Amazon reviewers can have more than five thousand reviews, which naturally calls into question their quality. If quantity was not a reputational mechanism, this type of behavior might not happen. Thus, descriptive mechanisms prescribe how to "game" the system.
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Lengthy essay on technological determinism with many good examples and citations.
Daniel Chandler's online textbook on technological determinism.


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When John Moeller first heard about the pretzel incident, he thought he was toast.
It was 13 January 2002, the memories of the 9/11 attacks still fresh, and President George W Bush was doing what millions of other Americans were doing: trying to feel normal for a little while. He was watching football on TV.
Alone in his White House quarters, Bush was popping pretzels while watching an NFL playoff game. One didn't go down right, and the president crashed to the floor after briefly losing consciousness. The fall caused only minor facial injuries – and perhaps a bruised ego.
Despite the passing, freakish nature of the incident, reporters wouldn't let it go. They were on the story like, well, mustard on pretzels. They wanted to know the source of the salty treat. The White House remained mum. "You're not going to get us to cough it up," press secretary Ari Fleischer deadpanned to the New York Times.
As a sous-chef in the White House kitchen, Moeller was one of the few people in the United States to know the bakery that produced the pretzel. Moeller, in fact, was the one who had introduced the snack to the White House, back during the Clinton administration. The handmade beauties came from Hammond Pretzel Bakery in Lancaster, Pennsylvania, near where Moeller grew up in Pennsylvania Dutch country. "Chelsea went wild on it for a little while," Moeller says about his hometown pretzel. Hillary Clinton wrote the bakery a letter, thanking it for the healthful and tasty treat.
Then came president Bush's snack-related scare, which practically caused Moeller to start choking himself. His first thought upon hearing the news: "Am I going to be working here tomorrow?"
Moeller kept his job, but he got another lesson in the tenuous status of the White House kitchen staff, which "serves at the pleasure of the president", as the oft-repeated phrase goes. What does that mean in real terms for the men and women who work at the White House, feeding the First Family and their many guests and dignitaries from around the world? It means that politics, personal tastes or even a pretzel can potentially send a chef packing from 1600 Pennsylvania Ave.
Particularly the executive chef, the person who leads the small, full-time White House culinary team. The position has become increasingly political over the years, and Moeller, who worked in the White House kitchen from 1992 to 2005, remembers when the head chef gig shifted from a mere job to a post invested with palpable symbolism.
It was in late 1992, just weeks after Moeller started his job in the George HW Bush White House. Alice Waters, founder of Chez Panisse restaurant and earth mother of the US locavore movement, sent a letter to the president-elect Bill Clinton and Hillary Clinton, urging them to install an American chef. The letter was signed by dozens of top chefs, including Wolfgang Puck, who was born in Austria.
At the time, Pierre Chambrin, a Frenchman, was leading the kitchen; feeling the outside pressure, "Pierre grew despondent and finally said, 'I've decided to leave,' " Moeller writes in his new book, Dining at the White House: From the President's Table to Yours, a pull-back-the-curtain look at cooking for the world's most powerful family.
It took more than a year, but Waters finally got her American chef. Chambrin eventually was replaced by Walter Scheib, a native of Oakland, California, who introduced his own spin on American cuisine.
Waters's letter "maybe did politicise the position more than it had been in the past. It became more volatile than it had been," says Moeller, 52, as we sit in Paul bakery, a very French shop not far from the White House. Henry Haller, for example, served as executive chef for the White House for 21 years before retiring in 1987.
"I see a lot more interviews with White House chefs and stuff like that, where before we were just working," Moeller adds. "We served at the pleasure of the president . . . and very rarely would we get any fanfare."
These days, cooking for the First Family may have its politics (and perks), but it remains a demanding job, requiring a chef who can plan and prepare both massive, high-profile state dinners and quotidian family meals. It also requires an unassuming chef who doesn't insist on forcing flavours on a president and family members who have their own likes and dislikes at the dinner table. The job, in essence, is that of a glorified personal chef.
Moeller likes to share an anecdote to explain why a White House chef needs to be ego-free. The Clintons, Moeller remembers, had just hired a new cook, and he was eager to impress. Chelsea Clinton wanted pancakes for breakfast. The newbie noticed real maple syrup in the refrigerator and was about to grab it. Moeller told him to forget it: Chelsea liked the imitation, bottled syrup.
"And he fought me about it," Moeller recalls. "I said, 'OK, fine. Put it up there.' It went up, and it came back two minutes later. . . . I said, 'You know and I know [real maple syrup] might be the better-quality thing. That is maybe something we do on the outside for people, but we're in a home. This is what she wants. We're going to give them what they want.' "
White House cooks may have to swallow their pride, but on occasion, they also have a chance to influence the president's palate. Moeller says that when a cook first starts, he or she is briefed on presidential food preferences, including dishes and ingredients to avoid. Everyone on the staff knew, for instance, never to serve broccoli to George HW Bush.
But Moeller also knew that the elder Bush was a well-travelled man who knew a lot about cuisine. So one evening, Moeller decided to take a risk. He prepared the president an Asian-flavoured meal: miso soup, California rolls, salmon teriyaki and other dishes. He even had White House carpenters build geta serving boards for a Japanese-style presentation.
"Afterwards, the president came back, and he shook my hand," Moeller remembers. "He goes, 'John, in the four years that I've been here, I've never had a meal like that. Thanks a lot. That was fun.'"
White House chefs have also been early adopters of practices that have only recently taken root in the public's consciousness. Local and regional sourcing for ingredients? Moeller says he was buying produce not only from farms in Pennsylvania Dutch country, but also from farms in Montgomery County, long before farmers' markets dotted the landscape. He even harvested ingredients from his own garden.
"I used to always let them know, 'Hey, those beets came from my garden," Moeller says about the Clintons. "The First Lady used to like that."
The kitchen staff was also a pioneer in menu labeling. Long before the US government mandated that chain restaurants with 20 or more locations start listing calorie counts, the Clinton White House demanded the same thing for its family dinner menus, Moeller says. (Joke all you want about now veg-only Bill Clinton's love of fast food when he was on the road; Moeller swears the president ate more healthy foods at the White House: "I'd make a couple of burgers from time to time, absolutely, but it was only once in a blue moon.")
"We read through books, and we were calculating the caloric value for every dish", Moeller recalls about the calorie mandate. "We attached that to all the menus that we presented."
Despite his many years of service, Moeller never rose to the position of White House executive chef. He says he was acting head chef for several months in 2005, after Scheib was reportedly fired for not meeting First Lady Laura Bush's "stylistic requirements".
Moeller didn't get the job. The Bush White House selected Filipino native Cristeta Comerford, the first woman to hold the position. She was another veteran of the White House kitchen, originally hired in 1995 under Scheib. Moeller says he has no hard feelings about being passed over, though he does wonder whether the White House was under pressure to hire a woman, by groups such as Les Dames d'Escoffier.
Whether politics played into the decision or not, Moeller opted to leave the White House several months after Comerford took over. "I figured it might be a good segue to just move on and start to do my own thing again," says Moeller, who now has his own catering company back in Lancaster, home of those infamous pretzels.
A version of this article appeared in the 'Washington Post'
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