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4 Simple Tips for Summer Ready Skin
Beautiful skin starts from within! To achieve radiant healthy looking skin all your friends will be envious of follow these simple tips!
Limit sun exposure
Too much sun is no fun. When spending time outdoors, wear an SPF that is strong enough to protect from burning and aging. We suggest one of our UVA/UVB broad spectrum sunscreens such as the Daily Defense Sunscreen Broad Spectrum SPF 50 PA+++ . Wearing a hat will protect your head, your hair, and your face! The sun is one of our favorite things about summer, but be sure to enjoy the rays safely.
Drink Up
Staying hydrated during the warm summer months is a given! Drinking water plumps the skins cells, and helps the cells to regulate and perform their functions effectively. This translates to healthy, quenched, glowing skin that radiates from within. When your skin is primed with the right ingredients inside, the products you use on top work more effectively. So what are you waiting for? Get your drink on!
Eat Right
Eat your fruits and veggies! They are loaded with good for you ingredients such as antioxidants to help promote overall skin health and bodily health as well. The same ingredients found in many of our beloved products here at boscia can be found in the food you eat!
Avoid Major Changes in Temperature
Heading out into the scorching heat from a cool, air-conditioned room does not bode well with our skin. Using adequate skincare and taking the time to layer a serum and moisturizer will help preserve your skins hydration all day long, both indoors and outdoors. You can also apply an essence such as the Cool Blue Hydration Essence to keep your skin cool all summer long!
And there you have it, 4 simple tips to get amazing summer skin! What other tips do you have when it comes to achieving perfect summertime skin? Drop us a note we love to hear from you!
xo boscia
Congrats to our Winner!
Congrats to @tractor04david on winning the #fathersdaymasking contest.
We hope you enjoy your Black Collection Set!
Thank you to everyone who participated – we appreciate all the love and support from our fans!
xo boscia
The Perfect Father's Day
Treat Dad to a relaxing, fun weekend this Father's Day. Hit the beach, go swimming, take a hike, crank up the BBQ – Summer time allows everyone to enjoy the warm weather and spend some time outdoors. Unwind after your action packed day with Dad and one of our beloved face masks. Our award-winning Luminizing Black Mask removes dirt and impurities, absorbs excess oil, and boosts skin clarity. Booth you and Dad will love how fun and easy it is to peel-off!
Finding the perfect gift for Dad can challenge even the savviest of shoppers. We've put together a few of our top rated skin-saving gifts he's sure to love!
Our newest addition, the Charcoal Deep-Pore Cleansing Stick Treatment, is great for the guy on the go. Packaged in a sleek, slim stick, this powerful cleansing stick draws out dirt and impurities to leave skin smooth and refreshed.
After cleansing the face, restore moisture and eradicate blackheads and oil with our Charcoal Pore-Minimizing Hydrogel Mask. This mask renews and revitalizes the skin, gently yet effectively treating blackheads and congested pores.
Combine our Exfoliating Peel Gel for gentle exfoliation with our Revitalizing Black Hydration Gel to restore moisture and keep oil at bay all day.
For the avid gym-goer, we created our unique Black Charcoal Cleansing Cloths. A great way to wipe off sweat and debris from the day post work out or before bed time, these black wipes cleanse and tone in one swipe.
With our carefully curated selection of gifts, you're ready to celebrate Father's Day in style. Upload your best masking photo with Dad and hashtag #fathersdaymasking for a chance to win several pieces from our Dad-approved Black Pore-Perfecting Collection! We will randomly select and announce the winner this Monday!
xo boscia
3 Ways to Exfoliate Sans-Scrub
With summer hot on our heels, our skin needs a little extra TLC to keep us looking radiant and glowing! At boscia, we strive to achieve mochi hada, "baby soft" skin year round. One way to put your best face forward is through exfoliation. Exfoliation removes the uppermost layer of debris and dead skin to allow product to penetrate the newly revealed skin effectively and provide a smooth finish to the complexion. Skin tends to dry a little during the summer with the change in climate, causing a loss in radiance and moisture. Typical scrubs can often irritate or cause damage to overly sun-kissed skin. We have three of our favorite boscia products that exfoliate without harsh scrubbing and make summertime smoothness a breeze!
If you dream of skin as smooth as a polished pebble, our Exfoliating Peel Gel will fulfill your skincare wishes! This peeling gel instantly gratifies – within seconds of massaging the product into dry skin, particles of dead skin mixed with the fruit enzyme complex "peel" off of the face revealing renewed, smooth skin. Our innovative gel works amazingly before makeup application. Skin feels soft, smooth, and polished – the fundamentals of "bare skin beauty", su hada be.
For those with drier skin types, our Tsubaki Oil-Infused Exfoliating Powder imparts a hydrated radiance to the skin. Rice Bran powder coated in Tsubaki oil gently removes dry, dead skin and hydrates areas that need a little more moisture. We suggest mixing Tsubaki Oil-Infused Exfoliating Powder with your favorite cleanser for an all-in-one cleanse, or with Tsubaki Beauty Oil for a deeply hydrating exfoliating treatment.
Our next undercover miracle worker provides gentle, yet thorough, exfoliation for not only the face, but every bit of the body! For those seeking the perfect summer glow, our Konjac Cleansing Sponge gently sloughs off dead skin on the face and on rougher areas of the body such as knees, elbows, and heels. Our sponge is gentle enough for the face, but thorough enough for tougher patches of skin on the body. Use the sponge before sunless tanning application to achieve a perfect glow every time. This insider trick prevents concentration of product on dead skin, and imparts smooth to the touch silkiness on areas beyond the face and décolleté.
Don't forget to protect your fresh face with sunscreen! Our Daily Defense SPF 50 PA+++ provides all day broad spectrum protection, while many of our moisturizers include a broad spectrum SPF to keep skin protected from dusk til dawn.
New Charcoal Innovations
Hi boscia beauties!
NEW PRODUCT ALERT: We've added 2 NEW additions to our Black Pore-Perfecting Collection! The Charcoal Deep-Pore Cleansing Stick Treatment and Black Charcoal Cleansing Cloth are the newest innovations to add to your cleansing ritual!
Packed with activated bamboo charcoal to deeply cleanse and detoxify pores, these products are a must-have for drawing out dirt, oil, and impurities while minimizing pores! The Charcoal Deep-Pore Cleansing Stick Treatment absorbs toxins and impurities leaving skin healthier, clearer, and more refined! Bamboo Charcoal acts as a natural antibacterial agent to deeply cleanse and detoxify pores, without irritation. Our Black Charcoal Cleansing Cloths, infused with a pore treatment blend of Charcoal Powder and Black Tea, absorb excess oil while minimizing pores – in one quick sweep!
Both products contain key ingredients like Glycolic Acid and Artichoke Leaf Extract which help to reduce wrinkles and hyperpigmentation to clarify and improve skin texture. And of course like most of our products, both products include our unique Proprietary Botanical Blend of Jojoba Leaf and Willowherb which helps calm skin inflammation and prevent free radical damage.
Using these products is just as simple as the ingredients that go into them. Check it out below:
How to use the Charcoal Deep-Pore Cleansing Stick Treatment:
While holding stick upright, twist base counterclockwise to reveal one centimeter of the cleansing stick. Apply to a wet face. Next, massage the cleansing stick in a circular motion directly onto skin to create a creamy lather. Lightly massage skin with fingertips to activate formula to reach deep into pores. Lastly, rinse face with water (and there you have it –instant gratification!).
How to use the Black Charcoal Cleansing Cloth:
Use the power of charcoal to wipe the day away! Incorporate these into your Japanese Cleansing Ritual as an added cleansing boost. Gently massage a cloth over your face in a circular motion (be sure this is done on dry skin!). You will instantly feel refreshed! These are the perfect addition to your gym bag and before and after a flight!
Be sure to grab both of our newest innovations on boscia.com to see what all the rave is about! We love to hear your thoughts – what are your favorite products from our Black Pore-Perfecting Collection, let us know below!
Skin Safety 101: National Sunscreen Day
In honor of National Sunscreen Day, we want to share boscia's superstar skin saviors ideal for your everyday (or those extra hours in the sun this summer!).
Preserving mochi-hada skin (a Japanese term for soft, supple skin) is very much achievable especially with a broad-spectrum sunscreen which will ensure your skin resists the effects of harsh environmental damage! Broad Spectrum sunscreens protect from both UVA and UVB rays. Both undetectable to the naked eye, these sun rays can cause major damage for different reasons. A great way to remember the difference between these two sun rays lies in their names – UVA, for Aging, and UVB, for Burning. UVA rays cause skin damage and can result in premature aging. UVB rays also cause skin damage, but lengthy exposure will typically leave behind a burn as well. Broad Spectrum sunscreens protect from both of these damaging rays.
SPF is essential and our Daily Defense Sunscreen Broad Spectrum SPF 50 PA+++ offers all day protection and hydration. It is perfect for those seeking a sunscreen to withstand the elements. Get a head start on your summer skincare routine by picking up a Daily Defense Sunscreen Broad Spectrum SPF 50 PA+++ for 50% off at Sephora.com until supplies last!
SPF stands for Sun Protection Factor. If your skin typically takes 30 minutes to redden, an SPF of 15 extends protection over your skin for 15 times longer – a little over 7 hours of protection! Most sunscreens containing an SPF of 15 or more will protect against burning. Our savviest skincare lovers enjoy using our Oil-Free Daily Hydration SPF 15. A favorite for many reasons, this moisturizer provides the perfect amount of protection for your day-to-day and sits beautifully beneath makeup.
Our B.B. Broad Spectrum SPF 27 PA+++ is another great product containing SPF. It protects, perfects, treats and hydrates skin for a one-step solution to the morning rush. With a self-adjusting pigment and three flexible shades, it's the perfect multi-tasking product for summer. For the delicate under-eye area, our All-In-One BB Eye Brightener SPF 20 offers broad spectrum sun protection while highlighting and treating the under-eye area.
If you could revitalize and repair your skin while shielding off harmful UV damage, would you? We make doing just that simple with Self-Defense Vital Antioxidant Moisture Broad Spectrum SPF 30. Besides fending off sun damage, this moisturizer packs a punch with eight powerful antioxidants to leave skin hydrated, restored and refreshed.
When you leave home this season, don't forget your sunscreen! Even if you spend most of your time in a classroom or office, sunlight from windows and low-level UV light emitted from computer monitors can affect your skin. boscia offers sun protection for everyone! xo – boscia beauties
May is for Multi-Masking
Masks have become a must for those seeking everyday luxury in their skin routine! Our skin fends off pollution, dirt and impurities daily – masking gives our skin an extra line of defense against these natural aggressors. While our tried and true Japanese Cleansing Ritual leaves skin cleansed and refreshed, masks replenish and nourish for optimal skin health and radiance.
Why target one concern when you can conquer them all? Here at boscia, we love "multi-masking." Our skin typically varies throughout. Some skin may produce more oil while others produce less, freckling and pigmentation can occur on some areas of the face and not on others. Using multiple masks allows for customized treatment on all areas of the face.
Here at boscia, our masks truly set us apart. There is a formulation for everyone with our several peel-off options, a sleeping mask, and our new Hydrogel masks. Our Luminizing Black mask changed the way the world masked when we launched it back in 2010. For all of our peel-off masks apply a thick layer, allow 20-30 minutes to dry (avoid the hairline), and peel to reveal your best skin!
Our top peel-off mask for reducing discoloration, dark spots and adding brightness is our Bright White Mask. This mask leaves skin moisturized and illuminated for a geisha-like glow! To minimize the appearance of pores, purify the skin and detox congestion we suggest our infamous Luminizing Black Mask. This mask absorbs excess oil, improves clarity and leaves skin radiant and glowing! For a refreshing dose of hydration, even the most sensitive of skin types will enjoy our Cool Blue Calming Mask. We especially love this mask during the summer to help restore moisture and cool the skin!
Are you a multi-masker?! Enjoy a FREE masking trio when you splurge on your favorite boscia must-haves. Check out this Special Offers for a limited time on our site. Below are a few multi-masking techniques to get you started. Get creative and let us know your preferred peel-off experience, we love to hear from you!


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Mfg.: Manitowoc Ice Machines
Model: Manitowoc IR-1800A
Please note: The dice size "Regular Cube", measuring 1-1/8" x 1-1/8" x 7/8", is not standard nor is it the most popular dice size. As such, there may be an extended lead time before this item will ship. Please contact us for more information, or with questions on availability.
Item: Manitowoc Indigo 48" Modular 1790lb Regular Cube Ice Machine Ice Head
Model: IR-1800A
Description:This modular ice head perfect for producing a high amount of ice per day which is perfect for hotel dining facilities, butcher shops, and seafood restaurants.
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WDRB Fox 41, in Louisville, KY, has installed a Utah Scientific UTAH-400/64 digital routing switcher and a two-channel MC-4000 master control switcher with two MCP-2020 master control panels.
The UTAH-400/64 unit provides routing for all incoming and outgoing HD signals supporting WDRB newscasts, as well as those of sister station WMYO, a MyNetworkTV affiliate. The master control channels integrate with WDRB's Utah Scientific GS-4000 graphics station. Because the sources for both stations are available to either channel via the routing switcher, it allows the two stations to share programming across both channels.
An Inside Look at Four Virtual Reality Start-Ups
What Moves the Social TV Needle?
Mark Kudsi Directs 'Art of Patron Virtual Reality Experience'
BT Renews Intelsat Deal
Top Twitter TV Shows for 2014-15 Season Unveiled
comScore Introduces MobiLens Plus
North Korean Propoganda Art Inspires the Credits of 'The Interview'
Imaginary Forces Creates Kaleidoscopic Titles for 'Bosch'
Filmmaker Embraces Short Documentary Format with Oscar-Nominated 'Crisis Hotline'
North Metro Television Goes Wireless with Comrex LiveShot
Spectra Logic and HauteSpot Networks Introduce Body-Worn Camera Video Surveillance Solution
Huge Ultra HD Display Lights Up Times Square


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awesome tie dye tablecloths for your next groovy event!
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A process for the resolution of an enantiomeric mixture of β-lactams containing an ester, the process comprising selectively hydrolyzing the ester of one of the enantiomers by combining the mixture with homogenized liver.
1. A process for the resolution of an enantiomeric mixture of an acyloxy substituted β-lactam, the process comprising combining the enantiomeric mixture with homogenized liver to form a reaction mixture, selectively hydrolyzing the acyloxy substituent of one of the enantiomers in the reaction mixture, and recovering β-lactam having an unhydrolyzed acyloxy substituent from the reaction mixture.
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X1 is —OX6;
X2 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or heterocyclo;
X3 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or heterocyclo;
X4 is hydrocarbyl, substituted hydrocarbyl, or heterocyclo;
X5 is hydrogen, hydrocarbyl, substituted hydrocarbyl, —COX10, —COOX10, or —CONX8X10;
X6 is acyl;
X8 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or heterocyclo; and
X10 is hydrocarbyl, substituted hydrocarbyl, or heterocyclo.
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This application claims the benefit of U.S. Provisional Application No. 60/160,103 filed Oct. 18, 1999.
The present invention relates to enzymatic processes for the resolution of enantiomeric mixtures of β-lactams useful in the preparation of taxanes.
The taxane family of terpenes, of which taxol and docetaxel are members, has attracted considerable interest in both the biological and chemical arts. Such taxanes may be prepared through a variety of semi-synthetic routes. In one, a β-lactam is coupled to a derivative of 10-deacetylbaccatin III to form a sidechain at the C-13 position of the derivative. As the stereochemistry of these taxanes may affect their pharmaceutical activity, methods allowing efficient stereospecific preparation of the intermediate β-lactam, as well as the final taxane products, have been the subject of investigation.
Brieva et al. (Brieva, R.; Crich, J. Z. and Sih, C. J., J. Org. Chem. 1993,58, 1068) reported that racemic β-lactam underwent selective kinetic hydrolysis with several Pseudomonas lipases and two penicillinases. Pseudomonas lipases used by Brieva et al. include P-30, AK and K-10.
Similarly, Patel reported in U.S. Pat. No. 5,879,929, that enantiomeric mixtures of certain β-lactams and, in particular, racemic mixtures of certain β-lactams, can be resolved by a stereoselective hydrolysis using a variety of lipases and enzymes. Lipases identified by Patel include Amano PS-30 (Pseudomonas cepacia), Amano GC-20 (Geotrichum candidum), Amano APF (Aspergillus niger), Amano AK (Pseudomonas sp.), Pseudomonas fluorescens lipase (Biocatalyst Ltd.), Amano Lipase P-30 (Pseudomonas sp.), Amano P (Pseudomonas fluorescens), Amano AY-30 (Candida cylindracea), Amano N (Rhizopus niveus), Amano R (Penicillium sp.), Amano FAP (Rhizopus oryzae), Amano AP-12 (Aspergillus niger), Amano MAP (Mucor meihei), Amano GC-4 (Geotrichum candidum), Sigma L-0382 and L-3126 (porcine pancreas), Lipase OF (Sepracor), Esterase 30,000 (Gist-Brocarde), KID Lipase (Gist-Brocarde), Lipase R (Rhizopus sp., Amano), Sigma L-3001 (Wheat germ), Sigma L-1754 (Candida cylindracea), Sigma L-0763 (Chromobacterium viscosum) and Amano K-30 (Aspergillus niger). Enzymes identified by Patel include enzymes derived from animal tissue such as esterase from pig liver, α-chymotrypsin and pancreatin from pancreas such as Porcine Pancreatic Lipase (Sigma). While these enzymes may be used in the stereoselective hydrolysis of β-lactams, the required purification of the enzyme can significantly increase the cost of the preparation of the β-lactam.
Whitesell et al. (Whitesell, J. K. Lawrence, R. M. Chimia, 1986, 40, 315) and Basavaiah et al. (Basavaiah,, D. and Rao, P. Tetrahedron. Asym., 1994, 5, 223-234) reported successful application of pig liver acetone powder (PLAP), bovine liver acetone powder (BLAP) and chicken liver acetone powder (CLAP), in the resolution of numerous chiral secondary alcohols. Experimental evidence obtained to date, however, suggests that the use of these materials results in a product having relatively low optical purity. While the reason for this is not entirely clear, it is believed that this is the result of incomplete reaction rather than the enzyme's lack of selectivity which, in turn, is likely a consequence of inconsistent amounts of active enzyme present in different batches of the liver acetone powder.
Among the objects of the present invention, therefore, is the provision of enzymatic processes for the resolution of enantiomeric mixtures of β-lactams useful in the preparation of taxanes which offers improved reproducibility as compared to processes which employ acetone powders of animal livers and which compares favorably in cost to processes which employ purified lipases and other enzymes.
Briefly, therefore, the present invention is directed to a process for the resolution of a racemic mixture of β-lactams which contain an ester. The process comprises selectively hydrolyzing the ester of one of the enantiomers by combining the mixture with homogenized liver.
Other objects and features of this invention will be in part apparent and in part pointed out hereinafter.
In general, the β-lactam enantiomers in the mixture have the following structural formula:
X1 is —OX6;
X2 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or heterocyclo;
X3 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or heterocyclo;
X4 is hydrocarbyl, substituted hydrocarbyl, or heterocyclo;
X5 is hydrogen, hydrocarbyl, substituted hydrocarbyl, —COX10, —COOX10, or —CONX8X10;
X6 is acyl;
X8 is hydrogen, hydrocarbyl, substituted hydrocarbyl, or heterocyclo; and
X10 is hydrocarbyl, substituted hydrocarbyl, or heterocyclo.
Preferably, X2 and X3 are hydrogen and the mixture contains the 3S,4R and 3R,4S enantiomers, and more preferably a racemic mixture of these enantiomers. Still more preferably, X2 and X3 are hydrogen; X5 is hydrogen, hydrocarbyl, substituted hydrocarbyl, —COX10, or —COOX10; X10 is alkyl, aryl or heterocyclo; and the mixture contains the 3S,4R and 3R,4S enantiomers, preferably a racemic mixture of these enantiomers. In a particularly preferred embodiment, X2 and X3 are hydrogen; X5 is hydrogen, hydrocarbyl, substituted hydrocarbyl, —COX10, or —COOX10; X10 is alkyl, aryl or heterocyclo; X4 is 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-thienyl, 3-thienyl, substituted phenyl (substituted with any of the substituents identified elsewhere herein as hydrocarbyl substituents such as halo or nitro with the phenyl being mono or poly substituted in one or more of the ortho, meta or para positions), cycloalkyl, or alkenyl, and the mixture contains the 3S,4R and 3R,4S enantiomers, preferably a racemic mixture of these enantiomers.
Enantiomeric mixtures of the β-lactam starting materials may be obtained as described in Example 1 herein, or by methods analogous to those described in U.S. Pat. No. 5,229,526 which is incorporated herein by reference.
Homogenates of fresh or fresh frozen crude liver may be prepared using a high speed blender or other grinder. The liver is ground into pieces of a relatively small size and suspended in an aqueous solution. Preferably, about 1 pound (about 450 grams) of liver is combined with sufficient liquid to form about 0.5 to about 2 liters of homogenate, more preferably about 0.75 to about 1.25 liters, and most preferably about 1 liter of homogenate. In a preferred embodiment, the homogenate is buffered, preferably to a pH of about 8 with a phosphate or other suitable buffering agent.
Derivatives of homogenates are also included within the invention, such as refined fractions. To obtain refined fractions one may subject the homogenate to a series of fractionation procedures, the number of fractionation steps employed being dependent on the degree of purification desired. The series of fractionation steps could involve column chromatography such as a gel filtration column, centrifugation, heat treatment, precipitation, filtration or various other appropriate means of purification.
In general, the liver may be obtained from any animal. Preferably, the liver is avian or mammalian, more preferably chicken, turkey, pig or beef, and most preferably beef.
In general, a solution of β-lactam mixture in an organic solvent is combined with the homogenate to form a reaction mixture which contains about 1 gram of β-lactam to about 5 ml. to about 100 ml. of homogenate, more preferably about 1 gram of β-lactam to about 50 ml. of homogenate (with the homogenate containing about 450 grams of liver and sufficient liquid to form about 1 liter of homogenate). The reaction mixture is preferably adjusted to and maintained at about pH 7 to pH 8, preferably with a buffer, more preferably with a phosphate buffer.
The hydrolysis is preferably conducted in an aqueous, such as a buffered aqueous (e.g., phosphate buffer), medium or in an aqueous medium containing a miscible or immiscible organic solvent. For example, the reaction may be conducted in a biphasic solvent system comprising an organic phase, immiscible in water, and an aqueous phase.
Solvents for the organic phase of a biphasic solvent system may be any organic solvent immiscible in water, such as toluene, benzene, hexane, cyclohexane, xylene, trichlorotrifluoroethane, dichloromethane, ether and the like, and is preferably ether or toluene. Typically, the concentration of the β-lactam mixture will be about 0.1 to about 1 millimolar. The aqueous phase is water, preferably deionized water, or a suitable aqueous buffer solution, especially a phosphate buffer solution. The biphasic solvent system preferably comprises between about 10 to 90 percent by volume of organic phase and between about 90 to 10 percent by volume of aqueous phase.
The reaction time may be selected based on the homogenate, the temperature and the enzyme concentration. Temperatures of from about 4� C. to about 60� C. are preferably employed.
The products of the stereoselective conversions may be isolated and purified by methodologies such as extraction, distillation, crystallization, column chromatography, and the like.
The terms "hydrocarbon" and "hydrocarbyl" as used herein describe organic compounds or radicals consisting exclusively of the elements carbon and hydrogen. These moieties include alkyl, alkenyl, alkynyl, and aryl moieties. These moieties also include alkyl, alkenyl, alkynyl, and aryl moieties substituted with other aliphatic or cyclic hydrocarbon groups, such as alkaryl, alkenaryl and alkynaryl. Preferably, these moieties comprise 1 to 20 carbon atoms.
The "substituted hydrocarbyl" moieties described herein are hydrocarbyl moieties which are substituted with at least one atom other than carbon, including moieties in which a carbon chain atom is substituted with a hetero atom such as nitrogen, oxygen, silicon, phosphorous, boron, sulfur, or a halogen atom. These substituents include halogen, heterocyclo, alkoxy, alkenoxy, alkynoxy, aryloxy, hydroxy, protected hydroxy, keto, acyl, acyloxy; nitro, amino, amido, nitro, cyano, and thiol.
The alkyl groups described herein are preferably lower alkyl containing from one to six carbon atoms in the principal chain and up to 20 carbon atoms. They may be straight or branched chain and include methyl, ethyl, propyl, isopropyl, butyl, hexyl and the like.
The alkenyl groups described herein are preferably lower alkenyl containing from two to six carbon atoms in the principal chain and up to 20 carbon atoms. They may be straight or branched chain and include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, and the like.
The alkynyl groups described herein are preferably lower alkynyl containing from two to six carbon atoms in the principal chain and up to 20 carbon atoms. They may be straight or branched chain and include ethynyl, propynyl, butynyl, isobutynyl, hexynyl, and the like.
The terms "aryl" or "ar" as used herein alone or as part of another group denote optionally substituted homocyclic aromatic groups, preferably monocyclic or bicyclic groups containing from 6 to 12 carbons in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl or substituted naphthyl. Phenyl and substituted phenyl are the more preferred aryl.
The terms "halogen" or "halo" as used herein alone or as part of another group refer to chlorine, bromine, fluorine, and iodine.
The terms "heterocyclo" or "heterocyclic" as used herein alone or as part of another group denote optionally substituted, fully saturated or unsaturated, monocyclic or bicyclic, aromatic or nonaromatic hydrocarbon groups having at least one heteroatom in at least one ring, and preferably 5 or 6 atoms in each ring. The heterocyclo group preferably has 1 or 2 oxygen atoms, 1 or 2 sulfur atoms, and/or 1 to 4 nitrogen atoms in the ring, and may be bonded to the remainder of the molecule through a carbon or heteroatom. Exemplary heterocyclo include furyl, thienyl, pyridyl and the like. Exemplary substituents include one or more of the following groups: hydrocarbyl, substituted hydrocarbyl, keto, hydroxy, protected hydroxy, acyl, acyloxy, alkoxy, alkenoxy, alkynoxy, aryloxy, halogen, amido, amino, nitro, cyano, and thiol.
The acyl moieties described herein contain hydrocarbyl, substituted hydrocarbyl or heterocyclo moieties.
The term "stereoselective conversion," as used herein, refers to the preferential reaction of one enantiomer relative to another, that is, asymmetric, enantioselective, reaction. Likewise, the terms "stereoselective hydrolysis", refers to the preferential hydrolysis of one enantiomer relative to another.
The term "mixture," as said term is used herein in relation to enantiomeric compounds, denotes mixtures having equal (racemic) or non-equal amounts of enantiomers.
The term "resolution" as used herein denotes partial, as well as, preferably, complete resolution.
The terms "hydroxyl protecting group" and "hydroxy protecting group" as used herein denote a group capable of protecting a free hydroxyl group ("protected hydroxyl") which, subsequent to the reaction for which protection is employed, may be removed without disturbing the remainder of the molecule. A variety of protecting groups for the hydroxyl group and the synthesis thereof may be found in "Protective Groups in Organic Synthesis" by T. W. Greene, John Wiley and Sons, 1981, or Fieser & Fieser. Exemplary hydroxyl protecting groups include methoxymethyl, 1-ethoxyethyl, benzyloxymethyl, (.beta.-trimethylsilylethoxy)methyl, tetrahydropyranyl, 2,2,2-trichloroethoxycarbonyl, t-butyl(diphenyl)silyl, trialkylsilyl, trichloromethoxycarbonyl and 2,2,2-trichloroethoxymethyl.
To a 4-L Erlenmeyer flask equipped with a mechanical stirrer was added a solution of 62 g (0.205 mol) of recrystallized racemic β-lactam in 1.0 L of toluene. The solid was completely dissolved by warming with a 40� C. water bath and then cooling to ambient temperature. To a 1-L graduated cylinder was added 87.1 g (0.5 mol) of K2HPO4, and 4.9 g (0.036 mol) of KH2PO4 diluted to the 1000 mL mark with RO water and mixed to dissolve completely. A beef liver suspension was prepared by adding 20 g of frozen beef liver (Premium Select Brand, Nebraskaland, Inc., New York) to a blender and then adding the pH 8 buffer to make a total volume of 1 L. The mixture was blended to make a homogeneous suspension which was then added directly to the toluene solution. The mixture was stirred for 22 h at ambient temperature. The layers were separated and the aqueous layer was extracted with 1 L of ethyl acetate. The organic layers were combined and concentrated to give 67 g of white powder. The powder was recrystallized from 600 mL of hot absolute ethanol to give 23.4 g (0.078 mol, 38%) of optically pure β-lactam (+)− m.p. 153-155� C.; [α]20 589=+38.1� (MeOH, c=0.7).
As noted previously, others have reported successful application of pig liver acetone powder (PLAP), bovine liver acetone powder (BLAP) and chicken liver acetone powder (CLAP), in the resolution of numerous chiral secondary alcohols. The application of a BLAP biphasic enzymatic resolution procedure to (�)-1a resulted in 37% yield of the hydroxy β-lactam (−)-2a and a 33% yield of the acetoxy β-lactam (−)-1a after 3 h at room temperature (Scheme 1).
a: R4=Ph, RN=H
b: R4=2-thienyl, RN=H
c: R4=3-thienyl, RN=H
d: R4=2-furyl, RN=H
e: R4=3-furyl, RN=H
f: R4=p-bromophenyl, RN=H
g: R4=1-(2-methyl-1-propenyl, RN=H
h: R4=cyclobutyl, RN=H
i: R4=p-nitrophenyl, RN=H
j: R4=2-pyridyl, RN=H
k: R4=Ph, RN=PMP
l: R4=2-pyridyl, RN=PMP
m: R4=2-pyridyl, RN=PMP
n: R4=4-pyridyl, RN=PMP
o: R4=p-nitrophenyl, RN=PMP
The hydroxy β-lactam (−)-2a was shown to be optically pure by comparison to the reported specific rotation and by 1H NMR studies on its Mosher ester as well as Eu(hfc)3 chemical shift analysis on the alcohol. The optical purity of recovered acetate (−)-1a varied from 76%ee to >95%ee, and was found to be dependent upon the batch of liver acetone powder used. Conversion of acetate (−)-1a to the desired hydroxy β-lactam (+)-2a was carried out using Liu's pyrolidine-pyridine procedure. Liu, J. H., Ph.D. Dissertation, The Florida State University, 1991. Thus, liver acetone powder is highly selective toward the 3S enantiomer of β-lactam. This selectivity was further confirmed by the fact that the optically pure (−)-3R,4S-β-lactam 1a was not hydrolyzed under the same conditions after 24 h. Therefore, the low optical purity of the recovered (−)-1a is the result of incomplete reaction rather than the enzyme's lack of selectivity. This is probably a consequence of inconsistent amounts of active enzyme present in different batches of the liver acetone powder. It was reasoned that this inconsistency could be eliminated if the enzyme was not subjected to the drying process in the acetone powder preparation.
Hence, a phosphate buffered beef liver solution (BBLS) was prepared by homogenizing 1 lb of frozen beef liver in a 0.5 M KH2PO4/K2HPO4 pH 8 buffer to make 1 L of total solution. A 50 mL aliquot of this BBLS was found to selectively hydrolyze the (+)-1a isomer from 1.0 g of (�)-1a in 15 minutes, leaving the (−)-1a isomer unchanged. The enantiomeric excess of both the acetate and the alcohol was found to be essentially 100% as determined by the methods described previously.
Similarly, buffered chicken (BCLS), pig (BPLS), and turkey (BTLS) liver solutions showed the same activity toward (�)-1a. Table I summarizes the enzyme sources used in the resolution and their efficiencies.
It is unclear which enzyme in the liver is responsible for this enantioselective lipase activity. Undoubtedly, there is more than one active enzyme in a crude solution of beef liver. Nevertheless, this enzymatic methodology was found to be ideally suited for the preparation of other optically active β-lactam analogs. Table II shows a variety of β-lactam substrates which were resolved by BBLS. As indicated in the table, the BBLS enzymatic resolution procedure proved effective for almost all of the substrates examined. Problems did arise in the hydrolysis of substrates containing highly polar groups. For example, when R4=p-nitrophenyl and RN=H, the resulting alcohol was not isolable. Similar problems were also encountered with substrates where R4=pyridyl. It is unclear whether the product was lost to the aqueous layer in these reactions or underwent decomposition during the course of the reaction.
To remedy this problem, the RN group was changed to the more hydrophobic p-methoxyphenyl (PMP) group. As can be seen from Table II, introduction of the PMP group increased the time required for the complete hydrolysis of the 3S,4R enantiomer. This is probably due to the loss of a hydrogen bonding site in addition to the increase in steric bulk. Nonetheless, this allowed the alcohol product to be isolated and characterized. Interestingly, it was found that the hydrolyzed products from the substrates having R4=2-pyridyl, 4-pyridyl and 4-nitrophenyl were a mixture of cis and trans hydroxy β-lactams.
Currently, this enzymatic resolution procedure is the most general and convenient protocol for the production of various optically active β-lactams suitable for the preparation of taxol C13 side chain analogs.
Frozen livers were bought from a local grocery store. Beef liver was packed by Fremont Beef Company, Fremont, Nebr. 68025.
General Procedure for Preparation of Liver Acetone Powder. Beef Liver Acetone Powder (BLAP).
Frozen beef liver (250 g) was homogenized with a blender, and 200 mL of acetone was added. The precipitate was collected by filtration through coarse filter paper and dried under high vacuum for 2 h. The dried mass was further powderized with a blender to give 78 g BLAP and was stored at −30� C.
General Procedure for Liver Acetone Powder Mediated Hydrolysis. β-Lactam (−)-1a.
To a solution of 1.0 g (4.87 mmol) of (�)-1a in 10 mL of diethyl ether at 25� C. was added 40 mL of 0.5 M phosphate buffer and 1.0 g of BLAP. After 3 h, 100 mL of brine was added. After 10 min, the mixture was diluted with 200 mL of ethyl acetate. The organic layer was separated, washed with brine and dried over Na2SO4 and concentrated. Flash chromatography eluting with 75% ethyl acetate in hexanes gave 0.33 g (1.6 mmol) of (−)-1a as the less polar fraction and 0.29 g (1.8 mmol) of (−)-2a as the polar fraction.
General Procedure for Phosphate Buffer Liver Solution. Buffered Beef Liver Solution (BBLS).
Frozen beef liver (500 g) was homogenized with a blender. The mixture was diluted to 1 L of volume with pH 8 (˜0.5 M of PO4 −2) phosphate buffer and stored at −30� C. (no loss of enzyme activity after 15 days).
General Procedure for Buffered Liver Solution Mediated Hydrolysis. β-Lactam (−)-1a.
To a solution of 1.0 g (4.87 mmol) of (�)-1a in 100 mL of diethyl ether at 25� C. was added 50 mL of the BBLS and 50 mL of phosphate buffer (0.5 M, pH 8). After 15 min, 10 mL of brine was added. The reaction mixture was diluted with 200 mL of acetone, filtered and concentrated. The residue was diluted with 200 mL of ethyl acetate, washed with brine, dried over Na2SO4 and concentrated to give a yellow solid. Flash chromatography eluting with 75% ethyl acetate in hexane gave 0.480 g (2.34 mmol, 48%) of (−)-1a as the less polar fraction and 0.354 g (2.17 mmol, 45%) of (−)-2a as the polar fraction.
1a: mp 187-189� C.; [α]578 25=−46� (c=1.0, CHCl3); >95% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 1.67 (s, 3H), 5.04 (d, J=4.5 Hz, 1H), 5.89 (dd, J=4.5, 2.8 Hz, 1H), 6.22 (bm, 1H), 7.34 (m, 5H).
2a: mp 190-192� C.; [α]578 25=−175� (c=1.0, MeOH); >95% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 1.95 (d, J=9.9 Hz, 1H), 4.96 (d, J=4.6 Hz, 1H), 5.12 (m. 1H), 6.15 (bm, 1H), 7.41 (m, 5H).
β-Lactam (−)-1b.
Following the general procedure, 0.57 g (0.65 mmol) of (�)-1b was treated with BBLS for 0.25 h to give 0.225 g (0.14 mmol, 30%) (−)-1b.
(−)-1b: mp 135-136� C.; [α]578 25=−93� (c=1.0, CHCl3); 1H NMR (300 MHZ, CDCl3) δ (ppm): 1.84 (s, 3H), 5.28 (d, J=4.6 Hz, 1H), 5.87 (dd, J=4.6, 2.7 Hz, 1H), 6.55 (bm, 1H), 7.02 (m, 2H), 7.33 (dd, J=4.6, 1.7 Hz, 1H).
2b: mp 144-145� C.; [α]578 25=−135� (c=1.0, MeOH); >95% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 2.55 (d, J=9.7 Hz, 1H), 5.1 (m, 1H), 5.17 (d, J=5.0 Hz, 1H), 6.33 (bm, 1H), 7.10 (m, 2H), 7.37 (dd, 4.5, 1.3 Hz, 1H).
β-Lactam (−)-1d.
Following the general procedure, 0.57 g (2.92 mmol) of (�)-1d was treated with BBLS for 0.25 h to give 0.225 g (1.15 mmol, 40%) of (−)-1d and 0.16 g (1.04 mmol, 35%) of (−)-2d.
(−)-1d: mp 158-159� C.; [α]578 25=−134� (c=1.1, CHCl3); >95% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 1.90 (s, 3H), 5.04 (d, J=5.0 Hz, 1H), 5.89 (d, J=5.0, 2.0 Hz, 1H), 6.20 (bm, 1H), 6.40 (bm, 2H), 7.44 (s, 1H)
2d: mp 144-145� C.; [α]578 25=−107� (c=1.0, MeOH); >95% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 2.78 (bm, 1H), 3.49 (d, J=5.0 Hz, 1H), 4.91 (d, J=5.0 Hz, 1H), 5.12 (bm, 1H), 6.13 (bm, 1H), 6.45 (m, 2H), 7.49 (d, J=1.2 Hz, 1H)
β-Lactam (−)-1i.
Following the general procedure, 0.1 g (0.4 mmol) of (�)1i was treated with BBLS for 1 h to give 0.030 g (0.14 mmol, 30%) (−)-1i.
(−)-1i: mp 198-199� C.; [α]578 25=−49� (c=1.0, CHCl3); 90% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 1.73 (s, 3H), 5.16 (d, J=4.7 Hz, 1H), 5.95 (dd, J=4.7, 3.1 Hz, 1H), 6.58 (bm, 1H), 7.52 (d, J=8.5 Hz, 2H), 8.24 (d, J=8.5 Hz, 2H)
β-Lactam (−)-1j.
Following the general procedure, 1.0 g of (�)-1j was treated with BBLS for 24 h to give 0.223 g of (−)-1j.
(−)-1j: mp 99-100� C.; [α]578 25=−5� (c=1.0, CHCl3); >95% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 1.74 (s, 3H), 5.15 (d, J=5.1 Hz, 1H), 6.06 (dd, J=5.1, 2.3 Hz, 1H), 6.46 (bm, 1H), 7.26 (m, 1H), 7.36 (d, J=7.8 Hz, 1H), 7.73 (ddd, J=8.5, 7.4, 2.1 Hz, 1H), 8.61 (d, J=4.9 Hz, 1H).
β-Lactam (−)-1k.
Following the general procedure, 1.0 g (3.21 mmol) of (�)-1k was treated with BBLS for 24 h to give 0.42 g (1.35 mmol, 42%) of (+)-1k and 0.377g (01.44 mmol, 45%) of (−)-2k.
(+)-1k: mp 164-165� C.; [α]578 25=+8� (c=1.0, CHCl3); >95% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 1.67 (s, 3H), 3.75 (s, 3H), 5.34 (d, J=5.0 Hz, 1H), 5.94 (d, J=5.0 Hz, 1H), 6.81 (d, J=8.4 Hz, 2H), 7.31 (m, 7H)
β-Lactam 1l: mp 154-155� C.; [α]578 25=+42� (c=1.0, CHCl3); >95% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 1.74 (s, 3H), 3.76 (s, 3H), 5.48 (d, J=5.3 Hz, 1H), 6.12 (d, j=5.3 Hz, 1H), 6.81 (d, J=9.1 Hz, 2H), 7.29 (m, 4H), 7.68 (ddd, J=7.7, 7.8, 1.7, Hz, 1H), 8.64 (d, J=4.7 Hz, 1H);
β-Lactam 1m: mp 158-160� C.; [α]578 25=+8.7� (c=1.0, CHCl3); >95% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 1.74 (s, 3H), 3.76 (s,3H), 5.38 (d, J=4.5 Hz, 1H), 5.98 (d, J=4.5 Hz, 1H), 6.81 (d, J=9.1 Hz, 2H), 7.25 (d, J=9.1 Hz, 2H), 7.30 (m, 1H), 7.64 (m, 1H), 8.61 (m, 2H).
β-Lactam 1n: mp 158-159� C.; [α]578 25=+25� (c=1.0, CHCl3); >95% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 1.74 (s, 3H), 3.76 (s, 3H), 5.32 (d, J=5.0 Hz, 1H), 5.98 (d, J=5.0 Hz, 1H), 6.83 (d, J=9.1 Hz, 2H), 7.23 (m, 4H), 8.62 (m, 2H);
β-Lactam 2n-trans: 1H NMR (300 MHZ, CDCl3) δ (ppm): 3.75 (s, 3H), 4.70 (s, 1H), 4.84 (s, 1H), 6.79 (m, 2H), 7.16 (m, 2H), 7.24 (d, J=5.5 Hz, 2H), 8.61 (d, J=5.5 Hz, 2H).
β-Lactam 1o.
Following the general procedure, 1.0 g (2.8 mmol) was treated with BBLS for 24 h to give 0.35 g (1.11 mmol, 35%) of (+)-1o, 0.11 g (0.35 mmol, 12%) of 2o and 0.13 g (0.41 mmol, 15%) of 2o-trans.
1o: mp 156-160� C.; [α]578 25=+48� (c=1.0, CHCl3); >95% ee; 1H NMR (300 MHZ, CDCl3) δ (ppm): 1.74 (s, 3H), 3.76 (s, 3H), 5.45 (d, J=5.1 Hz, 1H), 6.00 (d, J=5.1 Hz, 1H), 6.83 (d, J=8.9 Hz, 2H), 7.23 (d, J=8.9 Hz, 2H), 7.50 (d, J=9.2 Hz, 2H), 8.23 (d, J=9.2 Hz, 2H);
2o: mp 158-159� C.; [α]578 25=−52� (c=1.0, MeOH); >95% ee; 1H NMR (500 MHZ, CDCl3) δ (ppm): 2.37 (m, 1H), 3.76 (s, 3H), 5.31 (m, 1H), 5.35 (d, J=5.0 Hz, 1H), 6.38 (d, J=9.1 Hz, 2H), 7.24 (d, J=9.1 Hz, 2H), 7.52 (d, J=8.8, 2H), 8.27 (d, J=8.8, 2H);
2o-trans: mp 98-100� C.; 1H NMR (500 MHZ, CDCl3) δ (ppm): 3.40 (d, J=6.2 Hz, 1H), 3.74 (s, 3H), 4.73 (dd, J=6.3, 1.1 Hz, 1H), 6.79 (d, J=9.3 Hz, 2H), 7.16 (d, J=9.3 Hz, 2H), 7.51 (d, J=9.3 Hz, 2H), 8.25 (d, J=9.3 Hz, 2H).
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text: The best season opener by far! Battlestar just keeps bringing it. Makes the other shows look like wannabe's. Acting, writing, directing all brilliant. I also think that Roslin might just be a CYLON. If I were a cylon and saw how much power she had over the people that's what I would do.


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Aug 15
Aug 10
Lady and the Krunk is back in Asheville again for some Rootball, blues, and PBR.
Jul 14
Jun 14
Jun 1
Wilkesboro Summer Concert Seres
Sounds Like: Adele, Jerry Lee Lewis, Ray Charles, Peggy Lee (Norma Delores Egstrom), Stevie Wonder
Label: not signed
Bio: "ladyandthekrunk put on an absolutely fantastic show tonight. with their music one second you are in a saloon in 1888 out in the Old West with a Rock n Roll twist, the next minute your in 1935 New Orleans in a speakeasy listening to some fantastic bluesy torchsong, the next its 1973 New York and ...See Full Bio
Brand new tune "He Waits" http://www.kickstarter.com/projects/jchaffin/the-horror-in-clay-cthulhu-tiki-mug-production-run/posts .
"Musical fads come and go, but it looks like the blues is here to stay. "Murphy's Stride" is a slow-burn of song with Chaffin bringing her timeless delivery to the vocals and Golden adding nifty fuzz guitar licks.The band gets into a slow smooth groove for "Queen of Spades," a song that would be right at home in that night club where animated chanteuse Jessica Rabbit sang in "Who Framed Roger Rabbit?" Harris introduces the shuffle-esque "Can't Get Enough" with a bouncy upright bass line before Golden kicks in with the wah-wah pedal. It's the perfect title for the last song on the four-track CD that the band is utilizing to introduce club owners and reviewers to their sound. It leaves the listener wanting more. "


text:
Afghanistan will benefit if they get to play the IPL
Top Stories
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There are often very good reasons why schedules are the way they are and it is also true that those commenting on schedules have fewer variables to consider than those making them. So there must be a reason why the first four games of the World T20 are so underwhelming. I am writing this with the tournament three days old and that compelling game, the one that forces cricket lovers to stop what they are doing and watch, is still somewhere in the distance. Hopefully one of the qualifiers, or Bangladesh, will get this jamboree up and going because otherwise it doesn't really begin till the 27th when the Super Eights start.
That, either way, is a new beginning because teams don't carry their points from the qualifiers and that means there are a few dead rubbers. Like India vs England on the 23rd. As the tournament hopes to gather steam it is suddenly up against what should have been a marquee game but is really a warm-up game. To allow people to choose the matches they want to watch, and that is a valid reason, teams are pre-seeded into the Super Eights and so whether or not India beats England doesn't really matter to the tournament. Maybe there is a case for carrying points against the other qualifiers to inject greater value to the earlier games.
That is not to say it hasn't been fun watching them and I enjoyed watching Afghanistan's spirited cricketers try and make the most of the little opportunities thrown their way. Theirs has been the story of world cricket over the last five years and the good news is that it doesn't seem likely to end very quickly. They have withstood political turnoil, violence and displacement to come so far and hereafter other barriers must seem like small hurdles in the way of their spirit.
... contd.


text:
Sometimes, it feels as if we are eavesdropping on day-to-day conversations rather than just hearing the usual litany of platitudes and regrets.
Sometimes, it feels as if we are eavesdropping on day-to-day conversations rather than just hearing the usual litany of platitudes and regrets.
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An excerpt of Tony Fitzpatrick's column, "Dime Stories," which has its first published compilation in stores this month.
Nick Allen picks one of his favorite Roger reviews.
An excerpt of Tony Fitzpatrick's column, "Dime Stories," which has its first published compilation in stores this month.
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At the beginning of this film, Richard Pryor is clearly nervous. He is back on a stage for the first time since he set himself on fire. That means he is working with the stand-up comedian's greatest handicap, the audience's awareness of his vulnerability. Whatever else they do, comics must project utter confidence in their material, and when Pryor had his accident, he also had his whole hip image blown out from under him. So it's a shaky start. He begins by almost defiantly using the word "fuck" as an incantation, employing it not so much for shock value (does it still have any?) as for punctuation. His timing is a little off. He is not, at first, the supremely confident, cocky Richard Pryor of his earlier films. But as he gets rolling, as he populates the stage with a whole series of characters, we watch the emergence of a Richard Pryor who is older, wiser, and funnier than before. And the last fifty or sixty minutes of this film are extraordinary.
"Richard Pryor Live On The Sunset Strip" was filmed at the Hollywood Palladium, down at the unfashionable east end of that legendary street of rock clubs, restaurants, hookers and heroes, hot-pillow motels, and some of the most expensive real estate in the world. The movie opens with a montage of the strip's neon signs (including the Chateau Marmont, where John Belushi died). Then it cuts inside to the Palladium auditorium, and Pryor walks onstage and lays claim to being the most talented one-man stage show in existence right now.
His gift is to be funny and painfully self-analytical at the same time. Like Bill Cosby, he gets a lot of his material out of memories of growing up black in America. But he sees deeper than Cosby, and his vignettes capture small truths and build them into an attitude. In the brilliant middle sections of this film, he uses just his own voice and body to create little one-act plays, such as the one where he recalls working in a Mafia-owned nightclub in Ohio. In that one, his Italian-American-gangster accent is perfectly heard; in another skit, about the animals in Africa, he turns into a gifted physical comedian, getting laughs out of his impressions of the movements of gazelles, water buffaloes, and lions--and ending with a hilarious observation of the body language of two whites passing each other on the street in black Africa.
The whole middle passage of the film is that good. The last twenty minutes is one of the most remarkable marriages of comedy and truth I have ever seen. He talks with great honesty about his drug addiction, his accident, and how his life has changed since he stopped using drugs. He confesses that in the three weeks before his accident, he holed up alone in his room with his cocaine pipe, which talked to him in reassuring, seductive tones uncannily like Richard Nixon's. Then a friend, the actor Jim Brown, came to see him, and asked him flat-out, "Whatcha gonna do?" There was nothing he wanted to do but hide in drugs. What he finally did was set himself on fire.
I saw the film the same day that actor Shay Duffin opened his one-man evening with Brendan Behan at the Apollo Theater Center in Chicago. The papers that day carried the news that Belushi had overdosed. Behan, of course, killed himself with alcohol. Some day, inevitably, an actor will give us an evening with John Belushi. The dramatic structure is all there, for the Behans and Belushis: The genius, the laughter, and the doomed drive to self-destruction. Watching "Richard Pryor Live On The Sunset Strip", a breathtaking performance by a man who came within a hair of killing himself with drugs, was like a gift, as if Pryor had come back from the dead to perform in his own one-man memory of himself. It is good we still have him. He is better than ever.
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Three films starring Gina Lollobrigida have been released on Blu-ray; Glenn Kenny looks at them and her entire career.
MTV's Scream and CBS's Zoo premiere tonight. One is worth your time. Which one?


text:
Originally written on StraitPinkie.com | Last updated 7/16/13
2K announced the emphatic return of Ultimate Warrior to the ring – virtually – in WWE 2K14, the forthcoming installment in the flagship WWE video game franchise. Making his long-awaited arrival from Parts Unknown, the self-professed "Founding Father of Life Intensity" will be an exclusive playable character for those who pre-order the game at any participating retailer for the Xbox 360 games and entertainment system from Microsoft or PlayStation3 computer entertainment system. "Immortality is inspiration, pure and simple. An example to others that they, too, can do things larger than the life they are actually living, and Ultimate Warrior was the pure embodiment of this belief, in what has proven to be a very attention-getting and inspiring way," said Warrior. "It was my good fortune to be his creator and performer, and I am humbled by all those fans who've not only kept his legacy alive, but deepened it over time. In WWE 2K14, Ultimate Warrior's creed, 'Always Believe,' lives on." Making his WWE debut in 1987, Ultimate Warrior garnered worldwide attention and became a pop-culture phenomenon for his iconic music and ring entrance, zealous personality, boundless energy and dominant in-ring prowess. Though he faced many rivals throughout his career, including Honky Tonk Man, "Ravishing" Rick Rude, Sgt. Slaughter, "Macho Man" Randy Savage and Undertaker, perhaps his most celebrated match was against Hulk Hogan in "The Ultimate Challenge" at WrestleMania VI on April 1, 1990. Warrior defeated Hogan that day to unify the WWE Championship and Intercontinental Championship, becoming the first WWE Superstar ever to hold both titles simultaneously. "There has never been another WWE Superstar quite like the Ultimate Warrior – his intensity and energy is unmatched, and his legacy is undeniable," said Chris Snyder, Senior Director of Marketing at 2K. "Fans love him, opponents fear him and everyone can agree that he's one of the most iconic Legends in WWE history. Pre-ordering WWE 2K14 is the only way we mere mortals will ever have a glimpse into the greatness that is Ultimate Warrior." Become Immortal – 2K's lineup of premier sports simulation titles expands with the company's upcoming release in the renowned WWE video game franchise, WWE 2K14. Developed by Yukes for the Xbox 360 and PlayStation 3 system, WWE 2K14 is positioned to be the most electrifying, authentic and comprehensive WWE video game experience to date. WWE 2K14 is not yet rated by the ESRB. Players who pre-order WWE 2K14 will receive Ultimate Warrior at no extra cost on launch day on October 29, 2013 in North America and November 1, 2013 internationally. For more information on WWE 2K14 and 2K, visit wwe.2k.com, facebook.com/WWEgames and @WWEgames on Twitter.
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By Catholic Online (NEWS CONSORTIUM)
6/25/2014 (1 year ago)
Catholic Online (www.catholic.org)
Cigarettes have never been good - for health reasons, among many other things. It now appears that they're even worse today than they were 50 years ago. Tactics developed by tobacco companies to keep users hooked have become even more insidious.
LOS ANGELES, CA (Catholic Online) - The Campaign for Tobacco-Free Kids has produced a revealing new infographic which explains how cigarettes have changed in the last five decades.
Doctors at the charity say that cigarettes today pose an even greater risk of disease than those sold in 1964 when the first warning about the health dangers came from the Surgeon General in the U.S. Research, based on a review of scientific studies and tobacco industry documents, as well as the Surgeon General's report fuel these frightening new findings.
Learn how you can fill in the gaps to end world hunger -- by going here --
Today's smokers have a far higher risk of lung cancer and chronic obstructive pulmonary disease than in 1964, in spite of users smoking fewer cigarettes, due to "changes in the design and composition of cigarettes."
The Campaign for Tobacco-Free Kids has produced a revealing new infographic which explains how cigarettes have changed in the last five decades.
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By Nikky Andres (NEWS CONSORTIUM)
Consuming large amounts of orange juice or grapefruit may increase the risk of the most dangerous type of skin cancer, melanoma, according to recent studies. MUNTINLUPA, PHILIPPINES (Catholic Online) - Dr. Walter Willett of the Harvard School of Public Health, who ... continue reading
By Catholic Online (NEWS CONSORTIUM)
Heralded as one of the "greatest public health achievements possible," World Health Organization director-general Margaret Chan has declared that the Caribbean nation of Cuba has become the first nation to eliminate the transmission of HIV and syphilis from ... continue reading
By Nikky Andres (NEWS CONSORTIUM)
The World Health Organization (WHO), animal health and national defense officers announced on June 30 the need for a wider international cooperation to sidestep the spread of animal diseases that could potentially be utilized as deadly biological weapons. ... continue reading
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You might not be entirely aware, but according to the World Health Organization, physical inactivity is now the fourth most notorious global killer. In fact, the impact of physical inactivity has been claimed as the reason for more fatalities than the collective effect ... continue reading
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The need to use sunscreen is something emphasized everyday, not only by dermatologists but also by the beauty industry, media, etc. It's basically everywhere. It is not an alien fact to us that using sunscreen religiously will help us combat premature aging, the risk ... continue reading
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Plastic surgery may seem to be a common medical procedure for several individuals around the globe, but the Catholic Church still has different points of views when it comes to changing the naturally bestowed beauty from God. Some medical practitioners, on the other ... continue reading
By Catholic Online (NEWS CONSORTIUM)
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Instead of simply recording his doctor's post-operation instructions, as intended, a Virginian man accidentally recorded the anesthesiologist's verbal onslaught against him while he was asleep. Concealing his identity, the patient filed a lawsuit, including the doctor ... continue reading
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Movie Locations, Paris
8 Reviews
8 Reviews
If this scene looks familiar, it might be that you have seen the 1938 film Hôtel du Nord by Marcel Carné (or snippets of it on the internet) and recognize this as the place where Arletty delivered her now-famous line about "atmosphère".
Actually she didn't say it here at all, but on a film set that had been built at great expense outside the film studios in Billancourt to look like this section of the Canal Saint-Martin in Paris. Originally Carné wanted to shoot the film here, on location, but it turned out that there was too much noise from commercial barge traffic and the like, so he had to retreat to the studio.
I must admit that when I first looked at this scene on YouTube or DailyMotion I only understood one word, atmosphère, but after repeated listenings I started getting accustomed to Arletty's accent and began to understand what was going on.
It turns out that she wasn't talking about the romantic atmosphere of Paris. She was reacting to something nasty that was said to her by Edmond, her pimp and lover, played by Louis Jouvet.
Edmond in this scene is wearing a baggy 1930s suit and tie and has a fishing rod slung over his shoulder. Today he is just going fishing along the canal, but he knows he had better get out of France very soon because two of his former gangster buddies are looking for him and want to kill him. She says she wants to go with him, to a foreign country or the colonies or anywhere.
His reaction is: No, it would be the same anywhere. I'm suffocating. I need a change of atmosphere, and my atmosphere is you!
She replies: This is the first time I've ever been called an atmosphere. If I'm an atmosphere then you're some sort of hick town out the sticks. (t'es un drôle de bled)
Then after a short rant she delivers her famous line:
« Atmosphère ! Atmosphère ! Est-ce que j'ai une gueule d'atmosphère ? »
This is a puzzling line for us foreigners, but my current theory is that it simply means: Do I look like an atmosphere? Or: Have I got the mug of an atmosphere?
This line is not in Eugène Dabit's novel, in fact the whole scene was invented by the screenplay writer Henri Jeanson, who never dreamed it would become a cult scene that would be replayed over and over in drama workshops in the 21st century.
What makes the line so funny is the mocking, sarcastic way Arletty says it in her delightfully slutty lower-class 1930s Parisian accent. In effect she is informing Edmond that his days as her pimp and lover are over and he should bugger off and get the **** out of her life.
At the end of the scene she hands him his fishing bag and stomps off the bridge, shouting "Good fishing and good atmosphere!"
Second photo: For those who don't recognize the scene, the mayor's office has helpfully set up a sign entitled "Atmosphère, atmosphère…" next to the bridge with a drawing of the film set. What makes the scene look different today is that the trees, which were saplings in 1938, have now had over seventy years to grow up into large leafy chestnut trees.
Third photo: A small boat going through the locks of the Récollets.
Fourth photo: Square Eugène Varlin.
Next review from July 2012: Canal cruise on the Canal Saint-Martin
One of the text panels at the exhibition Paris au Cinéma in June 2006 said that so-and-so many hundred permits are issued each year to shoot films on the streets of Paris, and so-and-so many dozen films are being shot in Paris on a given day.
Later that afternoon I actually did see some folks shooting a film with a hand-held camera at the Place du Châtelet. The scene was of a young man with a silly grin on his face walking spastically past the café and turning left at the end. They shot the same scene about six times, and the director –- that's the grim-looking chap behind the cameraman –- did not seem at all happy with how it was going. (Is he famous? Should I have recognized him?)
But eventually they packed up and left, so I guess they must have got it in the can.
If you ever see it on the screen, please let me know.
Second photo: Sometimes these film shootings can get really elaborate, like here on the Boulevard Saint-Jacques in June 2007, where dozens of trucks were lined up with the equipment for the film company.
In the Salle Saint Jean at the northeast corner of the Hôtel de Ville (City Hall) there is usually some sort of interesting (and free) exhibition going on. In June 2006 it was Paris au Cinéma, a fascinating and very detailed account of Paris in the movies from the beginnings of moving pictures up to the present day.
Second photo: The brothers Lumière began experimenting with the first moving pictures –- in Paris, of course* –- as early as 1895. Some early examples were shown at the exhibition, as well as stills and samples from just about every year since then.
*Thanks to VT member JLBG for pointing out that this "is not completely true though not really wrong". He writes: "The brothers Lumière experimented in Lyon, their home. The first ever film they shot, « workers going out of the Lumière factory » was shot 25 rue Saint Victor, Montplaisir, in Lyon. The patent for their film process was taken on February 13th 1895. The film was officially presented to the public in Paris, exactly at the seat of the « Société d'encouragement à l'industrie nationale », rue de Rennes in Paris, on March 22nd 1895. The Lumière factory produced photography plates. In Lyon there is a « rue du premier film » and a « rue des Frères Lumière ».
Thanks, Jean-Louis, for this information! On my recent visit to Lyon I took your advice and went to the Lumière Institute and Museum.
There are now three tips/reviews about this on my Lyon page:
• Villa Lumière
• Lumière Museum
• Institut Lumière
• Plus, believe it or not, a tip about a nearby restaurant, Le Bistro Autrement
Third photo: At the end of the exhibition Paris au Cinéma they had several big screens showing excerpts from famous films that were set in Paris. Makes you wonder to what extent our perceptions of Paris have been influenced by what we have seen in the movies.
The activity I am recommending is a film about the history of Paris done in 3D but without the need for glasses. It was something highly recommended to me by many of my friends from the US and also several French friends. On my last visit to Paris I went to see this film with a few friends and was blown away.
Although the film is Paris-Story's main attraction they also feature an interactive miniature of the city for visitors to look at. On this miniature there are the descriptions of many sites of Paris and with a touch of a button visitors can see the sites light up. The best part about this miniature in my opinion is the option to illuminate the buildings that were constructed in the same style of architecture. I was so surprised when the owner himself explained this to me.
What a delight the film was.
If you're tried of walking and need a break or it's rainy outside go see a french comedy. They use slapstick in their comedies so they're pretty funny and you'll understand some of it. Animations are even easier to follow but not always playing. The plus side to seeing a comedy in French is that you'll laugh at different parts of the movie then everyone else, makes it even funnier. I thought it would be impossible to see a movie in French not speaking a word of the language but I had a great time.
In the movie Before Sunset, Céline (Julie Delpy) tells the limo driver that she lives at 18 rue des Petites Ecuries near the Chateau-d'eau Métro station but the actual film location that was used is Cour de l'Etoile d'Or off of rue du Faubourg St-Antoine which abuts onto the 11th/12th arrondissements (nearby you could also walk along the Promenade Plantée also featured in the movie as the beautiful garden they walk through - underneath is the Viaduc des Arts).
Get off at the Ledru-Rollin Métro station, walk west. You'll pass the Cour de l'Ours and the Cour de Trois Frères on the right-hand (north) side. To find the latter more easily on a map just note that it is across from rue St-Nicolas. The next passage/court will be the one you seek. It's so tiny it isn't even labeled on Pages Jaunes (France's Yellow Pages website)! However, you can find it on their Photos de Ville website.
And this concludes our tour of Céline & Jesse's walk through Paris that one fateful day, Before Sunset.
Click HERE to start Celine & Jesse's journey.
I like hunting down locations for my favorite films.
Since 'Le Dernier Tango a Paris' (Last Tango) is one of my alltime favorites; Marlon Brando likely my favorite actor; and the Passy an attractive place to walk around, this was a fun afternoon.
Only going to post a couple of the exterior location shots with some Passy fotos, but if you like, for grins see if you can identify the location (in the film they put up phony street signs / addresses on the apartment as they usually do so it's not "rue Jules Verne").
I also checked out some of the interior shot locations around Passy and Montparnasse when I was close by (obsessive???? moi -???? )
The panoramic view at the La Samaritaine department store is breathtaking and you can get some absolutely beautiful shots there. If you've seen The Bourne Identity it was here that its main character, Jason Bourne, had one of his fight scenes and it was on Pont Neuf below they filmed another scene.
There is an outdoor cafe on the terrace. So if you want a small snack and/or a cafe it's possible to order here.
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Since Rinne's last start, the Predators have dropped in the Western Conference standings. Entering Monday, they sit 12th in the conference and four points out of the last wild card spot.
So as Nashville looks to make a playoff charge with 21 games remaining, they'll be getting a big upgrade in net very soon. After missing 51 games, Rinne is re-joining the Predators this week, with an expected return start on Tuesday against Pittsburgh.
Rinne made two rehab starts with the Predators AHL affiliate in Milwaukee over the weekend, stopping 33 of 35 shots faced in two games.
"It's been a long time since I'd played games," said Rinne. "It was a great opportunity for me to come back here to Milwaukee. I feel like it went both ways. I feel like I helped the team out a bit and they helped me to get back into game action."
On the ice with the Predators for the practice on Monday, Rinne said after his final rehab start that he's "ready to go," giving head coach Barry Trotz a decision to make with the Penguins coming to town.
To make room for Rinne, Devan Dubnyk was sent down to Milwaukee, but not before having to pass through waivers first.
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Your Home For a Happy, Healthy Life with Diabetes
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David, Diabetes Educator @ Diabetes Counselling Online here. This September will be my 35th year as a registered nurse. In all that time I have done many things: midwife in delivery suite for 15 years; cardio-thoracic intensive care for 5 years, and now as a diabetes educator for the past 18 years. The one thing…Read More
Helen Edwards, Director and Founder Diabetes Counselling Online Remember nobody's winning and nobody's losing, we are all just bumbling along trying to have a life. Just take moments today to breeeeathe in and breeeeathe out xx Helen E Food and mental health are closely connected Published by Helen Edwards· 4 June…Read More
Living with diabetes is hard work. Understanding the changes in your blood glucose level can be frustrating and can lead to burnout. Here's some information that is not often discussed when the subject of blood glucose level is raised with health care professionals. There are other hormones other than insulin that affect the blood sugar levels…Read More
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My very first blog for Diabetes Counselling Online was written on label reading because as a dietitian I have found it is such a popular topic with clients, to help them be clear on how to make healthier food choices when shopping. To help demonstrate the points made in that first blog, I thought we'd take…Read More
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Oh Sleep..'tis a gentle thing, belov'd from pole to pole.. Our occasional blogger, Dave Barnes, has shared his thoughts on the 'night life' experienced by most people living with type 1 diabetes: the lack of sleep, the various physical needs that must be attended to through the night, the impossibility of an uninterrupted night's…Read More
One of the main conclusions the United Kingdom Prospective Diabetes Study (UKPDS) investigators themselves have drawn from their findings is that combinations of treatments will routinely be needed for type 2 diabetes. It proved that glycemic control limits retinopathy (and probably other microvascular complications) as much for type 2 diabetic patients as had previously been…Read More
It's been more than a year since I wrote about grains. Recently there has been a research push involving grains and microbiota that people with diabetes should really know about for cardiovascular health, insulin resistance management and improved mortality. The Dietitians Association of Australia's (DAA) annual conference was held in Perth last week, and there…Read More
Every day we support thousands of people here and in the Social media platforms of Facebook, Twitter etc. As we have a very small staff, we rely on many Volunteers who support us in a range of ways. Some help with fund raising, others provide Peer support, and others provide Professional support above and beyond…Read More
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Does anyone have experience with either the babytrend or graco seats that are both for up to 30 lbs? I'm trying to decide between the two. I have big babies. Both of them were too big for their 20 lb carriers by 4-5 months old, so this time I want one that goes to 30.
I like the handle of the babytrend, and it goes to one inch taller than the graco.
But the graco can be installed in the car with the handle in the up position, and by brother who works in a baby chain store said graco fabric holds up better than baby trend.
So which would you pick. I'm looking for stuff around the 100 dollar range, so chicco is out.


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Austin, TXUSA
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Targeting those mainly in their 20's or 30's, here is a group designed for getting together to enjoy happy hours/events/shows in the Austin area. Events include hikes, picnics, sport games, concerts, happy hour, and whatever else that attracts interest. Meet at bars, parks, baseball/basketball games, rec-leagues, or anywhere that sounds fun. Not just for singles, not just for couples... this is for ANYONE AND EVERYONE who wants to get off the couch.
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Arsenal Profile
Player Details
Name: Theo Walcott
Date of birth:16/03/1989
Place of birth: England
Height: 1.75m
Club: Arsenal
Squad: 14
Position: Attacking Midfielder
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England's tenth and final game of the 2014/15 season is one where they can take another giant stride towards Euro 2016.
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Bob Evans®
Original recipe yields 6 servings
Amount per serving ({{servings}} total)
Based on a 2,000 calorie diet
Ready In
Wow! What a great idea! I didn't really follow your exact recipe but I did use the basic idea. I hate omelets but so substituted one with this! :)
This recipe has plenty of potential, but following it by the book ended in a rather bland meal with more fat than should be necessary for the flavor offered. This poor opinion may stem from the...


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United States & Canada Customers: Call 1-800-813-6897
Available 24 hours a day, 7 days a week.
International Customers: Call 1-512-837-4810
Available 24 hours a day, 7 days a week. English language only.
Each of these ZTech 2-3/4" Launch Control Tees sports three different markings to help you control your trajectory. Simply tee it to the bottom line for low trajectory, the middle line for medium trajectory or the top line for high trajectory.
Online Shipping Information
Golfsmith.com offers simple, flat-rate shipping to destinations in the continguous U.S. via FedEx.
Our policy is to strive for the best possible combination of price and service for your shipment.
In order to better serve our guests, we will occassionally offer discounted shipping promotions. Any shipping discounts will be applied in your shopping cart.
"Overnight" shipments will arrive the next business day (excluding weekends and holidays) after departing Golfsmith. "2-Day Air" shipments arrive in two business days after departing Golfsmith. On-time delivery for both methods is guaranteed by FedEx. Shipping delays may occur during busy Holidays or in the spring -- we will do our best to accommodate last minute and expedited orders placed during these times.
Most orders are shipped within 48 hours of online placement. Orders must be placed by 9am (CST) Monday-Friday in order to be eligible for that day's "Overnight" or "2-Day Air" shipments. Orders for residential delivery placed on Sunday or Monday will not be shipped until Tuesday and orders for business delivery placed on weekends will not ship until Monday, so please take this into consideration when specifying expedited shipping requests.
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Lady Solaire 2 12-Piece Full Set
Men's ProDry Low-Cut Socks Two-Pack Socks
Men's Dry-18 Tech Short Sleeve Polo
Prior Generation Pro V1 Golf Balls
Lady Solaire 2 12-Piece Full Set
Men's TOUR Dri-FIT Flex Fit Cap
Men's D.N.A. BOA Golf Shoes - White/Gray (FJ# 53469)
Mid Slim 2.0 Splash Putter Grip
Launch Control 3 1/4" Golf Tees (50 Count)$5.99
Men's Closeout Contour Series Golf Shoes - Black (FJ#: 54904)


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