The present invention relates to trans-capsularly administering into a diseased joint a high specificity antagonist selected from the group consisting of:                i) an inhibitor of a pro-inflammatory interleukin;        ii) an inhibitor of TNF-α synthesis;        iii) an inhibitor of membrane-bound TNF-α;        iv) an inhibitor of a natural receptor of TNF-α;        v) an inhibitor of NO synthase,        vi) an inhibitor of PLA2 enzyme;        vii) an anti-proliferative agent;        viii) an anti-oxidant;        ix) an apoptosis inhibitor selected from the group consisting of EPO mimetic peptides, EPO mimetibodies, IGF-I, IGF-II, and caspase inhibitors, and        x) an inhibitor of MMPs; and        xi) an inhibitor of p38 kinase.

The natural articulating joint (diarthrodal joint) comprises adjacent bones having opposing hyaline cartilage surfaces held together by a fibrous collagenous capsule defining a joint space. The inner wall of this capsule is lined with synovial cells. Contained within the capsular joint space is an acellular synovial fluid. The function of the synovial fluid is to provide lubrication for the articulating surfaces.
In a healthy joint, cells within the articular cartilage produce an extracellular matrix (ECM) containing a high percentage of proteoglycans. These proteoglycans contain sulfated functional groups that retain water, thereby providing the cartilage with its lubricating qualities. These cells may also secrete small amounts of cytokines as well as matrix metalloproteinases ("MMPs"). These cytokines and MMPs help regulate the metabolism of the hyaline cartilage cells.
There appear to be many causes of degenerative joint disease (DJD). For example, gradual degeneration of the joint may be caused by wear, by trauma, by misalignment, by genetics, or by mechanical instabilities in other portions of the body. In many instances, gradual wear of the hyaline cartilage cause the cells therein (or invading macrophages) to emit larger than normal amounts of the above-mentioned cytokines. In other instances of DJD, genetic factors, such as programmed cell death, or apoptosis can also cause the cells within the hyaline cartilage to emit abnormally large amounts of these cytokines into the extracellular matrix of the hyaline cartilage and synovial fluid.
Although the progression of DJD (also called "osteoarthritis", or "OA") is largely dependent upon etiology, it is often the case that the high levels of the cytokines present in the hyaline cartilage begin to mediate the degradation of the extracellular matrix of the cartilage. Concurrently, enzymes in the synovial fluid both upregulate MMPs and downregulate MMP inhibitors. The MMPs (under mediation by the cytokines) begin cleaving the water-retaining portions of the proteoglycans, thereby reducing its water-retaining and lubricious qualities. This degradation leads to a less lubricious hyaline cartilage, thereby increasing the wear upon the hyaline cartilage. This degenerative cascade also often leads to inflammation of the synovial lining, which often produces a thickening and fibrillation of the synovium, and the creation of finger-like villae with the synovium. When the natural regeneration of these cartilage layers is slower than this degenerative process, these changes cause even more mechanical instability, thereby causing the hyaline cartilage cells, the synovium cells and the invading macrophages to emit even more cytokines, thereby typically upregulating MMPs.
In addition to the foregoing, posterior elements of the spine called the "facet joints" help to support axial, torsional and shear loads that act on the spinal column. Furthermore, the facet joints are diarthroidal joints that provide both sliding articulation and load transmission features. The facet's articular surfaces contact in extension, limiting rotation and increasing compressive load. The articular surfaces also contact on one side of the spine in lateral bending and axial rotation, also limiting rotation and transferring load. Early facet osteoarthrosis is relatively mild and is confined to the articular cartilage, capsule, and synovium, but eventually involves the subchondral bone and the margins equally on both sides of a motion segment. With advancing degeneration, the joint capsule undergoes significant changes including increasing fibrosis and vascularization, which has been reported to become hyperemic with infiltration of inflammatory cells, enlargement, and fibrosis.
The posterior zygo-apophyseal joints (facet joints) may be a significant source of spinal disorders and, in many cases, debilitating pain. The articular cartilaginous surfaces can degenerate due to mechanical or biological factors and cause pain as with other joint osteoarthritis. Synovial cysts of the facet joints occur most commonly in association with degenerative disease of the spine in older individuals. The association of these cysts with trauma, rheumatoid arthritis, spondylolysis and kissing spinous processes also has been reported. These cysts can cause symptoms and signs from direct compression of the dura. For example, a patient may suffer from arthritic facet joints, severe facet joint tropism or otherwise deformed facet joints, facet joint injuries, etc. There is currently a lack of suitable intervention procedures for facet joint disorders. Facet blocks with anesthetic and cortisone, facet denervation procedures, radiofrequency ablation of the nerve supply to the joint, or even spinal fusions have been recommended. In the early stages of degeneration, pain may be controlled by blocking the medial branch of the lumbar zygapophyseal (facet) joints (kryorhizotomy). However, this treatment mode of treatment is considered for temporary relief of pain. Facetectomy, or the removal of the facet joints, may provide some relief, but is also believed to significantly decrease the stiffness of the spinal column (i.e., hypermobility) in all planes of motion: flexion and extension, lateral bending, and rotation. Furthermore, problems with the facet joints can also complicate treatments associated with other portions of the spine. By way of example, contraindications for artificial discs include arthritic, deformed, unstable, or painful facet joints. Accordingly, there is a need for a facet joint treatment that addresses these concerns.
Accordingly, there is a need for a minimally invasive treatment of facet joints.
Braun, Expert Opin. Biol. Ther. 3(1):141-168 (2003) ("Braun I") reviews the efficacy of infliximab, a high specificity antagonist of TNF-α, in treating chronic inflammatory diseases. Braun reports that infliximab is delivered through essentially systemic administration routes. Braun does not report any local administration routes.
Braun, Ann. Rheum. Dis., 61 (Supp. III):;iii51-iii60 (2002), reviews the international experience of the use of anti-TNF α therapy for ankylosing spondylitis. Braun II reports that anti-TNF-α drugs are delivered through essentially systemic administration routes. Braun II does not report any local administration routes.
Olmarker, Spine, 26(8):863-9 (2001) ("Olmarker I") and Aoki, Spine, 27(15):1614-17 (2002) teach that TNF-α appears to play a role in the producing the pain associated with the nucleus pulposus contacting nerve roots of the spinal cord.
U.S. Published Patent Application No. US 2003/0039651 ("Olmarker II") teaches a therapeutic treatment of nerve disorders comprising administration of a therapeutically effective dosage of at least two substances selected from the group consisting of TNF inhibitors (both specific and non-specific), IL-1 inhibitors, IL-6 inhibitors, IL-8 inhibitors, FAS inhibitors, FAS ligand inhibitors, and IFN-gamma inhibitors. In the examples of Olmarker II, it is taught that these substances are to be administered through systemic pathways. In particular, Olmarker II teaches that "the major contribution of TNF-alpha may be derived from recruited, aggregated and maybe even extravasated leukocytes, and that successful pharmacologic block may be achieved only by systemic treatment".
U.S. Pat. No. 6,419,944 ("Tobinick I") discloses treating herniated discs with cytokine antagonists, including infliximab. However, Tobinick teaches that local adminstration involves an extradiscal injection between the disc and spinal cord. Accordingly, Tobinick does not teach a procedure involving directly administering a specific cytokine antagonist (such as infliximab) into a capsuled space.
U.S. Published Patent Application No. 2003/0049256 (Tobinick II) discloses that injection of such therapeutic molecules to the anatomic area adjacent to the spine is accomplished by interspinous injection, and preferably is accomplished by injection through the skin in the anatomic area between two adjacent spinous processes of the vertebral column.
Tobinick II discloses several spine and orthopaedic applications: Spinal Cord Injury (#12); neuropathic pain (#14); lumbar and Cervical Radiculopathy (#15); low back pain (#17), and Vertebral Disc Disease (#19). Tobinick teaches a parenteral/perispinal route of administration for spinal cord injuries; a perispinal route of administration for neuropathic pain; a perispinal route of administration for lumbar and Cervical Radiculopathy; a parenteral/perispinal route of administration for low back pain; and a perispinal route of administration for Vertebral Disc Disease. In each of applications Nos. 14, 15, 17 and 19, Tobinick appears to teach that the disc must be herniated, torn or leaking and so an extruded nucleus pulposus is the target tissue.
Tobinick II further teaches that TNF antagonists may be administered by interspinous injection in the human and that the dosage level is in the range of 1 mg to 300 mg per dose, with dosage intervals as short as two days. Tobinick II further discloses that Interleukin-1 antagonists are administered in a therapeutically effective dose, which will generally be 10 mg to 200 mg per dose, and their dosage interval will be as frequent as once daily.
Tobinick, Swiss Med. Weekly, 133:170-77 (2003), ("Tobinick III") teaches both perispinal and epidural administration of TNF inhibitors for spine related therapies.
Alini, Eur. Spine J., 11(Supp.2):S215-220 (2002), teaches therapies for early stage disc degeneration disease, DDD, including injection of inhibitors of proteolytic enzymes or biological factors that stimulate cell metabolic activity (i.e., growth factors) in order to slow down the degenerative process. Alini I does not teach any similar injections into joints having synovial fluid.
U.S. Published Patent Application US2002/0026244 ("Trieu") discloses an intervertebral disc nucleus comprising a hydrogel that may deliver desired pharmacological agents. Trieu teaches that these pharmacological agents may include growth factors such as TGF-B and anti-inflammatory drugs, including steroids. Trieu further teaches that these pharmacological agents may be dispersed within the hydrogel having an appropriate level of porosity to release the pharmacological agent at a desired rate. Trieu teaches that these agents may be released upon cyclic loading or upon resorption. Trieu does not teach any similar injections into joints having synovial fluid.
Maeda et al. Spine, 25(20):166-169 (2000), reports on the in vitro response to interleukin-1 receptor antagonist protein (IRAP) of rabbit annulus fibrosus exposed to IL-1. Maeda suggests that IRAP could be useful in inhibiting the degradation of the disc. Maeda does not teach any similar utility for joints having synovial fluid.
Igarashi et al., ISSLS Abstract #262 (May 13-17, 2003), sought to quantify the levels of various cytokines present within the facet joints of patients suffering from low back pain and sciatica. Igarashi appears to report that the levels of TNF-α were below the detection limits of the assay, but that the higher levels of IL-1β (for the patients with lumbar canal stenosis), and IL-6 were each statistically significant.
EP 1153607 A2 ("Dunn") discloses injecting anti-cytokines (and in particular, an anti-TNF antibody called "Enbrel™", which binds only soluble TNF), anti-kinases, anti-proteases, and anti-growth factors into orthopaedic joints, including those of the vertebrae. Dunn also discloses that these agents may be administered with a lubricant, such as hyaluronic acid.
U.S. Pat. No. 5,095,037 ("Iwamitsu") discloses local administration of a composition comprising (a) an effective amount of hyaluronic acid or its salt, and (b) an effective amount of an anti-inflammatory agent. Iwamitsu particularly discloses Diclofenac, a COX-2 enzyme inhibitor, as one suitable anti-inflammatory agent.
WO 03/000190 A2 ("Thompson") discloses a composition comprising glycosaminoglycans encapsulated in a liposomal delivery system for intra-articular administration for the treatment of osteoarthritis. Thompson further teaches that the composition may further include additional benefit agents such as p38 kinase inhibitors, TNF inhibitors, and inhibitors of enzymes that are involved in the destruction of articulating joints and synovial fluid components (such as hyaluronidase inhibitors, MMP inhibitors, aggrecanse inhibitors, or apoptosis inhibitors such as EPO), and cartilage enhancing factors such as TGF-β and BMP. Thompson does not specifically teach p38 kinase inhibitors having high specificity towards p38 kinase.
Certain molecules, such as tetravalent guanylhydrazone, non-specifically inhibit p38 kinase.
Wittenberg et al., Arthritis Rheum., 36(10):1444-50 (October 1993) investigated the major source of eicosanoid release in arthritic joint tissues. Release of prostaglandin E2 (PGE2), 6-keto-PGF1 alpha, leukotriene B4 (LTB4), and LTC4 were measured. Wittenberg reported in vitro experiments showing that the PG release was significantly inhibited by the addition of indomethacin or diclofenac (a COX-2 enzyme inhibitor) at either 10−5 moles/liter or 10−7 moles/liter. Wittenberg concluded that synovial tissue appears to be the major source of eicosanoids in synovial fluid, and that indomethacin and diclofenac inhibit the release of PG, but not LT, from various joint tissues.

Trans-capsular administration of high specificity cytokine inhibitors into orthopedic joints


Disclosed is a method for removing minerals from a cellulosic biomass. For example, the biomass may be prewashed with an acid solution and rinsed with water to remove minerals prior to acid saccharification. The removal of minerals may reduce overall acid requirements, and decrease pretreatment costs.

1. Field of the Invention
The present invention pertains to the field of processing biomass to produce fuels, chemicals and other useful products and, more specifically, to hydrolyzing cellulosic biomass to produce sugars for conversion to ethanol and other products. Use of a prewash to remove minerals before acidifying the biomass results in significantly improved acid pretreatment efficiency.
2. Description of the Related Art
Cellulosic biomass represents an inexpensive and readily available source of sugars. These sugars may be used alone, fermented to produce alcohols and industrial chemicals, or chemically converted to other compounds. For example, cellulosic biomass is useful for generating ethanol, which has a number of industrial and fuel uses. Of particular interest is the use of ethanol as a gasoline additive that boosts octane, reduces pollution, and partially replaces gasoline in fuel mixtures.
Generally speaking, biomass, e.g., wood, grass, forest or crop residue, contains cellulose wrapped in a recalcitrant lignin and hemicellulose sheath. The sheath must be chemically and/or physically disrupted in a pretreatment step that produces some sugars and provides access to cellulose. Typical pretreatment protocols involve mechanical size reduction, acid hydrolysis, ammonia or alkali treatment, and/or steam explosion. High capital and operating costs are associated with all of these pretreatment methods. For example, most of the pretreatments are carried out at high temperatures and a considerable amount of energy is used to heat the biomass. These high temperatures create the evolution of steam and other gaseous products which create high pressures, with concomitantly high containment costs. Further, the elevated pressures make it difficult to introduce solid materials into the reactor.
In acid pretreatments, nitric or hydrochloric acid may be used, but sulfuric acid is often favored because of its lower cost. However, pretreatment expenditures may still be large when sulfuric acid is used because substantial quantities of acid are required, and neutralization and disposal costs remain.
It has been found by A. Esteghlalian, A. G. Hashimoto, J. J. Fenske, and M. H. Penner, Bioresour. Technol., 59, 1997, 129-136 and J. N. BeMiller, Adv. Carbohydr. Chem., 22, 1967, 25-108, that cellulosic biomass can have a significant mineral content, and that these minerals neutralize some of the acid during dilute-acid pretreatment, which increases acid demand. For example, mineral oxides combine with sulfuric acid to form sulfate salts and water:Nm+2Om+mH2SO4Nm+2(SO4)m+mH2O  (1)where N is potassium, sodium, calcium, iron and other cations, and m is an integer equal to the charge of the cation. This neutralization reaction consumes hydrogen ions in the formation of water.
Specific to sulfuric acid is an equilibrium shift to formation of bisulfate that can further reduce hydrogen ion concentrations and compound the effect of neutralization, as reported by J. M Readnour and J. W. Cobble, Inorg. Chem., 8(10), 1969, 2174-2182. Equation (2) shows the sulfate salt formed in Equation (1) combining with hydrogen ions to form a bisulfate salt:Nm+2(SO4)m+mH+Nm+(HSO4)m+Nm+  (2)This equilibrium shift has a more pronounced effect at lower acid concentrations, where the quantity of hydrogen ion consumed in Equation (2) represents a large percentage of the total hydrogen ion concentration. Further, bisulfate salt formation is favored when dilute solutions are subjected to the high temperatures used for pretreatment reactions because the equilibrium constant, K2=([H+][SO42−])/[HSO4−], decreases as temperature increases. Due to both bisulfate salt formation and a shift in the sulfuric acid dissociation equilibrium, an increase in pH is observed and additional acid is required to achieve a particular reaction rate.

Removal of minerals from cellulosic biomass


The present disclosure discloses an OLED pixel circuit, a display apparatus, and a control method. The OLED pixel circuit includes an OLED; a driving transistor a drain electrode of which is connected with the OLED; a first switching unit configured to output, during a light-emitting stage, a power source signal to a source electrode of the driving transistor; a second switching unit configured to output, during a present scanning stage, a data signal to a gate electrode of the driving transistor; a compensation unit having a capacitor, and a charging control unit configured to output, during a charging stage, a charging signal to the capacitor for charging the capacitor so that the capacitor can maintain, during the light-emitting stage, a voltage of the gate electrode of the driving transistor. The charging signal has a voltage value greater than an actual voltage value of the data signal.

As a display apparatus, an organic light-emitting diode (OLED) is self-luminous, has a high contrast ratio, and has a wide color gamut. Besides these advantages, OLED has a simple manufacturing process, has a low power consumption, and is easy to realize flexible display. Thus, OLED becomes an important light-emitting element in a new flat panel display apparatus.
For the pixels of OLED display panel, each pixel includes a driving transistor. In an organic light-emitting diode pixel circuit, a current flowing though the OLED is not only controlled by a data signal Vdata, but also affected by a threshold voltage Vth of the driving transistor.
In different pixel circuits, characteristics such as the threshold voltage and carrier mobility of the TFT are different from each other, and the driving transistor included in each OLED pixel circuit cannot have exactly same performance parameters. Thus, currents flowing through the OLEDs may be different caused by a threshold voltage shift (Vth Shift) in the driving transistor. This may finally cause adverse effect to the luminance uniformity and constant brightness of the organic light-emitting diode display apparatus, and accordingly adversely affects a display effect of the organic light-emitting diode display apparatus.
With consideration of the above-described points, it is necessary to provide a threshold voltage compensation circuit to the pixel circuit in order to avoid the adverse effect caused by the threshold voltage shift to the luminance uniformity and constant brightness of the organic light-emitting diode display apparatus.
Usually, a threshold voltage compensation circuit may output a charging signal to a capacitor during a charging stage in order to charge the capacitor so that the capacitor can maintain a voltage of the gate electrode of the driving transistor during the light-emitting stage. With this configuration, the current flowing through OLED can be controlled to have no relation to the threshold voltage Vth of the driving transistor.
However, in the driving circuit according to the prior art, in some cases, a design of the data signal is restricted by the power source, and this may lower a design flexibility.

Organic light-emitting diode pixel circuit, display apparatus and control method


An evaporator device for water for installation in a steamer has a water tank having an encircling outer wall and an encircling inner wall, wherein a heating device is provided on the outer wall. The inner wall extends within the outer wall and with a clearance relative thereto, wherein a water zone is formed between the outer wall and the inner wall. A pump is arranged within the inner wall in order to pump water from a water reservoir into the water zone. A steam outlet emerges upwards from the water zone and leads into the steamer.

DE 102006029578 A1 discloses an evaporator device having a general heating system and a laterally arranged chamber. There, the water level in a water zone and thus in the evaporator device can be detected in a practical and reliable manner by means of sensors.
US 2010/083845 A1 discloses another evaporator device, which is designed in the manner of a round vertical tube. A heating device is provided on an outer wall of the tubular water tank. Steam emerges at the top from the evaporator device or a water zone formed in the tube.

Evaporator device for water and steamer having an evaporator device of this kind


The present invention pertains to a method for controlling the foaming of a waterborne composition or in an industrial process utilizing a waterborne composition by the incorporation of a foam controlling agent in an amount effective for controlling foam. The method comprises utilizing as the foam controlling agent an alkyl glycidyl ether-capped diamine compound of the formula:

The invention relates to the use of alkyl glycidyl ether-capped diamines as foam controlling agents.
Foam control or elimination in many waterborne applications and industrial processes is critical for obtaining optimal performance in application and high process efficiency [R. Hxc3x6fer and coworkers, in B. Elvers, J. F. Rounsaville and G. Schulz, eds., Ullmann""s Encyclopedia of Industrial Chemistry, Vol. A11, 5th Ed., VCH Publishers, New York, 1988, p. 466-488]. Foam problems can arise during production, processing and application. The importance of foam control and elimination is well-appreciated in applications such as waterborne coatings, inks, adhesives, lubricants, over-print varnishes and agricultural formulations and in industrial processes such as oil well drilling, completion and production, acid gas scrubbing, food processing, pulp and paper processing, fermentation, metal treatment, polymer and chemical synthesis, waste-water treatment and textile dying.
Undesirable foam can lead to inefficient mixing, poor productivity, reduced vessel capacity and equipment failure in many common industrial processes. For instance, foaming in refinery processes such as drilling, completion, production, distillation, extraction, gas and liquid scrubbing and other operations leads to a number of operating difficulties and significant economic consequences. In acid gas sweetening, or scrubbing, gases such as carbon dioxide and hydrogen sulfide are removed via scrubbing with an aqueous amine solution. Problematic foam can occur during both the scrubbing or regeneration steps in this process [V. E. Lewis and W. F. Minyard, Antifoaming and Defoaming in Refineries in Foams: Fundamentals and Applications in the Petroleum Industry, Adv. Chem. Ser., 1994, 242, p 461-483].
Defoamers and antifoams are additives that are used to reduce or eliminate problematic foam. An xe2x80x9cantifoamxe2x80x9d refers to a long-acting additive which prevents foam formation. A xe2x80x9cdefoamerxe2x80x9d is an additive that yields rapid knock-down of existing foam thereby reducing or eliminating the foam. Herein, the term xe2x80x9cfoam control agentxe2x80x9d is used to refer to additives that prevent and/or control foam since many applications and processes require both foam prevention and reduction or elimination.
Foam control agents act to prevent or eliminate foam by countering foam stabilizing forces and accelerating the rate of foam film drainage. Conventional foam control agents utilized in waterborne systems include silicones, dispersed hydrophobic solids, hydrocarbon fluids and polyalkyleneoxide polymers.
In many applications, foam control agents exhibit positive ancillary surface properties, such as wetting, dispersion, emulsification, solubilization, flow and leveling. For example, defoamers and antifoams that act as wetting agents will greatly reduce surface defects in coatings, inks, adhesives, over-print varnishes and agricultural formulations. In addition, such multi-functional materials will allow for the reduction or elimination of wetting agents in a waterborne composition, thereby reducing the total amount of additives. The ability of a material to act as a wetting agent in waterborne formulations is assessed by its ability to reduce the surface tension of water. Equilibrium surface tension performance is important when a system is at rest. However, the ability to reduce surface tension under dynamic conditions is of great importance in applications where high surface creation rates are utilized. Such applications include the spraying, rolling and brushing of coatings, adhesives or agricultural formulations, or high-speed gravure or ink jet printing. Dynamic surface tension is a fundamental quantity which provides a measure of the ability of a substance to reduce surface tension and provide wetting under high-speed application conditions. Also, the entrainment of air and the creation of foam is a problem under high-speed application conditions.
In addition to the development of multi-functional foam control agents, there is considerable interest in the industry in foam control agents with improved environmental characteristics. This increased environmental concern has been, in part, due to the poor environmental characteristics of currently used foam control agents and new environmental regulations. Such negative characteristics include poor biodegradation, a potential to bioaccumulate and high aquatic toxicity. Thus, not only is it desirable to obtain foam control agents which provide excellent foam prevention or elimination and dynamic wetting, but it is also highly desirable that such new materials are environmentally-friendly.
Highly effective foam control agents, which contain 100 percent active ingredient, have low color and low odor characteristics, can be used effectively under a wide range of operating conditions and do not adversely affect formulation performance or result in the disruption of downstream processes, are highly desirable. Moreover, there is a need in the industry for antifoaming and defoaming agents that exhibit positive ancillary surface properties, such as wetting, dispersion, emulsification, solubilization, flow and leveling.
Foam control agents are widely used in polymer production and processing since foam can lead to reduced production capacity, efficiency and equipment problems. In particular, severe foaming problems commonly result upon stripping unreacted monomers from the polymer product [H. F. Mark, N. M. Bikales, C. G. Overberger, G. Menges and J. I. Kroschwitz, Eds., Encyclopedia of Polymer Science and Engineering, 2nd Ed. Vol 2, John Wiley and Sons, New York, 1985, p. 59].
Selection of an appropriate foam control agent is key to the successful production, transfer and application of waterborne coatings, inks and adhesives. Defoamers are required in most waterborne coating formulations since they contain wetting agents, emulsifiers, dispersants and other additives which are capable of stabilizing foam [R. A. Reinhardt et. al., Defoamer Selection in Waterborne Coatings, Journal of Coatings Technology, 1998, 70, 157]. Problematic foam can lead to gloss and color loss, craters, pinholes, fish-eyes, orange peel, crawling, poor recoatability, poor color acceptance, adhesion loss and haze development.
U.S. Pat. No. 4,650,000 discloses that cationic quaternary ammonium salts of the adducts of diamines and C8-C18 alkyl glycidyl ethers are effective surfactants for the formation of microemulsions containing a hydrocarbon oil and aqueous acid solutions used to treat subterranean rock formations surrounding oil and gas wells.
U.S. Pat. No. 4,797,202 discloses N-(hydrocarbyl)-xcex1,xcfx89-alkanediamines as collectors for the recovery of minerals from mineral ores by froth flotation. In particular, the 1:1 adduct of ethylenediamine and butyl glycidyl ether was shown to be effective for copper recovery in the froth flotation of copper sulfide.
CH 313159 discloses a process for the preparation of stable dye and stripper baths containing positively charged amine additives. The baths contain 1:1 adducts of diamines and polyamines and C8 and greater alkylglycidyl ethers and the corresponding alkylated amines formed by subsequent reactions with ethylene oxide, dimethyl sulfate, chloroacetic acid and other reagents.
JP 2001-107083 discloses 1:1 adducts of amines and alkyl glycidyl ethers for use in laundry detergent compositions.
JP 450119973 discloses adducts prepared by the reaction of amines and C6 to C16 alkyl glycidyl ethers as effective bactericidal surfactants. These compounds all contain carboxylate groups.
JP 200010268 discloses the use of adducts containing ethylenically unsaturated groups in photosensitive pastes. In particular, adducts of diamines and glycidyl methacrylate were used.
U.S. Pat. No. 3,931,430 discloses a method for using the reaction products of diamines and polyamines and C4-C16 glycidyl esters and ethers as desensitizers for pressure-sensitive recording sheets. These desensitizers must be soluble in the oil vehicle used to make non-aqueous inks for offset printing.
The present invention pertains to a method for controlling the foaming of a waterborne composition or in an industrial process utilizing a waterborne composition by the incorporation of a foam controlling agent in an amount effective for controlling foam. The method comprises utilizing as the foam controlling agent an alkyl glycidyl ether-capped diamine compound of the formula:
L is a linker group comprising a linear, branched, or cyclic alkyl group having from 2 to about 6 carbon atoms or an alkyl ether group having from about 4 to about 8 carbon atoms. R is independently selected from hydrogen or xe2x80x94CH2CHOHCH2ORxe2x80x2. Rxe2x80x2 is an alkyl group having from about 4 to about 22 carbon atoms. The compound generates an initial foam height at least 30% less than a 0.1 wt % aqueous solution of dioctyl sodium sulfosuccinate (DOSS), when added at 0.1 wt % to the aqueous DOSS solution.
Another embodiment of the invention comprises an alkyl glycidyl ether-capped diamine compound which comprise ethylenediamine capped, or adducted, with from 3 or 4 iso-butyl glycidyl ethers and di(aminopropyl)diethylene glycol capped with from 1 to 4 n-butyl glycidyl ethers.
The present invention also pertains to an aqueous composition comprising a foam controlling agent. The composition manifests greater foaming in the absence of the foam controlling agent. The foam controlling agent is an alkyl glycidyl ether-capped diamine present in an amount effective for controlling foam and has the formula:
wherein L, R, and Rxe2x80x2 are as defined above.
This invention relates to the use of the reaction products of diamines and alkyl glycidyl ethers for controlling, i.e. reducing, preventing or eliminating, foam in waterborne compositions and industrial processes that otherwise manifest foaming. There are significant advantages associated with the use of these alkyl glycidyl ether-capped diamines as foam control agents in water-based compositions and processes. These advantages include: foam control agents which have low odor and color; foam control agents which contain 100 percent active ingredient and thus do not require carrier fluids, solvents or other additives and exhibit improved shelf stability; waterborne coatings and inks which have low volatile organic content, thus making these formulations environmentally favorable; foam control agents capable of reducing the dynamic surface tension of waterborne compositions; waterborne coatings, inks, adhesives and agricultural formulations which may be applied to a variety of substrates with excellent wetting of substrate surfaces including contaminated and low energy surfaces; a reduction in coating or printing defects such as orange peel and flow/leveling deficiencies in comparison to conventional foam control agents; waterborne compositions capable of high speed application and processing; and industrial processes which have no foam or greatly reduced amounts of problematic foam with a reduction in negative effects in down-stream applications.
Not all alkyl glycidyl ether-capped diamines are capable of significantly reducing or eliminating foam. Therefore, the correct combination of diamine and alkyl glycidyl ether and an optimum degree of adduction is essential for the reduction and/or elimination of foam. Thus, suitable alkyl glycidyl ether-capped diamines are those that generate an initial foam height at least 30% less than a 0.1 wt % aqueous solution of dioctyl sodium sulfosuccinate (DOSS) when added at 0.1 wt % to the aqueous DOSS solution, as measured according to ASTM D 1173-53 at ambient temperature.
The terms xe2x80x9cwater-basedxe2x80x9d, xe2x80x9cwaterbornexe2x80x9d, xe2x80x9caqueousxe2x80x9d or xe2x80x9caqueous mediumxe2x80x9d, for the purposes of this invention, mean a solvent or liquid dispersing medium which comprises water, preferably at least 90 wt %, and most preferably at least 95 wt %, water. Obviously, an all water medium is also included.
In another embodiment of the invention, the foam control agents may be utilized as wetting agents. It is desirable that an aqueous solution of the foam control agents exhibit ancillary wetting properties, as demonstrated by a dynamic surface tension xe2x89xa645 dynes/cm at a concentration of xe2x89xa61 wt % in water at 25xc2x0 C. and 0.1 bubble/second according to the maximum-bubble pressure method. The maximum-bubble-pressure method of measuring surface tension is described in Langmuir 1986, 2, 428-432, which is incorporated by reference.
The excellent defoaming and antifoaming properties of these foam control agents suggest that these agents will be useful in applications and processes in which the reduction, prevention or knock-down of foam are important. Such applications include coatings, inks, adhesives, agricultural formulations, oil well production, acid gas scrubbing of a gas stream, for example, petroleum or natural gas, food processing, pulp and paper processing, fermentation, metal treatment, polymer and chemical synthesis, waste-water treatment and textile dying and finishing. As used in this specification and the appended claims, xe2x80x9coil well productionxe2x80x9d is intended to comprise the drilling, completion, i.e., cementing, and/or pumping of the crude oil, as opposed to the stimulation of the oil well by treatment of formations surrounding the well. A preferred embodiment of the invention comprises a process for the removal of hydrogen sulfide and/or carbon dioxide from an acid gas-containing gas stream, such as natural gas, wherein the gas stream is contacted with an aqueous amine solution to adsorb the hydrogen sulfide, the aqueous amine solution is optionally regenerated, and an alkyl glycidyl ether-capped diamine according to the invention is added to control foam.
In addition, these materials can reduce the dynamic surface tension of waterborne compositions. Such attributes allow these materials to be used to control and eliminate foam with significantly less deleterious effects in application, making them extremely useful in coatings, inks and adhesives. Moreover, the wetting ability of these foam control agents allows these materials to be utilized in polymer production and processing without defects in downstream applications. In addition, such multi-functional materials will allow for the reduction or elimination of wetting agents in a waterborne composition, thereby reducing the total amount of additives.
From the data included in the examples, is evident that not all alkyl glycidyl ether-capped diamines are capable of reducing or eliminating foam and that certain adducts in fact add problematic foam to waterborne systems. Therefore, the correct combination of diamine and alkyl glycidyl ether group and an optimum degree of adduction as demonstrated in this work is essential for the reduction and/or elimination of foam. It is also unexpected that the foam control agents of this invention exhibit improved biodegradation in comparison to the corresponding adducts prepared from polyamines and alkyl glycidyl ethers.
In accord with the present invention, a method is provided for controlling the foaming of a waterborne composition or an industrial process by the incorporation of a foam controlling agent in an amount effective for controlling foam. The method comprises utilizing as the foam controlling agent an alkyl glycidyl ether-capped diamine compound of the formula:
The alkyl glycidyl ether-capped diamine compounds of the present invention generate an initial foam height at least 30% less than a 0.1 wt % aqueous solution of dioctyl sodium sulfosuccinate (DOSS), when added at 0.1 wt % to the aqueous DOSS solution. Preferably, the compound generates an initial foam height 40%, and more preferably 50%, less than a 0.1 wt % aqueous solution of dioctyl sodium sulfosuccinate.
In the alkyl glycidyl ether-capped diamine compounds, L is a linker group comprising a linear, branched, or cyclic alkyl group having from 2 to about 6 carbon atoms or an alkyl ether group having from about 4 to about 8 carbon atoms. Preferably, L is an alkyl group having from about 2 to about 5 carbon atoms, more preferably from about 2 to about 4 carbon atoms, and most preferably from 2 to 3 carbon atoms. Preferably, L is an alkyl ether group having from about 4 to about 10 carbon atoms, more preferably from about 10 carbon atoms.
R is independently selected from hydrogen or xe2x80x94CH2CHOHCH2ORxe2x80x2. Rxe2x80x2 may be an alkyl group having from about 4 to about 22 carbon atoms. Preferably, Rxe2x80x2 is an alkyl group having from about 4 to about 20 carbon atoms, more preferably from about 4 to about 16 carbon atoms, and most preferably from about 4 to about 12 carbon atoms.
In a specific embodiment, L is xe2x80x94CH2CH2xe2x80x94, R is independently selected from hydrogen or xe2x80x94CH2CHOHCHOxe2x80x94CH2CH2CH2CH3, i.e., Rxe2x80x2 is a butyl group. In another specific embodiment, L is xe2x80x94CH2CH2xe2x80x94, R is independently selected from hydrogen or xe2x80x94CH2CHOHCHOxe2x80x94CH2CH(CH3)2, i.e., Rxe2x80x2 is an iso-butyl group. Preferably, there are from 2 to 4 capping groups on the amine, i.e., the ratio of amine to alkyl glycidyl ether in the epoxide opening reaction is from about 1:2 to about 1:4.
In another embodiment, the present invention is directed to an aqueous composition comprising a foam controlling agent, which composition manifests greater foaming in the absence of the foam controlling agent. The foam controlling agent is an alkyl glycidyl ether-capped diamine present in an amount effective for controlling foam and has the formula:
wherein L, R, and Rxe2x80x2 are as defined above.
In a specific embodiment, the waterborne composition is a protective or decorative coating; an ink composition; an adhesive composition; an overprint varnish; a radiation cured coating, ink, overprint varnish, or adhesive composition; an agricultural composition; or an acid gas scrubbing composition. In another specific embodiment, the industrial process is oil well production, acid gas scrubbing, food processing, pulp or paper processing, fermentation, metal treatment, polymer or chemical synthesis, waste-water treatment, or textile dyeing or finishing.
The alkyl glycidyl ether-capped diamines of the invention may be prepared by the reaction of a diamine with one or more alkyl glycidyl ethers in an epoxide ring opening reaction. The reaction may be performed with or without solvent. Preferably, the alkyl glycidyl ether is added to the amine reagent and the reaction temperature is maintained between 60-120xc2x0 C. The product may be used with or without purification. The product obtained from the reaction of a diamine and an alkyl glycidyl ether is a mixture since the hydroxy group generated via the epoxide ring opening reaction may also react with an alkyl glycidyl ether. The reaction illustrated below shows one of the more common adducts contained in the product mixture:
where L, R and Rxe2x80x2 are as defined above.
All alkyl glycidyl ethers or mixtures of alkyl glycidyl ethers containing the requisite number of carbon atoms (C4 to C22) may be utilized for the preparation of the capped-diamine foam control agents of this invention. Alkyl groups which are suitable should have sufficient carbon atoms to confer surface activity, i,e., an ability to act as a foam control agent and reduce the surface tension of water.
The alkyl groups in the alkyl glycidyl ether-capped diamines of this invention may be the same or different. Examples of suitable linear or branched alkyl glycidyl ethers (CH2(O)CHxe2x80x94CH2ORxe2x80x2) include butyl glycidyl ether, isobutyl glycidyl ether, pentyl glycidyl ether, iso-amyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, lauryl glycidyl ether, myristyl glycidyl ether, cetyl glycidyl ether, and the like.
Examples of suitable diamines (H2Nxe2x80x94Lxe2x80x94NH2) include those with linear, branched and cyclic hydrocarbon spacers, such as ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, 2-methyl-1,5-pentanediamine and bis (p-amino-cyclohexyl) methane. In addition, suitable diamines may contain ether moieties in the spacer group. Optimal performance for a specific application can be achieved be appropriate manipulation of the starting amine and alkyl glycidyl ether and the degree of adduction.
The amount of alkyl glycidyl ether-capped diamine that is effective to reduce or eliminate the foam of the water-based, organic compound-containing composition is an amount effective for controlling foam. In general, this amount may range from about 0.001 to about 20 g/l 100 mL, preferably from about 0.01 to about 10 g/l 100 mL, of the aqueous composition. Naturally, the most effective amount will depend on the application and the efficiency of the foam control agent.
The alkyl glycidyl ether-capped diamines are suitable for use in an aqueous composition comprising in water an inorganic or organic pigment, a polymerizable monomer, such as addition, condensation and vinyl monomers, an oligomeric resin, a polymeric resin, a herbicide, a fungicide, an insecticide, or a plant growth modifying agent.
In a specific embodiment, the composition comprises in water an inorganic compound which is a mineral ore or a pigment or an organic compound which is a pigment, a polymerizable monomer, such as an addition, condensation or vinyl monomer, an oligomeric resin, a polymeric resin, a herbicide, an insecticide, a fungicide, or a plant growth modifying agent.
The alkyl glycidyl ether-capped diamines of the present invention may be employed along with conventional additives in water-based protective or decorative organic coatings, inks, adhesives, fountain solutions, agricultural, varnish, and acid gas sweetening compositions.
A typical water-based coating formulation to which the foam control agents of the invention may be added would comprise the following components in an aqueous medium at 30 to 80% xe2x80x9csolidsxe2x80x9d, i.e., listed ingredients:
(a) 0 to 50 wt % of a pigment dispersant/grind resin;
(b) 0 to 80 wt % of coloring pigments/extender pigments/anti-corrosive pigments/other pigment types;
(c) 5 to 99.9 wt % of water-borne/water-dispersible/water-soluble resins;
(d) 0 to 30 wt % of slip additives/antimicrobials/processing aids;
(e) 0 to 20 wt % of coalescing or other solvents;
(f) 0.01 to 10 wt % of surfactant/wetting agent/flow and leveling agents; and
(g) 0.01 to 5 wt % of an alkyl glycidyl ether-capped diamine foam control agent.
A typical water-based ink composition to which the foam control agent of the invention may be added would comprise the following components in an aqueous medium at 20 to 60% xe2x80x9csolidsxe2x80x9d, i.e., listed ingredients:
(a) 1 to 50 wt % of a pigment;
(b) 0 to 50 wt % of a pigment dispersant/grind resin;
(c) 0 to 50 wt % of a clay base in appropriate resin solution vehicle;
(d) 5 to 99.9 wt % of water-borne/water-dispersible/water-soluble resins;
(e) 0 to 30 wt % of coalescing solvents;
(f) 0.01 to 10 wt % of a surfactant/wetting agent;
(g) 0.01 to 10 wt % of processing aids/solubilizing agents;
(h) 0.01 to 5 wt % of an alkyl glycidyl ether-capped diamine foam control agent.
A typical water-based agricultural composition to which the foam control agent of the invention may be added would comprise the following components in an aqueous medium at 0.01 to 80% xe2x80x9csolidsxe2x80x9d, i.e., listed ingredients:
(a) 0.1-50 wt % of a pesticide or plant growth modifying agent;
(b) 0 to 5 wt % of a dye;
(c) 0 to 20 wt % of a thickener/stabilizer/co-surfactant/gel/Inhibitor;
(d) 0 to 25 wt % of an antifreeze;
(e) 0.01 to 50 wt % of a surfactant/wetting agent;
(f) 0.01 to 10 wt % of an alkyl glycidyl ether-capped diamine foam control agent.
A typical fountain solution composition for planographic printing to which the foam control agent of the invention may be added would comprise the following components:
(a) 0.05 to 10 wt % of a film formable, water soluble macromolecule;
(b) 1 to 25 wt % of an alcohol, glycol, or polyol with 2-12 carbon atoms;
(c) 0.01 to 20 wt % of a water soluble organic acid, inorganic acid, or a salt thereof;
(d) 30 to 70 wt % of water;
(e) 0.01 to 5 wt % of a wetting agent; and
(f) 0.01 to 5 wt % of an alkyl glycidyl ether-capped diamine foam control agent.
A typical pressure sensitive adhesive to which the foam control agent of the invention may be added would comprise the following components:
(a) 50 to 99 wt % of an acrylic copolymer emulsion or SBR/natural rubber latex;
(b) 0 to 50 wt % of a tackifier dispersion;
(c) 0 to 5 wt % of a rheology modifier;
(d) 0 to 10 wt % of water;
(e) 0.1 to 5 wt % of a wetting agent;
(f) 0.1 to 5 wt % of an alkyl glycidyl ether-capped diamine foam control agent.
A typical pressure overprint varnish to which the foam control agent of the invention may be added would comprise the following components:
(a) 20 to 80 wt %of a water-borne/water dispersible resin;
(b) 0 to 20 wt % of a wax;
(c) 2 to 50 wt % of water;
(d) 0 to 20 wt % of a biocide/optical brightener/crosslinker/scuff and water resistant additive;
(e) 0 to 20 wt % of a co-solvent;
(f) 0.01 to 5 wt % of a wetting agent;
(g) 0.1 to 5 wt % of an alkyl glycidyl ether-capped diamine foam control agent.
A typical acid gas scrubbing composition to which the foam control agent of the invention may be added would comprise in water 10 to 70 wt % of at least one amine, preferably an alkanolamine, as is well known in the art and 1 to 500 ppm of an alkyl glycidyl ether-capped diamine foam control agent.
The present invention can be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.

Alkyl glycidyl ether-capped diamine foam controlling agent

Abstract: L is a linker group comprising a linear, branched, or cyclic alkyl group having from 2 to about 6 carbon atoms or an alkyl ether group having from about 4 to about 8 carbon atoms. R is independently selected from hydrogen or xe2x80x94CH2CHOHCH2ORxe2x80x2. Rxe2x80x2 is an alkyl group having from about 4 to about 22 carbon atoms. The compound generates an initial foam height at least 30% less than a 0.1 wt % aqueous solution of dioctyl sodium sulfosuccinate (DOSS), when added at 0.1 wt % to the aqueous DOSS solution. The present invention also pertains to an aqueous composition comprising the foam controlling agent.


It is an object to provide a nonvolatile semiconductor memory device having excellent writing property and charge-retention property. A semiconductor layer including a channel forming region between a pair of impurity regions which are formed to be apart from each other is provided. In an upper layer portion thereof, a first insulating layer, a floating gate, a second insulating layer, and a control gate are provided. The floating gate has at least a two-layer structure, and a first layer in contact with the first insulating layer preferably has a band gap smaller than that of the semiconductor layer. Furthermore, by setting an energy level at the bottom of the conduction band of the floating gate lower than that of the channel forming region of the semiconductor layer, injectability of carriers and a charge-retention property can be improved.

1. Field of the Invention
The present invention relates to a nonvolatile semiconductor memory device that is electrically writable, readable, and erasable, and its manufacturing method. In particular, the present invention relates to a structure of a floating gate in the nonvolatile semiconductor memory device.
2. Description of the Related Art
The market is expanding for nonvolatile memories in which data can be electrically rewritten and data can be stored even after the power is turned off. Features of a nonvolatile memory lie in that its structure is similar to that of a MOSFET (Metal Oxide Semiconductor Field Effect Transistor) and a region capable of accumulating charge for a long period of time is provided over a channel forming region. Such a charge accumulating region is formed over an insulating layer and is also referred to as a floating gate since it is insulated and isolated from the peripheral portion. Since the floating gate is electrically insulated from the peripheral portion by being surrounded by an insulator, there is a feature that charge injected to the floating gate are retained. A gate electrode called a control gate is further provided over the floating gate with an insulating layer interposed therebetween. The control gate is distinguished from the floating gate since predetermined voltage is applied to the control gate in data writing or reading.
In a floating gate type nonvolatile memory having such a structure, data is stored through electrical control of charge injection to and discharge from the floating gate. Specifically, charge is injected to and discharged from the floating gate by application of high voltage between a semiconductor layer in which a channel forming region is formed and a control gate. It is said that Fowler-Nordheim (F-N) type tunnel current (NAND type) or thermoelectrons (NOR type) flow in an insulating layer over the channel forming region at this time. Accordingly, the insulating layer is also referred to as a tunnel insulating layer.
The floating gate type nonvolatile memory is required to have a property, for securing reliability, that charges accumulated in the floating gate are retained for 10 years or more. Accordingly, the tunnel insulating layer is required to be formed to have a high insulating property so that charge does not leak and a thickness which produces tunnel current flow.
In addition, the floating gate formed over the tunnel insulating layer is formed using silicon that is the same semiconductor material as that of the semiconductor layer in which the channel forming region is formed. Specifically, a method for forming the floating gate using polycrystalline silicon has been widely used, for example, a polysilicon film deposited with a thickness of 400 nm (refer to Patent Document 1: Japanese Published Patent Application No. 2000-58685, p 7, FIG. 7)

This patent is subject to a terminal disclaimer.

Semiconductor Energy Laboratory Co., Ltd.


The invention relates to compositions and methods for use in treating skeletal system disorders in a vertebrate at risk for bone loss, and in treating conditions that are characterized by the need for bone growth, in treating fractures, and in treating cartilage disorders. More specifically, the invention concerns the use of NO-bisphosphonate assembly for enhancing bone growth.

Bone is subject to constant breakdown and re-synthesis in a complex process mediated by osteoblasts, which produce new bone, and osteoclasts, which destroy bone. The activities of these cells are regulated by a large number of cytokines and growth factors, many of which have now been identified and cloned.
There is a plethora of conditions which are characterized by the need to enhance bone formation or to inhibit bone resorption. Perhaps the most obvious is the case of bone fractures, where it would be desirable to stimulate bone growth and to hasten and complete bone repair. Agents that enhance bone formation would also be useful in facial reconstruction procedures. Other bone deficit conditions include bone segmental defects, periodontal disease, metastatic bone disease, osteolytic bone disease and conditions where connective tissue repair would be beneficial, such as healing or regeneration of cartilage defects or injury. Also of great significance is the chronic condition of osteoporosis, including age-related osteoporosis and osteoporosis associated with post-menopausal hormone status. Other conditions characterized by the need for bone growth include primary and secondary hyperparathyroidism, disuse osteoporosis, diabetes-related osteoporosis, and glucocorticoid-related osteoporosis.
Bone fractures are still treated exclusively using casts, braces, anchoring devices and other strictly mechanical means. Further bone deterioration associated with post-menopausal osteoporosis has been treated with estrogens or bisphosphonates, which may have drawbacks for some individuals. Treatment of bone or other skeletal disorders, such as those associated with cartilage, can be achieved either by enhancing bone formation or inhibiting bone resorption or both.
Bone tissue is an excellent source for factors which have the capacity for stimulating bone cells. Thus, extracts of bovine bone tissue obtained from slaughterhouses contain not only structural proteins which are responsible for maintaining the structural integrity of bone, but also biologically active bone growth factors which can stimulate bone cells to proliferate. Among these latter factors are transforming growth factor β, the heparin-binding growth factors (e.g., acidic and basic fibroblast growth factor), the insulin-like growth factors (e.g., insulin-like growth factor I and insulin-like growth factor II), and a recently described family of proteins called bone morphogenetic proteins (BMPs). All of these growth factors have effects on other types of cells, as well as on bone cells.
The cells which are responsible for forming bone are osteoblasts. As osteoblasts differentiate from precursors to mature bone-forming cells, they express and secrete a number of enzymes and structural proteins of the bone matrix, including Type-1 collagen, osteocalcin, osteopontin and alkaline phosphatase. They also synthesize a number of growth regulatory peptides which are stored in the bone matrix, and are presumably responsible for normal bone formation. These growth regulatory peptides include the BMPs (Harris S., et al. (1994), supra). In studies of primary cultures of fetal rat calvarial osteoblasts, BMPs 1, 2, 3, 4, and 6 are expressed by cultured cells prior to the formation of mineralized bone nodules (Harris S., et al. (1994), supra). Like alkaline phosphatase, osteocalcin and osteopontin, the BMPs are expressed by cultured osteoblasts as they proliferate and differentiate.
These data are, however, contrary to reports that dexamethasone and other inducers, such as BMPs, induce osteoblastic differentiation and stimulate osteocalcin mRNA (Bellows, C. G., et al., Develop Biol (1990) 140:132-38; Rickard, D. J., et al., Develop Biol (1994) 161:218-28). In addition, Ducy, P., et al., Nature (1996) 382:448-52 have recently reported that osteocalcin deficient mice exhibit a phenotype marked by increased bone formation and bones of improved functional quality, without impairment of bone resorption. Ducy, et al., state that their data suggest that osteocalcin antagonists may be of therapeutic use in conjunction with estrogen replacement therapy (for prevention or treatment of osteoporosis). However, there continues to be a need for additional treatments to stimulate bone growth or to mitigate bone loss.
Bisphosphonates, formerly called diphosphonates are compounds characterized by two C—P bonds. If the two bonds are located on the same carbon atom, resulting in a P—C—P structure, the compounds are called germinal bisphosphonates. They are therefore analogues of pyrophosphate that contain a carbon instead of an oxygen. There are a number of known pharmacologically active bisphosphonates including alendronate, Clodronate, etidronate, ibandronate, icadronate, pamidronate, risedronate, tiludronate and zoledronate. The main effect of these pharmacologically active bisphosphonates is to inhibit resorption both in vitro and in vivo. These effects are related to the marked affinity of these compounds for solid-phase calcium phosphate, on the surface of bone to which they bone strongly. In essence they target bone and elicit there pharmacological inhibition of osteoclast activity there. The mode of action of the bisphosphonates is still not completely elucidated. There is no doubt that their action in vivo is mediated mostly, if not completely, through mechanisms other than the physiochemical inhibition of crystal dissolution. There is a general consensus that the bisphosphonates act by inhibiting the activity of osteoclasts. Osteoclasts are inhibited when they come into contact with bisphosphonates-containing bone. This supports the hypothesis that bisphosphonates are deposited onto bone because of their strong affinity for the mineral, and that the osteoclasts are then inhibited when they start to engulf bisphosphonates-containing bone. The biochemical mechanisms by which bisphosphonates inhibit osteoclast activity are still unclear and may well be that more than one mechanism is operating.
The bisphosphonates investigated up to now appear to be absorbed, stored, and excreted unaltered in the body. Thus, bisphosphonates seem to be non-biodegradable, both in animals and in solution. Most of the pharmacokinetics data on the bisphosphonates have been obtained with etidronate, clodronate and pamidronate. The intestinal absorption lies between 1% and 10%. Between 20% and 50% of the absorbed bisphosphonate is localized to the bone, the remainder being rapidly excreted in the urine.
Although the nitrogen-containing bisphosphonates such as alendronate and pamidronate, have been shown to be effective in preventing the bone loss these drugs also appear capable of causing injury to the upper gastrointestinal tract and their have been several case reports of severe oesophagitis in patients treated with alendronate. Alendronate has also been shown to cause erosions and ulcers in the human stomach and to interfere with the healing of pre-existing lesions when given to healthy volunteers at doses that are prescribed for the treatment of osteoporosis and Pagets disease of bone.
The half-life of circulating bisphosphonates is short, in the rat only of the order of minutes. In man it is somewhat longer, about 2 hours. Acute, subacute, and chronic administration in several animal species have revealed little toxicity. Teratogenic, mitogenic and carcinogenic tests have been negative.
Other agents appear to operate by preventing the resorption of bone. Thus, U.S. Pat. No. 5,280,040 discloses compounds described as useful in the treatment of osteoporosis. These compounds putatively achieve this result by preventing bone resorption.
Nitric oxide (NO) has recently been shown to have profound effects on the metabolic activity of bone. This biologically active molecule generated biologically by a set of enzymes called nitric oxide synthases. Three known forms of the enzyme exist. Firstly, iNOS which is the inducible form where the expression of the enzyme and therefore the production of nitric oxide can be induced by a number of inflammatory stimuli. Secondly eNOS which is the constitutive form which is cannot be induced.
Endothelial dysfunction defined as the impaired ability of vascular endothelium to stimulate vasodilation plays a key role in the development of atherosclerosis and in various pathological conditions which predispose to atherosclerosis, such as hypercholesterolemia, hypertension, type 2 diabetes, hyperhomocyst (e) inemia and chronic renal failure. The major cause of the endothelial dysfunction is decreased bioavailability of nitric oxide (NO), a potent biological vasodilator produced in vascular endothelium from L-arginine by the endothelial NO synthase (eNOS). In vascular diseases, the bioavailability of NO can be impaired by various mechanisms, including decreased NO production by eNOS, and/or enhanced NO breakdown due to increased oxidative stress. The deactivation of eNOS is often associated with elevated plasma levels of its endogenous inhibitor, N(G) N(G)-dimethyl-L-arginine (ADMA). In hypercholesterolemia, a systemic deficit of NO may also increase the levels of low density lipoproteins (LDL) by modulating its synthesis and metabolism by the liver, as suggested by recent in vivo and in vitro studies using organic NO donors. Therapeutic strategies aiming to reduce the risk of vascular diseases by increasing bioavailability of NO continue to be developed.
Nitric oxide (NO) is a free radical which has important effects on bone cell function. The endothelial isoform of nitric oxide synthase (eNOS) is widely expressed in bone on a constitutive basis, whereas inducible NOS is only expressed in response to inflammatory stimuli. It is currently unclear whether neuronal NOS is expressed by bone cells. Pro-inflammatory cytokines such as IL-1 and TNF cause activation of the iNOS pathway in bone cells and NO derived from this pathway potentiates cytokine and inflammation induced bone loss. These actions of NO are relevant to the pathogenesis of osteoporosis in inflammatory diseases such as rheumatoid arthritis, which are characterized by increased NO production and cytokine activation. Interferon gamma is a particularly potent stimulator of NO production when combined with other cytokines, causing very high concentrations of NO to be produced. These high levels of NO inhibit bone resorption and formation and may act to suppress bone turnover in severe inflammation. The eNOS isoform seems to play a key role in regulating osteoblast activity and bone formation since eNOS knockout mice have osteoporosis due to defective bone formation. Other studies have indicated that the NO derived from the eNOS pathway acts as a mediator of the effects of estrogen in bone. eNOS also mediates the effects of mechanical loading on the skeleton where it acts along with prostaglandins, to promote bone formation and suppress bone resorption. Pharmacological NO donors have been shown to increase bone mass in experimental animals and preliminary evidence suggests that these agents may also influence bone turnover in man. These data indicate that the L-arginine/NO pathway represents a novel target for therapeutic intervention in the prevention and treatment of bone diseases.
Because of the importance of nitric oxide in many biological events numerous NO releasing compounds are now being synthesized. Many of these involve the use of linking NO to non-steroidal anti-inflammatory drugs (NSAIDS) such as flurbiprofen, ketoprofen, diclofenac and naproxen. These agent have been shown to spare the GI-tract from the undesired effects the NSAIDs by increasing blood flow and mucus secretion as well as reducing free radical generation in the stomach.

Methods and compositions for stimulating bone growth using nitric oxide releasing bisphosphonate conjugates


A flame simulator of an electric fireplace, including: a light source (1); a flame board (3); a flame projection screen (4); and a rotary drum (2); wherein the light source (1) is provided in the rotary drum (2); the rotary drum (2) is transparent and a light-concentrating block (20) is provided on a surface thereof; a flame pattern (31) is provided on the flame board (3); light concentrated by the light-concentrating block (20) is projected onto the flame board (3) and reflected by the flame board (3) to the flame projection screen (4) for forming a flame image. The flame is bright and has a sufficient dynamic effect. The rotary drum (2) and the light-concentrating block (20) can be made by injection molding for a simple structure and convenient production.

1. Field of Invention
The present invention relates to an electric fireplace.
2. Description of Related Arts
Flame simulator of an electric fireplace usually utilizes electrical flame or simulated flame. The flame is not used for heating, but for visual effects and decoration.
A conventional electric fireplace with a flame simulator generally comprises two parts: a blowing heater and a flame simulator. Usually, there are two types of flame simulator. The first type utilizes a set of streamers hanging above a simulated burning object and behind a translucent plastic screen and mirror glass. The streamers blowing by air are projected onto the glass surface and flickering lights are formed for simulating the burning flame. Although the flickering visual effect of the flame is provided, spark movements due to intensely burning are not simulated. The second type installs a rotary light source driven by motor behind a simulated dendritic charcoal combustion medium and provides a flame-like wall, a translucent screen as well as a mirror glass in front of the rotary light source. The light from the rotary light source passes through flame holes on the fire wall for forming the shape of flame. Then the shape of flame is projected onto the translucent screen and the mirror glass for producing the visual effect of the jumping flame.
There are other types of flame simulator, but simulating effects thereof are not good enough, and producing methods thereof are complex.

Electric fireplace and flame simulator thereof


Methods and systems are provided for evaluating standing queries against updated contact entries configured as a stream of facts. The method includes resolving the standing queries into an array of rules, each rule having a first and a second condition; sorting t one of the facts into a first property and a second property; comparing the first property of the fact to the first condition of each rule in the array of rules to produce a first subset of matching rules; comparing the second property of the fact to the second condition of each rule in the first subset of rules to produce a second subset of matching rules; and reporting at least one of the second subset of rules to an author of the matching rule. The method further includes populating a first hash with indicia of the first subset, and populating a second hash with the second subset.

Modern software development is evolving away from the client-server model toward network-based processing systems that provide access to data and services via the Internet or other networks. In contrast to traditional systems that host networked applications on dedicated server hardware, a "cloud" computing model allows applications to be provided over the network "as a service" supplied by an infrastructure provider. The infrastructure provider typically abstracts the underlying hardware and other resources used to deliver a customer-developed application so that the customer no longer needs to operate and support dedicated server hardware. The cloud computing model can often provide substantial cost savings to the customer over the life of the application because the customer no longer needs to provide dedicated network infrastructure, electrical and temperature controls, physical security and other logistics in support of dedicated server hardware.
Multi-tenant cloud-based architectures have been developed to improve collaboration, integration, and community-based cooperation between customer tenants without sacrificing data security. Generally speaking, multi-tenancy refers to a system where a single hardware and software platform simultaneously supports multiple user groups (also referred to as "organizations" or "tenants") from a common data storage element (also referred to as a "multi-tenant database"). The multi-tenant design provides a number of advantages over conventional server virtualization systems. First, the multi-tenant platform operator can often make improvements to the platform based upon collective information from the entire tenant community. Additionally, because all users in the multi-tenant environment execute applications within a common processing space, it is relatively easy to grant or deny access to specific sets of data for any user within the multi-tenant platform, thereby improving collaboration and integration between applications and the data managed by the various applications. The multi-tenant architecture therefore allows convenient and cost effective sharing of similar application features between multiple sets of users.
Robust customer relationship management (CRM) systems and applications for managing contacts have been developed for use in the multi-tenant environment. Consequently, maintaining business and professional contact information has migrated from the Rolodex™ to the cloud. Commercial databases currently maintain millions—or even tens of millions—of business, professional, technical, and social contact entries. In a typical contact database environment, subscribers interrogate the database through structured searches using, for example, structured query language (SQL) formatted queries. Even though a relatively small amount of the contact data changes on a daily basis, for example, on the order of one to three percent, continuously or periodically processing a large number of standing queries on the changed data requires significant computing resources.
Systems and methods are thus needed for processing standing queries, also referred to as event streams, efficiently to conserve computational resources, to thereby keep pace with the need for real time or near real time searching of continuously updated contact data.

System and method for fast evaluation of standing queries in conjunctive normal form


An output, representing synaptic weights of a neural network can be received from first memory elements. The output can be compared to a known correct output. A random number can be generated with a tuned bias via second memory elements. The weights can be updated based on the random number and a difference between the output and the known correct output.

Memory devices are typically provided as internal, semiconductor, integrated circuits in computers or other electronic devices. There are many different types of memory including volatile and non-volatile memory. Volatile memory can require power to maintain its data (e.g., host data, error data, etc.) and includes random-access memory (RAM), dynamic random access memory (DRAM), and static random access memory (SRAM), among others. Non-volatile memory can provide persistent data by retaining stored data when not powered and can include NAND flash memory, NOR flash memory, read only memory (ROM), Electrically Erasable Programmable ROM (EEPROM), Erasable Programmable ROM (EPROM), and resistance variable memory, such as phase change random access memory (PCRAM), three-dimensional cross-point memory (e.g., 3D XPoint™), resistive random access memory (RRAM), ferroelectric random access memory (FeRAM), magnetoresistive random access memory (MRAM), and programmable conductive memory, among other types of memory.
A physical layout of a resistance variable memory device may resemble that of a DRAM device where the capacitor of the DRAM cell is replaced by a phase change material (e.g., Germanium-Antimony-Telluride (GST) or other chalcogenide materials). An access device such as a diode or metal oxide semiconductor field effect transistor (MOSFET) can be connected in series with the phase change material. Chalcogenide materials can include compounds of sulfides, selenides, and tellurides, among others. A physical layout of an RRAM device may include memory cells including a resistance variable thin film (e.g., a colossal magnetoresistive material). The thin film can be connected to an access device such as a diode, a field effect transistor (FET), or a bipolar junction transistor (BJT).
Memory cells can be programmed to a programmed level. The resistance of a resistance variable memory device can be altered by applying energy pulses to the resistance variable material. For example, material properties of a phase change material may be altered by heating it with a programming current. Generally, a higher resistance level may be associated with a more amorphous state (e.g., a RESET state) of the phase change material, and a lower resistance level may be associated with a more crystalline state (e.g., a SET state) of the phase change material. The resistance of a thin film RRAM device can be increased and/or decreased by applying positive and/or negative electrical pulses across the film.
Neural networks are networks that process information by modeling a network of neurons, such as neurons in a human brain, to process information (e.g., stimuli) that has been sensed in a particular environment. Similar to a human brain, neural networks typically include multiple neuron models to process information, which can be referred to as artificial neurons.

Memory element for weight update in a neural network


A steering system includes: a steering member that is provided on a vehicle and that is used for a steering operation; an actuator that assists the steering operation of the steering member; and a steering control device that executes returning operation assist control in which the actuator is controlled to assist a returning operation for returning the steering member to a neutral position, the returning operation corresponding to a turning operation for turning the steering member from the neutral position, and that determines a returning operation time at the time of executing the returning operation assist control on the basis of a steering operation amount of the steering member at the time of the turning operation.

1. Field of the Invention
The invention relates to a steering system, a steering control device and a steering control method.
2. Description of Related Art
For example, Japanese Patent Application Publication No. 2007-099053 (JP 2007-099053 A) describes a control device for an electric power steering system as an existing steering system or steering control device. The control device for an electric power steering system transmits steering assist force generated by a motor to a steering mechanism to reduce steering force. The control device for an electric power steering system includes a steering angle sensor that detects a steering angle of a steering shaft, a torque sensor that detects a steering torque applied to the steering shaft, a vehicle speed detecting unit that detects a vehicle speed, and a control unit that controls the motor on the basis of a steering angle, a steering angular speed, a steering torque and a vehicle speed.
Incidentally, in the above described control device for an electric power steering system, described in JP 2007-099053 A, the control unit has a steering wheel return control function, and corrects steering feeling on the basis of a steering angle through the steering wheel return control function. However, for example, further improvement in steering feeling is desired.

Steering system, steering control device and steering control method


A data weighted average (DWA) structure including a first delay unit, a binary to thermometer code converter, an adder, a second delay unit, a decoder, a barrel shifter, and a plurality of signal lines is provided. The first delay unit delays an input digital signal. The binary to thermometer code converter converts an output signal of the first delay unit into a thermal code. The second delay unit delays an output signal of the adder. The adder adds the input digital signal to an output signal of the second delay unit. The decoder decodes the output signal of the second delay unit. The barrel shifter generates an output signal from the thermal code in accordance with an output signal of the decoder. The signal lines route the output signal of the barrel shifter into two independent control signal groups.

1. Field of the Invention
The present invention generally relates to a data weighted average (DWA) structure and a digital-to-analog signal conversion method, in particular, to a DWA structure and a digital-to-analog signal conversion method for reducing errors caused by element mismatch.
2. Description of Related Art
Digital-to-analogy converters (DACs) and analog-to-digital converters (ADCs) have been broadly applied to communication systems, consumer electronic products, and audio equipments etc. However, within DACs or ADCs, non-linear problems caused by element mismatch are inevitable, and such problems are very crucial to a sigma-delta modulator (SDM).
Dynamic element matching (DEM) has been provided for resolving the non-linear problems in DACs, wherein data weighted averaging (DWA) is a well-known DEM algorithm. Generally speaking, DWA realizes first-order noise shaping and reduces element mismatch effect. In addition, DWA can reduce capacitor mismatch at the input terminal of analog circuits (for example, a switched-capacitor reconstruction filter, SCF) in DACs; thus, DWA has good signal noise ratio (SNR) and total harmonic distortion (THD) performance.
However, the existing DWA structures still have some problems. For example, in-band tone may be produced in the existing DWA structures, thus, the spur-free dynamic range (SFDR) performance may not be satisfactory. In addition, existing high resolution DACs have low efficiency and large circuit area.
Accordingly, a new DWA structure having foregoing and/or other advantages but without foregoing and/or other problems is to be provided.

DWA structure and method thereof, digital-to-analog signal conversion method and signal routing method


This invention provides a rechargeable cell comprising an electrode including: a plurality of porous clusters of silver particles, wherein each cluster includes: (a) a plurality of silver particles, and (b) crystalline particles of zirconium oxide (ZrO2), wherein at least a portion of the crystalline particles of ZrO2 is located in pores formed by a surface of the plurality of silver particles. Electrodes of the present invention catalyze the reduction of oxygen in alkaline solution. When the cell is charged, the silver in the electrodes can be oxidized to Ag2O and further to AgO. Upon discharge, the reduction of the oxidized silver results in additional available energy. This invention provides electrodes for use in rechargeable cells or batteries and methods of making thereof.

Electrically rechargeable (or secondary) metal-air cells or batteries are very attractive power sources in light of their potential high energy density. In this type of cells the oxidizing reactant (oxygen) which undergoes reduction during discharge is supplied from outside the cell. This reaction of oxygen reduction occurs in the presence of water and gives hydroxide ions (OH−). The oxygen is reduced on the surface of the cathode during discharge. The cathode comprises a material that catalyzes the above-mentioned oxygen reduction. Such catalyst includes, inter alia, silver, platinum, perovskite-type oxides, mixed metal oxides with spinel structure etc.
However, until now this type of cells or batteries has not been satisfactory realized because of the degradation of the catalyst material during recharging.
There are many uses for silver catalysts, including the chemical industry (e.g., in reaction of ethylene oxidation), cells or batteries (both primary and rechargeable) and fuel cells with alkaline electrolyte, oxygen sensors, and electrolysis cells.
Sub-micron and nano-size silver metal powder and silver based bulk alloy catalysts can be produced by different methods, including the Raney method of making a "skeleton" catalyst from Ag—Ca, Ag—Mg, Ag—Al and others alloys, chemical precipitation, leaching of Al from heat treated strips of Al—Ag alloys (see, by way of example, U.S. Pat. No. 5,476,535, which is incorporated herein by reference).
The above methods result in a porous silver agglomerate or cluster of primary particles in a range of sizes from tenths of microns to a few millimeters, consisting of primary particles having an average size from about sub-micron to a few hundred microns.
While all the above-described methods can produce silver powder catalysts having sub-micron or nano-size primary particles, these techniques have been found to have a drawback if the final product is used as a catalyst for air or oxygen electrodes for batteries and fuel cells with alkaline electrolyte. This drawback relates to the phenomenon of silver catalyst dissolution in alkaline electrolyte.
Silver, by itself, has a very low rate of dissolution in alkaline solutions. On the other hand, silver oxides have a much higher dissolution rate. At an anodic oxidation of silver in alkaline solution, the first phase transition at a potential of +0.24V (here and throughout this application the potentials are vs. Hg/HgO reference electrode) is Ag→Ag2O. The next phase transition is Ag2O→AgO at a potential of about +0.5V.
These values of potentials were determined in various classic studies for smooth silver foil (see M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions, (1966), p. 393). For fine silver powder and for any kind of nano-sized silver catalyst in particular, the formation of silver oxides starts at much more cathodic potentials. Y. Golin, et al. (Electrochimia, Vol. 18, p. 1223) disclose that Ag2O appears on the surface of ultra-fine silver catalyst at a potential of about +0.1V. This range of potentials corresponds to the open circuit voltage (OCV) of oxygen/air electrodes in alkaline electrolyte. If a silver-catalyzed cathode works as a bi-functional electrode, the potentials in the charge mode of operation could reach +0.4-0.5V and even higher, until the process of oxygen evolution occurs. This means that substantially all the problems of silver catalyst dissolution result from the formation of different types of silver oxides at OCV and anodic polarization, and their subsequent decomposition and precipitation.
While there has been some discussion in the technical literature as to the nature of the dissolution of silver oxide, it is generally agreed that the silver is present in alkaline electrolyte in the form of anions, like Ag(OH)2− or AgO− (H. Fleischer, (ed.), Zinc-Silver Oxide Batteries, J. Wiley (1971)), and has a tendency, during decomposition, to slowly form a finely divided black deposit of metallic silver. The rate of decomposition increases with increasing concentration of dissolved silver oxide, temperature and the presence of various kinds of impurities.
The precipitated silver black has tremendous diffusion ability, which results in roughening of the primary ultra fine porous structure, decreased surface area of the catalyst, and correspondingly, reduced electrode performance.
While the dissolution of silver may be inhibited or diminished by deliberate, continuously maintained polarization of the electrochemical power sources having silver-catalyzed or bulk-silver-alloy-catalyzed air or oxygen cathodes, this is highly disadvantageous, and in many cases, practically impossible.
There is therefore a recognized need for, and it would be highly advantageous to have, a silver material, modified chemically, that inherently is stable and resistant to dissolution.

Porous clusters of silver powder comprising zirconium oxide for use in gas diffusion electrodes, and methods of production thereof


Techniques for case allocation are disclosed. In one particular embodiment, the techniques may be realized as a method for case allocation comprising receiving, by at least one computer processor, at least one case allocation allocated using a first pairing strategy, and then reassigning, by the at least one computer processor, the at least one case allocation using behavioral pairing.

In some customer service centers, cases may be assigned to agents (e.g., analysts, specialists) for servicing. For example, insurance claims may be assigned to insurance adjusters or other agents for subrogation or other processing; patients or other insureds may be assigned to nurses, pharmacists, or other clinical support specialists; debt collectors may be assigned to debtor cases; and so on. These cases may be assigned in a variety of ways. In some customer service centers (including, for example, workflow, case management, or transaction processing service or support organizations), cases may be assigned to agents based on time of arrival. This strategy may be referred to as a "first-in, first-out", "FIFO", or "round-robin" strategy. In some customer service centers, management (e.g., managers or supervisors) may assign cases to agents (including other types of specialists such as those mentioned above), possibly with a particular rationale based on information known to the management, such as information about an agent's skills or historical performance. For some cases, management may have low confidence in their assignments or lack relevant information to make optimal assignments.
Also, in some customer contact centers, cases or contacts may be assigned to agents for servicing. For example, a "lead list" of contacts may be generated for each agent to contact (e.g., using an outbound dialer). These contacts may be assigned to agents using a FIFO strategy. In other environments, contacts may be assigned to agents using other methods such as management-based assignments.
In view of the foregoing, it may be understood that there may be significant problems and shortcomings associated with current FIFO or management-assigned strategies.


A method for providing open access to vehicle data is disclosed. From a vehicle under service, the method receives vehicle-diagnostic data in a manufacturer-specified format at a vehicle-service tool, and converts the vehicle data in the manufacturer-specified format into vehicle data in an open format.

As vehicles typically require servicing over their lifetime, vehicle-scan tools may receive vehicle-diagnostic data relating to a given vehicle. The vehicle-diagnostic data may be used to diagnosis problems relating to the vehicle.
Typically, a vehicle-scan tool receives vehicle-diagnostic data in a manufacturer-specified format, and converts the vehicle-diagnostic data from the manufacturer-specified format into vehicle-diagnostic data that is stored in a closed format. A technician may use the vehicle-scan tool to display the vehicle-diagnostic data stored in the closed format, and use the displayed vehicle-diagnostic data to diagnose a fault experienced by the vehicle.
The vehicle-diagnostic data in the closed format may typically be viewed by an application on the vehicle-scan tool itself and by like tools that include similar applications created (perhaps created by the manufacturer) specifically to view the vehicle-diagnostic data in the closed format.
Manufacturers of vehicle-scan tools may have an incentive to keep the vehicle-diagnostic data produced by the vehicle-scan tool in a closed format. For instance, if the vehicle-diagnostic data on the vehicle-scan tool is kept in a closed format, the only way for a technician to further view or analyze the vehicle-diagnostic data would be to perhaps purchase additional applications provided by the same manufacturer. Hence, using the vehicle-scan tool to view closed formatted files may also require use of additional products and services provided by the manufacturer. Hence, the use of vehicle-diagnostic data in a closed format may help increase manufacturer sales.

Methods and systems for providing open access to vehicle data


A steam reformer, with a combustion chamber, catalyst tubes arranged in several rows, with burners for heating the catalyst tubes, with feed conduits each for supplying the catalyst tubes with educt gas and the burners with air and fuel gas, with collecting conduits for discharging the product gas, with channels for discharging the burner waste gases from the combustion chamber, wherein the ceilings of the channels each are formed by the bottom or the ceiling of the combustion chamber, and wherein the channels for discharging the burner waste gases are designed such that the flow velocity of the burner waste gases is constant along the entire length of the channels, as seen vertically to the catalyst tubes.

Steam reformers for the conversion of gaseous hydrocarbons with steam into synthesis gas chiefly consisting of carbon monoxide and hydrogen are known. The steam reformation process is described in principle, for example in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, Vol. 15, chapter "Gas Production", section 2.2. The different types of tubular reactors proven for this process are discussed in section 2.2.3 of the same chapter. There are shown tubular reactors in which the burners are installed in the roof or in the side walls of the reformer housing. It should be noted in addition that variants with burners installed in the bottom of the housing, with flames directed vertically upwards into the housing, also are possible, as is mentioned e.g. in the document DE 2521683 A1.
For the uniform heating of all reformer tubes filled with a catalyst fixed bed, which are disposed in the reformer housing, the design and the arrangement of the channels for discharging the burner waste gases from the housing is very important. As shown in FIG. 6 of the above-mentioned Ullmann section 2.2.3, a proven design of the reformers consists in arranging the burners in the housing roof and the waste gas collecting channels at the bottom of the housing. The burners and the channels, each one opposite the other, are disposed between the rows of the reformer tubes. From the document DE 102011120938 A1 it also is known that it is possible to arrange the waste gas collecting channels directly below the bottom of the reformer housing. The bottom of the reformer housing at the same time forms the cover of the channels. Through openings in the cover, the burner waste gas passes from the reformer housing into the waste gas collecting channels. Via a collecting conduit the ends of the channels are connected with an apparatus for sucking off the waste gas, such as a blower or a chimney. The flow resistance which the waste gas stream is subject to within each of the channels leads to a pressure loss from the beginning of a channel to the end of a channel. Furthermore, the waste gas quantity sucked off cumulatively increases along the length of the channels, as via additional openings in the longitudinal directions of the channels additional burner waste gases are discharged from the reformer housing. This results in non-uniform turbulences in the burner waste gas, which are distributed along the channel length or in the bottom region of the reformer housing, and hence to a non-uniform heating of the reformer tubes.

Reformer for producing synthesis gas having improved burner waste gas flow

L'Air Liquide Societe Anonyme Pour L'Etude Et L'Exploitation Des Procedes Georges Claude


A solid, spheroidal polymerization catalyst having a particle size distribution characterized by a Dm*/Dn of less than 3.0, the catalyst comprising a phosphinimine catalyst, a cocatalyst and a magnesium chloride support. A process for the polymerization of ethylene with one or more alpha olefin catalyzed by a solid, spheroidal polymerization catalyst having a particle size distribution characterized by a Dm*/Dn of less than 3.0, the catalyst comprising a phosphinimine catalyst, a cocatalyst and a magnesium chloride support.

The use of solid, spheroidal catalysts for use in the heterogeneous polymerization of ethylene is well known. The prior art catalysts are typically based on metallocene catalysts or Ziegler-Natta catalysts and are supported on spheroidal magnesium chloride supports. Methods for preparing such catalysts include methods which rely on emulsion, spray drying, and controlled precipitation techniques. These catalysts may provide for improved product morphology and bulk density.
U.S. Pat. Nos. 5,106,804 and 5,439,995 describe the use of a spheroidal catalyst based on a zirconocene single site catalyst supported on spheroidal magnesium chloride particles. Pre-polymerization, followed by polymerization using these catalysts gave polymer with good morphology. The spheroidal magnesium chloride support particles are made in the presence of a non-reactive electron donor compound such as a non-protic ether compound. For further descriptions of spheroidal magnesium chloride particles and their use as supports see CA Pat. Nos. 1,189,053; 2,036,767 and 2,092,769.

Spheroidal catalyst for olefin polymerization


Coincident with the evolution, maturation, etc. of wireless messaging ecosystems an infrastructure that provides for enhanced content delivery in new and creative ways. The delivery model leverages the features, capabilities, etc. that are offered by MMS to deliver various types of content (e.g., content that would otherwise be difficult or impossible to display on a wireless device using the wireless device's native facilities) to wireless devices by, possibly inter alia, processing the content (including, possibly among other steps, formatting the content, rendering the content as one or more images, etc.) and subsequently delivering the processed content to a wireless device via MMS. The infrastructure may optionally leverage the capabilities of a centrally-located Messaging Inter-Carrier Vendor.

1. Field of the Invention
The present invention relates generally to telecommunications services. More particularly, the present invention relates to capabilities that enhance substantially the value and usefulness of various messaging paradigms including, inter alia, Short Message Service (SMS), Multimedia Message Service (MMS).
2. Background of the Invention
As the 'wireless revolution' continues to march forward the importance to a Mobile Subscriber (MS), for example a user of a Wireless Device (WD) such as a mobile telephone, a BlackBerry, etc. that is serviced by a Wireless Carrier (WC), of their WD grows substantially.
One consequence of such a growing importance is the resulting ubiquitous nature of WDs—i.e., MSs carry them at almost all times and use them for an ever-increasing range of activities.
Coincident with the expanding presence of WDs has been the explosive growth of:
1) Content—both structured and unstructured on or within, possibly inter alia, all of the different information, entertainment, etc. sites that are available on the World Wide Web (WWW); WWW Logs (blogs); social networking facilities; etc.
2) Messaging—a steady annual increase, year over year, in the number of (SMS, MMS, etc.) messages that have been exchanged by and between WDs. That steady increase shows no sign of abating. For example, as reported by the industry group CTIA (see www.ctia.org) in the U.S. there were over 158 billion SMS messages sent during 2006 (representing a 95% increase over 2005) and there were over 2.7 billion MMS messages sent during 2006 (representing a 100% increase over 2005).
Under various circumstances it may be difficult, or even impossible, to display some types of content on a WD using the WD's native (e.g., E-Mail, SMS, Instant Messaging [IM], etc.) facilities. Examples of such content might include, possibly inter alia, languages that support or require double-byte characters (such as Japanese, Chinese, Korean, Arabic, etc.), mathematical equations, scientific equations, chemical formulas, etc. Several illustrative examples of such content are presented under FIG. 6 and reference numeral 600.
The specific examples that were described above are illustrative only and it will be readily apparent to one of ordinary skill in the relevant art that numerous other examples are easily possible and indeed are fully within the scope of the present invention.
For such types of content it would be desirable to leverage the features, capabilities, etc. that are offered by MMS to be able to deliver such content to WDs by, possibly inter alia, processing the content (including, possibly among other steps, formatting the content, rendering the content as one or more images, etc.) and subsequently delivering the processed content to a WD via MMS.
The present invention facilitates such enhanced content delivery capabilities and addresses various of the (not insubstantial) infrastructure, etc. challenges that are associated with same.

System and method for enhanced content delivery