A currency-operated liquid dispensing machine includes removable and replaceable containers such as carboys or bags that can be drained sequentially or in parallel. The containers are coupled to a furcated passage having an outlet. Such a vending machine dispenses metered quantities of water in response to an amount paid.

Vending machines have been used for many years for dispensing a variety of goods, ranging from clothing, to beverages, to food. Beverages may be dispensed in bottles, cans or into a cup or other suitable container.
In recent years, bottled water has been made available in vending machines. The increase in water purchases results from concerns that consumers have about the quality of tap water. Additionally, consumers find it convenient to carry water in bottles rather than looking for a source of water. There are, however, problems associated with the sale of bottles of water that are sized for individual usage. According to some records, 1.5 million tons of plastic are used to bottle water every year. These bottles have to be recycled or disposed of, both of which lead to pollution.
As an alternative to bottled water, many businesses provide water coolers or water dispensers. As disclosed in U.S. Pat. No. 5,409,094 these may be coin-operated. Water dispensers usually provide both chilled and ambient temperature water from a five gallon carboy. The carboy is inverted into a reservoir, which is usually gravity fed. This means that for water to be released from the reservoir and carboy, air must replace the water. Accordingly, water dispensers of this type generally have an open reservoir to allow air exchange. Concern over the safety of these water dispensers has resulted in the development of closed system dispensers as disclosed in U.S. Pat. No. 5,222,531 and U.S. Pat. No. 6,442,960. While this overcomes the concern over cleanliness, the problem of a limited supply of water remains, as these are designed to deliver water from a five gallon carboy. Accordingly, they are not well suited for commercial sales of water.
Another approach to providing clean drinking water is to provide a reverse osmosis machine. These are attached to a water supply, most typically, a municipal water system, hence the constraint of limited water supply is overcome. The water passes through a series of filters in addition to undergoing reverse osmosis. Unfortunately, there have been many problems associated with the cleanliness of the filters, pipes and storage tanks for these machines. Despite these problems, reverse osmosis machines have been installed in, for example, shopping centres where they are coin operated.
It is an object of the invention to overcome the deficiencies in the prior art.

Vending machine for dispensing potable liquid

University of Victoria Innovation and Development Corporation


Novel trisubstituted piperazine compounds of the formula (I) and pharmaceutically acceptable salts thereof: ##STR1## wherein R.sup.1, R.sup.2 and R.sup.3 are lower alkyl groups; A is a phenyl group, a hydrocarbon group formed by condensation of two or three 5- to 8-membered rings, a monocyclic 5- to 8-membered heterocyclic group containing 1 to 3 hetero-atoms selected from the class consisting of nitrogen, oxygen and sulfur, a dicyclic heterocyclic group formed by condensation of a benzene ring with a 5- to 8-membered hetero-ring containing 1 to 3 hetero-atoms selected from the class consisting of nitrogen, oxygen and sulfur, a tricyclic heterocyclic group formed by condensation of (i) a 5- to 8-membered hetero-ring containing 1 to 3 hetero-atoms selected from the class consisting of nitrogen, oxygen and sulfur, and (ii) a benzene ring, and (iii) a benzene ring or a 5- to 8-membered hetero-ring containing 1 to 3 hetero-atoms selected from the class consisting of nitrogen, oxygen and sulfur, or a styryl group of the formula: Ar--CR.sup.4 .dbd.CR.sup.5 -- wherein Ar is a phenyl group, and R.sup.4 and R.sup.5 are independently hydrogen or a lower alkyl group, the phenyl group represented by A or Ar, the hydrocarbon group represented by A, the monocyclic 5- to 8-membered heterocyclic group represented by A, the dicyclic heterocyclic group represented by A and the tricyclic heterocyclic group represented by A being unsubstituted or substituted by one or more substituents selected from the class consisting of a lower alkyl group, a halo lower alkyl group, a hydroxy lower alkyl group, an acyloxy lower alkyl group, a lower alkoxy lower alkyl group, a lower alkoxy group, a halo lower alkoxy group, a lower alkoxycarbonyl lower alkoxy group, a lower alkenyloxy group, aralkyloxy group, a lower alkoxy lower alkoxy group, a lower alkoxycarbonyl group, carboxyl group, carbamoyl group, an N,N-di-lower alkylcarbamoyl group, an N-lower alkylcarbamoyl group, halo group, cyano group, nitro group, hydroxy group, acyloxy group, amino group, a lower alkylsulfonylamino group, acylamino group, a lower alkoxycarbonylamino group, acyl group, mercapto group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group and oxo group; X is methylene group, carbonyl group or thiocarbonyl group and G is a group of the formula: --CH.sub.2 --.sub.n Z--R.sup.6 wherein n is an integer of 0 to 2, Z is a chemical bond, O, S, SO, SO.sub.2, CO, COO, OCO, OCONR.sup.7, CONR.sup.7 or NR.sup.7 (wherein R.sup.7 is hydrogen, a lower alkyl group, a lower haloalkyl group, a lower alkenyl group or a lower alkoxycarbonyl group), and R.sup.6 is hydrogen, a lower alkyl group, a lower haloalkyl group or a lower alkenyl group, provided that, when n is O and Z is chemical bond, R.sup.6 is not hydrogen or a lower alkyl group are useful as a platelet activating factor antagonist.

This invention relates to trisubstituted piperazine compounds useful as medicines. More specifically, the present invention relates to compounds represented by the formula: ##STR2## wherein R.sup.1, R.sup.2, and R.sup.3 represent a lower alkyl group, A stands for an optionally substituted phenyl group, an optionally substituted condensed polycyclic hydrocarbon group, an optionally substituted hetero-cyclic group or a styryl group represented by the formula Ar--CR.sup.4 .dbd.CR.sup.5 -- wherein Ar stands for an optionally substituted phenyl group, and R.sup.4 and R.sup.5 respectively stand for hydrogen or a lower alkyl group, X stands for a methylene group, carbonyl group or thiocarbonyl group, and G stands for a group represented by the formula: --CH.sub.2 --.sub.n Z--R.sup.6 wherein n denotes an integer of 0 to 2, Z stands for a chemical bond, O, S, SO, SO.sub.2, CO, COO, OCO, OCONR.sup.7, CONR.sup.7 or NR.sup.7 (wherein R.sup.7 stands for hydrogen, a lower alkyl group, a lower haloalkyl group, a lower alkenyl group or a lower alkoxycarbonyl group), and R.sup.6 stands for hydrogen, a lower alkyl group, a lower haloalkyl group, a lower alkenyl group, a lower alkynyl group or a lower cycloalkyl group, provided that, when n=O and Z=chemical bond, R.sup.6 is not hydrogen or a lower alkyl group and pharmaceutically acceptable salts thereof. The compounds are useful as platelet activating factor (PAF) antagonists.
PAF has a phospholipid structure and is a chemical transmitter existing in a living body. It has been made clear that PAF is closely concerned with allergy, anaphylaxis, inflammation, etc. and it has also been known that PAF has a strong hypotensive activity and platelet agglutinating activity. On administering PAF to an animal, the animal may in some cases be killed from shock. Symptoms caused by the shock from PAF have much resemblance to those caused by the shock from endotoxin, and it has been considered that PAF is concerned with the endotoxin shock.
On the other hand, while a variety of compounds having PAF-antagonistic activity have been known, very few of them are satisfactory in PAF-antagonistic activity in a living body. And, even when the PAF-antagonistic activity in a living body is satisfactory, not a few of those compounds have some restrictions in the administration method.

Trisubstituted piperazine compounds, their production and use


An MRI apparatus has a plurality of shim coils 102 and gradient magnetic field coils 104, which are connected to power sources 103 and 105 respectively. These power sources are controlled by a computer 112 to correct intensity of a static magnetic field generated by a magnet. For this purpose, the power sources 103 and 105 supply composite current of DC and AC so that the shim coils and the gradient magnetic field coils generate a rotating magnetic field. As a result, the uniformity of the static magnetic field in a region of an object under examination is improved and image distortion is suppressed. The MRI apparatus can be effectively applied to a fast imaging technique, an imaging technique where NMR signals of adipose tissue are suppressed, and a high resolution spectrum.

This invention relates to a magnetic resonance imaging apparatus and method using a nuclear magnetic resonance (hereinafter referred to as "NMR") phenomenon to obtain an NMR spectrum or tomographic image of a desired inner region of an object under examination non-invasively. In particular, it relates to a method for obtaining a substantially high uniformity of a static magnetic field in the apparatus.
The magnetic resonance imaging (hereinafter referred to as "MRI") apparatus uses an NMR phenomenon to obtain an NMR spectrum or tomographic image of a desired inner region of an object under examination non-invasively.
An object to be examined is placed in a uniform static magnetic field generated by a permanent magnet or a superconductive magnet. A high frequency magnetic field with a frequency equal to that of the Larmor precession (Larmor frequency .omega.) of a specified atom, e.g., hydrogen (proton), constituting tissues of the object (e.g., human body) is applied to excite the nuclear spins and NMR signals emitted from the excited spins are measured as free induced decay or spin echo signals when the spins return to the ground state. Here, the Larmor frequency .omega. is calculated by the following formula and depends on the intensity of the magnetic field. EQU .omega.=.gamma..multidot.Ho
In the above equation, .gamma. is a magnetic rotational ratio inherent in each atomic nuclei. Ho is the intensity of the static magnetic field.
In ordinary MRI, gradient magnetic fields are superimposed on the static magnetic field to produce spatial difference in the magnetic field and a measuring sequence is repeated at a predetermined repetition time TR while adding location information to the NMR signals, thereby obtaining a plurality of NMR signals required for an image of one slice or spectrum. The static magnetic field in such MRI is required to be highly uniform in order to obtain high spatial resolution with a small gradient magnetic field.
Recently, fast imaging techniques have been developed and applied to clinical applications including a technique in which a plurality of echo signals with different phase encodes are measured within a single repetition time (JPA No.60-42906) or echo planer imaging (EPI) in which all of the phase encoded signals required for one image are measured at single excitation of the spins. These fast imaging techniques require still higher uniformity of the static magnetic field. As shown in FIG. 7, in the fast imaging technique in which the numbers (n) of echo signals are generated by switching the polarity of a readout gradient magnetic field and added with different phase encodes, the number n depends on decay characteristic of the signals. The phenomenon of an excited spin returning to its original state is called "relaxation" and when the nuclear spins are assumed to be macroscopic magnetization, relaxation in which the longitudinal magnetization component is in accord with the direction of the static magnetic field is called "longitudinal relaxation" and relaxation in which the lateral magnetization component is zero is called "lateral relaxation (T2 relaxation)." The relaxation rate of the T2 relaxation becomes rapid if the uniformity of the static magnetic field is bad. The relaxation occurring in a non-uniform static magnetic field is called "effective lateral relaxation (T2*)." When the effective lateral relaxation rate is rapid, the number n of echo signals measured at a single excitation is limited. Therefore, in order to measure more echo signals at a single excitation, the effective lateral relaxation rate should be slow, that is, the static magnetic field should have high uniformity.
Apart from this, a technique has been developed in which protons of adipose tissue are selectively saturated using the fact that resonance frequency .omega.' of protons of adipose tissue differs from that .omega. of protons of the other tissue (mainly water molecules). In this technique, since the difference between the resonance frequencies (.omega.'-.omega.) is approximately 4 ppm, the value of uniformity of the static magnetic field must be better than 4 ppm. However, it has been difficult to attain uniformity of this order for every examined object and, as a result, the signals from adipose tissue are not sufficiently suppressed in some cases.
To meet the requirement for the high uniformity of the static magnetic field, a conventional MRI apparatus is provided with shim coils for generating correcting magnetic field between the magnet for the static magnetic field and the coils for generating the gradient magnetic field. The shim coils consist of a combination of a plurality of coils such as X, Y. Z, X.sup.2, Y.sup.2. Z.sup.2 . . . , which correct local deviation of the static magnetic field. The uniformity of the static magnetic field, which is several ppm/40 cmdsv for a superconductive coil having high uniformity, is improved to some extent (around 1 ppm) by incorporating a plurality of shim coils.
A technique for separating protons of fatty acid group from those of hydroxy group of water using chemical shift (.delta.) information included in NMR signals (spectroscopic imaging) has been developed and utilized for diagnosis of specific diseases (see, for example, JP No7-51124, J. Japan Magnetic Resonance Medical Science "Quantitative measurement of adipose using chemical shift imaging--Study on Duchenne-type muscular dystrophy" issued 1991). Since the proton chemical shift usually ranges around 7 ppm (maximum 20 ppm), a uniformity of the static magnetic field of better than 7 ppm is required. However, as mentioned above, the conventional MRI apparatus with shim coils achieves uniformity of only several ppm and thus chemical shift information of higher resolution can not be utilized.
Further, when a human body is the object to be examined, the rate of magnetization varies from place to place depending on the difference of tissues, blood or gases in the coelome or the like. This variation in the rate of magnetization leads to local changes in the uniformity of the applied static magnetic field. This variation can not be corrected by the shim coils, because it occurs locally. Thus, use of high-resolution spectrum has been severely limited in medial diagnosis.
On the other hand, the NMR spectrometer utilized for measuring high resolution spectrum in the field of analytical chemistry is provided with shim coils of various shapes, which are applied with an electric current to generate a magnetic field for correcting the ununiformity of magnetic field of the space where the samples are placed. Uniformity of the magnetic field ranging 10.sup.-7 .about.10.sup.-8 can be obtained by the shim coils. In addition, the samples are subjected to high speed rotation so that all of the spins in the samples are subjected to an average of the uneven magnetic field intensity. This improves the substantial uniformity of the magnetic field in the samples to a level of 10.sup.-9 (0.001 ppm) and enables a high resolution spectrum to be obtained.
However, this method can not be applied to an MRI apparatus where the object to be examined is a human body, while rotation of the magnet or shim coils can not be realized because of their weight.

Magnetic resonance imaging apparatus and method for correcting the intensity of the static magnetic field of the apparatus


A reflector substrate (1) adapted for use in illumination device (8) comprises an a molded aromatic polyimide film wherein the film has a glass transition temperature from 210 to 290xc2x0 C. and said polyimide film has structural units of general formula (I) and (II):

The present invention relates to a formable polyimide film molded article used as a reflector substrate for an illumination device. The reflector substrate has deposited onto it a reflecting surface to form a reflector. The reflector is used as a lamp reflector mainly in automotive headlights or fog lights.
Lamp reflectors generally used in automotive headlights and fog lights are composed of reflector substrates made of glass, metal (e.g., aluminum), or injection or compression-molded plastic (e.g., polyphenylene sulfide, unsaturated polyester resin) on to which a metal reflective layer is deposited using aluminum, nickel-chromium alloy, titanium oxide or the like as the reflecting layer.
Because light sources such as halogen bulbs and xenon bulbs are primarily used in automotive headlights and fog lights for high luminescence, the temperature of the fixture near the base of the bulb rises to over 200xc2x0 C. For this reason, current reflector substrates are made of glass or metal which are heavy, or are made as an injection or compression molded plastic article containing an additional inorganic reinforcement layer such as glass fibers or calcium carbonate (i.e., a reinforced resin molding) which is currently adhered to the substrate by subsequent processing steps.
The use of glass as the reflector substrate presents a number of problems, such as its heavy weight and the ease with which it breaks if placed under stress. When a metal or a reinforced resin molding is used as the reflector substrate, the heavy weight is compounded by other problems, primarily the need to carry out secondary processing steps, such as resin coating prior to vapor deposition, to the reflective substance. The result is an increased number of manufacturing steps to form the part.
Reinforced resin moldings provide a lightweight alternative to metal reflector substrates. However, these resin moldings must have considerable wall thickness both to provide the substrate with the necessary strength and because of inherent limitations in the actual molding technique. One adverse result is the low heat dissipation of the substrate itself. In lamps for example, where the construction is prone to heat buildup (e.g., projector type lamps), the thermal stability of the resin molding is not entirely adequate for good shape retention in the presence of heat. Moreover, the thick wall of the substrate (an insulating material) promotes a temperature rise within the housing, which in turn, shortens the life of the bulb.
Another problem encountered with the use of a reinforced resin moldings as the reflector substrate is that the material can generate gases such as chlorine compounds when the unit is lit and upon heating of the lamp. These gases will condense and deposit, for example, on the front lens of an automotive headlight. This can form a mist, or condensate, on the inside of the lens housing which of course impedes the performance of the lamp.
Previous art describes a sheet-type reflector made of a film sheet that has been mirror-treated by the vapor deposition of aluminum, and discloses that this sheet-type reflector does not require pretreatment such as degreasing to achieve the desired properties. However, the film sheet used in this case is made of polyethylene, which has a poor heat resistance. Accordingly, a polyethylene sheet-type reflector cannot be used as a reflector substrate in headlamps that employ lights which generate a high amount of heat, such as halogen bulbs or xenon bulbs, due to the film sheet""s inadequate shape retention upon heat exposure.
Other art discloses a reflecting mirror comprising a visible light-reflecting infrared light-transmitting multi-layer film on a reflector base made of a polyimide resin and polyetherketone resin film. In addition to having a high resistance to breakage, this reflecting mirror is also described as capable of withstanding heat generation from halogen bulbs and the like because it is made of polyimide resin. Yet, given that this reflecting mirror is composed of a visible light-reflecting, infrared light-transmitting multi-layer film formed on the substrate, it cannot be put to practical use as a reflector in automotive headlights and fog lights.
The present invention was ultimately arrived at following investigations aimed at resolving the above-described problems in the related art.
It is therefore the first goal of the invention to provide a reflector substrate formable into a main body for use as an illumination device which, is lightweight, has excellent surface smoothness, is safe, is easily processable, is heat resistance, and is easy to handle.
A second goal of the invention is to provide a low-cost, high-quality lamp reflector which is suitable for large-volume production because it does not require pre-treatment of the reflector substrate at the time the reflecting layer is formed.
To achieve the first goal, the main body of the illumination device of the present invention is comprised of a shaped article made of a formable thermoplastic aromatic polyimide film having excellent heat resistance. Accordingly, it has a good surface smoothness and does not require pre-treatment at the time of reflective layer formation. Moreover, it is the use of a thermoplastic aromatic polyimide formulation having a glass transition temperature of 210 to 290xc2x0 C. which enables the main body of the illumination device to be produced rapidly and at low cost by a vacuum forming process. In addition, it is lightweight and resistant to breakage which makes it an excellent, safety, and handleable unit.
To achieve the second goal the illumination device of the invention is comprised of a main body composed of a shaped article made of a specific plastic film having excellent heat resistance and surface smoothness on which a reflective substrate has been formed by vapor deposition. Accordingly, there is no need for pre-treatment such as resin coating prior to vapor deposition of the reflective substrate, which enables the lamp reflector to be mass-produced at low cost. Moreover, the illumination device does not degas which becomes a practical obstacle when other devices are lit. Hence, in addition to polyimide""s excellent heat dissipation and safety, the reflector substrate exhibits other high quality performance features such as high heat resistance and excellent specular properties. This combination of features make it advantageous for use as an illumination device in automotive headlights and fog lights, and also large floodlights.

Reflector substrate for illumination device and reflector for illumination device

Abstract: wherein R1 is selected from the group consisting of:

Abstract: wherein R2 is selected from the group consisting of:

Abstract: and said polyimide film has the molar ratio X:Y from 100:0 to 20:80.


Disclosed is method of manufacturing a lighting arrangement (100) comprising a plurality of conductive wires (110) organized in a flexible grid comprising a plurality of grid nodes (115), each grid node comprising a first one of said conductive wires and a second one of said conductive wires, at least some of the grid nodes further comprising a solid state lighting element (120) conductively coupled to the first one of said conductive wires and the second one of said conductive wires, wherein each grid node comprises a mechanical support member (130, 134) including a polymer portion (130) embedding the first one of said conductive wires and the second one of said conductive wires.

Solid state lighting, e.g. lighting based on light emitting diodes (LEDs), is increasingly considered as the environmentally responsible replacement of more energy-inefficient traditional alternatives such as fluorescent and incandescent light sources. In addition, solid state lighting has found its way into new application domains, such as liquid crystal display technology, where backlights made from LEDs yield a superior viewing experience compared to more traditional backlighting.
One particular drawback of solid state lighting solutions is cost. For instance, because LEDs are fragile, the LEDs are usually mounted on a carrier such as a printed circuit board, which may be diced and packaged into single units. This increases the cost of the lighting arrangement, in particular if a large number of LEDs are required in the arrangement, such as for instance in a backlighting panel.
US-2009/0091932 discloses a lighting arrangement according to the opening paragraph. A flexible wire grid is provided as a support for the LEDs such that large area carriers for the LEDs can be avoided, thus reducing the cost of the arrangement. The protection of the LEDs on this grid against damage however may be improved. Especially the stresses generated during the stretching step of its manufacturing process can damage the interconnects between the LEDs and the wires on which the LEDs are mounted.
WO-2012/095812 discloses a method for embedding a non-embedded or bare LED network, wherein the method comprises the steps of providing said non-embedded LED network associated with a continuous flexible support; applying in a continuous manner a flexible insulation layer on a liquid basis (for example a non-thermoplastic material such as a silicone derivative) onto said non-embedded LED network associated with said continuous flexible support.

Method for manufacturing a lighting arrangement


An apparatus for holding a plurality of solar cell units includes a mounting member to be fixed onto a roof, a plurality of fixtures, and a frame member having to-be-sandwiched portions to be sandwiched and fixed between the mounting member and the fixtures, and grooves that support the ends of the plate-shaped solar cell units. The to-be-sandwiched portions of the frame members are positioned inside projection plane regions that project the solar cell units and the grooves immediately below, whereby the distance between adjacent solar cell units reduces.

A solar cell module includes a solar cell unit having a plate-shaped solar cell main body consisting of solar cells, and frame members having frame bodies to be attached to the ends of the solar cell unit. Conventionally, Patent Document 1 discloses an attaching structure for attaching such a solar cell module onto a roof. FIG. 15 and FIG. 16 depict an attaching structure for a solar cell module shown in Patent Document 1.
As shown in FIG. 15, solar cell units (solar cell main bodies) 100 are fitted into fitting portions 101a of frame bodies 101, whereby solar cell modules are formed. A C-shaped mount 103 with its open side facing upward is fixed with a screw 102 onto a roof, via waterproof rubber 110. Flange portions 101b of the frame bodies 101 are placed on upper surfaces 103a of the C-shaped mount 103. The flange portions 101b of the frame bodies 101 and the upper surfaces 103a of the C-shaped mount 103 are sandwiched and fixed between a between-module cover 105 and a module fastening 106 by fastening a cover fixing bolt 104, whereby solar cell modules adjacent to each other are fixed to the C-shaped mount 103.
Patent Document 1 discloses that, as shown in FIG. 16, the inside of the C-shaped mount 103 is used as an electrical wiring space of the solar cell modules. Namely, electrical cables 108 to be connected to terminal boxes 107 of adjacent solar cell modules are guided to the inside of the C-shaped mount 103 via a connecting hole 103b formed in the lower portion of the C-shaped mount 103, and these electrical cables 108 are properly connected. By loosening the cover fixing bolt 104 and removing the between-module cover 105 and the module fastening 106, the internal space of the C-shaped mount 103 is exposed, and then wire connection is made.
Patent Document 1: Japanese Published Unexamined Patent Application No. H10-159284


An apparatus comprises a distributed acoustic sensing (DAS) optical fiber, a DAS interrogator coupled to the DAS optical fiber, and a connector. The connector couples the DAS interrogator, a first digitizer, and a second digitizer, wherein the first digitizer is to generate a first digitized DAS signal based on an analog DAS signal from the DAS interrogator, and the second digitizer is to generate a second digitized DAS signal based on the analog DAS signal. The apparatus also comprises one or more processors and a machine-readable medium having program code executable to cause the apparatus to simultaneously generate a first set of values that correlate with a first physical property based on the first digitized DAS signal and generating a second set of values that correlate with a second physical property based on the second digitized DAS signal.

The disclosure generally relates to the field of subsurface fault detection, and more particularly to subsurface fault detection based on seismic data interpretation.
Distributed acoustic sensing (DAS) signals are used for a variety of purposes. DAS signals are used to provide information during a seismic job. DAS signals can also be used to monitor a well during stimulation activities (e.g. for fracture monitoring). DAS signals are generated by a DAS interrogator connected to one or more DAS optical fibers (i.e. optical fiber capable of responding to acoustic waves, including dynamic strain coupled to the optical fiber from seismic waves propagating through rock formations or from waves propagating in wellbore fluids). During DAS monitoring, the DAS interrogator (either directly or through an intermediary device) transmits optical pulses to and receives optical signals from the DAS optical fiber. Optical signals received by the DAS interrogator are received as analog DAS signals and can be sent through a connector to another device.

Simultaneous acquisition of distributed acoustic sensing for monitoring


The invention relates to a method for preparation of ruthenium-based carbene catalysts with chelating alkylidene ligands (so-called “Hoveyda-type catalysts”) in a cross metathesis reaction by reacting a ruthenium-alkylidene complex with an olefin derivate in the presence of a polymer-supported cation-exchange resin (PSR) acting as a ligand (i.e. phosphine or amine) scavenger. Preferably, penta-coordinated ruthenium benzylidene or indenylidene carbene complexes are employed. The polymer-supported cation-exchange resin (PSR) may be an acidic resin (comprising sulfonic acid or carboxylic groups) or a resin containing carboxylic acid chloride (—COCl) groups or sulfonyl chloride (—SO2Cl) groups. The process is versatile and environmentally friendly; high yields are obtained.

The present invention relates to the preparation of ruthenium-based catalysts for metathesis, in particular to the synthesis of Ru-based metathesis catalysts, which comprise a chelating alkylidene ligand (so called "Hoveyda type" catalysts). The catalyst preparation method is based on a cross metathesis reaction in the presence of a polymer-supported cation exchange resin acting as a ligand scavenger. The method of the present invention is simple, straightforward, environmentally friendly and provides high yields.
Olefin metathesis is a fundamental catalytic reaction and one of the most versatile ways to make carbon-carbon bonds and build molecules. Various metathesis reaction pathways are known, such as ring-closing metathesis (RCM), ring-opening metathesis polymerization (ROMP), cross metathesis (CM) and their combinations. In the past years, olefin metathesis has become a widely used method for the formation of carbon-carbon bonds in organic synthesis and polymer chemistry. The development of well-defined ruthenium-based carbene catalysts by Schrock and Grubbs has led to a fast growth in the field of metathesis, particularly for industrial applications.
The Grubbs-type "first generation" catalyst, a ruthenium benzylidene complex with two tricyclohexylphosphine ligands, having the structure (PCy3)2Cl2Ru═CHPh (ref to Scheme 1; catalyst 1a was one of the first metathesis catalyst widely used in organic synthesis. It was followed by a more active "second generation" analog, in which N-heterocyclic carbene (NHC) ligands, such as "saturated" SIMes (=1,3-dimesityl-imidazolidine-2-ylidene) replaces one tricyclohexylphosphine (PCy3) ligand (catalyst 1b).
Recently, the so-called "Hoveyda-type" catalysts are gaining increased importance. Hoveyda et al. disclosed latent metathesis catalysts based on a benzylidene-ether fragment connected to an alkylidene (carbene) moiety (ref to S. B. Garber, J. S. Kingsbury, B. L. Gray, A. H. Hoveyda, J. Amer. Chem. Soc. 2000, 122, 8168-8179) and WO 02/14376 A2. These type of Ru-catalysts comprise chelating alkylidene ligands (typically alkoxybenzylidene ligands) and either a PCy3 ligand (first generation, catalyst 3a) or a NHC ligand (second generation, catalyst 3b). The cyclic benzylidene moiety and the chelating donor group may be further substituted.
The development of well-defined ruthenium catalysts has rendered olefin metathesis an efficient and reliable tool for the formation of carbon-carbon double bonds. The Grubbs-type catalysts 1a and 1b have found various applications in synthetic chemistry and the ruthenium indenylidene type catalysts 2a and 2b have proven to represent splendid alternatives. Hoveyda-type catalyst 3a and its phosphine-free congener 3b exhibit enhanced activity in various metathesis reactions compared to catalysts 1 and 2 and hold as a benchmark for further catalyst development.

Ru-indenylidene catalyst 2c was described recently by D. Burtscher, C. Lexer et al (ref to J. of Polymer Science, Part A: Polymer Chemistry 2008, Vol. 46, 4630-4635). Over the past years, Hoveyda-type catalysts with functional substituents at the aryl bridging group have been developed (ref to catalyst 3c). As an example, catalyst 3d, bearing a keto-group in the O-containing side chain, is described in WO 2008/034552.
The Hoveyda-type catalysts exhibit a broader application profile in metathesis reactions and allow to reduce the catalyst loading in some applications considerably. In some cases, these compounds can form latent catalyst species and are reported to be partially recyclable. Therefore, this type of catalysts is important for commercial applications. Consequently, appropriate catalyst manufacturing processes are required, which allow economical production in industrial scale.
The general preparation route for Hoveyda-type catalysts is based on the use of ruthenium carbene complexes of the type X2L1L2Ru═CHPh (wherein L1 is a neutral 2-electron donor and L2 preferably is a phosphine of the type PPh3 or PCy3) as starting complexes. These compounds are reacted with suitable styrenylether precursor ligands, which comprise an additional donor group. The new carbene bond is generated by cross metathesis reaction ("CM"), while one phosphine ligand is replaced by the donor group of the styrenylether ligand, thus forming a chelating ring complex.
More specifically, the Hoveyda-type catalysts 3a and 3b are generally prepared from reaction of 1a/b or 2a/b with 2-isopropoxystyrene in presence of copper(I)chloride (CuCl). In this reaction, CuCl acts as a phosphine scavenger, shifting the reaction towards closure of the κ2-(C,O)-chelate. Unfortunately, CuCl is easily oxidized in presence of atmospheric oxygen which complicates handling during preparation of metathesis catalysts and during long-term storage. In addition, application of excess CuCl requires specific workup since it can not be quantitatively retained using column chromatography. Although alternative procedures have been reported in the literature, these methods require multiple preparative steps and/or post-end column chromatography.
S. Gessler, S. Randl and S. Blechert (Tetrahedron Letters 2000, 41, 9973-9976) report a 2-step procedure for preparation of catalyst 3b based on the exchange of PCy3 by SIMes when starting from catalyst 3a. The product was purified by chromatography in 75% overall yield. Due to the multiple steps involved, this route is not commercially feasible.
A. Fuerstner, P. W. Davies and C. W. Lehmann (Organometallics 2005, 24, 4065-4071) report the preparation of bidentate ruthenium vinylcarbene catalysts derived from standard metathesis catalysts by enyne metathesis with phenylacetylene derivatives.
M. Bieniek, A. Michrowska, L. Gulajski and K. Grela (Organometallics 2007, 26, 1096-1099) describe a 2-step preparation method for the nitro-substituted Hoveyda-type catalyst 3c, using a metathesis exchange reaction.
S. Blechert et al. (Synlett 2001, 3, 430-432) report the use of a SIMes- and PPh3-substituted Ru-indenylidene complex as a precursor for the preparation of catalyst 3b by cross metathesis with a phenylether. The product was purified by column chromatography. Yields of 40% are reported, thus this method seems not to be economical.
M. Barbasievicz et al. (Organometallics 2006, 25(15), 3599-3604) report the synthesis of chelating ruthenium quinoline and quinoxaline complexes starting from the Grubbs-type catalyst 1b (SIMes)(PCy3)Cl2Ru═CHPh and using Cu(I)Cl as phosphine scavenger.
WO 2004/112951 describes the preparation of ruthenium-based olefin metathesis catalysts by a cross metathesis reaction using Ru-indenylidene carbene complexes and an olefin. The preparation of Hoveyda-type catalysts comprising chelating alkylidenes is not disclosed.
U.S. Pat. No. 7,026,495 and US 2009/0088581 are related to chelating carbene ligand precursors for the preparation of olefin metathesis catalysts. Methods of preparing Hoveyda-type catalysts without the use of copper(I) chloride are disclosed. Organic acids, mineral acids (such as HCl), mild oxidants (such as bleach) or even water are employed. When employing gaseous HCl, yields of 82% for catalyst 3b are reported. Still, precipitation, separation and purification steps are needed in these methods. Furthermore, excess acid cannot be removed and thus remains in the reaction mixture.
In summary, despite considerable research in the field, the preparation methods for Hoveyda-type metathesis catalysts still suffer from various drawbacks. The synthesis routes starting from the Grubbs-type catalysts 1a and 1b usually employ hazardous chemicals, such as diazo reagents (e.g. diazoalkenes) for the preparation of the educt complex. Furthermore, precipitation, separation and purification steps (such as column chromatography etc) are needed in these methods. Finally, the yields and the purity of the resulting products need to be improved.
It was therefore an objective of the present invention to provide an improved process for preparation of ruthenium-based carbene catalysts with chelating alkylidene ligands ("Hoveyda-type" catalysts). The new method should not employ CuCl as a phosphine scavenger and should not require time-consuming isolation and/or purification steps. Furthermore, the method should provide the ruthenium carbene catalysts in high yields and high product purity (i.e. without residues of phosphine ligands, phosphine oxides or Cu ions). Finally, the method should be clean and simple, easily scalable, environmentally friendly, inexpensive and applicable to commercial, industrial scale.

Process for preparation of ruthenium-based carbene catalysts with chelating alkylidene ligands


A system and method for utilizing a pressurized volume of oxygen in a cathode plumbing of a fuel cell system. The system and method includes calculating an air/oxygen balance that is based on an air balance and an oxygen balance in the cathode plumbing. The system and method further include determining the number of moles of oxygen available for fuel cell chemical reactions using the calculated air/oxygen balance and drawing current from a fuel cell stack using the moles of oxygen available for fuel cell chemical reactions.

1. Field of the Invention
This invention relates generally to a system and method for improving an overall efficiency of a fuel cell system using stored cathode oxygen and, more particularly, to a system and method for utilizing a pressurized volume of oxygen that is available in cathode plumbing of the fuel cell system to produce energy that is provided to fuel cell system components.
2. Discussion of the Related Art
Hydrogen is a very attractive fuel because it is clean and can be used to efficiently produce electricity in a fuel cell. A hydrogen fuel cell is an electro-chemical device that includes an anode and a cathode with an electrolyte there between. The anode receives hydrogen gas and the cathode receives oxygen or air. The hydrogen gas is dissociated at the anode catalyst to generate free protons and electrons. The protons pass through the electrolyte to the cathode. The protons react with the oxygen and the electrons at the cathode catalyst to generate water. The electrons from the anode cannot pass through the electrolyte, and thus are directed through a load to perform work before being sent to the cathode.
Proton exchange membrane fuel cells (PEMFC) are a popular fuel cell for vehicles. The PEMFC generally includes a solid polymer electrolyte proton conducting membrane, such as a perfluorosulfonic acid membrane. The anode and cathode typically, but not always, include finely divided catalytic particles, usually a highly active catalyst such as platinum (Pt) that is typically supported on carbon particles and mixed with an ionomer. The catalytic mixture is deposited on opposing sides of the membrane. The combination of the anode catalytic mixture, the cathode catalytic mixture and the membrane define a membrane electrode assembly (MEA). MEAs are relatively expensive to manufacture and require certain conditions for effective operation.
Several fuel cells are typically combined in a fuel cell stack to generate the desired power. For example, a typical fuel cell stack for a vehicle may have two hundred or more stacked fuel cells. The fuel cell stack receives a cathode input gas, typically a flow of air forced through the stack by a compressor. Not all of the oxygen is consumed by the stack and some of the air is output as a cathode exhaust gas that may include water as a stack by-product. The fuel cell stack also receives an anode hydrogen input gas that flows into the anode side of the stack.
A fuel cell stack includes a series of bipolar plates positioned between the several MEAs in the stack, where the bipolar plates and the MEAs are positioned between two end plates. The bipolar plates include an anode side and a cathode side for adjacent fuel cells in the stack. Anode gas flow fields are provided on the anode side of the bipolar plates that allow the anode reactant gas to flow to the respective MEA. Cathode gas flow fields are provided on the cathode side of the bipolar plates that allow the cathode reactant gas to flow to the respective MEA. One end plate includes anode gas flow channels, and the other end plate includes cathode gas flow channels. The bipolar plates and end plates are made of a conductive material, such as stainless steel or a conductive composite. The end plates conduct the electricity generated by the fuel cells out of the stack. The bipolar plates also include flow channels through which a cooling fluid flows.
Proper airflow measurement and control to the cathode side of a fuel cell stack is critical for the operation of a fuel cell system. If too much air is delivered to the stack, energy is wasted and the fuel cells in the stack may become too dry, affecting fuel cell durability. Too little air delivered to the stack can result in fuel cell instability due to oxygen starvation. Therefore, fuel cell systems typically employ an airflow meter in the cathode input line or cathode output line to provide an accurate measurement of the flow of air to the fuel cell stack. If the airflow meter fails, it has typically been necessary to shut the fuel cell system down because by not knowing the amount of air being delivered to the fuel cell stack with enough accuracy could have detrimental effects on system components.
During a fuel cell system power down-transient, stack current is often reduced abruptly, thereby leaving unreacted pressurized oxygen available in the cathode plumbing volume because the pressure in the cathode plumbing does not drop immediately. Normally the pressurized oxygen is released out of a backpressure control valve and wasted. Thus, there is a need in the art for a way to utilize the pressurized oxygen available in the cathode plumbing such that energy is created from the pressurized oxygen instead of simply releasing and wasting the oxygen.

FCS overall efficiency by using stored cathode oxygen during down-transients


A non-invasive level sensing system for monitoring the amount of content in at least one container includes a platform for supporting the at least one container, at least one holder associated with the at least one container supported by the platform, a source for generating a radio frequency signal, circuitry in communication with the at least one holder for transmitting the radio frequency signal through the at least one holder into the at least one container and receiving a portion of the radio frequency signal reflected at a content-air interface in the at least one container, and circuitry for processing the reflected radio frequency signal and determining the amount of content in the at least one container.

Levels within containers, bottles, vials and similar holders utilized within the healthcare, industrial and numerous other industries often require non-invasive monitoring. A common example where such monitoring is required in the healthcare industry is in vaccine vials. Vaccine vials typically hold between 5 to 10 ml of liquid or vaccine therein. With a representative dosage of 0.5 ml, it would be beneficial to the medical practitioner to know whether the vaccine vial had enough liquid available to accommodate another 0.5 ml dose or whether a replacement vaccine vial should be ordered from a pharmacy or the like. Such monitoring could also be used to pre-order vaccine vials based on a typical amount of vaccine used in a given period.
In order to meet the needs of such monitoring requirements, a level monitoring apparatus needs to be non-invasive and able to determine a level with sufficient resolution to distinguish between a liquid level of 2.49 ml and 1.99 ml. Such an apparatus further needs to be able to monitor more than one vaccine vial at a time whether in a serial or parallel manner, and should not require any modification to the containers being monitored so as to accommodate as many industries as practical.
Since support trays are often used in a medical setting to support multiple vaccine vials containing the same or different vaccines, it would be beneficial if the amount of vaccine, i.e., the liquid level, in each of the multiple vaccine vials be could ascertained while positioned on the support trays. This would provide a medical practitioner the desired information concerning the amount of vaccine in a given vial in an economic and timely manner. In other words, it would be desirable for the medical practitioner to be able to either have the liquid levels available at any point, upon request, or at a designated time. Monitoring in this manner could be done for each of the vaccine vials essentially simultaneously or at least serially but within a very minimal amount of time.
Various level monitoring apparatus are well known in the prior art. One such apparatus, for example, utilizes a capacitive probe attached with adhesive to a wall of a holding container. While affective in determining liquid levels, the use of such a probe to monitor a plurality of containers would require either the use of multiple probes at a considerable expense or for someone to physically remove the probe from one container and subsequently re-adhere the probe to the next in line container. This process would necessarily need to be repeated for each container each time liquid levels are desired to be known. Clearly, neither scenario seems workable or practical especially in today's real-time, cost conscious health care environments.
Even more, the above-referenced probe is by definition invasive. The probe must be inserted into the liquid. Further, the structure of the probe makes its ability to accurately determine a liquid level dependent on a thickness of a wall of the container. If the walls of the container are too thick, for instance, the probe may not be able to determine the liquid level with sufficient accuracy. In other words, the thickness of the container wall could cause only partial penetration in the container and not throughout the bulk of the liquid resulting in a lesser sensitivity than what may be required. This could lead to inaccurate liquid level determinations.
Other prior art apparatus are known to utilize slow-wave structures to measure liquid level and rely on the confinement of electromagnetic energy in a small volume. In one such apparatus, an electrodynamic element is placed outside of a container. However, fields generated by the electrodynamic element attain only partial penetration due to this positioning and do not penetrate through the bulk of the liquid. As a result, the apparatus is unlikely to provide consistent monitoring or a sufficient level of sensitivity in many applications.
Accordingly, a need exists for an apparatus and related method for non-invasively sensing liquid levels in one or more containers in environments where it is desirable for the content of the containers not to be touched by a probe or the like. In addition, the apparatus would preferably not require a specialized container in order to facilitate measurement of the liquid levels but would provide the ability to monitor the liquid level in any container irrespective of size or shape. Even more, the apparatus would be able to monitor and determine liquid levels in multiple containers without the need for multiple probes or devices, or for human intervention to move the apparatus from one container to another. All of the said features are provided by the following invention. Naturally, any improvements along such lines should contemplate good engineering practices, such as simplicity, ease of implementation, unobtrusiveness, stability, etc.


A halogenated aromatic monomer-metal complex useful for preparing a polymer for electronic devices such as a light-emitting diode (LED) device is described. The aromatic monomer-metal complex is designed to include a linking group that disrupts conjugation, thereby advantageously reducing or preventing electron delocalization between the aromatic monomer fragment and the metal complex fragment. Disruption of conjugation is often desirable to preserve the phosphorescent emission properties of the metal complex in a polymer formed from the aromatic monomer-metal complex. The resultant conjugated electroluminescent polymer has precisely controlled metal complexation and electronic properties that are substantially or completely independent of those of the polymer backbone.

The present invention relates to an aromatic monomer-metal complex, an aromatic polymer-metal complex, which can be prepared from the monomer-metal complex, and an organic electronic device that contains a film of the polymer-metal complex.
Organic electronic devices are found in a variety of electronic equipment. In such devices, an organic active layer is sandwiched between two electrical contact layers; the active layer emits light upon application of a voltage bias across the contact layers.
Polymers containing pendant metal-complex groups constitute a class of polymers suitable for light emitting applications, particularly in active matrix driven polymeric LED displays. These polymers can be prepared, for example, by first polymerizing a monomer containing a ligand capable of complexing with a metal, then contacting the polymer with an organometallic complexing compound to insert the metal center into the polymer bound ligand. For example, in Macromolecules, Vol. 35, No. 19, 2002, Pei et al. describes a conjugated polymer with pendant bipyridyl groups directly coordinating with various Eu+3 α,β-diketones.
Similarly, in WO 02/31896, pp 17-18, Periyasamy et al. describes lanthanide metal-complexed polymers prepared by either a one- or two-step synthetic route. In the one-step route, an MLn emitter is reacted with a polymer having metal-reactive functionality (X) to form a polymer with pendant -X-MLn-1 groups. In the two-step route, a polymer with pendant hydroxyethyl functionality is first condensed with a bipyridyl compound containing carboxylic acid functionality to form a polymer containing bipyridyl ester functionality (X-L′), which is then reacted with MLn to form a polymer with pendant X-L′-MLn-1 functionality.
One of the problems with these metal complexed electroluminescent polymers is the incomplete reaction of pendant ligands with the metal complexing reagent. This inefficient coupling results in unpredictability of the properties of the final polymer due to the difficulty in controlling the degree of metal-ligand complexation. Accordingly, it would be advantageous to prepare a luminescent polymer with precisely controlled metal complexation.

Aromatic monomer-and conjugated polymer-metal complexes


A chip packaging method using a hydrophobic surface includes forming superhydrophobic surfaces forming hydrophilic surfaces on predetermined positions of the superhydrophobic surfaces formed on the one of a first chip or the first board and the one of a second chip or a second board, respectively, generating liquid metal balls on the hydrophilic surfaces formed on the one of the first chip or the first board and the one of the second chip or the second board, respectively, and packaging the one of the first chip or the first board and the one of the second chip or the second board by combing the liquid metal ball of the one of the first chip or the first board and the liquid metal ball of the one of the second chip or the second board with each other.

Embodiments of the inventive concepts relate to a method of packaging a chip using a hydrophobic surface and a chip package formed thereby. More particularly, embodiments of the inventive concepts relate to a technique of packaging chips or boards on which superhydrophobic surfaces and hydrophilic surfaces are formed, respectively.
The terminologies of hydrophobic, superhydrophobic and hydrophilic used herein imply the properties of wettability of such liquid materials as liquid metals and liquid polymers on solid surfaces. These terminologies are used just to lead easy understanding of the characteristics of our invention, based on the well-known wettability property of the surface for water, i.e. 'hydro', and thus not limited to the property for water.
Conventional techniques of packaging chips or boards may mainly use a flip chip bonding technique. According to the flip chip bonding technique, chips or boards may be bonded to each other in such a way that surfaces of electrodes respectively formed on the chips or the boards face each other.
For example, Korean Patent publication No. 2012-0000152 discloses a semiconductor package including a semiconductor chip coupled to a substrate by a conductive bump.
However, in the conventional technique of packaging the chips or boards, an alignment error range of 10 μm or more may occur during a process of bonding the chips or the boards. Thus, a misalignment problem of the chips and/or the boards may be caused.

Chip packaging method and chip package using hydrophobic surface

Korea Advanced Institute of Science and Technology


A method and system are disclosed for implementing touch screen text entry on a screen in a first orientation. A web page is used for presenting a touch screen display, which allows text selection via a virtual keyboard. Selected alphanumeric characters are displayed on the screen in an orientation matching the first orientation of the screen.

Some digital signage venues need to be interactive to be effective, e.g., kiosk applications. User interactions may include text entries on a virtual keyboard, e.g., email addresses, or keywords for searching various items, among others. In certain situations, it is desirable to have the video display in portrait mode. However, there are technical issues associated with mounting digital signage screens in a portrait orientation.
For example, if the screen is mounted in a portrait orientation, digital content cannot be presented using web technology, because it is not possible for hypertext markup language (HTML) to write sideways (i.e., text display can only be presented in an upright orientation in landscape mode). Although some video cards are capable of rotating the entire video output to match a portrait screen orientation, the relatively high costs and poor full motion video support make them unsuitable for use in advertising venues.

Method and system for touch screen text entry


The cord stopper (1) comprises a plug (10), and a socket (20) into which the plug (10) is inserted. The plug (10) comprises a plug body (11) having a first string passage hole (111) and one or more elastic leg pieces (12). The socket (20) has a second string passage hole (23) capable of being in communication with the first string passage hole (111) and a third string passage hole (24). The elastic leg pieces (12) hold the string inserted and passed through the third string passage hole (24) by themselves, or together with an inner surface of the socket (20). With this configuration, when the cord stopper (1) is fixed on the string (3), it is not necessary to form an edge section of the string into a loop form, and therefore can easily be fixed. Further as the string (3) is held with the elastic leg pieces (12), the holding state can easily be released, and the cord stopper (1) can easily be replaced with another one.

1. Field of the Invention
The present invention relates to a cord stopper attached to a string provided on a cloth, a hat, a bag, a tent, a knapsack or the like for adjusting the tightening state or a locking position of the string.
2. Description of Related Art
As a cord stopper for tightening a string provided on a jacket or the like, there has been known the one comprising a plug and a socket (Refer to, for instance, FIG. 11 in Japanese Utility Model Publication No. HEI 1-39449).
The cord stopper as described above is generally fixed only to a string to be tightened, but there has been known a type of cord stopper also fixed to a cloth or the like on which the string is provided (Refer to, for instance, FIG. 3, FIG. 4 and other figures in Japanese Patent Laid-Open Publication No. HEI 8-89316).
The cord stopper has an arm section or a hole for passing the other tape or string (than the aforementioned string), which is attached to the cloth or the like by, for instance, stitching it on the cloth or the like.
Namely a fixing tape to be stitched on a cloth or the like is inserted and passed through an arm section or the like of the cord stopper, and an edge section of the tape is formed into a loop by, for instance, stitching one edge of the tape at a position near the arm section so that the cord stopper will not move against the tape.
With the configuration as described above, however, it is required that an edge portion of the fixing tape is stitched to a tape for fixing the cord stopper and the other edge portion thereof is stitched to the cloth or the like, so that the excessively complicated works are required.
Further, after the fixing tape is stitched, if it is required to exchange the cord stopper with another one or to change a position at which the cord stopper is set due to any change in the design, it is necessary to unbind and remove the stitched fixing tape, which is disadvantageously troublesome.


A medicated module attachable to a drug delivery device comprises a connecting body configured for attachment to the drug delivery device. A first needle is fixed within the connecting body and a movable needle hub is operatively coupled to the connecting body. A needle guard is operatively coupled to the connecting body and a biasing member is positioned between the connecting body and needle guard. A second needle is fixed within the needle hub. A first cavity within the connecting body defines a reservoir containing at least one dose of a medicament. The reservoir configured for fluid communication with the first and the second needle. The reservoir comprises a bypass configured to allow medicament from the drug delivery device to bypass the reservoir and exit the second needle.

Certain disease states require treatment using one or more different medicaments. Some drug compounds need to be delivered in a specific relationship with each other in order to deliver the optimum therapeutic dose. This invention may be of particular benefit where combination therapy is desirable, but not possible in a single formulation for reasons such as, but not limited to, stability, compromised therapeutic performance and toxicology.
For example, in some cases it might be beneficial to treat a person suffering from diabetes with a long acting insulin and with a glucagon-like peptide-1 (GLP-1), which is derived from the transcription product of the proglucagon gene. GLP-1 is found in the body and is secreted by the intestinal L cell as a gut hormone. GLP-1 possesses several physiological properties that make it (and its analogs) a subject of intensive investigation as a potential treatment of diabetes mellitus.
There are a number of potential problems when delivering two or more active medicaments or "agents" simultaneously. The two or more active agents may interact with each other during the long-term, shelf life storage of the formulation. Therefore, there are certain advantages to storing the active components separately and only combine them at the point of delivery, e.g. injection, need-less injection, pumps, or inhalation. However, the process for combining the two agents needs to be simple and convenient for the user to perform reliably, repeatedly and safely.
A further concern is that the quantities and/or proportions of each active agent making up the combination therapy may need to be varied for each user or at different stages of their therapy. For example, one or more active agents may require a titration period to gradually introduce a patient to a "maintenance" dose. A further example would be if one active agent requires a non-adjustable fixed dose while the other is varied in response to a patient's symptoms or physical condition. This problem means that pre-mixed formulations of multiple active agents may not be suitable as these pre-mixed formulations would have a fixed ratio of the active components, which could not be varied by the healthcare professional or user.
Additional concerns arise where a multi-drug compound therapy is required, because certain users cannot cope with having to use more than one drug delivery system or make the necessary accurate calculation of the required dose combination. This is especially true for users with dexterity or computational difficulties.
Other problems arise where a user may attempt to re-use a non-sterile needle after a certain dose combination has been delivered. Using such a non-sterile needle could lead to the transmission of certain diseases and therefore there exists a need for a medicated module that prevents needle re-use. There is a further concern of inadvertent needle sticks for care works/healthcare professionals with certain needle assemblies where the injection needle is not concealed or covered. As such, there is also a general need to reduce certain patient's needle anxiety that may heighten a patient's fear or phobia of exposed needles.
Accordingly, there exists a strong need to provide devices and methods for the delivery of two or more medicaments in a single injection or delivery step that is simple and safe for the user to perform and that also tends to reduce a patient's anxiety towards injections or needles. The present application discloses specific embodiments of methods, devices and drug delivery kits that overcome the above-mentioned concerns by providing separate storage containers for two or more active drug agents that are then only combined and/or delivered to the patient during a single delivery procedure. According to a preferred embodiment of the invention, such devices may be provided in separate storage containers or provided in a kit form comprising at least one medicated module and at least one non-medicated module.
According to the disclosure the term medicated module is preferably used to characterize a needle sub-assembly comprising a containment or reservoir of a (secondary) drug compound. Consequently, a non-medicated module is preferably characterized as a needle sub-assembly, however without having a containment or reservoir of a (secondary) drug compound. As such the medicated module and/or the non-medicated module may comprise at least one double ended needle. Furthermore the medicated module and/or the non-medicated module may comprise a needle guard. The medicated module and/or the non-medicated module may be configured to be attachable to a drug delivery device, e.g. a pen-type drug delivery device.
According to a specific embodiment described in the following, setting a dose of one medicament automatically fixes or determines the dose of the second medicament (i.e., a non-user settable dose). The present application may also give the opportunity for varying the quantity of one or both medicaments. For example, one fluid quantity can be varied by changing the properties of the injection device (e.g., dialing a user variable dose or changing the device's "fixed" dose). The second fluid quantity can be changed by manufacturing a variety of secondary drug containing packages or kits with each variant containing a different volume and/or concentration of the second active agent. The user or healthcare professional would then select the most appropriate secondary package or series or combination of series of different packages or kits for a particular treatment regime.
In some cases where priming of the drug delivery system is desirable, the system, devices, and/or kits disclosed herein comprise a bypass that allows medicament from the primary reservoir to bypass a reservoir or capsule contained within a medicated module. This medicament can then exit the injection needle.
These and other advantages will become evident from the following more detailed description of the invention.

Medicated module with bypass and needle guard


A hydrogen generator includes: a desulfurizer including a desulfurization catalyst that removes a sulfur compound in a raw material by a desulfurization reaction, the desulfurization catalyst being arranged so as to be heated by a first heat source; a reformer configured to generate a hydrogen-containing gas using the raw material having flowed through the desulfurizer; a first temperature detector configured to detect a temperature of a predetermined portion of the desulfurization catalyst; a second temperature detector configured to detect the temperature of a portion of the desulfurization catalyst, the portion being located such that a distance between the portion and the first heat source is longer than a distance between the predetermined portion and the first heat source; and a controller configured to control an operation of heating the desulfurization catalyst by the first heat source, based on detection results of the first temperature detector and the second temperature detector.

PTL 1 discloses a hydrogen generator including: a desulfurizer including a hollow container in which a catalyst that adsorbs a sulfur compound contained in a material gas is contained; a reformer portion configured to generate a hydrogen-containing reformed gas by a reforming reaction using the material gas having flowed through the desulfurizer and water; and a heater configured to heat the desulfurizer, wherein: the desulfurizer is arranged outside the reformer portion so as to be spaced apart from the reformer portion; and the heater is formed in a spiral shape along an inner wall of an outer surface of the desulfurizer and is arranged so as to be spaced apart from the reformer portion.

Hydrogen generator and fuel cell system including same

Panasonic Intellectual Property Management Co., Ltd.


A robot control method capable of eliminating any influence of motion in a preceding path section to assure an accurate path movement with respect to a portion of a path section toward an end point. In a motion statement, a path-assurance section is previously designated in terms of length, time or path-assurance ratio for a moving path 2!.fwdarw.3!. A path motion plan EFGH for the moving path 2!.fwdarw.3! is created so that a path section represented by DHGK is the path-assurance section designated in the motion statement, assuming that D represents a terminal point of the motion along the moving path 1!.fwdarw.2!. Consequently, an influence of motion of the moving path 1!.fwdarw.2! is not exerted on the motion after a point in time represented by D or K, to assure a movement on the path 2!.fwdarw.3! in the path-assurance section.

In moving a robot by a playback operation, an acceleration/deceleration control is performed for individual taught points in accordance with a positioning ratio designated in a motion statement in an operation program. Generally, it is advantageous to designate a lower positioning ratio for saving time for acceleration/deceleration to reduce a cycle time. Consequently, it has been a common practice to designate a lower positioning ratio for a taught point which does not require a high degree of positioning accuracy.
However, in a robot for performing an assembling operation by handling a workpiece, for example, if the lower positioning ratio is designated even for the taught point which does not require a high degree of positioning accuracy, there is a problem in operation reliability. FIGS. 1 and 2 show a typical case having such problem.
FIG. 1 shows a moving path in assembling a workpiece 3 by fitting it to another workpiece 4 by gripping the workpiece 3 by a hand 2 attached to a robot arm end 1. FIG. 2 is a chart showing the content of a path motion plan in which a smooth motion of 100% (a positioning ratio of 0%) is designated for the position 2! and a positioning motion of 100% is designated for the position 3!, with an axis of abscissa representing time t and an axis of ordinate representing speed V.
In FIG. 1, 1!, 2! and 3! represent the taught points for a tool point whose position is predetermined with respect to the hand 2 of the robot, and a straight motion is designated for each of the path sections 1!.fwdarw.2! and 2!.fwdarw.3!. Since the position 3! located right under the position 2! is a position at which the fitting operation is completed, a positioning of 100% is necessarily designated in the motion statement. Contrary, since the position 2! is only a transit point where the direction of the movement is changed from horizontal to vertical, it is advantageous to designate "100% smooth", i.e. a positioning ratio of 0% for the position 2! in the motion statement in order to reduce the cycle time.
However, if a lower positioning ratio is designated for the position 2!, an accuracy of the locus would be lowered around the position 2! which forms a corner. Namely, as indicated by reference numeral 5, the robot moves toward the position 3! on a path deflected off the taught path near the position 2!.
Specifically, when "100% smooth" is designated for the position 2! and "100% positioning" is designated for the position 3!, a path motion plan is created so that a motion EFGH (instruction speed V23) for the path 2!.fwdarw.3! in the Z-axis direction starts simultaneously with a start (a point C of time) of a deceleration control movement contained in a motion ABCD (command speed V12) for the path section 1!.fwdarw.2! in the X-axis direction, as shown in FIG. 2. This means that a part (from the point C to the point D) of the motion for the preceding path section 1!.fwdarw.2! has not been completed even at a point (point H) when the motion for the succeeding path section 2!.fwdarw.3! is completed.
As a result, a path approaching the position 3! is deflected from the straight path 2!.fwdarw.3! and there is a possibility that the fitting operation is not performed smoothly. In general, this tendency would be more remarkable when the command speed V12 for the path section 1!.fwdarw.2! is higher and the length L23 of the path section 2!.fwdarw.3! is shorter.
In order to avoid the foregoing problems, it has been a common practice to make a try-and-error adjustment operation including (1) lowering the command speed V12 for the path section 1!.fwdarw.2!; (2) designating a high positioning ratio (for example, 100%) for the position 2!; and (3) locating the position 2! remote from the position 3!.

Robot control apparatus and method eliminating any influence of motion in a preceding path and a recording medium storing the same


A child safety seat may include a base portion configured to be disposed on a vehicle seat base of a vehicle seat, a back portion configured to be disposed proximate to a vehicle seat back of the vehicle seat, and a top tether operably coupled to a portion of the child safety seat to enable the child safety seat to be tethered to an anchor disposed in the vehicle. The top tether may include a quick connect coupler and a first strap portion having a distal end and a proximal end. The distal end of the first strap portion may be configured to engage the anchor. The quick connect coupler may be operably coupled to the first strap portion proximate to the proximal end of the first strap portion. The quick connect coupler may also be configured to enable the first strap portion to be coupled or decoupled from the back portion of the child safety seat.

Child safety seats (or simply child seats or car seats) are secured inside a vehicle to protect children in vehicles from the effects of either accidents, sudden deceleration, or other impacts or jarring events. The child safety seats may include various different protective features relating to securing the child safety seats in the vehicle, securing the child to the child safety seat, and protecting the child once the child is secured in the child safety seat. Some of these protective features may be prescribed by regulation in certain jurisdictions, but others may provide optional, additional protection for children. Thus, child safety seats can have a variety of different features, and even different structural arrangements for providing many of those features.
Top tethers are a piece of equipment that can be useful for securing child safety seats within the vehicle, particularly for forward facing seats. The top tether is a strap that is attached to the top portion of the back of a forward facing child safety seat (or combination or convertible seat). The top tether may be attached to an anchor point at any of various locations within the vehicle and is then tightened between the top back of the child safety seat and the anchor point. The top tether may, when anchored properly, prevent movement of the back of the child safety seat forward during an impact or sudden deceleration. This can prevent a number of inches of forward movement of both the back of the child seat, and the head of the child, which can correspondingly reduce the likelihood of injury.
The anchor points can be different in different vehicles. Some anchor points are on the back of the seat to which the child safety seat is attached. However, other anchor points may be on the back wall of the vehicle, ceiling or frame of a rear door of the vehicle, rear shelf of the vehicle, a cargo floor of the vehicle, or under the back side of the seat to which the child safety seat is attached. Some of these anchor points may be relatively easy to find and connect to, but others may be difficult to connect to or find.
Compliance with attachment of the top tether is estimated to be less than 50%, and by some estimates far below 50%. This is, of course, an unfortunate statistic given the potential advantages of employing the top tether. Factors such as movement of the child safety seat between vehicles, familiarity with the locations of the anchor point, ease of access to the anchor point, etc., may contribute to this relatively low rate of employment. In a typical situation, the final attachment point for the top tether to the anchor point is done at the anchor point. Moreover, adjustment controls for the tightness of the tether are either located also at the anchor point, or at a separate location from the final attachment point (which is at the anchor point). Given that the anchor point is typically remote from the back of the child safety seat, the performance of final attachment and adjustment at either difficult to reach locations or separate locations tends to increase the potential for operators to find usage of the top tether to be inconvenient and therefore omit this important step. Additionally, when the installer is forced to work in tight spaces or from uncomfortable positions, the quality of the installation (e.g., the tension put on the top tether) may be reduced as well. Thus, it may be desirable to improve the ease of use of the top tether so that the rate of employment may be increased.

Quick connect coupler for a child safety seat top tether


A digital to analog converter (DAC) system comprising, a first segment, wherein a segment comprises, a first path including an array of resistors connected in series between a first reference voltage node and a second reference voltage node, wherein the array is connected to a first switch device disposed between nodes of the array and an output node, and a third path including a second resistor in series with a second switch device, wherein the third path is connected in parallel with the first path.

1. Field of the Invention
This invention relates generally to systems and methods involving digital to analog converters, and specifically to systems and methods for operating digital and analog converters more efficiently.
2. Description of Background
Some digital to analog converters (DACs) include a network of series resistors that is disposed between a first reference (VREF1) and a second reference (VREF2). A prior art example of a DAC is shown in FIG. 1. Each of the resistors in the network is similar to the other resistors in the network. The voltage (VREF1-VREF2) is divided such that an equal voltage drop occurs across each resistor in the network. A series of analog multiplexor (MUX) devices is disposed between each of the nodes between the resistors in the network and an output node. Activation of a MUX device allows propagation of a selected voltage node from the resistor network to the DAC output (DAC Out). The DAC Out has some capacitive loading and may drive a high-swing operational amplifier to drive off-chip circuits or remain unbuffered to drive an on-chip ADC reference input.
The resistor network of FIG. 1 grows with an increasing number of bits into the incoming digital signature or address. A 2-bit resolution DAC uses 4 resistors; a 4-bit resolution DAC uses 16 resistors; an 8-bit resolution DAC uses 256 resistors and a 10-bit resolution DAC uses 1024 resistors in series. As the number of resistors grows, the total resistance of the network grows, increasing the RC time constant for charging and discharging output DAC Out as the address changes. As a result, performance of the resistor DAC is limited. With growth in resistor count, resistor tracking becomes a concern across the larger array, impacting DAC integral non linearity (INL) and differential non linearity (DNL). The size of the unit resistor in the network can be reduced, but cannot be scaled at the same rate that the number of resistors is increased. Further, decreasing the unit resistance may contribute to increased DAC INL and DNL if resistor length is decreased to decrease total resistance and will increase area if resistor width is increased to decrease total resistance of the DAC.

Design structures and systems involving digital to analog converters

International Business Machines Corporation


An apparatus and method for setting up a session between devices in a mobile communication system. The method is for setting up a session in a Policy and Charging Rules Function (PCRF) of a mobile communication system that includes a first terminal and a second terminal. The method includes receiving a first message including Internet Protocol (IP)/Port information of the first terminal from a Policy and Charging Enforcement Function (PCEF), receiving a second message including IP/Port information of the first terminal and IP/Port information of the second terminal from a Proxy Call Session Control Function (PCSCF), and setting up a session to the PCEF and a session to the PCSCF, based on the IP/Port information of the first terminal included in the first message and the IP/Port information of the first terminal included in the second message. The first terminal is a mobile terminal and the second terminal is a relay terminal that transmits and receives packet data between the PCEF and the PCSCF.

With the rapid development of communication technologies, mobile communication systems provide a packet service for enabling a multimedia service such as e-mail, still images, videos, and so forth, as well as a conventional voice service, to terminals.
So-called 3rd Generation (3G) mobile communication systems, which support both conventional voice service and the packet service, include a Code Division Multiple Access (CDMA) 2000 system using a synchronous scheme and a Universal Mobile Telecommunications System (UMTS) using an asynchronous scheme. The 3G mobile communication systems provide the multimedia service to the terminal through interworking with a particular network. In particular, the 3G mobile communication systems provide the multimedia service to the terminal by interworking with a communication network, an Internet Protocol (IP) Multimedia Subsystem (IMS) network that performs IP-based communication.
The mobile communication systems that interwork with the IMS network establish a Quality of Service (QoS) policy and charging rules for service usage and provide a service to terminals according to the established policy and charging rules. To this end, a Policy and Charging Rules Function (PCRF) is provided with service information from an Application Function (AF) to create Policy and Charging Control (PCC) rules. The PCRF provides the created PCC rules to a Policy and Charging Enforcement Function (PCEF). Then, the PCEF provides a QoS corresponding to a service flow to the terminal based on the PCC rules.
To transmit and receive the PCC rules, the PCRF determines whether an IP provided from the PCEF is identical to an IP provided from the AF and, if both IPs are identical to each other, the PCRF forms a session between the PCRF and the PCEF and a session between the PCRF and the AF. This process is referred to as a PCRF session binding setting process.
If the PCRF session binding setting process is not normally completed in the PCRF, the PCC rules cannot be created. Hence, a need exists for a scheme capable of efficiently performing the PCRF session binding setting process regardless of which device is included in the mobile communication system.
The above information is presented as background information only to assist with an understanding of the present disclosure. No determination has been made, and no assertion is made, as to whether any of the above might be applicable as prior art with regard to the present disclosure.

Scheme for setting up session in a mobile communication system


Process for the preparation of 4-aminobut-2-enolide compounds of the formula (I):

1. Field of the Invention
The present invention relates to a process for the preparation of 4-aminobut-2-enolides starting from 4-alkoxyfuran-2(5H)-one or 4-arylalkoxyfuran-2(5H)-one.
2. Description of Related Art
Certain substituted 4-aminobut-2-enolide compounds are known as insecticidally effective compounds from EP-A-0 539 588 and WO 2007/115644. They can be synthesized by various methods.
Thus, for example, Heterocycles Vol. 27, No. 8, pages 1907 to 1923 (1988) and EP-A-0 539 588 describe that enaminocarbonyl compounds (3) can be prepared from anhydrous tetronic acid (1) and an amine (2), as shown in Scheme 1. However, this process is not very suitable for the large-scale industrial production of enaminocarbonyl compounds since the anhydrous tetronic acid (1) cannot be produced in a cost-effective manner.

To date, tetronic acid has not been commercially available in relatively large amounts, meaning that it has to be prepared starting from acetoacetic ester via bromination and subsequent hydrogenation (cf. Synthetic Communication, 11(5), pages 385 to 390 (1981)) for use in the process described above. The relatively low yield of tetronic acid (usually less than 40%) and the condition that tetronic acid must be anhydrous gives rise to high costs.
A further process for the preparation of tetronic acid is described in Swiss Patent Specification 503 722. 4-Chloroacetoacetic ester is reacted with an aromatic amine to give 3-arylaminocrotono-lactone, the tetronic acid being liberated following subsequent treatment with mineral acid. The tetronic acid can be isolated only by distillation under a high vacuum, which is disadvantageous for the large-scale industrial use of this process.
EP-A-0 153 615 likewise describes a multi-stage process for the preparation of tetronic acid which starts from 2,4-dichloroacetoacetic esters and which is not very suitable for large-scale industrial production. This process requires many complex stages and produces the desired tetronic acid in a comparatively moderate yield of 65%.
A further process for the preparation of tetronic acid starting from malonic esters and chloroacetyl chloride is known from J. Chem. Soc. Perkin Trans. 1 (1972), 9/10, pages 1225-1231. This process produces the desired target compound, but with a yield of only 43%.
Tetrahedron Letters, No. 31, pages 2683 and 2684 (1974) describes inter alia the preparation of tetronic acid, which is shown in Scheme 2. The starting material used here is dimethyl acetylenedicarboxylate.

A disadvantage of this process is the low overall yield of only 30%, and the use of expensive starting materials, such as, for example, lithium aluminium hydride (LiA1H4).
WO 2007/115644 describes the preparation of specific 4-aminobut-2-enolides. For example of 4-[[(6-chloropyridin-3-yl)methyl](3,3-dichloroprop-2-en-l-yl)amino]furan-2(5H)-one by reacting 4-[[(6-chloropyridin-3-yl)methyl] amino] furan-2 (5 H)-one with 3-bromo -1,1-dichloroprop -1-ene or by reacting 4-[[2-fluoroethyl)amino]furan-2(5H)-one with 2-chloro-5-chloromethylpyridine. The reactions are preferably carried out with hydrides of lithium or sodium. Here too, these substrates are expensive and can only be handled with difficulty for safety reasons.
A further process for the preparation of substituted 4-aminobut-2-enolides is described by Mowafak. et al. in J. Heterocyclic Chem., 21, pages 1753-1754 (1984). This process starts from methyl tetronate, the desired compounds being prepared as a result of reaction with amines. However, this described exchange of the methoxy group described therein via a "Michael Addition" can only be carried out with electron-rich cyclic or primary amines, which is demonstrated by the example in the experimental section of this patent application.

Process for the preparation of 4-aminobut-2-enolides starting from 4-alkoxyfuran-2(5H)-one or 4-arylalkoxyfuran-2(5H)-one

Abstract: comprising    reaction of a 4-alkoxyfuran-2(5H)-one compound or 4-arylalkoxyfuran-2(5H)-one compound of the formula (II)

Abstract: with an amine of the formula (III)

Abstract: in which R1, R2 and A have the definitions given in the description, in the presence of a Brønstedt acid.


A method and apparatus are provided for improving the performance of branch prediction using a combination of a speculative branch target buffer (SBTB) and an architectural branch target buffer (ABTB). According to one embodiment, speculative branch data is maintained for in-flight branches (i.e., those that have been fetched but not yet retired). A branch entry is speculatively allocated in a line of the SBTB after decoding an instruction containing a branch, such as a conditional branch, a return from a subroutine, a call to a subroutine, or an unconditional branch. Subsequently, the branch data associated with the branch entry is speculatively updated after branch prediction has been completed for the branch. Finally, the branch data is corrected after the branch has been executed. According to another embodiment, a novel branch prediction circuit includes both a speculative branch target buffer (SBTB) cache and an architectural branch target buffer (ABTB) cache. The SBTB cache contains multiple branch entries to maintain speculative branch data associated with in-flight branches. The speculative branch data includes a speculative history of taken/not-taken outcomes associated with the in-flight branches. The ABTB cache is coupled to the SBTB cache. The ABTB cache also includes multiple branch entries, however, they are for maintaining architectural branch data including the actual taken/not-taken outcomes associated with retired conditional branches.

1. Field of the Invention
The invention relates generally to the field of branch prediction. More specifically, the invention relates to the use of a Speculative Branch Target Buffer (SBTB) to maintain speculative branch data for in-flight branches.
2. Description of the Related Art
Early microprocessors generally processed instructions one at a time. Each instruction was processed using separate sequential stages (e.g., instruction fetch, instruction decode, execute, and result writeback). Within such microprocessors different dedicated logic blocks performed each different processing stage. Each logic block waited until all the previous logic blocks completed operations before beginning its operation
To improve efficiency, microprocessor designers overlapped the operations of the logic blocks for the instruction processing stages such that the microprocessor operated on several instructions simultaneously. In operation, the logic blocks and hence the corresponding instruction processing stages concurrently process different instructions. At each clock tick, the result of each processing stage is passed to the subsequent processing stage. Microprocessors that use the technique of overlapping instruction processing stages are known as "pipelined" microprocessors. Some microprocessors further divide each processing stage into substages for additional performance improvement. Such processors are referred to as "deeply pipelined" microprocessors.
An example of a simplified instruction pipeline 100 is shown in FIG. 1. According to this simplified example, the instruction pipeline 100 comprises five major stages 105–125. The five major stages are the fetch stage 105, the decode stage 110, the dispatch stage 115, the execute stage 120, and the writeback stage (also referred to as the retirement stage) 125. Briefly, during the first stage, the fetch stage 105, one or more instructions are retrieved from memory, and subsequently decoded into micro-ops during the decode stage 110. Then, the micro-ops are dispatched to the appropriate execution unit for execution during the dispatch stage 115 and execution takes place during the execute stage 120. Finally, as the micro-ops complete execution, they are marked as being ready for retirement and are subsequently retired (e.g., their results are committed to the architectural registers) during the retirement stage 125. Consequently, the fetch unit (not shown) at the head of the pipeline provides the pipeline with a continuous flow of instructions, hence keeping the microprocessor busy. The fetch unit keeps the constant flow of instructions so the microprocessor does not have to stop its execution to fetch an instruction from memory. Such fetching guarantees continuous execution, as long as the instructions are stored in order of execution. However, due to branch instructions, such as conditional branch instructions included in software loops or conditional jumps, instructions encountered by the fetch unit are not always presented in a sequence corresponding to the order of execution. Thus, branch instructions can cause pipelined microprocessors to speculatively execute down the wrong path such that the microprocessor must later flush the speculatively executed instructions and restart at a corrected address.
As a result, many pipelined microprocessors employ branch prediction techniques to predict the outcome of branch instructions (e.g., determine which instruction to fetch next). Generally speaking, branch prediction seeks to guess whether or not a branch encountered in the instruction stream will be taken or not; and to fetch executable code from the appropriate location in the instruction stream. When a branch instruction is executed, it and the branch target address (i.e., the address of the of the instruction to be executed if the branch is taken) are stored in a branch target buffer (BTB). This and other information is subsequently used to predict which way the instruction will branch the next time it is executed. Mispredicted branches still cause the instruction pipeline to stall while the incorrect sequence of instructions that have been fetched and have begun execution are flushed from the instruction pipeline. However, when the branch prediction is correct (as it is over 90 percent of the time), executing a branch does not cause a pipeline stall as the processor may fetch and begin executing the proper sequence of instructions in advance.
An earlier branch target buffer cache implementation is illustrated in FIGS. 2 and 3. The branch target buffer (BTB) 200 depicted in FIG. 2 is a set-associative cache that stores information about branch instructions in 128 individual "lines" of branch information. Each line of branch information in the BTB 200 contains four branch entries that each contains information about a single branch instruction that the microprocessor has previously executed (if the valid bit is set in the entry). Each line also includes a branch pattern table 221 and least recently replaced (LRR) bits 220. The branch pattern table 221 is used for predicting the outcome of conditional branch instructions in the line of branch entries. The LRR bits 220 are used by the branch prediction circuit to select a branch entry in the line when information about a new branch will be written into the line of branch entries.
FIG. 3 illustrates the branch information stored within each branch entry of the BTB 200. As illustrated in FIG. 3, each branch entry contains a tag field 310, a block offset field 320, a branch type field 330, a true history field 340, a speculative history field 350, a history selection bit 370, a valid bit 380, and a branch target address field 390. The tag address 310 and the block offset 320 are used to identify a memory address of the branch instruction associated with the branch entry. The branch type field 330 specifies what type of branch instruction the branch entry identifies (e.g., conditional branch, return from subroutine, call subroutine, unconditional branch). The true history field 340 maintains the actual (fully-resolved) taken or not-taken history of the branch instruction for a predetermined number of prior executions. The speculative history field 350 maintains the "speculative" taken or not-taken history of the branch instruction for the predetermined number of prior executions. The history selection bit 370 indicates which of the true history field 340 or the speculative history field will be used to index into a pattern state table when calculating a branch prediction. The valid bit 380 indicates whether or not the branch entry contains valid branch information. The valid bit 380 is typically set during the execute or retirement stage when the branch prediction circuit allocates and fills the corresponding branch entry. The valid bit 380 is cleared when the branch entry is subsequently deallocated by the branch prediction circuit.
Because many of the fields (e.g., tag 310, valid 380, block offset 320, LRR 220, pattern table 221, true history 340, and speculative history 350) of the BTB 200 must be accessed by various pipeline stages the BTB 200 must include multiple ports for reading/writing the appropriate fields at prediction time and reading/writing the appropriate fields during allocation, update, and deallocation of branch entries.
In such a prior BTB 200, branch entries are typically allocated at execute or retire time to avoid allocating entries along a mispredicted path. This, however, results in mispredicting tight loops until they are allocated. For deallocation, two consecutive lines of instruction are deallocated when a bogus branch is encountered, resulting in deallocation of good branches. Finally, branches are typically updated at execute time instead of retirement to improve prediction. This, however, often results in corruption since not all executed branches retire.

Branch target buffer (BTB) including a speculative BTB (SBTB) and an architectural BTB (ABTB)