A tubular shaped collar (22) of predetermined mass having internal threads (23) and an internal tapered area (21) which is threaded onto a tubular shaped insert (26) of flexible composition that has threads (44) that match the threads (23) of the collar and is tapered in a manner to match the taper (21) of the collar. The insert has a plural of longitudinal slits (25) in the tapered area. The insert is threaded into the collar and the collar and insert are slid over the muzzle end of a firearm barrel where they are locked in place by tightening the collar onto the insert whereby the predetermined angle of the taper (21) of the collar compresses the insert tightly against a firearm barrel. The insert and collar are adjustably positioned on the firearm barrel and held in place while being tightened by a tubular shaped tool (32) which has means of mating with the insert and has a means of calibration to determine the relative position of the collar and insert on a firearm barrel. The collar and insert are moved axially along the firearm barrel to a location whereby the predetermined mass of the collar will tune the harmonic vibrations of the firearm barrel and promote greater accuracy.

1. Field of Invention
The present invention relates to a removable system that allows altering or tuning of the harmonic vibration pattern of a wide variety of firearm barrels which imparts an improvement to the accuracy of a firearm such equipped with no modification or alteration to the barrel.
2. Background and Description of Prior Art
Upon discharge, a firearm barrel begins a pattern of harmonic vibrations moving from chamber to muzzle and back. This vibration pattern is affected by the volume of the powder charge, the weight of the bullet, the design of the bullet shape, the seating depth of the bullet in relation to the bore, the rifling twist, the diameter of the barrel and the way in which the action and barrel are mounted to the stock of the firearm.
Each new combination of elements, such as changing from one brand of ammunition to another or changing bullet weight or bullet style will impart a new vibration pattern to the barrel. With each new combination the accuracy of the firearm can be affected. The normal shape of an impact pattern on a downrange target shows that the actual vibration pattern of the firearm muzzle is circular in nature around the axis of the bore. This circular vibration is caused by the spin imparted to the bullet by the spiral rifling in the bore. Additional vibrations are imparted by the sound created by the discharge of the propellant as well. This vibration pattern is present along the entire length of the barrel and moves in a wave motion along the axis of the bore in a series of vibration patterns. These patterns move first toward the muzzle along the barrel and then away from the muzzle, thus creating a harmonic effect not unlike a tuning fork.
Upon firing, if the bullet departs the muzzle at the greatest point of circular deflection in the harmonic vibration pattern the size of the impact pattern will be larger than if the bullet were to depart while the muzzle is at it's smallest circular deflection. Firearms designed for target shooting are normally equipped with a very heavy barrel of large diameter to minimize the vibration pattern and impart greater accuracy. Hunting firearms are designed with smaller diameter light weight barrels to provide greater portability and are therefore less likely to be accurate with all types of ammunition due to varying vibration patterns.
To a lesser extent, the design of the crown of the muzzle or what is actually beyond the end of the bore can affect accuracy as well. This is known as muzzle dynamics and deals with the action of expanding gases on the base of the bullet once it has departed the bore.
The harmonic vibration characteristics of a barrel can be altered by changing ammunition, changing the length of the barrel, changing the point at which a barrel contacts the forestock of the firearm or by changing the diameter or mass of the barrel.
Previously the reduction or control of barrel vibration has been approached in numerous ways. A Ballistic Optimizing System for Rifles (BOSS) patented by Rose of South Weber, Utah, U.S. Pat. No. 5,279,200 utilizes a permanently attached tube with vents or ports that can be adjusted to tune the vibration pattern of the barrel used in conjunction with a flexible barrel and action bedding compound where these contact the stock of the firearm. Unfortunately, this device is available only by purchasing a Browning or Winchester rifle equipped with the system. The most obvious drawback to this device is that it affords no improvement to a shooter's current firearm. If it were available, it would require permanent alteration of the barrel of the gun, another drawback that affects future value of a gun. Contrary to the patent claims, the BOSS also increases muzzle blast noise, it deflects propellant gas rearward with it's series of ports and even warns of the noise increase in advertising literature covering the BOSS system. Such additional noise can create a hazard for the shooter and any nearby observers. Another drawback to the BOSS is increased overall length since it is mounted such that it extends beyond the end of the muzzle. Since the BOSS is a permanent attachment, it cannot be removed and mounted on another gun. Were the BOSS available as an aftermarket product, it would require gunsmith installation and permanent modification to the barrel as well as permanent modification of the gunstock in applying the required flexible bedding compound. The BOSS system also has an effect on the muzzle dynamics of the gun that change with each new adjustment of the device.
A follow-up device similar to the BOSS U.S. Pat. No. 5,509,345 by Cyktich of Everett, Wash. also requires mounting a device substantially beyond the end of the muzzle. This device also has porting and was more or less permanently mounted onto the barrel of the gun with a type of heat shrink material. Drawbacks include increase in muzzle blast, it is not transportable from gun to gun, it requires a custom sized mounting device for each barrel, and an increase in overall length of a gun so equipped.
A Rifle Control Tube as patented by Shapel of Boise, Id. U.S. Pat. No. 2,796,005 utilized a combination of weight for dampening effect coupled with a system of vents to deflect propellant gases upward to reduce muzzle flip and recoil. The drawback to this system is the permanent modification necessary to the barrel of the gun, namely threading the muzzle for mounting. In addition, the venting system creates an increase in noise due to the deflection of muzzle blast. The system had no means of actually changing or tuning the vibration pattern to impart better accuracy with different types of ammunition. A further drawback to this type of system is the change in muzzle dynamics whereby the bullet departing the bore can be affected by deflected propellant gases. Another drawback is the additional length added to the barrel which makes gun handling more difficult. This device cannot be removed from one gun and placed on another without permanent barrel modification. This device could not be installed by an untrained shooter, and requires a professional to modify the firearm and mount the device.
Other means of dampening barrel vibration have been used. U.S. Pat. No. 4,726,280 by Frye relates to a means of mounting a muzzle member by threading the end of the barrel. This muzzle member could add sufficient weight to dampen or alter the vibration of the barrel, however, a permanent modification to the gun barrel is required. A further drawback is the additional length added to the gun. In addition, this device can adversely affect the muzzle dynamics of a firearm so equipped. This device also lacks the ability to be adjusted to tune the vibration pattern of the barrel for best accuracy.
Other muzzle "Brakes" have been utilized to lessen the recoil of a firearm by venting propellant gases in an attempt to offset rearward movement at discharge. These devices all require permanent modification of the gun barrel and cannot be attached by the average shooter. While most of these devices can add some weight to the end of the barrel, they all lack the ability to be adjusted or tuned for optimum accuracy. In many instances, barrels that have been modified and a muzzle brake added no longer shoot as accurately as before. All these devices tend to increase muzzle blast by deflecting propellant gases rearward toward the shooter.
A more recent development in an attempt to alter barrel vibration without adding significant weight was developed by Christianson Arms of Fayette, Utah (patent pending). This approach encases the entire barrel with a carbon fiber sleeve that adds stiffness to reduce barrel vibration. This design effectively creates a heavy barrel characteristic without the associated weight of a larger diameter barrel. The drawback to this system is high cost of a complete rifle. If the system were available as an aftermarket modification it would require barrel replacement and as a further drawback this barrel has no capability of adjusting or tuning for different types of ammunition because even heavy barrels have a certain amount of vibration to contend with.
U.S. Pat. No. 5,423,145, by Nasset of Aumsville, Oreg. is a device that tunes barrel vibrations by altering the contact point of the barrel to the forestock. This effectively changes the length of the vibration pattern from contact point to muzzle thus changing barrel harmonics. This system requires permanent modification of the gunstock which can affect future value. Another drawback is the device cannot be moved from gun to gun. Also, any barrel contact by the stock can affect point of impact if the stock gets wet. Wood stocks can swell and warp, fiberglass or composite stocks are stable in all conditions, but any moisture between the barrel and the contact point will affect the point of impact due to hydraulic effect. This device is also best installed by a competent gunsmith since a good deal of stock material must be removed from the barrel channel for installation and the barrel contact must be accurately centered below the barrel with a certain amount of pressure on the contact point.
Another approach to barrel vibration is addressed by American Safe Arms, Inc. as described in the January 1997 issue of Shooting Sports Retailer. This method is a complete redesign of the entire gun barrel. It has an inner barrel encased by an outer sleeve or barrel with a device at the muzzle that keeps the inner barrel stationary. The inner barrel is ported to direct propellant gases out and back inside the inner sleeve. This design lowers noise and reduces recoil at the same time. While a unique approach to the problem, the system is not something that a shooter can install themselves on their existing firearm. Another drawback is the lack of tuning capability within the system. This system obviously has no flexibility to move from gun to gun.
Another approach is an embodiment of the present invention as produced by Bill Shaw of Austin, Tex. in February of 1997. This proof of concept prototype was constructed for me by Mr. Shaw from my original drawings but he modified the design considerably. Mr. Shaw used a custom designed insert that was press fit onto the barrel and externally threaded to accept a tuning device of a nominal weight. The drawback to this design was the need for custom sized inserts for each different size barrel and no indexing capability for adjustments to the location of the tuning device. A further drawback was the lack of transportability between guns because a custom sized insert would be required for each.
In addition to these systems mentioned, the search for accuracy improving products has run to other types of devices such as improved bench rest devices, improved stock mounting systems, improved stock materials that are more stable under all conditions, interchangeable barrel weights of different sizes to dampen vibration, and custom tailored ammunition to match each gun specifically. All lack the ability to tune barrel vibrations with the same device and the ability to transport the device from gun to gun without custom modifications.

Removable harmonic tuning system for firearms


Methods and systems for relative inertial measurement may include a user device comprising an inertial measurement device and/or a camera. A second inertial measurement device may be configured to move with a reference frame. One or more processors may receive inertial measurements from the first and second inertial measurement devices and determine movement of the user device relative to the reference frame by comparing the received inertial measurements. Additionally reference objects in a view of a camera may be used to calibrate the determined motion of the user device within the reference frame.

Virtual reality (VR) allows users to experience and/or interact with an immersive artificial environment, such that the user feels as if they were physically in that environment. For example, virtual reality systems may display stereoscopic scenes to users in order to create an illusion of depth, and a computer may adjust the scene content in real-time to provide the illusion of the user moving within the scene. When the user views images through a virtual reality system, the user may thus feel as if they are moving within the scenes from a first-person point of view. Similarly, augmented reality (AR) combines computer generated information with real world images to augment, or add content to, a user's view of the world. The simulated environments of virtual reality and/or the enhanced content of augmented reality may thus be utilized to provide an interactive user experience for multiple applications, such as interacting with virtual training environments, gaming, remotely controlling drones or other mechanical systems, viewing digital media content, interacting with the internet, or the like. In addition, VR systems and/or AR systems may utilize inertial measurements from an inertial measurement unit (IMU) included in a VR or an AR device to determine how images are to be displayed. Also, an IMU may be included in various other types of devices such as controllers used with a VR or an AR device or controllers used for various other purposes.
Conventional virtual reality and augmented reality systems may not be able to separate motion of a user or a body part of a user from motion of a reference frame in which the user is travelling, such as a vehicle in which the user is travelling. For example, a user wearing a conventional VR or AR device may be seated in a vehicle and the vehicle may accelerate from a stopped position to a high speed while the user wearing the VR or AR device sits in the vehicle without moving within the vehicle (e.g. no relative motion of the user relative to the reference frame of the vehicle). Because the conventional VR or AR device cannot separate the motion of the user's body from the motion of the vehicle, the conventional VR or AR device may attribute the motion of the vehicle to the user. Thus images displayed to the user on the VR or the AR device may appear to the user as if the user is running through a scene at the same speed and in the same direction the vehicle is travelling. A similar phenomenon occurs in regard to angular motion. For example, a user wearing a conventional VR or AR device may be riding in a vehicle that turns, however the user may not actually turn the user's head when the vehicle turns. A conventional AR or VR device may not be able to separate the motion of the user's head (e.g. not turning) from the motion of the vehicle (e.g. turning). Therefore, the turning motion of the vehicle may be attributed to the user and images displayed to the user on the VR or AR device may appear to be turning or spinning despite the user not turning the user's head. Such discrepancies between a user's relative motion within a vehicle and motion observed by the user via a scene displayed to the user may lead to nausea and sickness of the user. For example, nausea may be caused by oculovestibular mismatch. Likewise, in the case of other types of devices that include IMUs, such as controllers, motion of a vehicle being attributed to the controller may lead to erratic control and unintended consequences.
Also, some VR or AR devices may include cameras or other sensors that are used to correct for drift resulting from small errors that accumulate over time when determining a location of the AR or VR device from motion measurements from an IMU. For example, a visual inertial odometry (VIO) algorithm may correct a position for an AR or VR device determined based on IMU measurements by comparing a change in distance from the AR or VR device to a reference point in a view of a camera of the AR or VR device over a period of time to a change in distance according to positions determined based on IMU measurements for the AR or VR device over the period of time. However, such VIO algorithms may not function properly when a VR or AR device is used in a moving reference frame. For example, some objects in a view of camera of the AR or VR device may move with the reference frame while other objects may not move with the reference frame. Also, some of the objects that do not move with the reference frame may be stationary or mobile objects, for example other vehicles on the road. When a VIO algorithm inadvertently selects an object that does not move with the reference frame as a reference point, motion of the reference frame or the object may be attributed to drift error and the VIO algorithm may over compensate for drift. This may lead to erratic behavior of the AR or VR device.

Relative inertial measurement system with visual correction


Various methods and systems are provided for an engine system for a vehicle. In one example, the engine system includes a turbocharger including a turbine, the turbocharger configured to be driven via exhaust gas from an engine during a turbocharger mode and via the exhaust gas from the engine and mechanical output from the engine during a supercharger mode. The engine system further includes a bypass control element to decrease an amount of energy extracted from exhaust flow through the turbine in a regeneration mode of operation and to increase an amount of energy extracted from exhaust flow through the turbine during a non-regeneration mode of operation, and an aftertreatment system disposed downstream of the turbocharger and including a particulate filter.

During operation, internal combustion engines generate various combustion by-products that are emitted from the engine in an exhaust stream. As such, various approaches may be utilized in order to reduce regulated emissions. In some examples, particulate emissions may be reduced by employing an aftertreatment system with a device such as a particulate filter in an exhaust passage of the engine. Further, turbochargers may be used in an engine system to increase a pressure of air supplied to the engine for combustion. In one example, the turbocharger includes a turbine coupled in an exhaust passage of the engine which at least partially drives a compressor via a shaft to increase the intake air pressure.
Over time, a particulate load of the particulate filter may increase such that regeneration of the particulate filter needs to be carried out to clean the particulate filter so that a backpressure on the engine does not increase, for example. The inventors herein have recognized when the particulate filter is positioned downstream of the turbine of the turbocharger in the exhaust passage, an exhaust gas temperature upstream of the particulate filter and downstream of the turbine may not be high enough to passively regenerate the particulate filter. Thus, active regeneration may be carried out by injecting fuel upstream of the particulate filter or heating the particulate filter via a heater, for example. In such an approach, efficiency of the system may be reduced due to increased fuel consumption and/or a cost of the system may be increased due to addition of components such as the heater.


An image forming method and an image forming apparatus, wherein a thin film of an electroconductive polymer which holds and releases a dye by means of an electric field enables a construction including a driving circuit, a driving device and an image forming medium to be used for the transfer of an image pattern. The image forming method includes forming a thin film of the electroconductive polymer on an electroconductive substrate, which can take in, hold and release ionic dye molecules in accordance with the change of the state of the electroconductive polymer, that can assume at least two physicochemical states among an oxidized state, a neutral state and a reduced state of the thin film; and bringing the thin film into contact with an image receiving medium. The image receiving medium has suppressed electroconductivity. When a voltage is applied to the thin film holding ionic dye molecules and the image receiving medium between the electroconductive substrate and an image formation controlling electrode, ionic dye molecules are transferred to a localized area, but not to the entire surface, of the image receiving medium.

1. Field of the Invention
The present invention relates to an image forming method and to an image forming apparatus. More particularly, the present invention relates to an image forming method and to an image forming apparatus by use of an electroconductive polymer layer which takes in a dye and release the dye.
2. Description of the Related Art
Methods, which are currently utilized in a printer or the like for the purpose of transferring an image from an electric signal or optical signal to a recording medium such as paper, include, for example, dot-impacting, thermal transfer, thermal sublimation, ink jet and laser printing methods in electrostatic photography. These methods are roughly divided into three groups.
The methods, which are included in the first group, are those based on dot-impacting, thermal transfer and thermal sublimation. According to these methods, a sheet, which is in the form of an ink ribbon or a donor film and which contains a dispersed dye, is superposed on a paper or the like and the dye is transferred to the paper by the application of a mechanical impact or heat. Therefore, these methods always need expendable supplies and are associated with such disadvantages as high running costs due to difficulty in high-speed operation and poor energy efficiency. Further, the qualities of images are poor except for those obtained by the thermal sublimation method.
An ink jet method, which is included in the second group and is based on the mechanism that the ink is directly transferred to a paper from a head, is characterized by a low level of running costs, because no expendable supplies are necessary except for ink. However, the ink jet method is associated with a difficulty in high-speed operation, because it is difficult to electrically control all of the dots and to form a head corresponding to the width of a paper. Other disadvantages are that the minimal image unit is restricted by the size and interval of heads and that the printing speed decreases and the energy efficiency becomes poor with improving print quality.
An electrostatic photographic method such as a laser-printing method, which is included in the third group, is based on the mechanism that an image is formed via an intermediate transferring member. That is, according to an electrostatic photographic method, toner particles are caused to adhere to an electrostatic latent image created by laser spots and then the toner particles are transferred to a paper to forman image. This method is featured by a capability to form a relatively fine image and by a low level of running costs, because no expendable supplies are necessary except for toner. However, this method is associated with the problem that a high voltage is necessary for forming an electrostatic latent image and for adhering/transferring toner particles. Further, a large amount of electricity is consumed and, therefore, ozone and nitrogen oxides are generated. Furthermore, all of the above-mentioned printing methods generate noisy sounds when the printers are operated.
On the other hand, other conventional image forming methods, such as an ordinary printing method and a silver salt photographic method, provide images with high quality.
The ordinary printing method, which involves the formation of a printing plate and provides low running costs in the case that a number of identical images are formed, is not suitable for general uses. In the case of a silver salt photographic method, media, which are not reusable, such as photographic films and papers, need to be employed so that the running costs are high and a high-speed operation of the method is impossible.
As stated in the above, none of aforementioned methods, in which an image from an electric signal or optical signal is transferred to a recording medium such as paper, can provide a desirous method featured by a high-quality image, a relatively high speed, a low level of running costs, energy saving, resource saving and advantage both to environment and to users.
A conceivable means to solve the above-mentioned problems is the utilization of an image forming medium which can form and transfer or directly form an image distribution created by image forming elements such as toner particles or ink corresponding to an object image in such a manner that the image distribution is in the same scale (the same width) as that of an image receiving medium (such as a paper) onto which the image is transferred. Although this medium also functions as a temporary carrying member of the image forming elements, the intake or release (delivery) of the image forming elements needs to be performed with relatively low energy and a continuous gradation. Another required function is that the unit of the image forming element be minimized.
An image forming medium, which is considered to have the above-mentioned functions, is an electroconductive polymer layer represented, for example, by polypyrrole, polythiophene and polyaniline. It has been known that the three states, i.e., oxidized state, neutral state and reduced state, of this type of polymer layer can be controlled chemically, electrically or electrochemically so that doping or dedoping of a counter ion takes place. The details of these characteristics are shown, for example, "Electroconductive Polymers" by S. Yoshimura (Polymers Society of Japan), "Functions and Designs of Electroconductive Organic Films" by K. Yamashita and H. Kitani (Surface Science Society of Japan) and "Fundamentals and Applications of Electroconductive Polymers" by K. Yoshino (I.P.C.). In short, if an ion itself, which is doped into and dedoped from an electroconductive polymer layer is a sort of image forming element, the ion is expected to exhibit its ability as a temporary carrying member of the image forming elements that fulfill the aforementioned requirements.
One of the problems, however, is that the counter ions which are doped into and dedoped from an electroconductive polymer are those which cannot be expected to become an image forming element, such as usual metals or anions and cations of electrolytes having a low molecular weight. Another problem is that, if an electroconductive polymer is synthesized in the presence of a high molecular weight anion, for example, such an anion cannot be dedoped from the polymer.
According to H. Shinohara et al., described in J. Chem. Soc., Chem, Commun, pp. 87 (1986), the size of an ion, which can be reversibly doped/dedoped, is determined by the microstructure of an electroconductive layer and is controllable, for example, by the size of a counter ion present at the time when the electroconductive polymer is polymerized from a monomer. This report, however, deals with ions having a molecular weight up to about 100 and discloses that the doping/dedoping characteristic becomes insufficient as the molecular weight increases. H. Shinohara et al. also report, in Journal of Chemical Society of Japan, No. 3, pp. 465 (1986), glutamic acid as a relatively large molecule that exhibits a reversible doping/dedoping characteristic, but this molecular weight is still below 150. Meanwhile, a dye generally used, which can be expected to be an image forming element, has a molecular weight mostly in the range of 500 to 1,500. Heretofore, a substance having this level of molecular weight has never been thought to be capable of being doped/dedoped reversibly.
It has been known that an ion having a small molecular weight, as mentioned above, is subjected to doping into and dedoping from an electroconductive polymer layer in order to utilize a color change accompanied by the doping and dedoping. However, this kind of technique has been centered on such applications as protective coatings for battery or solar cell and electrochromic displays. Therefore, none of these techniques has been used to replace a conventional image forming method.
One of a few examples of a known technique, whereby an electroconductive polymer itself is used as a material related to a marking application, is disclosed in Japanese Patent Application Laid-Open (JP-A) No. 2-142,835 titled "A method for controlling wettability of a thin film surface of a polymer and an image forming method and an image forming material utilizing said method". According to this technique, a printing plate is prepared by electrically switching a difference in the wettability between an oxidized state and a neutral state of the electroconductive polymer layer. Therefore, none of image forming elements (such as ink) is held within the electroconductive polymer layer by way of doping. Further, an adhered amount or transferred amount of a dye such as ink cannot be controlled by this technique.
Based on the above-described background, the present applicant has already filed an application of an invention providing an image forming method and an image forming apparatus and a thin film of an electroconductive polymer usable therefor, which are featured by such advantages as a high-quality image, a relatively high speed, a low running cost, energy saving, resource saving and usefulness both to environmental preservation and to users (Japanese Patent Application No. 7-287,491 filed on Nov. 6, 1995, which is hereinafter simply referred to as "the prior application").
According to the invention of the prior application, a thin film of an electroconductive polymer is utilized for the purpose of providing an image forming medium, where an ionic dye is taken in among molecules of the thin film of the electroconductive polymer in at least one state of the electroconductive polymer capable of changing between at least two states of an oxidized state, a neutral state and a reduced state. This thin film of an electroconductive polymer is formed on an electroconductive substrate (the same as "electrode substrate" in the prior application) and is controlled in an oxidized state or in a reduced state corresponding to a target image so that a distribution of concentration in accordance with an intaken amount or a released amount of the ionic dye corresponding to the target image is formed on the thin film of the polymer. The distribution of concentration of the ionic dye thus formed is transferred to an image receiving medium onto which an image is transferred (the same as "recording medium" in the prior application) (for convenience, a medium consisting of an electroconductive substrate and the above-mentioned electroconductive polymer formed on the substrate is herein referred to as "an image forming medium").
Most generally, the transfer is conducted by the steps comprising bringing a thin film of an electroconductive polymer formed on an electroconductive substrate into close contact with an image receiving medium provided with an electroconductivity and applying an electric field between the thin film of the electroconductive polymer and the image receiving medium.
According to the method proposed by the prior application, the transfer of the dye in the form of a pattern was conducted in the following process.
The process comprised the steps of forming an image forming medium having a complex construction where a thin film of an electroconductive polymer was formed on each of a plurality of fine electroconductive substrates (fine electrodes) and then applying a voltage independently to each of the fine electrodes in conformity with an image pattern. Accordingly, the construction comprising a driving circuit, a driving means and an image forming medium was complex. In addition, an independent design was necessary for the driving circuit and the driving means.

Image forming method and image forming apparatus including electroconductive polymer layer for dye intake and release


An adsorption-desorption material having a high carbon dioxide adsorption-desorption capability, a low pressure loss, a high thermal diffusion efficiency, and high resistance to repeated stresses, e.g., expansion and shrinkage, as well as an adsorption-desorption apparatus including the adsorption-desorption material, is provided. The adsorbent is composed of a three-dimensional network skeleton structure or a structure having three-dimensional network voids, the structure constructed by a compound having a carbon dioxide adsorption-desorption capability. The carbon dioxide adsorption-desorption apparatus is provided with this adsorbent.

Currently, as much as about 6 billion tons a year of carbon dioxide is emitted into the air due to the use of fossil fuels in the world. It is said that since carbon dioxide exerts the greenhouse effect, an increase in the atmospheric concentration of carbon dioxide causes an increase in atmospheric temperature on a global scale so as to raise serious environmental issues, e.g., a rise in sea level and abnormal weather. On the other hand, the speed of fixation of carbon dioxide in nature is very slow. Therefore, to take measures against the carbon dioxide is an urgent necessity. Under these circumstances, Japan made a political commitment on a worldwide basis to reduce the overall amount of emission of greenhouse effect gases by at least 6% below the 1990 level in the period 2008 to 2012 based on the international agreement in the 3rd Session of the Conference of the Parties to United Nations Framework Convention on Climate Change (COP3) held in December 1997.
With respect to technologies to make effective use of carbon dioxide, synthesis of methanol serving as a fuel through a catalytic hydrogenation reaction by using a catalyst has been attempted. However, the reaction requires a temperature of 250° C. or more and hydrogen and, therefore, if a fossil fuel is used as an energy source thereof, it becomes useless since fresh carbon dioxide is generated.
It has also been considered as a workaround therefor to generate hydrogen through the electrolysis of water by using electric energy converted from natural energy and to generate methanol through synthesis of the resulting hydrogen and carbon dioxide in the presence of a catalyst. However a large-scale development of natural energy is required and, therefore, the practicability is believed to be low since the cost becomes very high.
As described above, carbon dioxide is in a low energy state and it is difficult to use as energy. However, Japan is a carbon dioxide emission power and emits as much as 1.23 billion tons of carbon dioxide a year. Therefore, to take more down-to-earth measures directed toward the reduction of carbon dioxide is an urgent necessity, and efforts must be made in combination of the development of technology for a high energy conversion efficiency, an energy-conservation policy, and the like.
Under these circumstances, attempts to separate, recover, and fix carbon dioxide without emitting into the atmosphere from thermal power plants, chemical plants, and the like which make up 60 percent of the overall amount of emission of carbon dioxide, and to reserve in the ground or under the sea have been conducted all over the world. Consequently, emergence of a high-temperature reversible reaction type material capable of repeatedly adsorbing and desorbing carbon dioxide, exhibiting a low pressure loss, and having a high adsorption-desorption efficiency is desired in order to reduce the separation and recovery costs as well.
Examples of up-and-coming clean energy include a fuel cell system by using hydrogen. Attempts to use a natural gas which is an abundant resource and in a high energy state or methane which is a primary component of a methane hydrate as a means for producing hydrogen serving as a fuel have been intensively conducted at present. Since the generation of hydrogen from methane is based on a steam reforming reaction of methane, carbon dioxide is generated as a by-product.
As described above, in a social form in which the fuel cell has become the mainstream as well, it is believed that the establishment of technologies for separation, recovery, and fixation of carbon dioxide is an inevitable issue to prevent global warming.
In order to efficiently recover carbon dioxide, it is desirable to separate a gas having as high a concentration as possible, and a method of separation before combustion has been studied, in which carbon dioxide is separated at a stage of a reformed fuel gas before combustion. Since the steam reforming reaction of methane is generally conducted within the range of 400° C. to 600° C., it is desirable to separate and recover carbon dioxide from a high-temperature gas in order to achieve separation of carbon dioxide before combustion from the viewpoint of the effective use of thermal energy as well.
Examples of previously known technologies to absorb carbon dioxide include a chemical absorption method by using β-aminoethyl alcohol or an alkaline aqueous solution, e.g., potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, or lithium hydroxide; a membrane separation method by using a cellulose acetate membrane; and a physical adsorption method by using a physical adsorbent, e.g., zeolite or molecular sieve. However, these known technologies cannot efficiently separate and recover carbon dioxide from a high-temperature gas exceeding 400° C. because of limitation of heat resistance.
With respect to the technology for separating and recovering carbon dioxide from a high-temperature gas, Japanese Unexamined Patent Application Publication No. 9-99214 has introduced a technology through the use of lithiated zirconium, as a method for separating carbon dioxide by using a temperature difference as a driving source without pressure control. Japanese Unexamined Patent Application Publication No. 2001-96122 has introduced that lithium silicate having an average particle diameter of 0.1 to 10 μm is used as a material for absorbing carbon dioxide at a temperature within the range of 100° C. to 700° C. Japanese Unexamined Patent Application Publication No. 2001-232186 has introduced a method in which lithium zirconate is dispersed in lithium silicate is introduced as a method for directly separating and recovering carbon dioxide in a high-temperature exhaust gas from an apparatus to burn hydrocarbon. Furthermore, Japanese Unexamined Patent Application Publication No. 2001-170480 has introduced a technology for improving carbon dioxide absorption capability over a wider concentration range by adding an alkali carbonate to lithium silicate.
In the case where a carbon dioxide adsorption-desorption material is filled in an adsorption-desorption tower or the like and is used for adsorbing and desorbing carbon dioxide, examples of material characteristics required of the material for the structure include high carbon dioxide adsorption-desorption capability, a low pressure loss, a high thermal diffusion efficiency, and high resistance to repeated stresses, e.g., expansion and shrinkage.
However, each of the forms of carbon dioxide adsorption-desorption materials introduced by these documents is in the shape of a powder or is molded into the shape of pellets by a method of pressure molding in a mold. Consequently, in the case where these carbon dioxide adsorption-desorption materials are used actually by being filled in apparatuses, the capabilities of these carbon dioxide adsorption-desorption materials cannot be fully used since problems may occur resulting from the pressure loss, satisfactory amounts of materials may not be filled in, or heat may not be uniformly transferred throughout the carbon dioxide adsorption-desorption materials filled in.
In addition, emergence of a high-temperature reversible reaction material capable of repeatedly adsorbing and desorbing carbon dioxide is desired in order to reduce the separation and recovery cost as well. However, the material is subjected to repeated stresses of expansion and shrinkage by adsorption-desorption operations. On the other hand, with respect to the material processed by a method of pressure molding in a mold, there are very small spaces to relax the stresses. Consequently, a problem occurs in that the molded pellets cannot withstand the repeated stresses and are gradually powdered.

Carbon dioxide adsorption-desorption material and adsorption-desorption apparatus


An improved tape measure apparatus which can be used as a marking gauge and/or compass comprising a tape measure, an insert comprising a base, a guide rigidly attached to the base and generally parallel to graduated indicia markings of the rule blade when extended from the tape measure whereby the graduated markings of the tape measure""s rule blade may be read. An alternative embodiment includes an insert enabling standard tape measures to be used as marking gauges and/or compasses.

Not applicable
Not applicable
Not applicable
1. Field of the Invention
The present invention relates generally to carpentry tools and, more specifically, to an improved tape measure apparatus which can be used as a marking gauge and/or compass.
2. General Background of the Invention
Standard tape measures include a length of tape wound on a spool with a spring return mechanism so that after the tape is taken out of a housing, the spring return mechanism automatically retracts the tape into the housing. A locking mechanism, typically a sliding button, locks the tape for the purpose of reading the length of the deployed tape.
Numerous tape measures have been provided in prior art. For example, U.S. Pat. No. 2,624,120 to Mills; U.S. Pat. No. 4,574,486 to Drechsler; and U.S. Pat. No. 5,390,426 to Hull are illustrative of the prior art and incorporated herein by reference to show the conventional construction of tape measures. While these units may be suitable for the particular purpose to which they address, they would not be as suitable for the purposes of the present invention as heretofore described. Tape measures are well adapted for measuring distances but their utility is usually restricted to this single function.
Many instances arise where workpieces must be scribed at uniform distances or have arcs or circles marked thereupon. In these instances tools such as marking gauges and compasses are required in addition to standard tape measures.
While certain novel features of this invention shown and described below are pointed out in the annexed claims, the invention is not intended to be limited to the details specified, since a person of ordinary skill in the relevant art will understand that various omissions, modifications, substitutions and changes in the forms and details of the device illustrated and in its operation may be made without departing in any way from the spirit of the present invention. No feature of the invention is critical or essential unless it is expressly stated as being xe2x80x9ccriticalxe2x80x9d or xe2x80x9cessential.xe2x80x9d
The apparatus of the present invention solves the problems confronted in the art in a simple and straightforward manner. What is provided in one embodiment is an adapter for tape measures which, after insertion, enables standard tape measures to be used as marking gauges and/or compasses. Another embodiment includes a tape measure apparatus with the casing being redesigned and/or adapted to include an insert that enables the tape measure to be used as a marking gauge and/or compass.
An object of the present invention is to provide a tape measure with insert which can be used in combination with a marking/cutting tool, such as a pencil or knife, to make a mark, score or cut line at a measured distance on a workpiece.
An alternative object of the present invention is to provide a tape measure with insert which can also be used in combination with a marking/cutting tool, such as a pencil or knife, to make a mark, score or cut line on a workpiece in the shape of an arc or circle and measured radius.
An additional object of the present invention is to provide a tape measure with insert which protects the finger of the person using the tape measure and insert as a marking gauge to make a mark, score or cut line.
An additional object of the present invention is to provide a tape measure with insert which allows the user to grip the extended portion of the rule blade lying on top of the insert and thereby stabilize the tape measure and insert during use as a marking gauge.
An additional object of the present invention is to provide a tape measure and insert whereby the insert fits into the tape measure casing to minimize the overall change in dimension of the tape measure""s casing when the insert is not being used.
A further object of the present invention is to provide a tape measure with insert that is simple and easy to use as a marking gauge or compass.
A still further object of the present invention is to provide an insert for a standard tape measure that is economical in cost to manufacture.
A still further object of the present invention is to provide a tape measure and insert combination which can be used in combination with a marking/cutting tool, such as a pencil or knife, to make a mark, score or cut line at a measured distance on a workpiece.
Further objects of the present invention will appear as the description proceeds.
For a further understanding of the nature, objects, and advantages of the present invention, reference should be had to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements. However, the drawings are illustrative only, and changes may be made in the specific construction illustrated and described within the scope of the appended claims.

Tape measure apparatus which can be used as a marking gauge and/or compass


The invention provides improved apparatuses and related methods for the detection of needle penetration into negative pressure corporal spaces such as the epidural space. In one aspect, the invention provides a needle hub that includes a fluid reservoir chamber and a plunger engaged therewith, so that insertion of the plunger into the chamber displaces fluid causing a hanging drop to form.

Epidural anesthesia is a popular method of treating acute and chronic pain. Most commonly, the "loss of resistance" (LOR) technique has been used to detect needle penetration into the space. This technique involves connecting the needle, such as a Tuohy needle, via a needle hub to a syringe filled with saline solution and continuously pushing on the piston of the syringe while the needle is inserted toward the epidural space until a loss of resistance is encountered indicating that the needle tip has entered the space. An alternative method of detection is the "hanging drop" (HD) technique which relies on visualizing the aspiration of a small volume of fluid from the hub of the needle as the pressure at the needle tip decreases below atmospheric level upon entry into the epidural space. However, conventional application of the hanging drop technique is less than optimal due to the number of manipulations required while the needle is inserted in a patient.
What is needed and provided by the present invention are new and improved apparatuses and methods for detecting needle penetration into a negative pressure (subatmospheric) space such as the epidural space.

Apparatus for hanging drop detection of epidural space penetration


The present invention provides a novel dioxin analogue for use in the search for organisms capable of degrading dioxin. The dioxin analogue is represented by the following chemical formula (1) or (2):

Dioxins are environmental pollutants that have raised public concern because of their toxicity and their ability to remain in the environment for a long time. No practical solution has been proposed so far to effectively eliminate dioxins from the environment. One approach is to collect dioxin-polluted materials in one place for physical and chemical processing. This approach is considered difficult, however, especially when materials contaminated with low-level dioxins are spread over a large area. Bioremediation, a process that takes advantage of biological activities of microbes in cleaning the environment, is currently considered the most effective solution to address such low-level pollution. In constructing an effective bioremediation system, it is crucial to isolate naturally occurring organisms that have a strong ability to rapidly degrade, metabolize, and detoxify dioxins.
Conventional screening processes for dioxin-degrading organisms involve use of dioxins themselves or radioactively labeled other compounds in order to evaluate the ability of organisms to degrade dioxins.
Some of these processes require a pre-treatment in evaluating organisms' capability while others require special instruments to detect radioactively labeled compounds. Also, analytical procedures such as gas chromatography and HPLC employed in these processes are time-consuming.
Accordingly, it is an objective of the present invention to eliminate the above-described drawbacks of the conventional screening techniques for dioxin-degrading organisms by providing a novel screening method that permits even more efficient screening for desired organisms. The present invention also provides compounds and a screening kit for use in this screening process.

Dioxin analogues and methods and kits for searching out dioxins-decomposing organisms or enzymes or dioxin-decomposing enzyme genes

Forestry and Forest Products Research Institute


In one embodiment, a device in a network receives an indication of a traffic shaping rate adjustment by a node due to a network condition. The device identifies a set of network nodes that are associated with the network condition. The device detects a traffic shaping rules violation by an offending node in the set of network nodes. The device sends an instruction that causes the offending node to use a different traffic shaping rate.

Enterprise networks are carrying a very fast growing volume of both business and non-business critical traffics. Often, business applications such as video collaboration, cloud applications, etc., use the same hypertext transfer protocol (HTTP) and/or HTTP secure (HTTPS) techniques that are used by non-business critical web traffic. This complicates the task of optimizing network performance for specific applications, as many applications use the same protocols, thus making it difficult to distinguish and select traffic flows for optimization.
As the number of business and non-business critical applications increases, so too are the number and variety of service level agreements (SLAs) that may be in use by a network. In general, an SLA refers to a target or threshold level of performance guaranteed by the network, and may be associated with a particular type of traffic. For example, many real-time business applications are very bandwidth demanding and having corresponding SLAs that are used to ensure that a certain amount of network bandwidth is available for a particular flow of traffic.
Traditionally, reactive techniques have been used to enforce network performance criteria, such as SLAs. First, the network itself is engineered by defining the application SLAs, quality of service (QoS) parameters, security settings, etc. Next, the performance criteria are monitored in view of the network's performance. If the performance criteria are not met, adjustments may then be made to the network in a reactive manner. However, such a reactive approach may also, by its very nature, mean that the network experiences periods of reduced performance before corrective measures are taken.

Ensuring dynamic traffic shaping fairness


A therapy for a disease, e.g., gastric cancer, comprising endoscopic local administration of a vector having a gene for treatment or cells producing the vector to a lesion to transduce the gene into target cells. The direct in vivo transduction of a gene for treatment into the affected site is expected to produce therapeutic effects specific on the lesion. Since the gene is introduced also into lymph nodes which may have developed a metastatic lesion, both the primary lesion and the metastatic lesion in the surrounding lymph nodes can be treated simultaneously.

The rapid progress of genetic engineering has enabled development of various molecular biological techniques. With the development, remarkable advancements have been shown in analyses of genetic information and functions, and a number of attempts to apply the results to actual therapy have been made. Above all, gene therapy is mentioned as one of the fields which received the greatest development. Various genes relating hereditary diseases have been discovered and decoded, while methods for introducing these genes into cells through physical and chemical techniques have been developed. Thus, gene therapy has now stepped up from the stage of fundamental experiments to actual clinical application.
As it has been clarified that the abnormal gene participates in congenital diseases, such as familial hypercholesterolemia and adenosine deaminase (ADA) deficiency, and cancers and AIDS which are considered as acquired hereditary diseases, gene therapy by transducing the gene to the somatic cells of a patient has been attracting attention as a new method of therapy. After the first clinical test of gene therapy in the United States in 1989, clinical tests were commenced also in Italy, The Netherlands, France, England, and China. In the U.S., in particular, 81 protocols for gene therapy were approved by Recombinant DNA Advisory Committee (RAC) of National Institute of Health (NIH), and about 500 cases underwent gene therapy by June, 1995.
By the kind of the cells to which genes are transduced (target cells), gene therapy is divided into germ cell gene therapy and somatic cell gene therapy. It is also divided into augmentation gene therapy (a new (normal) gene is added with an abnormal gene as it is) and replacement gene therapy (an abnormal gene is replaced with a new (normal) gene). For the time being, only augmentation gene therapy to somatic cells are allowed due to bioethical and technical limitations.
A great technical subject in the above-mentioned clinical application of gene therapy is how to introduce foreign genes into target cells efficiently and safely. Early in 1980, application of physical techniques such as microinjection was attempted but not turned to practical use because the efficiency and stability of gene transduction were low and also because the technique of large scale cell culture was limited in those days. Thereafter, recombinant viruses (virus vectors) serving as a vector for efficient transduction of an foreign gene into target cells were developed, which enabled clinical application of gene therapy for the first time.
One of the most general methods of gene therapy is ex vivo gene therapy by autograft, in which target cells are taken from a patient and, after transducing thereto a gene for therapy, the cells are returned to the patient (see Science, Vol. 249, p. 1285 (1990)). Application of ex vivo gene therapy is limited to those cases in which the cells subject to the therapy can be taken outside the body. In addition, since special equipment is required for mass culture of the cells taken from the patient, the facilities available for the therapy are limited.
On the other hand, for the cases where the target cells are fixed at an organ or tissues, so-called in vivo gene therapy has been studied, in which a gene for treatment is administered directly to the site from which the disease is originated. For example, a method for transducing a gene into an organ, such as the heart or the liver, comprising inserting a balloon catheter through a blood vessel and, after stopping the blood flow, directly infusing the gene to the inner wall of the blood vessel has been proposed (see unexamined published Japanese patent application 6-509328 based on a PCT application PCT/US92/05242 (International Publication No. WO93/00051)).
Clinical researches of in vivo gene therapy for cerebroma (see Human Gene Therapy, Vol. 4, p. 39 (1993)) or malignant melanoma (Blood, Vol. 80, p. 2817 (1992)) have also been carried on. Such in vivo gene therapy is expected as a new method taking the place of conventional surgical treatment or chemotherapy.
Gene therapy for cancers is generally divided into indirect killing of cancer cells and direct killing of cancer cells.
The former is a method for treating a cancer by making use of immunity essentially possessed by a living body. More specifically, this method is to make a tumor disappear by enhancing the anti-tumor immunity of the patient by transducing of a gene which codes cytokines, such as interleukin (IL) 2 (see Cell, Vol. 60, p. 397 (1990)), IL 4 (see Cell, Vol. 57, p. 503 (1989)), interferon (INF) .gamma. (see Proc. Natl. Acd. Sci. U.S.A., Vol. 86, p. 9456 (1989)), a granulocyte-macrophage colony-stimulating factor (GM-CSF) (see Proc. Natl. Acd. Sci. U.S.A., Vol. 90, p. 3539 (1993)), and a tumor necrosis factor (TNF) (see J. Immunolo., Vol. 146, p. 3227 (1991)), and an intercellular adhesive factor (see Science, Vol. 259, p. 368 (1993)). With respect to the mechanism of the tumor disappearance, induction of cytotoxic T lymphocytes (CTL) and tumor infiltrating lymphocytes (TIL) has been reported (see Science, Vol. 256, p. 808 (1992)).
The latter therapy is a method of introducing a gene directly acting on cancer cells. Specifically, this method is characterized in that a gene coding an enzyme capable of converting a cytotoxin precursor to an activated form is transduced into cancer cells, and the cytotoxin precursor is administered locally or systemically thereby to specifically kill the transduced cancer cells. The method is called virus-directed enzyme/prodrug therapy (VDEPT). For example, introduction of a self-killing gene, such as a thymidine kinase (tk) gene of herpes simplex virus (HSV), combined with ganciclovir (GCV) is mentioned (see Science, Vol. 256, p. 1550 (1992)). The cells to which the tk gene has been transduced metabolize GCV to produce cytotoxic GCV-triphosphate (GCV-TP) and thereby suffer injury and death. At this time, a lethal effect occurs also in the cancer cells into which the gene has not been integrated (a so-called bystander effect) and the tumor reduces (see Human Gene Therapy, Vol. 4, 725 (1993)). Further, in cases where carcinogenesis is induced by variation of anti-oncogene, such as p53 and Rb, transduction of the anti-oncogene has been suggested in an attempt to normalize the cells (see Science, Vol. 249, p. 912 (1990)).
About a half of cases of gastric cancer, one of digestive organ cancers, are now found in the initial stage owing to the recent highly advanced medical techniques, and more than a half of the cases can be cured completely. However, advanced cases of gastric cancer are still incurable even with every possible treatment, and establishment of new therapy has been keenly demanded.
The conventional treatment for gastric cancer is generally divided into (1) surgical treatment and (2) chemotherapy as described below.
(1) Standard surgical therapy generally applied to gastric cancer is the extended radical surgery comprising complete extirpation of not only the stomach inclusive of the lesion but the surrounding lymph nodes. However, the recent rapid advancement of medical treatment on gastric cancer has allowed application of reduced surgery comprising removal of the affected site to cases with gastric cancer at the early stage with little possibility of spread to lymph nodes. The reduced surgery includes endoscopic mucosal resection, laparoscopic local resection of the stomach, and the like, and the scale of the operation is decided according to the depth of the affected part. PA0 (2) For the gastric cancer that cannot be completely resected or with observed metastasis to lymph nodes, endoscopic chemotherapy is adopted for the purpose of extirpation of the affected lymph nodes. This method is medication for complete extirpation chiefly aiming at metastatic lesions in lymph nodes that are difficult to extirpate by surgical means. Drugs comprising a lymph-directed carrier, such as an emulsion, liposomes, or fine activated carbon powder, having included therein or adsorbed thereon an anticancer agent are used for the chemotherapy. The anticancer agents include 5-FU, adriamycin, mitomycin C, and so on. However, there is a possibility of occurrence of side effects, such as epilation, reduction of leucocytes, and internal organ disturbances. While it has been proposed to previously transduce a multidrug-resistant gene (MDR-1) into hematopoietic stem cells to endow the patient with resistant against chemotherapy, chemotherapy serves as nothing but preoperative auxiliary treatment for the time being.
Endoscopic mucosal resection (see Takemoto, T. et al., Digest Endosco., Vol. 1, No. 1, p. 4 (1989)) is a surgical treatment involving no laparotomy. Strip biopsy is widely performed as one embodiment of endoscopic mucosal resection, in which the lesion is lifted by submucous infusion of physiological saline and resected by means of a direct vision 2-channel scope. Strip biopsy is advantageous in that the time for an operation and anesthesia can be reduced and the amount of transfused blood is smaller than that needed in a standard surgical operation so that hepatic disorders can be minimized and the pain or burden on a patient can be alleviated. Although complete extirpation of the surrounding lymph nodes is difficult because the resectable area is limited, an increased capacity of the remaining stomach is secured, making it possible to improve the patient's postoperative quality of life (QOL). However, the cases to which strip biopsy is applicable are limited to those with protuberant tumors having a diameter of smaller than 2 cm and depressed tumors having a diameter of smaller than 1 cm.
For the management of larger lesions which should be removed by divided endoscopic mucosal resection and raise a possibility of increasing an incomplete resection ratio, laparoscopic local stomach resection (see Ohgami, M. et al., Dig. Surg., Vol. 11, pp. 64-67 (1994)) is effective. However, the gas in the stomach may escape through the possible perforation made for the resection. It may follow that the visual field is lost due to deflation of the stomach, which sometimes forces switch-over to laparotomy.
The above-mentioned reduced surgery gives rise to problems of occurrence of multiple cancer and carcinogenesis of the residual stomach and also involves a possibility of metastases. Therefore, care should be taken in resection not to bring the tumor tissue into contact with other tissues. Further, the target of the reduced surgery is a primary cancer that can be surgically resected with ease and accordingly is not expected to have effects on metastatic lesions in lymph nodes.
Anyway, the above-mentioned therapeutic methods differ in applicability, and there has not been established therapy aiming at a tumor site and surrounding lymph nodes at the same time.

Endoscopic administration of an HSV-tk gene to treat digestive organ cancer


The present invention pertains generally to the field of chemical synthesis, and more particularly to methods for the chemical synthesis of a thiosulfonic acid of Formula (1) by a step of periodate mediated oxidative coupling of a thiosulfonic acid of Formula (2) with an aniline of Formula (3), as described herein. The present invention also relates to such methods which incorporate one or more additional (subsequent and/or preceding) steps, for example, to prepare compounds of Formula (5) from compounds of Formula (1); to prepare compounds of Formula (6) from compounds of Formula (5); and to prepare compounds of Formula (2) from compounds of Formula (4), as described herein.

A number of publications are cited herein in order to more fully describe and disclose the invention and the state of the art to which the invention pertains. Each of these references is incorporated herein by reference in its entirety into the present disclosure, to the same extent as if each individual reference was specifically and individually indicated to be incorporated by reference.
Throughout this specification, including the claims which follow, unless the context requires otherwise, the word "comprise," and variations such as "comprises" and "comprising," will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
It must be noted that, as used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a pharmaceutical carrier" includes mixtures of two or more such carriers, and the like.
Ranges are often expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by the use of the antecedent "about," it will be understood that the particular value forms another embodiment.
This disclosure includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
Any sub-titles herein are included for convenience only, and are not to be construed as limiting the disclosure in any way.
Methylthioninium Chloride (MTC) (also known as Methylene Blue)
Methylthioninium Chloride (MTC) (also known as Methylene Blue (MB); methylthionine chloride; tetramethylthionine chloride; 3,7-bis(dimethylamino) phenothiazin-5-ium chloride; C.I. Basic Blue 9; tetramethylthionine chloride; 3,7-bis(dimethylamino) phenazathionium chloride; Swiss blue; C.I. 52015; C.I. Solvent Blue 8; aniline violet; and Urolene Blue®) is a low molecular weight (319.86), water soluble, tricyclic organic compound of the following formula:

Methylthioninium Chloride (MTC) (also known as Methylene Blue), perhaps the most well-known phenothiazine dye and redox indicator, has also been used as an optical probe of biophysical systems, as an intercalator in nanoporous materials, as a redox mediator, and in photoelectrochromic imaging.
See, for example, Colour Index (Vol. 4, 3rd edition, 1971) and Lillie et al., 1979, and references cited therein.
MTC is currently used to treat methemoglobinemia (a condition that occurs when the blood cannot deliver oxygen where it is needed in the body). MTC is also used as a medical dye (for example, to stain certain parts of the body before or during surgery); a diagnostic (for example, as an indicator dye to detect certain compounds present in urine); a mild urinary antiseptic; a stimulant to mucous surfaces; a treatment and preventative for kidney stones; and in the diagnosis and treatment of melanoma.
MTC has been used to treat malaria either singly (Guttmann & Ehrlich, 1891) or in combination with chloroquine (Schirmer et al. 2003; Rengelhausen et al. 2004). Malaria in humans is caused by one of four protozoan species of the genus Plasmodium: P. falciparum, P. vivax, P. ovale, or P. malariae. All species are transmitted by the bite of an infected female Anopheles mosquito. Occasionally, transmission occurs by blood transfusion, organ transplantation, needle-sharing, or congenitally from mother to fetus. Malaria causes 300-500 million infections worldwide and approximately 1 million deaths annually. Drug resistance, however is a major concern and is greatest for P. falciparum, the species that accounts for almost all malaria-related deaths. Drugs or drug combinations that are currently recommended for prophylaxis of malaria include chloroquine/proguanil hydrochloride, mefloquine, doxycycline and primaquine.
MTC (under the name Virostat, from Bioenvision Inc., New York) has shown potent viricidal activity in vitro. Specifically Virostat is effective against viruses such as HIV and West Nile Virus in laboratory tests. West Nile virus (WNV) is a potentially serious illness affecting the central nervous system. The large majority of infected people will show no visible symptoms or mild flu-like symptoms such as fever and headache. About one in 150 will develop severe symptoms including tremors, convulsions, muscle weakness, vision loss, numbness, paralysis or coma. Generally, WNV is spread by the bite of an infected mosquito, but can also spread through blood transfusions, organ transplants, breastfeeding or during pregnancy from mother to child. Virostat is also currently in clinical trials for the treatment of chronic Hepatitis C. Hepatitis C is a viral infection of the liver. The virus, HCV, is a major cause of acute hepatitis and chronic liver disease, including cirrhosis and liver cancer. HCV is spread primarily by direct contact with human blood. The major causes of HCV infection worldwide are use of unscreened blood transfusions, and re-use of needles and syringes that have not been adequately sterilized. The World Health Organization has declared hepatitis C a global health problem, with approximately 3% of the world's population infected with HCV and it varies considerably by region. The prevalence in the US is estimated at 1.3% or approximately 3.5 million people. Egypt contains the highest prevalence of hepatitis C in the world, estimated at over 20% of the nation's approximately 62 million people.
MTC, when combined with light, can prevent the replication of nucleic acid (DNA or RNA). Plasma, platelets and red blood cells do not contain nuclear DNA or RNA. When MTC is introduced into the blood components, it crosses bacterial cell walls or viral membrane then moves into the interior of the nucleic acid structure. When activated with light, the compounds then bind to the nucleic acid of the viral or bacterial pathogen, preventing replication of the DNA or RNA. Because MTC is designed to inactivate pathogens, it has the potential to reduce the risk of transmission of pathogens that would remain undetected by testing.
MTC and derivatives thereof (e.g., "diaminophenothiazinium compounds") have been found to be useful in the treatment of tauopathies (such as, for example, Alzheimer's disease) (see, for example, Wischik, C. M., et al., 1996, 2002).
Oral and parenteral formulations of MTC are commercially available in the United States, usually under the name Urolene Blue®. However, these formulations contain substantial amounts of metal impurities. These impurities are highly undesirable, and many (e.g., including Al, Cr, Fe, Cu) exceed the safety limits set by European health agencies.
Consequently, there is a great need for higher purity (e.g., pharmaceutical grade purity, e.g., a purity safe for human consumption, e.g., with low or reduced metal content) diaminophenothiazinium compounds, including MTC.
MTC was first described in a German Patent in 1877 (Badische Anilin- und Soda-Fabrik, 1877). In that patent, MTC was synthesized by nitrosylation of dimethylaniline, subsequent reduction to form N,N-dimethyl-1,4-diaminobenzene, and subsequent oxidative coupling in the presence of hydrogen sulphide (H2S) and iron(III) chloride (FeCl3).
Iron based oxidative coupling in the synthesis of MTC was more recently discussed in CN105130926.
Bernthsen described subsequent studies of MTC and methods for its synthesis (see Bernthsen, 1885a, 1885b, 1889).
Fierz-David and Blangley, 1949, also describes methods for the synthesis of MTC from dimethylaniline, as illustrated in the following scheme:

In step (a), nitrosodimethylaniline is prepared from dimethylaniline by treatment with nitrite (NaNO2) in aqueous acid (HCl) solution. In step (b), the nitroso compound is reduced to form p-aminodimethylaniline using additional aqueous acid (HCl) solution using zinc dust. The metal residue after step (b) is removed by filtration and the filtrate is oxidised in the presence of thiosulfonic acid, sulphuric acid and non-reducing zinc chloride solution, step (c).
Oxidation in the presence of dimethylaniline results in the thiosulfonic acid of Bindschedlers green, step (d). This oxidation is carried out using a dichromate based oxidising agent, Na2Cr2O7. The oxidation is then continued in the same reaction pot to provide MTC, step (e).
More specifically, a clear neutral solution of p-aminodimethylaniline is acidified (H2SO4), and a non-reducing zinc chloride solution is added (ZnCl2 with Na2Cr2O7). Aqueous aluminium sulphate (Al2(SO4)) and crystalline sodium thiosulphate (Na2S2O3) are added. Aqueous sodium dichromate (Na2Cr2O7) is added. The mixture is heated by dry steam. Aqueous acidic (HCl) dimthylaniline is then added. Aqueous sodium dichromate (Na2Cr2O7) is added. The mixture is heated with dry steam, and becomes dark greenish-blue in colour due to the formation of the thiosulfonic acid of Bindschedler green. An aqueous slurry of manganese dioxide or copper sulfate is added, and the mixture heated by dry steam, and the dye precipitates from the concentrated zinc chloride solution. To recover the dye from the mixture it is cooled and acidified (H2SO4) to dissolve the aluminium, manganese and chromium salts. The mixture is cooled further and the crude dye collected by filtration. Purification from water, sodium chloride and zinc chloride gives the zinc double salt of methylene blue as bronzy red crystals.
Very similar synthesis methods are described in the Colour Index (Vol. 4, 3rd edition, 1971), p. 4470.
U.S. Pat. No. 4,212,971 A and CN1970548 A describes the synthesis of MTC using manganese dioxide in the formation of the thiosulfonic acid intermediate and its subsequent oxidative coupling to the thiosulfonic acid of Bindshedler's green. The manganese dioxide is used in stoichiometric amounts in the synthesis.
Masuya et al., 1992, describe certain phenothiazine derivatives, and methods for their preparation and use in photodynamic therapy of cancer and in immunoassays utilizing chemiluminescence. The compounds are prepared by routes similar to those discussed above.
Leventis et al., 1997, describe methods for the synthesis of certain MTC analogs, which employ phenothiazine as a starting material and which add the desired 3,7-substituents by halogenation followed by amination. The authors assert that MTC is synthesized commercially by oxidation of N,N-dimethyl-p-phenylene diamine with Na2Cr2O7 in the presence of Na2S2O3, followed by further oxidation in the presence of N,N-dimethylamine.
Fierz-David et al., 1949, describes the synthesis of the zinc chloride double salt of MTC and the removal of zinc by chelation with sodium carbonate followed by filtration to generate zinc free methylene blue. However, the authors acknowledge that this technique cannot be used on a large scale, because the yields are poor.
WO 2006/032879 describes a method for synthesizing MTC via an oxidative coupling. The oxidative coupling is carried out according to the following scheme:

The oxidative coupling step is carried out using a dichromate oxidising agent, Na2Cr2O7. The oxidative coupling is discussed generally on page 23 line 35 to page 25 line 28 and in the examples from page 67 to 75, therein.
EP0510668 and EP0966957 describes a method for synthesizing derivatives of MTC via an oxidative coupling. The oxidative coupling is carried out using potassium dichromate or manganese dioxide.
WO2010/130977 describes a method for synthesizing MTC via an oxidative coupling. The oxidative coupling is carried out according to the following scheme:

The oxidative coupling step is carried out using a persulfate oxidising agent, Na2S2O8. A subsequent ring closure step is carried out using copper sulfate to provide MTC. This method provides MTC in 16% yield calculated over the two steps (oxidative coupling and ring closure) with 85% purity measured by HPLC peak area. The oxidative coupling is discussed generally on page 28 to page 33 and in the examples, see 'Synthesis 2', page 50 therein.
WO 2015/052496 also describes a method for synthesizing MTC via an oxidative coupling. The oxidative coupling is carried out according to the following scheme:

The oxidative coupling is carried out using a chromium based oxidising agent, Na2Cr2O7. In this method, the oxidative coupling step is combined with the previous step, thiosulfonic acid formation, into a one-pot chromium mediated reaction. The oxidative coupling is discussed generally on page 21 to page 33 and in the examples therein.
Improved Methods of Synthesis
It is generally desirable that chemical compounds which are intended to be used as pharmaceuticals are provided in a form that is sufficiently free of undesired impurities. This is especially true for chemical compounds that are intended to be used as part of long-term therapy, for example, daily administration for a period of months or years (or, indeed, indefinitely).
The presence of even relatively small amounts of certain undesirable impurities can render a chemical compound unacceptable for use in therapy, for example, accordingly the specifications set by national regulatory bodies (e.g., the US Food and Drug Administration, the European Medicines Agency, etc.).
Among the many undesired impurities are certain metals, including iron (Fe), manganese (Mn) and especially chromium (Cr). For example, the European Pharmacopoeia (version 8.6) limits the amount of residual manganese that may be present in pharmaceutical MTC to less than 10 ppm. It is often extremely difficult to remove these metal impurities from a chemical compound that has been prepared by a method of chemical synthesis which used them.
For example, a method of chemical synthesis which employs, as an oxidizing agent, a chromium compound (e.g., chromate, CrO42-; dichromate, Cr2O72-), a manganese compound (e.g., manganese dioxide, MnO2) and/or an iron compound (e.g., iron (III) chloride, FeCl3) often yields a product with residual chromium, manganese and/or iron, which cannot easily (or at all) be reduced to acceptable levels.
As discussed above, alkylthioninium salts (such as MTC) and derivatives thereof have utility in the long-term treatment of chronic conditions (such as Alzheimer's disease) and accordingly must be provided in a form with extremely low metal (including, e.g., chromium, manganese and iron) content.
Such compounds are conventionally prepared by methods of chemical synthesis which involve one or more oxidation steps which frequently use chromium, manganese and/or iron-based oxidizing agents. Consequently, the resulting product must undergo substantial purification in order to reduce the chromium and/or iron content to acceptable levels.
Accordingly, there is a need for alternative methods of chemical synthesis of such alkythioninium salts and their derivatives which avoid the need to use such metal-based (e.g., chromium-based) oxidizing agents and provide the products with high yields and purities.
The inventors have identified such methods, which are described herein. For example, alkythioninium salts of Formula (5) (such as MTC) can be prepared by methods described herein which avoid the use of chromium oxidizing agents.
More specifically, the methods described herein include the step of preparing a thiosulfonic acid of Formula (1) by a step of periodate mediated oxidative coupling of a thiosulfonic acid of Formula (2). The thiosulfonic acid of Formula (1) is then cyclized to give the corresponding thioninium compound of Formula (5).
Surprisingly and unexpectedly, the periodate mediated oxidative coupling described herein is successful and avoids the use of chromium oxidising agents. Furthermore, the periodate mediated coupling provides the desired compounds with improved yields and purity.
Consequently (and surprisingly and unexpectedly), compounds of Formula (5) can be obtained in good yield and purity without the use of chromium oxidizing agents, and thus with less need for further purification to remove residual chromium.

Synthesis of a thiosulfonic acid by a step of periodate mediated oxidative coupling of a thiosulfonic acid with an aniline


An apparatus and process for electronically measuring rotational characteristics of a rotating part that rotates with a crankshaft of an internal combustion engine. The rotating part has reference marks and measuring scale marks thereon. The apparatus includes a first pick up for detecting the passage of reference marks and a second pick up for detecting the passage of measuring scale marks. A counter connected to the second pick up counts the detected measuring scale marks. A timer controls the stage of the counter. A load sensor detects the load on the engine. A computer is connected to the first pick up, the counter, the timer, and the load sensor. The computer calculates the instantaneous rotational speed of the rotating part by differentiating the counts obtained during instantaneous counter stages. The computer includes decision logic with a predetermined threshold value. When the engine load is less than the predetermined threshold value, the computer measures the speed during at least several rotations of the rotating part. When the engine load is greater than the predetermined value or when the engine load is changing, the computer measures the number of rotations, the rotational speed or the change in rotational speed during a partial rotation of the rotating part.

1. Field of the Invention
This invention relates to an apparatus for an electronic measurement of the speed of internal combustion engines, comprising a computer, which serves to compute the speed and is connected to receiving means for detecting the passage of reference marks and of measuring scale graduations on a member which revolves with the crankshaft, and to a timer. This invention relates also to a method of operating such apparatus in monitoring an internal combustion engine.
2. Description of the Prior Art
Apparatuses of that kind are mainly used in combination with electronic control systems for metering the fuel, for determining the ignition timing and for performing other control measures for controlling the engine. The most important information for such control systems is the information on the instantaneous speed of the motor. In that connection the term "speed" may also be used to describe the angular or circumferential velocity during each revolution of the engine. Particularly in internal combustion engines having small flywheels, particularly in engines having a small volume and a small number of cylinders, that circumferential velocity varies relatively strongly as a result of the expansion of the combustion gases after the ignition and the compaction of the combustion gases before the ignition and the largest fluctuations occur when the speed is low and the load on the engine is high. Speed fluctuations over a plurality of revolutions may occur when the combustion is irregular or when the ignition and the fuel injection have intentionally been omitted during single revolutions. By means of the known apparatuses of the kind described first hereinbefore said fluctuations cannot be determined with sufficient accuracy so that the desired real-time control is adversely affected.
In known apparatuses of the kind described first hereinbefore the time of a revolution or the circumferential velocity of the crankshaft is detected for the speed measurement. In the first variant, a counter counting at a constant rate is basically provided and is controlled or read under the control of the reference marks provided on a rotating member so that the counter detects the repetition time of the reference marks. For the determination of the circumferential velocity, graduations which constitute a measuring scale are provided on the periphery of a member which rotates in unison with the crankshaft, e.g., on a very simple timing disk, and a timer is used to determine a gating time during which the graduations of the measuring scale moving past the receiver are counted. That count is proportional to the average circumferential velocity or angular velocity of the crankshaft but will not reflect the above-mentioned speed fluctuations over a plurality of revolutions so that such fluctuations cannot be evaluated.
Whereas it is known from DE-A-34 21 640 to store the measured values obtained during each revolution and to compare them with the measured values obtained during the next following revolution so that speed changes can thus be detected, the speed change is detected in that case only after it has taken place so that a control action cannot be taken in time.
From GB-B-2,198,241 it is known that inaccurancies in the pitch of graduations of a control disk or teeth of a control gear can be compensated in that correcting tables for the several graduations or teeth are stored in a computer, by which each measured-value signal generated during the passage of a mark or tooth is modified by a corresponding correcting signal so that the measurements will be taken in dependence on the corrected signals and will correspond to the measurements which would be obtained if the control disk or control gear had exactly the correct pitch. When the disks or gears are manufactured in series it will be assumed that the correcting values will also be the same so that the computer can be provided with fixedly programmed correcting tables.

Apparatus for electronically measuring the speed of internal combustion engines and method of operating such apparatus in monitoring an internal combustion engine


A puzzle solving aid in combination with a sudoku-type numerical puzzle. The puzzle solving aid (PSA) comprises a square or rectangular sheet having opaque or clouded portions at the four outer corners thereof and clear portions forming a vertical see-through column and a horizontal see-through row. The puzzle solving aid includes a central open area so a puzzle solver can pencil in the possible solution numbers for a particular space on a puzzle grid. A method of use related to puzzle solving and a business method for marketing a combined puzzle and puzzle solving aid are described.

The present invention is generally related to the game, puzzle and puzzle solving arts and, in particular, to a novel puzzle solving aid structure and method of use.
Sudoku-type puzzles have been used in the art for many years. The term "sudoku" is generic and broadly signifies number placement. Many different styles and configurations of sudoku-type puzzles are known in the art.
FIG. 1 shows a sudoku puzzle configuration which is widely used in the United States and internationally. It includes a nine-by-nine grid totaling eighty-one (81) spaces and is subdivided into nine boxes of nine spaces each.
The puzzle is presented by the puzzle creator to the puzzle solver in the format shown in FIG. 1, i.e. about 25 to 31 of the spaces are filled in by the puzzle creator. The solver must fill in the empty spaces using numerals 1-9 in the manner of sudoku play.
Various sudoku publications and puzzle books have described suggested methods of solving a sudoku puzzle. Such methods typically involve having the puzzle solver focus on a particular number or a particular area of the puzzle to begin a process of elimination and to thus make a tentative beginning regards solving the entire puzzle.
It is an object of the present invention to set forth a puzzle solving aid which is utilized to make a first pass through the entire puzzle and to quickly and easily list all of the possible solution numbers. Such listing is done, in pencil, on the puzzle by means of a central aperture on the puzzle solving aid.
It is also an object of the invention to show a method of sudoku puzzle solving in combination with a specially designed puzzle solving aid.
It is a further object to demonstrate a novel puzzle solving apparatus which may be economically manufactured for widespread commercial appeal.
It is a still further object of the overall invention to teach a unique business method in which a specially designed sudoku puzzle solving apparatus is marketed in combination with a sudoku puzzle book to promote ease of solution and consequent enhanced sales for the publication.
These and other objects and advantages of the described invention will be apparent to those of skill in the art from the description and drawings which follow.


A bipolar spin transistor is provided. In one embodiment of the present invention, the bipolar spin transistor includes a first semiconductor region having a first conductivity type, a second semiconductor region having a second conductivity type that is different from the first conductivity type and also having a spin polarization, and a third semiconductor region having a conductivity type that is the same conductivity type of the first semiconductor region. The first semiconductor region and the second semiconductor region are adjacent to each other so as to form a first charge depletion layer therebetween, the first charge depletion layer having a first side facing the first semiconductor region and an opposing second side facing the second semiconductor region. Additionally, the second semiconductor region and the third semiconductor region are adjacent to each other so as to form a second charge depletion layer therebetween, the second charge depletion layer having a first side facing the second semiconductor region and an opposing second side facing the third semiconductor region.

1. Field of the Invention
The present invention generally relates to a transistor. More particularly, the present invention relates to a bipolar transistor through a mechanism based on spin polarization.
2. Description of the Related Art
Most semiconductor devices are based on the p-n diode or the transistor. A large class of transistors are the so-called bipolar transistors consisting of back to back p-n diodes either in a p-n-p or n-p-n arrangement. By controlling the chemical potential of the middle region (called the base) the collector current (IC) can be varied, and IC depends on the base voltage (VEB) exponentially.
The development of transistors and its later evolution into the integrated circuit or microchip revolutionized people's daily life and the world. Continuous efforts have been made to find new types of diodes and transistors.
Until recently, the emerging field of magneto electronics has focused on magnetic metals for conducting components (hereinafter "[n]" referring to the nth reference in the attached list of references at the end of the specification). Multilayer magnetoelectronic devices, such as giant magnetoresistive ("GMR") and magnetic tunnel junction (MTJ) devices, have revolutionized magnetic sensor technology and hold promise for reprogrammable logic and nonvolatile memory applications. The performance of these devices improves as the spin polarization of the constituent material approaches 100%, and thus there are continuing efforts to find 100% spin-polarized conducting materials.
Doped magnetic semiconductors are a promising direction towards such materials, for the bandwidth of the occupied carrier states is narrow. For example, for nondegenerate carriers and a spin splitting of 100 meV the spin polarization will be 98% at room temperature. To date high-temperature (TCurie>100K) ferromagnetic semiconductors such as Ga1-x. Mnx, As are effectively p-doped. Semi-magnetic n-doped semiconductors like BeMnZnSe, however, have already been shown to be almost, 100% polarized (in the case of BeMnZnSe in a 2T external field at 30K). Both resonant tunneling diodes (RTDs) and light-emitting diodes (LEDs) have been demonstrated which incorporate one layer of ferromagnetic semiconductor. It is inevitable that devices incorporating multiple layers of ferromagnetic semiconducting material will be constructed. Note that "ferromagnetic semiconducting material" or "ferromagnetic semiconductor" as used in this specification includes any magnetic and semi-magnetic semiconductors that is a semiconductor and has a spin polarization, which can be affected by or interact with a magnetic field.
Previous research efforts have been directed to the transport properties of specific device geometries based on multilayers of spin-polarized unipolar doped semiconductors, including spin transport in homogeneous semiconductors and calculations of spin filtering effects in superlattices. Reference is made to commonly assigned U.S. patent application Ser. No. 10/014,925 and its entire contents are hereby incorporated by reference thereto into the present patent application.
One motivation for semiconductor spin electronics has been the seminal suggestion of Datta and Das of a "spin transistor". A burst of recent activity demonstrating controllable fabrication of ferromagnetic semiconductors and their incorporation into heterostructures has led to several additional device suggestions. These include a "spin filter", "spin-RTD", "unipolar spin transistor", "magnetic Zener tunnel diode", and "magnetic p-n diode". At the same time, progress on the problem of spin injection into nonmagnetic semiconductors has been reported, both from magnetic semiconductors and from magnetic metals. Hybrid transistor devices incorporating both semiconductors and ferromagnets, such as the spin-valve transistor, have demonstrated magnetoresistances exceeding 300%, but suffer from low efficiency for current transport through the base to the collector. Additional hybrid systems are also under development.

Bipolar spin transistors and the applications of the same