The present invention relates to a process for preparing the hexanoic acid, 6-(nitrooxy)-, (1S,2E)-3-[(1R,2R,3S,5R)-2-[(2Z)-7-(ethylamino)-7-oxo-2-hepten-1-yl]-3,5-dihydroxycyclopentyl]-1-(2-phenylethyl)-2-propen-1-yl ester of formula (I).

Hexanoic acid, 6-(nitrooxy)-, (1S,2E)-3-[(1R,2R,3S,5R)-2-[(2Z)-7-(ethylamino)-7-oxo-2-hepten-1-yl]-3,5-dihydroxycyclopentyl]-1-(2-phenylethyl)-2-propen-1-yl ester of formula (I)

is a prostaglandin analogue that has proved effective as IOP-lowering agent (Impagnatiello F, Toris C B, Batugo M, Prasanna G, Borghi V, Bastia E, Ongini E, Krauss A H P; Invest Ophthalmol Vis Sci. 2015; 56:6558-64).
A process for preparing compound of formula (I) is disclosed in WO 2009/136281.
WO 2009/136281 specifically discloses the synthesis of compound (I) and in general the preparation of 15-alkyl nitrate esters of bimatoprost.
WO 2009/136281 discloses the synthesis of compound of formula (I) (Example B-1) by reacting bimatoprost in a boronate protected form (compound of formula (II)) with 6-bromohexanoyl chloride to give the 15-(6-bromohexanoyl) ester of bimatoprost in a boronate protected form (compound of formula (VIII)) that is converted into the nitrate derivative by silver nitrate in acetonitrile and deprotected/purified under reverse phase chromatography yielding compound of formula (I).

The main disadvantages of the above synthesis are the use in the esterification reaction of more than an equimolar amount of 6-bromohexanoyl chloride, which presents a structural alert for potential mutagenicity, and, in the last step, the use of silver nitrate that generates a large amount of silver salts in wastewater. Another main disadvantage of this process is the formation of impurities and by products such as 15-(6-bromohexanoyl) ester of bimatoprost (compound (IX)) and 15-(6-chlorohexanoyl) ester of bimatoprost (compound (X)) which are difficult to be removed even after multiple purifications, as they have similar polarity in chromatography, similar lipophilicity and/or solubility as those of compound (I).

According to the procedure disclosed in WO 2009/136281, 15-(6-bromohexanoyl) ester of bimatoprost (compound (IX)) is an impurity deriving from uncompleted reaction of compound (VIII) with silver nitrate, after removal of the boronate protection. 15-(6-Chlorohexanoyl) ester of bimatoprost (compound (X)) is a by-product formed by halogen exchange reaction between the bromine atom of 15-(6-bromohexanoyl) ester of bimatoprost in a boronate protected form (compound (VIII)) and the free chlorine anion of 4-dimethylaminopyridine hydrochloride formed during the esterification step. The 15-(6-chlorohexanoyl) ester of bimatoprost in a boronate protected form (VIIIa) (FIG. 3—Scheme 3) does not react with silver nitrate and, after removal of the protective group, yields compound (X).
WO 2009/136281 also discloses an alternative process for the preparation of 15-acylalkynitrate bimatoprost derivatives (Examples N-1 and O-1). The synthesis comprises reacting bimatoprost in a boronate protected form (compound of formula (II)) with a nitrate-alkyl carboxylic acid chloride in the presence of 4-dimethylaminopyridine (DMAP) supported on resin (PS-DMAP), followed by removal of the boronate protecting group and purification using silica gel chromatography.
The above process avoids the use of 6-bromohexanoyl chloride and the removal of the silver salts from the final product. However, this method presents another main disadvantage that is the use of 4-dimethylaminopyridine supported on resin which makes the process unsuitable for commercial scale-up and expensive. Furthermore, nitrate-alkyl carboxylic acid chloride is added in two successive steps and in high excess with respect to compound of formula (II), indeed the alkyl carboxylic acid chloride is added in an amount from about 2 to 4 equivalents.
WO 2009/136281 also discloses another process (Examples Q1) for the preparation of 15-acylalkynitrate bimatoprost derivatives. In this process the compounds were obtained by esterification of bimatoprost in a boronate protected form (II) with an excess of nitrate-alkyl-(p-nitrophenyl)-carboxylate in the presence of 4-dimethylaminopyridine.
The removal of the unreacted nitrate-alkyl-(p-nitrophenyl)-carboxylate and of the by-product p-nitrophenol, formed in equimolar amounts to compound of formula (I), using chromatography methods are the main disadvantages of this process.
WO 2016/155906 discloses 15-nitrooxyderivatives of fluprostenol and it reports the synthesis of the 15-nitrooxy-hexyl ester of fluprostenol isopropyl ester. The compound was prepared by reacting fluprostenol isopropyl ester in a boronate protected form with (4-nitrophenyl)-6-nitrooxyhexanoate in the presence of 4-dimethylaminopyridineexcess.
As reported above the removal of the unreacted nitrate-alkyl-(p-nitrophenyl)-carboxylate and, especially, the removal of the p-nitrophenol by-product by chromatography methods are the main disadvantages of this process.
In the past few years various regulatory authorities have been emphasizing on the purity requirements and the identification of impurities in the Active Pharmaceutical Ingredients (API). Currently, any impurity is considered as an organic material, besides the drug substance, that may influence the efficacy and safety of the pharmaceutical products. Therefore the identification of each impurity and the quantification of the impurities, especially those bearing structural alert for mutagenicity, have become a mandatory regulatory requirements. In addition, since the products are intended for pharmaceutical use, the range of industrially acceptable reagents, solvents, catalysts, etc. which can be used in the synthesis of the active ingredient is limited to those having pharmaceutical industry acceptability.
The compound of formula (I) is an oil and its purification in large scale quantities is difficult as it cannot be crystallized, therefore the presence of impurities is a critical issue for a large scale production. Since the main sources of impurities are the intermediates and the by-products of the synthesis, the purity of the intermediates and the control of the reactions conditions are important requirements for obtaining the final product having a pharmaceutical acceptable purity.
The prior art processes for the preparation of compound of formula (I) have some disadvantages; e.g. the use of bromohexanoyl chloride and the reaction conditions lead to the formation of the by-product 15-(6-chlorohexanoyl) ester of bimatoprost (compound (X)) that has a structural alert for potential mutagenicity; the use of silver nitrate for the preparation of the intermediate nitrate-alkyl carboxylic acid chloride or for the nitration of the 15-(6-bromohexanoyl) ester of bimatoprost in a boronate protected form (compound (VIII)) lead to the management of a large amount of silver nitrate wastewater, moreover metal content in the Active Pharmaceutical Ingredients must satisfy specific acceptance criterion.
Thus there is a need to provide compound of formula (I)) with high purity and in a good yield.
It has been found that compound of formula (I) can be prepared with high purity by using the 6-(nitrooxy)hexanoyl chloride intermediate efficiently prepared by ring-opening reaction of caprolactone followed by nitration.
The present invention provides a large scale production process that provides compound of formula (I) having a high chemical purity and, in particular, with a content of the 15-(6-chlorohexanoyl) ester of bimatoprost impurity below the safety level.

Process for the preparation of a nitric oxide donating prostaglandin analogue

Abstract: In accordance with the present invention, the compound (I) can be efficiently prepared with high purity by coupling bimatoprost in a boronate protected form with 6-(nitrooxy)hexanoyl chloride and removing the boronate protecting group.

Abstract: The 6-(nitrooxy)hexanoyl chloride intermediate is prepared by ring-opening reaction of 2-caprolactone and subsequent nitration of the 6-hydroxyhexanoic acid potassium salt with a mixture of HNO3 and H2SO4 in dichloromethane.


Disclosed is a method for fabricating a semiconductor device which prevents generation of imperfections in an aluminum alloy as an upper wiring even when part of a refractory metal pillar, which fills in a contact hole connecting lower and upper wiring layers, is exposed due to displacement of the upper wiring layer. The method comprises forming a third insulation film, a second insulation film and a second wiring layer, on a first wiring layer, forming holes which extend to the first wiring layer therethrough, forming refractory metal pillars by filling in the holes with a refractory metals, and forming a fourth insulation film. The second wiring layer is formed within a groove formed by removing the third and fourth insulation films to expose top and side surfaces of the refractory metal pillar. Even when displacement is caused between the refractory metal pillar and the second wiring layer, the reliability does not decrease, since the refractory metal pillars are covered with the fourth insulation film. The second wiring layer is preferably formed by polishing.

1. Field of the Invention
The present invention relates to a method for fabricating a semiconductor device, and more particularly to a method of fabricating a semiconductor device which comprises a high-melting point refractory metal pillar to connect between a device element and a wiring or between wirings.
2. Description of the Related Art
In conventional semiconductor devices, contact holes for connecting between the semiconductor device elements and the wirings, and via holes for mutual connection between upper and lower wirings are designed with the widths of the wirings larger than the diameters of those contact holes and via holes in consideration of misalignment displacement between the devices and the wirings, or between the wirings, so that the wirings do not miss the holes due to the wide margin even when such displacement is caused, thereby ensuring electrical connection. However, with the increase in the degree of integration of semiconductor devices, the contact holes and via holes have become more and more minuscule, and the above-mentioned displacement margin, i.e., the difference in size of the holes and the wirings is being diminished accordingly, and is recently closing in to almost zero.
In addition, although the diameters of the contact holes and the via holes have been reduced, their depths remain unchanged, and this naturally results in increased aspect ratios (the dept/diameter ratios of the holes) which cause poor coverage with aluminum formed by the conventional sputtering methods. As a result, the problem has arisen that the connection resistance is increased and the wirings tend to be disconnected. For these reasons, it is presently usual to fill in such holes with tungsten (W) formed by chemical vapor deposition (CVD) which exhibits excellent covering properties. When no positioning margins are provided between the holes and the wirings, and when the holes are filled in with tungsten pillars, however, the areas of connection between the tungsten and the wirings are reduced if displacement is caused during formation of the upper wirings. This leads to increased connection resistance, as well as an additional problem of increased tendency for the connection resistance to increase due to electro-migration. These problems are described in, for example, in an article titled "The Dependence of Electromigration Endurance on Contact Area in W-Viahole", Abstract No. 19a-ZD-4, in Extended Abstracts (The Autumn Meeting, 1994) of the Japan Society of Applied Physics.
Therefore, in order to reduce the connection resistance between the hole-filling tungsten pillars and the upper wirings, it has been suggested to provide the tungsten pillars with portions protruding above the holes to obtain additional connections with the sides of the tungsten pillars to thereby lower the resistance (see for example, Japanese Unexamined Patent Application Disclosure (KOKAI) HEI 5-311394). With such a structure in which the tungsten pillars protrude through the holes, the heights of the protrusions of the tungsten pillars through the holes must be appropriately controlled. As a method for the control, there has been suggested a method in which: an interlayer insulation film is first formed of two insulation films with different etch rates, a hole is made through the films, the hole is filled in with a conductor, and the upper insulation film is etched off under such conditions that the etch rate of the upper insulation film is higher than the etch rate of the lower insulation film (see, for example Japanese Unexamined Patent Application Disclosure (KOKAI) HEI 5-318939).
An example of the formation of such a contact hole will now be described with reference to FIG. 7. First, as illustrated in FIG. 7(a), a silicon oxide film 32 and a silicon nitride film 33 are successively formed on a device-formed silicon substrate 31 by CVD. The film thickness of the silicon oxide film 32 is set to a necessary amount to provide insulation between the silicon substrate 31 and the wiring layer, and the film thickness of the silicon nitride film 33 is set to be the same as the height of protrusion of the conductor pillar through the contact hole. A contact hole which extends to the silicon substrate 31 is then made through the silicon nitride film 33 and the silicon oxide film 32 by conventional lithography and reactive ion etching. Thereafter, titanium 34 and titanium nitride 35 are successively laminated by sputtering, and then, tungsten 36 is grown by low pressure chemical vapor deposition (LPCVD) to a film thickness greater than or equal to the radius of the contact hole so as to fill in the contact hole with the tungsten.
Then, as illustrated in FIG. 7(b), the entire surface of the tungsten 36 is etched by reactive ion etching until the titanium nitride 35 is exposed, and the entire surfaces of the titanium nitride 35 and the titanium 34 are then etched by reactive ion etching as well until the silicon nitride film 33 is exposed, thereby forming a pillar of tungsten 36 left only in the contact hole.
The silicon nitride film 33 is then removed by plasma etching so that the pillar of the tungsten 36 protrudes through the contact hole, as illustrated in FIG. 7(c). The height of the protrusion of the pillar of the tungsten 36 through the contact hole is made to be the same as the thickness of the silicon nitride film 33.
Thereafter, as illustrated in FIG. 7(d), an aluminum alloy 37 is formed by sputtering, and the aluminum alloy 37 is then patterned into a desired configuration by conventional lithography and dry etching, to form an aluminum wiring. With the configuration of the contact hole made in this way, therefore, the connection with the aluminum alloy is ensured at both the top surface of the pillar of the tungsten 36 and the side of the protrusion to thereby prevent increase in the electrical resistance.
However, when the positioning margin between the contact hole and the aluminum wiring is small, the displacement causes exposure of some portions of the tungsten 36. This has presented the following problems. A first problem is that the exposure of the tungsten causes generation of defects in portions of the aluminum alloy located near the exposed portions of the tungsten, and thus reliability of the device is decreased. This is because aluminum and tungsten have different ionization tendencies, thus causing the aluminum to be dissolved due to a local battery cell effect generated during water rinsing procedures after the aluminum alloy has been etched.
A second problem involves difficulties associated with planarization of the interlayer insulation film formed on the aluminum wiring and difficulty in establishing connection through the via hole penetrating the interlayer insulation film. This is because the wiring layer on the contact hole section is elevated by the height of the protrusion through the contact hole making it difficult to form a flat interlayer insulation film 38 overlying the entire wiring layer, particularly when two or more contact holes are located close to each other under the wiring layer, as illustrated in FIG. 8(a), in which case a cavity is formed between the wirings causing the reliability of the device to decrease. In addition, since planarization of the interlayer insulation film 38 results in the portion of the interlayer insulation film 38 other than the portion over the contact hole to have a greater thickness, corresponding to the height of the tungsten pillar 36 protrusion than required, that a via hole formed on such a portion has a correspondingly increased depth than actually necessary.

Method for fabricating a semiconductor device having a refractory metal pillar for electrical connection


The present technique includes a case member of a body and a supporting mechanism. The case member of a body includes a holding compartment having a shaft support at one end of the holding compartment. The supporting mechanism is receivable in the holding compartment of the case member and holds a display monitor. The supporting mechanism includes a first supporting member and a second supporting member, the first supporting member having, at a first end, a pivoting portion pivotally supported on the shaft support of the holding compartment, and a shaft support at a second end, and the second supporting member having a pivoting portion pivotally supported on the shaft support of the first supporting member. The supporting mechanism is configured to move the shaft support of the first supporting member and the pivoting portion of the second supporting member in an extrusion direction from the holding compartment.

1. Field of the Invention
The present technique relates to an electronic device such as a digital camera with a rotatable display unit.
2. Description of the Related Art
Unexamined Japanese Patent Publication No. 2001-333298 discloses an electronic device such as a digital camera with a display monitor rotatable relative to its body.

PANASONIC INTELLECTUAL PROPERTY MANAGEMENT CO., LTD.


A gaming machine, having a display unit that displays a game image for use in a game, including: an image data storage unit that stores common image data that is common to user countries in which the gaming machine is used and individual image data that differ from user country to user country; and a position changing unit that changes the display position of the game image displayed on the display unit, on a per user country basis, using the common image data and the individual image data, stored in the image data storage unit.

1. Field of the Invention
The present invention relates to a gaming machine which includes a display unit that displays an image for use in a game, such as a liquid crystal display device, and in which the game proceeds using the image displayed on the display unit.
2. Description of the Related Art
Conventionally, there is a gaming machine which includes a display unit that displays an image for use in a game (a game image), such as a liquid crystal display device, and in which the game proceeds using the image displayed on the display unit. As the gaming machine of this type, for example, there are the following gaming machines: a gaming machine that is operated by a player to rotate or scroll reels (hereinafter called "pseudo-reels") displayed as images on the liquid crystal display device, thus performing variable display (which gaming machine is a so-called video slot machine), and a gaming machine such that card images showing cards are displayed and, in accordance with player's operational entry, display of the card images is changed to allow a game to proceed (which gaming machine is also called a card gaming machine). In the video slot machine out of these gaming machines, winning or losing of the game and a mode in which the game is won (winning mode) are determined from a combination of symbols (hereinafter called a "symbol combination") falling on a predetermined valid line (pay line) when the reels are stopped, and payout of media for use in the game, such as medals and coins, (hereinafter called "coins") is performed in response to the winning mode.
For example, JP-A-2002-537874 discloses a gaming machine capable of performing a video simulation as rotating reels are displayed on a display unit.
As in the aforesaid conventional gaming machines, a gaming machine, which includes a display unit that displays a game image and in which a game proceeds using the game image displayed on the display unit, is in most cases configured such that image data for displaying the game image is stored in a storage unit such as an image ROM and is read therefrom to display the game image on the display unit.
However, because of the regulations of a country in which to install and use the gaming machine, laws, rules and the needs of the market, the specification (mainly the layout) of the image game sometimes varies from country to country, in which case there is the following problem. That is, it is required that the gaming machines of this type be broken out according to country in which to use them (hereinafter called "user countries", e.g., the United States and Australia) and that image data that meets the specification of each user country be generated and stored into the storage unit for each of the gaming machines. In other words, an each country's individualized response is required, such that image data are generated and stored according to different specifications for different countries, which contributes to the requirement of time and cost to develop the gaming machine.
Besides, there is a need of, on the one hand, an individualized response not only for each country but also for each state, province, district, etc. and, on the other hand, an individualized response for each month, season, year, etc.


A financial methodology for examining, explaining and predicting the spread between analyst targets and stock prices, by analyzing how investor confidence is impacted by media coverage and correlating this to the spread. The methodology is based on a quantitative approach suitable for numerical processing. It measures the confidence along several categories, and allows for industry benchmarking.

Just in the United States, more than 80 million people invest and speculate in the shares of thousands of publicly traded companies and in many other financial instruments. The day to day price of a given instrument is essentially a manifestation of the investors' (or sellers, brokers, advisors and other market participants') confidence in the future financial performance of a company or the price of a commodity.
Equity investors obtain some information directly from the listed corporations, perhaps through corporate websites, conference calls or mail. However, tight regulatory restrictions regarding shareholder communication and the obvious need for unbiased opinion mean that investors rely chiefly on indirect channels, principally financial analysts and media.
Analysts employ numerically based models of the commodities or businesses they track, including the associated industry and economic parameters. They must weigh up different factors, pulling in different directions, to arrive at buy/sell recommendations and price targets/fair price estimates.

Financial methodology for the examination and explanation of spread between analyst targets and market share prices


The invention provides for a medical instrument (100, 300, 400) comprising: a memory (110) for storing machine executable instructions (112) and a processor (106) for controlling the medical instrument. Execution of the machine executable instructions cause the processor to: receive (200) three dimensional medical image data (114) descriptive of a subject (318), wherein the three dimensional medical image data comprises voxels; receive (202) a segmentation of the three dimensional medical image data, wherein the segmentation divides the three dimensional image data into non-tumor voxels (700) and tumor voxels (500); choose (204) a center point (118) of the tumor voxels; divide (206) the tumor voxels into multiple groups (120) using a set of orthogonal planes (502, 504, 600), wherein the center point is within each of the orthogonal planes; calculate (208) at least one group radiomic feature (122) selected from a set of radiomic features for each of the multiple voxel groups; compute (210) a statistical measure (124) for each of the at least one group radiomic feature; calculate (212) a scalar value (128) by calculating the sum of each statistical measure multiplied by a predetermined group weighting value (126), wherein the predetermined group weighting value is unique for each statistical measure; and provide (214) a signal using a signaling interface device (108, 402) if the scalar value is above a predetermined threshold (130).

Medical imaging techniques such as magnetic resonance imaging (MRI), positron emission tomography (PET), single photon emission computed tomography (SPECT), and other are effective in quantitatively mapping the internal structure of a subject. A knowledge of tumor heterogeneity on the molecular level (e.g. heterogeneity in terms of tumor pathways) would be useful for therapy planning. Multiple biopsies would provide this type of information, but are inconvenient for the patient, and impose some risks.
United Stated patent application US 2016/0260224 discloses a method for analyzing three-dimensional image data of a target region of a subject, the method comprising identifying a region of interest within the target region containing imaging information predictive of a disease state of the target region, calculating at least two radiomic features associated with the region of interest, and classifying the region of interest based on the calculated radiomic features.


A high temperature molten salt thermal cell is provided including an alkali etal containing anode, a molten lithium halide electrolyte and at least one binary sulfide of chromium as the cathode.

High temperature molten salt thermal cells have been required for applications in fuses, projectile rockets, bombs, missiles, decoys, jammers, and torpedos. Amongst the many molten salt thermal cell systems that have been studied over the past many years, the lithium alloy/metal sulfide cells have shown considerable promise for these applications. In the past, these cells have used a lithium alloy (Li-A1) as the anode, an electrolyte including a lithium halide-alkali halide mixture (LiCl-KCl) eutectic and a cathode having as the cathode active material a binary metal sulfide of the general formula YS or YS.sub.2 where Y=Fe, Co or Ni. Though the use of these cathode materials has been generally satisfactory, it would be desirable to obtain cathode material that can deliver even higher energy densities at high temperatures.

The United States of America as represented by the Secretary of the Army


Apparatuses, methods, and systems are disclosed for a spacer for a manufactured structure. A spacer includes a plurality of legs where each leg includes an elongate member that extends from a proximal end to a distal end. The proximal end of each leg is connected to one another at a central point such that the legs are spaced radially about the central point and substantially equidistant from one another. The distal ends of the legs include a material that has a predefined melting point such that the distal ends attach to a surface in contact with the distal ends responsive to the predefined melting point being reached during a molding process.

Manufactured structures with relatively large areas defining internal voids can suffer from instability. Attempts to stabilize these sections of manufactured structures include void-spanning or gap-spanning formations. In molded structures, "kiss-offs" are created which are points formed in the structure at which the surface is deformed to bridge a separation between two portions through the void and create contact between opposite portions or sides of the structure. In implementing stabilization approaches, the opposite portions of the manufactured structure cannot be truly flat as the kiss-offs or other deformations result in depressions, pits, rises, or other irregularities in the surface of the structure and provide only a singular point of contact at each kiss-off or other connection.


A positive resist composition capable of forming a resist pattern having excellent shape is provided. This composition is a positive resist composition including a base resin component (A) and an acid generator component (B) generating an acid under exposure, which are dissolved in an organic solvent, wherein the base resin component (A) is a silicone resin, and the organic solvent contains propylene glycol monomethyl ether (x1) and a solvent (S2) having a boiling point higher than that of the propylene glycol monomethyl ether.

1. Field of the Invention
The present invention relates to a positive resist composition.
This application claims priority from Japanese Patent Application No. 2004-98184 filed on Mar. 30, 2004, the disclosure of which is incorporated by reference herein.
2. Description of the Related Art
In the production of semiconductor devices and light crystal display devices, fine working has rapidly advanced, recently with progress in lithography techniques. A light source having a shorter wavelength is generally employed for fine working. Specifically, ultraviolet rays typified by g-rays and i-rays have conventionally been used, but now KrF excimer laser (248 nm) and ArF excimer laser (193 nm) have been introduced.
As one of the resist materials which satisfy the conditions of high definition capable of reproducing a pattern having a fine size, for example, there is known a chemically amplified resist composition comprising a base resin and an acid generator generating an acid under exposure, which are dissolved in an organic solvent, wherein alkali solubility changes due to an action of an acid generated from the acid generator.
As the base resin component of the chemically amplified resist, for example, there can be used polyhydroxystyrene (PHS) having high transparency to KrF excimer laser (248 nm), PHS resin wherein a portion of hydroxyl groups of PHS are protected with an acid dissociable dissolution inhibiting group and a copolymer derived from a (meth)acrylate ester. As the acid generator, for example, onium salt-based acid generators such as iodonium salt and sulfonium salt are now used most popularly.
As the organic solvent, for example, propylene glycol monomethyl ether acetate (which hereinafter referred to as PGMEA), ethyl lactate (which hereinafter referred to as EL), methyl amyl ketone (which hereinafter referred to as MAK) and propylene glycol monomethyl ether (which hereinafter referred to as PGME) are used alone or in combination. However, when these solvents are used alone, there arise a problem that a base resin may be agglomerated in a resist composition.
As the solvent mixture, a solvent mixture of PGMEA and EL (which hereinafter referred to as EM) is used most popularly because it is excellent in the effect of inhibiting agglomeration of the base resin (see, for example, Patent Document 1). It is considered that the effect of inhibiting agglomeration of the base resin in the solvent mixture such as EM is exerted because polarity of the entire organic solvent changes by mixing two kinds of solvents having different polarities.
As a method capable of forming a resist pattern having a high aspect ratio with high resolution, for example, a two-layer resist method using a chemically amplified resist has been proposed (see, for example, Patent Documents 2 and 3). According to this method, an organic film as a lower resist layer is formed on a substrate and then an upper resist layer is formed thereon using a chemically amplified resist containing a silicone resin as a base resin. After forming a resist pattern on the upper resist layer by a photolithography technique, the resist pattern is transferred to the lower resist layer by etching using the resist pattern as a mask to form a resist pattern having a high aspect ratio.
Patent Document 1: Japanese Patent Application, First Publication No. 2003-167364
Patent Document 2: Japanese Patent Application, First Publication No. Hei 6-202338
Patent Document 3: Japanese Patent Application, First Publication No. Hei 8-29987
However, when the resist pattern is formed by using the chemically amplified resist containing the silicone resin, there arise problems such as line width roughness (LWR) wherein the upper portion of the resist pattern has roundness and the line pattern has non-uniform line width, and line edge roughness (LER) wherein the side wall of the line pattern has irregular surfaces, and thus the resulting pattern has poor shape. With the recent increase of demand for high definition, it becomes important to solve the problems of the shape such as LWR and LER.


A lens barrel includes a movable frame for holding an optical system, a fixed drum for supporting the movable frame so as to be movable in the direction of an optical axis, and a cam drum for moving the movable frame, wherein the movable frame is movably disposed between the fixed drum and the cam drum, and an outer peripheral portion of the fixed drum is provided with a support portion, penetrating through the movable frame, for rotatably supporting the cam drum.

1. Field of the Invention
The present invention relates to a lens barrel having a structure for moving a lens unit with a predetermined quantity by use of a cam ring when in focusing and in zooming as well.
2. Related Background Arts
A conventional lens barrel includes a movable frame holding a focusing lens unit and moving an optical-axis direction, a fixed drum for supporting this movable frame so as to be movable in the direction of the optical axis, and a cam ring for giving a driving force for moving the movable frame. According to this type of lens barrel, when in such an optical system that a moving quantity of the focusing lens unit which quantity is needed for focusing up to a closest focusing distance is comparatively small, the cam ring can be fitted to the fixed drum while securing a sufficient length in the direction of the optical axis and can be therefore held on the fixed drum with a stability.
According to a lens barrel having a large maximum photographing magnification and therefore capable of executing, e.g., a close-up photography, however, when in such an optical system that the moving quantity of the focusing lens unit which is required for focusing up to the closest focusing distance is large, the movable frame for holding the focusing lens unit and the cam ring for moving the focusing lens unit, become elongate in the direction of the optical axis. Therefore, in the same positional relationship, the movable frame requires a space having a considerable length in the direction of the optical axis, and the cam ring can not be fitted to the fixed drum while securing the sufficient length in the direction of the optical axis, resulting in such a problem that the cam ring is stably held on the fixed drum with a difficulty.


This invention relates to a method of manufacturing a martensitic stainless steel.

A martensitic stainless steel that is excellent in the mechanical strengths such as a yield strength, a tensile strength and a toughness is also excellent in corrosion resistance and heat resistance. Among the martensitic stainless steels, a martensitic stainless steel containing about 13% Cr, such as 420 steel in AISI (American Iron and Steel Institute), is excellent in corrosion resistance especially under an environment exposed to carbon dioxide gas. The martensitic stainless steel containing about 13% Cr is generally called as "13% Cr steel".
However, this 13% Cr steel has a lower maximum temperature that is applicable for practical use. Therefore, exceeding the lower maximum temperature gives a less corrosion resistance, which may result in restricting the applicable field of use of this 13% Cr steel.
In this context, another martensitic stainless steel has been improved by adding an Ni element to the 13% Cr steel. This improved martensitic stainless steel is generally called as "super 13Cr steel". The improved martensitic stainless steel has not only higher mechanical strength such as a yield strength, but also better corrosion resistance for hydrogen sulfide, as compared with the 13% Cr steel. Then, this super 13Cr steel is particularly suitable for an oil well tube in an environment containing a hydrogen sulfide.
In manufacturing the improved martensitic stainless steel, a method has been adopted in order to induce a martensite transformation during quenching the steel from a temperature of not less than the AC3 point, followed by tempering. Excessive high mechanical strength is not preferable because higher mechanical strength steel is more susceptible for a sulfide stress cracking. The quenching leads to a martensite structured steel having an excessively high strength, but the subsequent tempering adjusts it to a structured steel that has the desired mechanical strength.
Several methods of manufacturing a martensitic stainless steel in which tempering process was improved to adjust mechanical strength are disclosed as described below.
Japanese Patent Unexamined Publication Nos. 2000-160300 and 2000-178692 disclose a method of manufacturing a high Cr alloy with a low carbon for oil well tube, which has an improved corrosion resistance or stress corrosion cracking resistance with 655 N/mm2 (655 MPa) grade yield strength. The method is as follows: heat treatment of austenitizing, cooling, first tempering at a temperature not less than AC1 point and not more than AC3 point, cooling, and second tempering at a temperature that is not less than 550° C. and not more than AC1 point.
Also, Japanese Patent Unexamined Publication No. H08-260050 discloses a method of manufacturing a martensitic stainless steel seamless steel tube, in which a steel is tempered at a temperature that is not less than AC1 point and not more than AC3 point, and then cooled in order to perform a cold working so that the steel is adjusted to have a desired yield stress.

Method of manufacturing a martensitic stainless steel

Abstract: The method comprises the following steps (a) to (c):    (a) preparing a steel having a chemical composition consisting of, by mass %, C: 0.003 to 0.050%, Si: 0.05 to 1.00%, Mn: 0.10 to 1.50%, Cr: 10.5 to 14.0%, Ni: 1.5 to 7.0%, V: 0.02 to 0.20%, N: 0.003 to 0.070%, Ti: not more than 0.300% and the balance Fe and impurities, and P and S among impurities are not more than 0.035% and not more than 0.010% respectively, and that it also satisfies the following equation:([Ti]−3.4×[N])/[C]>4.5wherein [C], [N] and [Ti] mean the content (mass %) of C, N and Ti, respectively,    (b) heating the steel at a temperature between 850 and 950° C.,    (c) quenching the steel, and    (d) tempering the steel at a temperature between Ac1−35° C. and Ac1+35° C. and in a condition of not more than 0.5 of the value of variation ΔLMP1 in the softening characteristics LMP1, which is defined by the following equation:LMP1=T×(20+1.7×log(t))×10−3 wherein T is a tempering temperature (K), and t is a tempering time (hour).

Abstract: The steel could further contain 0.2 to 0.3 % of Mo.


A method of biologically producing an aromatic carboxylic acid by contacting a substrate containing an aromatic carboxylic acid having a para-hydroxy group with a biocatalyst that removes the para-hydroxy group.

Field of the Invention
The present invention relates to the biological production of aromatic carboxylic acid and its derivatives. More particularly, the present invention relates to a process of biologically producing aromatic carboxylic acid and its derivatives by degrading lignin through chemical or biological conversion and biologically converting the lignin breakdown product into aromatic carboxylic acid or derivatives thereof.
Description of the Related Art
Today's chemical industry is highly dependent on crude oil as a feedstock to produce almost every commodity chemical or material. Aromatic hydrocarbons are among the most important raw materials in the chemical industry, and are obtained exclusively from fossil resources.
Benzoic acid, which is structurally the simplest among aromatic carboxylic acids, is used as intermediate for the manufacture of caprolactam, terephthalic acid, dyes and perfumes, and as a preservative in food and drugs. In addition, oxidative decarboxylation of benzoic acid is an important route in the manufacturing of phenol. Phenol is used mainly in the production of phenolic resins and bisphenol A.
Benzoic acid is prepared industrially by liquid-phase oxidation of toluene in the presence of cobalt or manganese naphthenic acid catalysts. However, increases in crude oil prices results in high manufacturing costs for aromatic raw materials, such as toluene. Furthermore, conventional petroleum-based benzoic acid production is recognized as nonrenewable and generates a lot of greenhouse gases. In this context, there is an increasing demand for an alternative route for benzoic acid production via industrial biotechnology using renewable biomass as feedstock.
WO 2012006039 discloses a process for producing a renewable benzoic acid, comprising dehydrogenating cyclic monoterpene into p-cymene, followed by contacting p-cymene with benzene to yield toluene, and oxidizing toluene into renewable benzoic acid. However, the oxidation of toluene into benzoic acid is carried out using a conventional chemical conversion process.
Elena et al. describes the synthesis of benzoic acid by formic acid-mediated didehydroxylation (Elena et. al., ChemSusChem. 3(7):811-3). However, the final product undergoes sublimation deposition during distillation. To avoid this problem, the usable solvents are limited.
There is, therefore, a strong need for a biological process of producing benzoic acid from renewable biomass.

Process of biologically producing aromatic carboxylic acid and derivative thereof


Methods and apparatuses for use in a MIMO transmission is provided. The method comprises: receiving a rank reported by a user equipment; determining a rank at least partly based on a transmission block size, TBS, index generated from link adaptation decision; and overriding the reported rank with the determined rank. By utilizing downlink link adaption decision, such as TBSidx and rank to quantify PDSCH radio channel quality, improper RI value can be combated, so that transmission of multiple layers only occurs at high SINR region and single layer transmission happens at low SINR region.

This section introduces aspects that may facilitate a better understanding of the invention(s). Accordingly, the statements of this section are to be read in this light and are not to be understood as admissions about what is in the prior art or what is not in the prior art.
In multiple-input multiple-output (MIMO) wireless communication systems, both of the transmitter and the receiver use antenna arrays to provide a rich diversity and a large communication capacity. The downlink transmission process in Long Term Evolution (LTE) and LTE-Advanced (LTE-A) may comprise steps of: generating code words by channel coding and modulating of data from an upper layer; layer mapping of different code words; and precoding the layer mapped data so as to transmit from the antenna array. The number of layers is the degree of freedom of the MIMO channel matrix, which is also referred to the rank of the MIMO system.
A LTE enhanced Node B (eNB) performs downlink and uplink link adaptation so that the data transmission matches with the radio link quality experienced by a user equipment (UE). To be more specific, the eNB dynamically determines the number of layers, or rank, in case MIMO is enabled, as well as selects a Modulation and Coding Scheme (MCS), which includes Transport Block Size (TBS) and modulation scheme.
To facilitate downlink link adaptation in LTE/LTE-A, the UE reports its measured Channel State Information (CSI) to the eNB, such as Channel Quality Indicator (CQI) and Rank Indicator (RI) when MIMO or spatial multiplexing is enabled.
However, CSI is often with errors, i.e., either over-estimated or under-estimated. To cope with errors in the reported CQI, the eNB often adopts outer-loop link adaptation, i.e., adjusting CQI based on received downlink Hybrid Automatic Repeat Request Acknowledgement (HARQ-ACK) feedback from the UE. After CQI adjustment, the selected MCS better reflects the UE experienced radio link quality on Physical Downlink Shared Channel (PDSCH) reception.
In contrast to CQI adjustment, the eNB usually follows RI reported from the UE and determines the rank accordingly in the MIMO transmission. However, like any CSI, RI reported from the UE is often with errors, i.e., over-estimated or under-estimated.
In case of un-shifted Cell specific Reference Symbol (CRS) configuration in a LTE network deployment, the reception of CRS at UE side is interfered by all neighbouring cells, while PDSCH reception does not always experience the same interference since the interference level depends on the load situation in neighbouring cells. For example, in an un-loaded network with un-shifted CRS configuration, based on measured CRS quality UE under-estimates the radio link quality on PDSCH reception and reports more RI=1 than it should do. Consequently, the eNB only schedules rank 1 transmission even though the radio condition allows rank 2 transmission for PDSCH, i.e., radio spectrum is under-utilized and user throughput is lower than what it can be achieved. The miss-match between CRS quality and PDSCH quality could also happen in TM8 (Transmission Mode 8, dual-layer beam-forming in TD-LTE) transmission, where CSI report based on CRS does not grasp the beam forming effect on PDSCH. Another factor causing the improper rank is the estimation error of the rank in the UE or the impairments in UE implementation.
On the other hand, field tests revealed that sometimes TM3 (Transmission Mode 3, open-loop MIMO) transmission with rank adaptation is worse than single-stream transmission at low to medium signal to interference and noise ratio (SINR). It is suspected that worse MIMO performance is probably caused by wrongly reported RI, i.e., RI=1 should have been reported instead of RI=2.
In "Downlink Transmission Mode Selection And Switching Algorithm For LTE", Shubhodeep Adhikari, LTE Systems Engineering Group, Motorola Networks, Bangalore, India, Third International Conference on Communication Systems and Networks (COMSNETS), 2011, it is disclosed that making MIMO transmission mode selection at the eNB based solely on mobile feedback can result in significant throughput loss, and an algorithm is described which can prevent such throughput reduction. The algorithm works by enabling the eNB to selectively override the mobile's channel feedback and make a better choice of transmission mode.
In PCT patent application WO2012044236, a mechanism that may be used as a tool for the sending node or eNB to perform rank override of the UE or receiving node feedback reporting is provided. Specifically, by setting a very high Power Measurement Offsets (PMO) value or scaling factor for a certain rank, the receiving node or UE can be made to always report only that rank.


The instant invention relates to a lawn trimmer and an associated shield. The shield, in the preferred embodiment, is entirely formed from an impact resistant plastic. Additionally, the shield is defined by both an inner peripheral region and an outer peripheral region. An annular raised ring serves to define the boundary between these inner and outer regions. This shield is adapted to be removably secured to the drive shaft of a lawn trimmer. The interconnection between the drive shaft and shield is such that the shield can be rotated independent of the drive shaft. Such independent rotation of the shield allows the trimmer to be easily guided along either horizontal or vertical surfaces. Lastly, a spool of cutting filament is adapted to be removably secured to the drive shaft. The construction of the present invention allows for the removal and replacement of both the filament spool and the shield.

1. Field of the Invention
The present invention relates to a lawn trimmer and more particularly pertains to a rotatable trimmer shield.
2. Description of the Prior Art
The use of a lawn trimmers is known in the prior art. More specifically, such lawn trimmers are known to consist basically of familiar, expected and obvious structural configurations, notwithstanding the myriad of designs encompassed by the crowded prior art which have been developed for the fulfillment of countless objectives and requirements.
By way of example, U.S. Pat. Nos. 4,959,904 and 4,203,212 Proulx discloses a simple flail feed out mechanism for a rotary mower. U.S. Pat. No. 3,139,940 to Randell discloses a lawn edger construction. U.S. Pat. Nos. 34,815 and 5,115,870 to Byrne disclose a flexible flail trimmer with combined guide and guard. U.S. Pat. No. 4,458,419 to Proulx discloses a simplified flail feedout mechanism for a rotary mower. Lastly, U.S. Pat. No. 4,145,809 to Proulx discloses a rotary mower cutting head with flexible cutting blades.
In this respect, the lawn trimmer of the present invention substantially departs from the conventional concepts and designs of the prior art, and in so doing provides an apparatus primarily developed for the purpose of enhancing trimming efficiency.
Therefore, it can be appreciated that there exists a continuing need for improvement in lawn trimmer designs. In this regard, the present invention substantially fulfills this need.


A method, performed in an apparatus for energy control in an energy storage, for determining a composition of energy in the energy storage using a data storage holding information of a determined composition of the energy in the energy storage. The composition of energy comprises one or more energy types and a proportion of each energy type. The method includes measuring a quantity of energy provided in the energy storage, obtaining from the energy provider data indicative of a property of the energy, calculating a proportion of each energy type in the energy based on the obtained data, determining the composition of energy based on the calculated proportion of each energy type in the energy in the energy storage and the measured quantity of energy, and storing the determined composition in the data storage.

There is in the general public a growing attention towards the protection of the environment and an increasing awareness to issues related to energy. It has become a priority for some people to minimize their overall energy consumption, by e.g. using more energy-efficient appliances and/or travelling using energy-responsible means of transportation. Consumers know that energy can be produced using various energy sources, including renewable sources of energy. Renewable sources of energy are considered more respectful of the environment because they derive from natural processes that are continually replenished such as sunlight, wind, rain, tides, waves and geothermal heat.
However, it is hard for the consumers to monitor if and to what extent renewable energies are parts of the energy currently provided to them. Moreover, energy is usually provided to a "grid" (i.e. energy network) by several suppliers across countries, from various sources, some being renewable energies and some being non-renewable energies and each with various degrees of carbon emissions generated. An attempt to live a more environmentally responsible lifestyle results in a relatively unclear combination of types of energies supporting this lifestyle. In this context, it becomes increasingly hard to assess how a consumer's effort towards an environmentally friendly lifestyle accounts for in terms of environmental impact.
Existing systems have tried to address the issue of transparency of energy composition. US20120173034A1 provides an electric power visualization device for a household which visualizes content of electric power for an input-side electric power or load-side electric power in an electric power management system which receives electric power generated by a plurality of power generation methods as the input-side electric power and supplies to a load as the load-side electric power based on the input-side electric power, comprising a display unit which classifies the input-side electric power or the load-side electric power into generated electric power of each of the power generation methods, and displays with different display methods for each classification of the power generation method.
US2010235008A1 discloses a method for determining carbon credits earned as a result of a control event in which power is reduced to at least one service point serviced by a utility.
However, these existing solutions work only on energy consumed at one point of consumption in the energy grid and do not help in assessing energy stored in an energy storage.
Energy stored in the storage is most of the time not connected to a point of consumption in the energy grid. Indeed, the relative merit of e.g. choosing to drive an electrical vehicle instead of an internal combustion engine vehicle involves a higher level of complexity as the vehicle is most of the time disconnected from the energy grid. Consumers are entitled to be provided with a means to understand what energy types are involved in a system (e.g. a vehicle) operating on energy stored in an energy storage.

Method and apparatus for energy control in an energy storage