A selective, fluorescent “turn-on” probe and method for the detection of ozone in biological and atmospheric samples, wherein the method of detecting ozone in a sample comprises the steps of (1) contacting the sample with a fluorophore capable of undergoing allylic ether or allylic ester cleavage and (2) detecting fluorescence in the sample.

Ozone exposure is a growing global health problem, especially in urban areas. While ozone in the stratosphere protects the earth from damaging ultraviolet light, tropospheric or ground level ozone is toxic resulting in damage to the respiratory tract and the exact mechanism by which ozone damages the respiratory system is poorly understood. It has been shown that ozone may be produced endogenously in inflammation and antibacterial responses of the immune system; however, these results have sparked controversy due to the use of a non-specific colorimetric probe.
Reactive oxygen species (ROS) have had a rather controversial history. The existence of singlet oxygen and superoxide was first proposed in the late 1960s; however, due to the lack of sensitive and specific probes these results were met with skepticism, and these observations were only confirmed in the late 1980s. Research indicates that ozone is produced endogenously from singlet oxygen in both neutrophils and atherosclerotic plaque implicating ozone in inflammatory responses. This conclusion was drawn from the premise that the colorimetric dye, indigo carmine 1 (See FIG. 1), differentially reacted with ozone as opposed to other ROS. However, similar to the singlet oxygen/superoxide story, the colorimetric dye, indigo carmine 1 has since been proven to not only react with ozone but also with superoxide in a similar manner, thus, calling into questions these findings of endogenous ozone.
Chemiluminescent methods, including the use of the colorimetric dye, indigo carmine 1, have also been used to measure ozone in ambient air; however, other atmospheric compounds are known to also absorb in this region of the electromagnetic spectrum and false-positive ozone readings are often reported. In addition, many of these methods are sensitive to humidity.
There are several problems associated with the use of the colorimetric dye, indigo carmine 1 as a specific sensor for ozone. First, the dye readily undergoes oxidative cleavage, which is most likely responsible for the lack of specificity. Additionally, the reaction of blue with ROS yields compound 2 (See FIG. 1), which is colorless and cannot be directly visualized without the use of a spectrometer. In biological samples, high-performance liquid chromatography (HPLC) or mass spectrometry are often required in combination with such spectroscopic techniques because the signal for compound 2 (UV: λmax=245 and 298 nm) overlaps with many other bioorganic compounds.
Useful sensors generate virtually no signal in the absence of an analyte, while producing a strong signal in its presence. Small molecule-based fluorescent sensors are particularly useful because they possess spectral properties that are easily discernable and are often soluble in aqueous media. Also, fluorescent samples can be visualized easily with the aid of a hand-held fluorescent spectrometer, fluorescent microscope or even a simple hand-held laser pen.

University of Pittsburgh—Of the Commonwealth System of Higher Education


A fault diagnosing method based on a simulated vaccine is provided. The fault diagnosing method comprises steps of: establishing a dynamic simulation model for simulating a start-up operation and a steady-state operation of a technological process according to process information, an operating procedure and historical data of the technological process; running the dynamic simulation model; extracting data within a first predetermined time from the simulated normal sample set to generate a normal simulated vaccine, and extracting data within a second predetermined time from the simulated fault sample set to generate a fault simulated vaccine; acquiring the historical data of the technological process; obtaining an immune antibody coefficient of the normal simulated vaccine, and generating a normal antibody library; and obtaining an immune antibody coefficient of the fault simulated vaccine, and generating a fault antibody library according to the fault simulated vaccine.

With the development of modern science and technology, the complexity of process industries such as a chemical process, a refining process or a biopharmaceutical process has been increasing. More and more auxiliary devices such as a distributed control system (DCS) or a manufacturing execution system (MES) have been widely used for monitoring an on-line production operation so as to ensure the stable and safe running of a technological process. At the same time, with the improvement of a production automation level, the number of operators in a plant is greatly reduced in recent years than in the past years, so that one operator may need to operate one or even more production units or devices. A simple variable alarm is insufficient to provide the most direct signal for the operator to handle emergency situations, and the operator needs to determine a possible state of the technological process with a lot of experience, which may cause more serious consequences due to the misjudgment or operating lag of a less experienced operator.
Currently, a separate fault diagnosing system is established to detect and diagnose a cause of a fault and to show the type of a fault which may occur to the operator through an interface, which may not only ensure the stability of a production running and prevent the occurrence of major accidents but also may help the operator to handle and repair the fault so as to reduce losses caused by the fault effectively.
Firstly, a perfect on-line fault diagnosing system must be able to quickly detect a fault after a disturbance occurs and be able to accurately diagnose the possible type of the fault based on a rapid effective fault diagnosing method. Secondly, the on-line fault diagnosing system must be able to have a complete structure, be able to acquire data from an on-line running device, and be able to show a diagnostic result to the operator through a friendly interface after a core diagnosis is completed. Finally, the fault diagnosing method must have a self-adaptive capacity and a self-learning ability, and the on-line fault diagnosing system must use on-line data to achieve the self-learning of the on-line fault diagnosing system and to improve the on-line fault diagnosing capability of the on-line fault diagnosing system according to the feedback of the operator.
An artificial immune system is an integrated intelligent system, which combines immunology with engineering and uses mathematics, computer technology, etc. to establish an immune mechanism model and applies the immune mechanism model to the design, implementation, etc. of a technological process. Judgment of self and non-self in the artificial immune system is introduced into the field of a fault diagnosis. A dynamic artificial immune system is configured to perform an on-line fault diagnosis for a technological process by calculating a difference degree of an antigen and an antibody using dynamic variable data of the technological process as a drive, using a historical data time sequence matrix as the antibody and using an on-line data time sequence matrix as the antigen on account of the dynamic characteristics of the technological process.
However, many new technological processes have not experienced a long-time running and lack available historical samples. In this case, due to the lack of historical data, the dynamic artificial immune system may not diagnose a fault effectively. Accordingly, it is necessary to propose a newer mechanism to produce an antibody which may be used for a dynamic artificial immune fault diagnosis.

Fault diagnosing method based on simulated vaccine


Embodiments of the present invention provide a system and method of assigning unique identifiers in a multi-master directory service. In particular, each server in the system assigns numeric user identifiers in a linear fashion that compliments the series of user identifiers assigned by the other servers. In particular, a first server is selected and assigned a first starting number. Each subsequent server is then assigned their own starting series number by incrementing from the first starting number. Then, all servers are assigned an additive, which is an integer greater than or equal to the number of servers in the system. Each server then generates its own series of unique numeric identifiers based on its own starting series number and the additive.

Computer systems typically include two or more computers networked together to allow the sharing of applications, resources, services and information by a number of users. Applications running in this de-centralized environment need information about the system from time to time, including, for example, information about users, host name resolution, passwords, and file locations. Typically, a network service known as a "directory service" (or "name service") is used to store, maintain, and provide this information to clients of the system. A directory service typically keeps track of resources on a network and makes this information available to users and applications. For example, when a user logs on, the login program on the local computer may communicate with the directory service to check the user's username, password and other authentication information. The local computer may further communicate with the directory service to obtain information about the user's permissions in the network.
Typically, a directory service includes a database where the directory data is stored, as well as programs for administering the database and programs for communicating with client applications. The directory service may be implemented on one or more servers on the network.
A directory service that utilizes multiple master servers may be implemented in what is known as a loosely coupled distributed environment. In such a system, each server independently creates and modifies entries of the directory service independent of the other servers. The data is later replicated and synchronized among the master servers of the directory service.
To keep track of users and groups of users who are members of the directory service, it is helpful for the directory service to assign each user and each group a unique numeric identifier. For example, in the well known POSIX directory service schema of UNIX, users and groups of users are assigned a unique numeric identifier for each user and group.
Unfortunately, in a loosely coupled directory service (i.e., a service with including multiple masters), it is difficult to guarantee the uniqueness of any numeric identifier assignment. For example, two master servers may assign the same number to different entities without realizing there is a conflict because data will be synchronized after the conflicting assignments have been made. Known systems attempt to resolve conflicts by using timestamps and simple conflict resolution rules. However, many situations require manual intervention of a system administrator to resolve a conflict. Accordingly, most loosely coupled directory services require the system administrator to manually assign numeric identifiers to users and groups.
It would therefore be desirable to provide methods and systems that assist the user in assigning unique numeric identifiers to users and groups associated with a loosely coupled multi-master directory service.

Numeric identifier assignment in a networked computer environment


Embodiments of methods and systems for inspecting a structure for a crystallographic imperfection are provided. In the method, an X-ray wavelength that is particularly susceptible to diffraction by the crystallographic imperfection is identified. Then an X-ray source is provided to emit X-rays in the identified X-ray wavelength. While placing the structure at a sequence of positions relative to the X-ray source, X-rays are directed at the structure in multiple, non-parallel arrays to create sequential patterns of diffracted X-rays. The patterns of diffracted X-rays are digitally captured and communicated to a computer that compares them to locate the crystallographic imperfection. For a surface imperfection, the imperfection may be marked with a target to allow for physical removal.

Currently, superalloys are widely used for applications in which high stresses must be endured at elevated temperatures, for instance in the components of gas turbine engines, such as blades and vanes. Improvements in manufacturing methods have led to casting of components in single-crystal form, resulting in improved high-temperature lives and strength over conventionally prepared metallic materials that included a plurality of grains separated by grain boundaries.
Due to the improved performance of single-crystal superalloy components, the ability to withstand severe operating conditions is expected. However, one or more significant departures from single-crystal perfection may seriously limit the ability of a single-crystal superalloy component to perform under severe operating conditions, and may shorten the service life of the component. Because, the likelihood of fracture and separation along crystallographic boundaries around imperfections is increased, castings for turbine blades and vanes require close inspection for spurious grains and other crystallographic imperfections. The current industry practice is to use an etching process to reveal the spurious grains and crystallographic imperfections on the surface of single-crystal castings. After etching, the casting is visually inspected to evaluate the etched surface relative to the appropriate acceptance criteria for the intended use of the casting.
While etching processes have historically provided good grain contrast for revealing the external grain structure of equiaxed and polycrystalline directionally solidified superalloy castings, these etching processes tend to be inspector dependant, are time-consuming, and may result in dimensional nonconformance due to excessive stock loss, especially given the relatively thin walls of internally cooled components. Stock loss can be very significant if the overall etching process has to be repeated due to insufficient 'readability' of grain. Further, the etching processes may suffer issues with the presence of scale, with a lack of reflectivity, or with various confounding or masking effects such as anodizing iridescence (aka bluing), which may result in failure to reveal, identify, or locate imperfections, or in difficulty in revealing, identifying or locating imperfections.
Accordingly, it is desirable to provide methods and systems for inspecting single-crystal superalloy castings without etching. Also, it is desirable to provide methods and systems for inspecting single-crystal superalloy castings that use X-ray diffraction (XRD) to locate surface and subsurface imperfections. Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description of the invention and the appended claims, when taken in conjunction with the accompanying drawings and this background of the invention.

Methods and systems for inspecting structures for crystallographic imperfections


Provided is a speaker fall prevention structure, which includes a speaker device formed by housing a speaker unit in a housing independent of a main appliance, a speaker attaching part provided to the main appliance to allow the speaker device to be attached, an attached part facing the speaker attaching part in the speaker device, a fall prevention wire set between the speaker device and the main appliance, and a fastening member for attaching the attached part to the speaker attaching part. Using the fastening member, a first end of the fall prevention wire is fastened and fixed to the main appliance along with the attached part.

Conventionally, there is an optional speaker that has a housing independent of a main appliance such as a monitor and that is attached to the main appliance. The optional speaker is attached to a lateral portion of the main appliance using fixing means such as screws (e.g., see Patent Document 1).
Incidentally, due to an excessive external force to the speaker device or degradation caused by long-term use of the speaker device, there is a risk of an attached part facing the main appliance becoming broken in the housing of the speaker device. In particular, when the main appliance is installed at a high position, repair of such damage becomes an issue.
On the other hand, there is a speaker which is installed on a wall of a house and to which a fall preventing wire is provided (e.g., see Patent Document 2). This provides a structure in which a signal wire rod and the fall preventing wire are used as a speaker cord in a bundle, and in which a fixing part, in which the wire is fixed to the wall of the house, is configured so that the signal wire rod is in a conducted state in accordance with the fixing work. Thereby, in comparison with a case in which the signal wire rod and the fall preventing wire are separately provided, the layout of the speaker cord can be simplified, and the fall preventing wire can be reliably operated by accompanying the fixture of the fixing part with the conduction of the signal wire rod.

Structure for preventing a fall of a speaker device from a main appliance


An underreamer for forming a cavity within a well bore includes a housing adapted to be rotatably disposed within the well bore and a piston slidably coupled to the housing. The underreamer also includes a first cutter having a first end and a second end. The first end of the first cutter is pivotally coupled to the housing. The underreamer further includes a second cutter having a first end and a second end. The first end of the second cutter is coupled to the piston. The second end of the first cutter is coupled to the second cutter such that an axial force applied to the piston is operable to slide the piston relative to the housing and extend the second end of the second cutter radially outward relative to the housing from a retracted position to form the cavity when the housing is rotated relative to the well bore.

This invention relates in general to the field of subterranean exploration and, more particularly, to a pantograph underreamer.
Underreamers are generally used to form an enlarged cavity in a well bore extending through a subterranean formation. The cavity may then be used to collect resources for transport to the surface, as a sump for the collection of well bore formation cuttings and the like, or for other suitable subterranean exploration and resource production operations. Additionally, the cavity may be used in well bore drilling operations to provide an enlarged target for constructing multiple intersecting well bores.
One example of an underreamer includes a plurality of cutting blades pivotally coupled to a lower end of a drill pipe. Centrifugal forces caused by rotation of the drill pipe extends the cutting blades outwardly and diametrically opposed to each other. As the cutting blades extend outwardly, the centrifugal forces cause the cutting blades to contact the surrounding formation and cut through the formation. The drill pipe may be rotated until the cutting blades are disposed in a position substantially perpendicular to the drill pipe, at which time the drill pipe may be raised and/or lowered within the formation to form a cylindrical cavity within the formation.
Conventional underreamers, however, suffer several disadvantages. For example, the underreamer described above generally requires high rotational speeds to produce an adequate level of centrifugal force to cause the cutting blades to cut into the formation. An equipment failure occurring during high speed rotation of the above-described underreamer may cause serious harm to operators of the underreamer as well as damage and/or destruction of additional drilling equipment.
Additionally, density variations in the subsurface formation may cause each of the cutting blades to extend outwardly at different rates and/or different positions relative to the drill pipe. The varied positions of the cutting blades relative to the drill pipe may cause an out-of-balance condition of the underreamer, thereby creating undesired vibration and rotational characteristics during cavity formation, as well as an increased likelihood of equipment failure.
Accordingly, a need has arisen for an improved underreamer that provides increased control of subterranean cavity formation. The present invention provides a pantograph underreamer that addresses shortcomings of prior underreamers.
According to one embodiment of the present invention, an underreamer for forming a cavity within a well bore includes a housing adapted to be rotatably disposed within the well bore and a piston slidably coupled to the housing. The underreamer also includes a first cutter having a first end and a second end. The first end of the first cutter is pivotally coupled to the housing. The underreamer further includes a second cutter having a first end and a second end. The first end of the second cutter is coupled to the piston. The second end of the first cutter is coupled to the second cutter such that an axial force applied to the piston is operable to slide the piston relative to the housing and extend the second end of the second cutter radially outward relative to the housing from a retracted position to form the cavity when the housing is moved relative to the well bore.
According to another embodiment of the present invention, a method for forming a cavity within a well bore includes providing an underreamer within the well bore. The underreamer includes a housing and a piston. The piston is slidably positioned in the housing. The underreamer further includes a plurality of cutter sets, each cutter set having a first end coupled to the housing and a second end coupled to the piston. The method also includes applying an axial force to the piston and extending the cutter sets radially outward from a retracted position relative to the housing in response to movement of the piston relative to the housing from the applied force. The method further includes moving the underreamer within the well bore to form the cavity.
Embodiments of the present invention provide several technical advantages. For example, according to certain embodiments of the present invention, a downwardly directed force is applied to a piston of the underreamer to cause outwardly directed movement of cutters into a subterranean formation. The downwardly directed force applied to the piston may be varied to produce corresponding varying pressures on the formation by the cutters. Thus, the present invention may be used to accommodate a variety of formation densities and compositions. Additionally, decreased rotational speeds of the underreamer may be used to form the cavity, thereby substantially reducing or eliminating hazards associated with high speed rotating mechanisms.
Particular embodiments substantially reduce or eliminate out-of-balance conditions resulting from rotation of the underreamer within a well bore. For example, according to certain embodiments of the present invention, an end of each cutter set is coupled to the piston, thereby resulting in substantially uniform extension of each of the cutter sets relative to the underreamer housing. Thus, out-of-balance conditions caused by varying positions of cutting blades is substantially reduced or eliminated.


The invention relates to a surface-modified layer systems, a method for the production and use thereof. The invention in particular relates to surface-modified layer systems, comprising a substrate and a mono-layer at least partially arranged on said substrate. Said mono-layer is cross-linked in the lateral direction and covalently bonded by anchor groups to at least one surface of said substrate. Said mono-layer is also composed of low molecular weight aromatic and/or heteroaromatic compounds. The mono-layer which is cross-linked in the lateral direction is composed of low molecular weight aromatic and/or heteroaromatic compounds and is integral with the surface-modified layer system, and exhibiting the characteristics of a cross-linked solid. Said mono-layer protects the surfaces of the corresponding substrate from damage caused by friction and corrosion in a particularly advantageous manner.

The present invention relates to surface-modified layer systems, a method for the production and use thereof. The present invention relates in particular to surface-modified layer systems that include a substrate and, at least partially disposed thereon, a laterally cross-linked monolayer, composed of low molecular weight aromatic and/or heteroaromatic compounds, that is covalently bonded via anchor groups to at least one surface of the substrate. The laterally cross-linked monolayer of the surface-modified layer systems according to the invention, that is composed of low molecular weight aromatic and/or heteroaromatic compounds, exhibits the characteristics of a cross-linked solid and consequently protects the surfaces of the corresponding substrates, particularly advantageously against damage from friction and corrosion.
According to the current state of the art, surfaces are usually protected against corrosive actions and mechanical stress, due to friction, by physisorbed thin fluid films (e.g., oils, waxes) or polymer coatings applied thereon. These conventional films usually have layer thicknesses in the range of a few micrometers up to millimeters. Their exact layer thickness, however, is difficult to control by process technology.
In the prior art, non-cross-linked monolayers, in particular those based on aliphatic hydrocarbon chains, have low mechanical stability and therefore provide insufficient protective action. Moreover, non-cross-linked monolayers desorb on contact with corrosive agents, since individual molecules at defect sites are displaced from the surface and detachment of the layer progresses from such sites.
Conventional methods for producing such non-cross-linked monolayers of organic molecules on various substrates are described in more detail in, for example, A. Ulman, xe2x80x9cAn Introduction to Ultrathin Films,xe2x80x9d Academic Press, Boston 1991, and A. Ulman, Chem. Rev. 96, 1533 (1996).
The aim of the present invention is therefore to provide coating systems in which the coatings have high mechanical and chemical stability and the underlying substrate surfaces should be effectively protected against damage from friction or corrosive agents. The layer thickness for such protective layers should be precisely controllable and range from 0.3 nm to 3 nm. Such systems should be particularly suitable for surface protection of mechanically moving devices with small working clearances in the micrometer or nanometer range, such as hard disk drives for electronic data storage, or for surface protection of micromechanical devices with moving parts of dimensions in the micrometer range and smaller.
This aim is achieved by the embodiments specified in the claims. In particular, a surface-modified layer system is provided that includes a substrate and, at least partially disposed thereon, a laterally cross-linked monolayer, composed of low molecular weight aromatic and/or heteroaromatic compounds, that is covalently bonded via anchor groups to at least one surface of the substrate.
In contrast to coating systems available in the prior art, for example those based on physisorbed thin fluid films or polymer coatings, the protective layers according to the invention can be precisely controlled or, as the case may be, adjusted by virtue of the spatial extent of the molecules that make up the laterally cross-linked monolayer and are covalently bonded to the substrate surface via anchor groups.
The monolayer of the surface-modified layer system according to the invention preferably has a layer thickness in the range from 0.3 nm to 3 nm.
By means of covalent bonding to the substrate surface, the monolayer of the surface-modified layer system according to the invention effectively protects the underlying substrate surface against damage from friction or corrosive agents.
The laterally cross-linked monolayer of the surface-modified layer system according to the invention is preferably composed of aromatic compounds selected from the group consisting of phenyl, biphenyl, terphenyl, naphthalene, and anthracene, and/or composed of heteroaromatic compounds selected from the group consisting of bipyridine, terpyridine, thiophene, bithienyl, terthienyl, and pyrrole.
In one embodiment of the present invention, the monolayer, composed of low molecular weight aromatic compounds and/or heteroaromatic compounds, can have on its surface functional groups selected from halogen atoms, carboxy, trifluoromethyl, amino, nitro, cyano, thiol, hydroxy, or carbonyl groups. The low molecular weight aromatic and/or heteroaromatic molecules or units that comprise the monolayer are then, with the help of an anchor group, coupled chemically to the underlying substrate surface or covalently bonded to the latter.
Cross-linking of the monolayer in the lateral direction can in particular be achieved by treatment with electron beam radiation, plasma radiation, x-ray radiation, xcex2-radiation, xcex3-radiation, or UV radiation.
The substrate, which is given high mechanical and chemical stability by the laterally cross-linked monolayer according to the invention and whose surface is therefore effectively protected against damage from friction or corrosive agents, is preferably selected from the group consisting of gold, silver, titanium, zirconium, vanadium, chromium, manganese, tungsten, molybdenum, platinum, aluminum, iron, steel, silicon, germanium, indium phosphide, gallium arsenide, and oxides or alloys or mixtures thereof as well as indium-tin oxide (ITO) and silicate or borate glasses.
If the surface of the substrate material is atomically flat and homogeneous, i.e., if for example it has no edge dislocations or defects, then the protective layer is also atomically flat, homogeneous, and defect-free, and forms a nearly perfectly smooth protective film on the substrate surface to be protected. The protective layer matches the morphology of the substrate almost perfectly. In this way, objects with three-dimensional surface morphologies can also be covered with a cross-linked protective layer of defined thickness.
The monolayers of the surface-modified layer system according to the invention can also exhibit electrical conductivity by means of passage of electrons or holes. This makes it possible to use the monolayers according to the invention in devices in which the passage of charge through the surface can be controlled by means of a stable protective layer, as for example in coated electronic components or electrodes.
The anchor group that chemically anchors the monolayers according to the invention to the substrate material is preferably selected from the group consisting of carboxy, thio, trichlorosilyl, trialkoxysilyl, phosphonate, hydroxamic acid, and phosphate groups, where the anchor groups, with the help of a spacer with length from 1 to 10 methylene groups, can be covalently bonded to the laterally cross-linked monolayer composed of low molecular weight aromatic and/or heteroaromatic compounds.
The nature of the anchor group is tailored to the particular substrate material, in a way known to one skilled in the art. For example, trichlorosilanes or trialkoxysilanes such as trimethyloxysilane, triethoxysilane, etc. are particularly suitable as anchor groups for oxidized silicon surfaces. Alcohol groups can be used for anchoring for hydrogenated silicon surfaces. For gold and silver surfaces, thio groups for example can be used as anchor groups; for oxidized metal surfaces such as iron or chromium, suitable anchor groups are phosphonic acids, carboxylic acids, or hydroxamic acids.
In a particularly preferred embodiment of the present invention, the surface-modified layer system includes a monolayer composed of biphenyl units that is covalently bonded to the corresponding substrate surface, such as for example gold or silver surfaces, via thio groups as anchor groups.
A further object of the present invention is to provide a method for production of surface-modified layer systems, according to the invention, that includes the steps:
(a) preparation of a substrate,
(b) modification of the substrate surface, if necessary,
(c) application of a monolayer of low molecular weight aromatic and/or heteroaromatic compounds with covalent bonding to a substrate surface via anchor groups, and
(d) Treatment of the substrate obtained in step (c) with high-energy beam radiation so that the monolayer, composed of low molecular weight aromatic and/or heteroaromatic compounds and covalently bonded to the substrate surface via anchor groups, is covalently cross-linked in the lateral direction.
Surprisingly, it was found within the context of the present invention that the monolayers applied in step (c), when treated with high-energy radiation, preferably x-ray radiation, xcex2-radiation, xcex3-radiation, or UV radiation, covalently cross-link in the lateral direction so that a chemically completely covalently bonded, thin, and tough protective layer is formed on the substrate surface. By cross-linking in the lateral direction, the monolayers, composed of low molecular weight aromatic and/or heteroaromatic compounds, acquire high mechanical and chemical stability, and effectively protect the underlying substrate surface against damage from friction or corrosive agents.
In one embodiment of the method according to the invention, in step (d) the cross-linking with lateral structuring can be carried out by means of finely focused ionizing electron, ion, or photon beam radiation. The focusing and scanning of the beam over the areas to be structured can be done by electron optics or ion optics elements, as for example in electron beam lithography with scanning electron microscopes, or focused ion beam (FIB) lithography. The structuring can also be carried out preferably by means of a local probe method. Focusing of the electrons, ions, or photons in the latter case is assured by the small size of the electron, ion, or photon source (local probe). The local probe is then moved over the region to be structured at intervals between 0.1 nm and 1000 nm. Particularly suitable local probes for electrons include tips of scanning tunneling microscopes (STM), atomic force microscopes (AFM), and atomically defined field-emitter tips, that for example have been made by the method of Muller et al. (Ultramicroscopy 50, 57 (1993)). The latter are particularly suitable as local probes for structuring with larger distances ( greater than 10 nm) between probe and sample, and can also be used as field ion sources. Fine tips made of glass or another photon-conducting material, as are used in near-field optical microscopes (SNOM), are suitable for structuring with photons. In any local probe method, the local probe is positioned directly over the area to be exposed by means of a positioning device, for example one made of piezoceramic elements.
If in step .(c) instead of applying a monolayer of low molecular weight aromatic and/or heteroaromatic compounds, for example, saturated molecules or units such as cyclohexyl, bicyclohexyl, tercyclohexyl, partially or completely hydrogenated naphthalene or anthracene, or partially or completely hydrogenated heteroaromatic compounds that are covalently bonded to the substrate surface by means of an anchor group, are applied, then in treatment with high-energy beam radiation in step (d), dehydrogenation to the corresponding aromatic or heteroaromatic compounds can occur in addition to cross-linking in the lateral direction. If nitro groups are bonded to the surface of the monolayer composed of low molecular weight aromatic and/or heteroaromatic compounds, then in step (d) of the method according to the invention, these nitro groups can also be converted to amino groups in the impact zone of the cross-linking beam radiation.
In a further embodiment of the method according to the invention, treatment with high-energy beam radiation using a shadow mask can be carried out so that only spatially defined areas of the monolayer applied to the substrate surface are exposed, as a result of which a structured surface is formed on the substrate with protected and unprotected areas, i.e., the exposed regions are protected. The surface-modified layer system according to the invention can therefore be used as a negative resist.
For irradiation with electrons, a large-area illuminating electron source can be used, for example, a xe2x80x9cflood gunxe2x80x9d or a setup as described in FIG. 2 of Hild et al., Langmuir, 14, 342-346 (1998). The electron energies used can then be adapted to the respective organic films and their substrates over a broad range, preferably from 1 to 1000 V. For example, 50 eV electron beam radiation can be used for cross-linking 4-biphenyl thiol on gold.
A large-area illuminating electron source combined with a shadow mask can be used for lateral structuring, so that only the open areas are exposed to the electrons. Also suitable for lateral structuring are focused electron beams, which can be positioned over the areas to be cross-linked by a scanning electron microscope. In addition, electron sources such as field emitter tips, from which the electrons are emitted in a small angular range, can be directly used if they are positioned over the areas to be cross-linked by means of suitable displacement devices (step motors, piezotranslators).
For large-area cross-linking by means of electromagnetic radiation (for example, x-rays, UV radiation), light sources available in the prior art can be used. For lateral structuring, masks appropriate for the respective wavelength range or scanning by means of a suitable light guide (optical fiber) are available.
The monolayers according to the invention, laterally cross-linked by irradiation, exhibit a clear reduction in loading on the substrate material resulting from mechanical or chemical stress. Standard corrosion tests according to DIN 50905 with electron-beam cross-linked biphenyl monolayers on steel (anchor group: phosphonic acid), gold and silver (anchor group: thiol) show a reduction in anodic current and pinhole formation of up to 99.5%. Friction tests according to DIN 50281 on coated silicon surfaces, with electron-beam cross-linked biphenyl monolayers and trichlorosilyl groups as the anchor group, show a reduction in wear by up to 95%.
The substrate surface can be cleaned or chemically modified before the monolayer is applied. Cleaning can be performed by simple rinsing of the surface with water or organic solvents such as ethanol, acetone, or dimethylformamide, or by treatment with an oxygen plasma generated by UV irradiation. If monolayers with anchor groups such as phosphonic acid, carboxylic acid, or hydroxamic acid groups are to be applied to oxidized metal surfaces, prior controlled oxidation of the metal surface is advantageous. This can be done by treating the metal surface with oxidizing agents such as hydrogen peroxide, Caro""s acid, or nitric acid. A further option for modification of a substrate surface is to apply a first organic monolayer with terminal reactive groups such as amino, hydroxy, chloro, bromo, carboxy, or isocyanate groups, to which in a second step the monolayer actually to be cross-linked is chemically coupled by means of appropriate functional groups.
In step (c) of the method according to the invention, the application can be carried out, for example, by a dipping/spin casting method or by adsorption from dilute solution.
Mechanical wear of non-cross-linked monolayers of individual molecules proceeds faster and to a greater extent than for the cross-linked monolayers of the surface-modified layer systems according to the invention.
Furthermore, in the case of aliphatic hydrocarbon chains, treatment with high-energy beam radiation leads to degradation of the monolayers.
The aromatic monolayers according to the invention are especially suitable for surface protection of substrates that are used as mechanically moving devices with small working clearances in the micrometer and nanometer range. They are particularly suitable for use on substrates such as hard disks for magnetic data storage, on micromechanical devices, diskettes or compact disks. Furthermore, they can be used as molecular negative resists for production of integrated circuits and micromechanical components.


This invention is a unique method and apparatus for improving the techniques employed in crocheting. The method and apparatus are characterized by the utilization of a support means for supporting a supply of crocheting thread and means for guiding such thread through guide means which are mounted on fingers of the person conducting the crocheting process. The method and apparatus are further demonstrative inasmuch as the support means can be a storage and transporting means for the guiding elements and the thread. Additional storage is provided for crocheting needles, and the like. Minimal irritation and injury results in the fingers and hand of the user because of the method and apparatus.

I. Field of the Invention
This invention is in the general field of aids to the improvement of crocheting procedures. In particular, it is in the field of storing, transporting, and dispensing certain elements that are used in the art of crocheting such as thread supply, thread supply supporting means, guiding means for the thread that is dispensed from the supply means and the guiding of such thread to the implements that weave the thread into an article. The invention is further directed toward the elimination to a great extent of injury and irritation caused by the passage of the thread through fingers of a hand that is used by the operator to direct the thread from the supply to the point of being worked by the crocheting implements that are conventionally used in the aart.
II. Description of the Prior Art
There have been many attempts by persons that are crocheting to eliminate or decrease the irritation and injury to the hand guiding the thread to the article being formed One of the most common methods is the placement of adhesive type tape about the digits of the hand guiding the thread in order that the constant movement and pulling of the thread which brings about the friction that causes most of the problems is somewhat eliminated. This irritation is especially true of persons that suffer from the afflictions to the hands such as rashes and arthritis and many common ailments These conditions are especially aggravated in older persons and those that have very sensitive skin. Allergies contribute to many of such ailments. Metallic threads are often used in the art of crocheting, along with twine and ribbon-like materials. In all of these previous problems that occur, there has not been any technique or use of apparatus that has easily and economically accomplished the elimination of the problems. In this respect, the present invention is completely unique in which the above mentioned problems have been virtually eliminated by the method and apparatus of the inventor.

Method and apparatus for improving crocheting procedures


A genetically engineered strain WSJ-IA for producing isovaleryl spiramycin I. Also provided is a method for preparing the strain, including the steps of: (a) constructing a recombinant plasmid including a double gene ist-acyB2; (b) transforming the plasmid into an isovaleryl spiramycin I-producing strain to obtain the strain WSJ-IA. The level of isovaleryl spiramycin I produced by fermentation of the strain WSJ-IA is increased 1.7 times and the fermentation potency thereof increased 4.14 times in comparison with the strain exclusively including a single gene ist.

Bitespiramycin (primitive name: Shengjimycin) [patent no.: ZL97104440.6] is a derivative of spiramycin formed by isovalerylation of the 4″-position hydroxyl group of the mycarose moiety in spiramycin molecule. It is produced using genetic engineering technology, to generate bacterial genomic combination between the isovaleryl spiramycin gene ist of heat resistant streptomyces and spiramycin. Bitespiramycin has relatively strong activity against Gram-positive bacteria, especially Streptococcus pneumonia, Mycoplasma pneumonia and chlamydia, it exhibits antibacterial activity against erythromycin- and (β-lactam antibiotic-resistant bacteria such as influenza bacillus, Legionella, Clostridium perfringens; it does not exhibit complete cross-resistance with similar drugs. Bitespiramycin has a relatively high lipophicity, its oral absorption is fast with strong permeability into tissues and a wide distribution in the body and a long maintaining time. Therefore it shows a good post-antibiotic effect. Phase III clinical trials for Bitespiramycin produced with genetic engineering technology has been finished, the results showed good therapeutic effect and safety. Application for class I new drug certificate has been put forward for this drug.
Clinic research shows Bitespiramycin is a safe and effective antibiotic. Its therapeutic effect is comparative to antibiotic azithromycin, generally accepted to be the best macrolide currently. Nevertheless, due to the fact that Bitespiramycin is a multi-component drug, for all the efforts to establish tablet production process to be able to obtain products with controllable component proportions and a stable quality, yet the demands on the control of extraction as well as purification processes are relatively rigorous, and the quality inspection process is complex. Meanwhile, to enhance its therapeutic effects, it is necessary to development its injection formulation. It is well known that injections bring about therapeutic effects very quickly, is especially applicable to critically ill patients or those who are not suitable to take the drugs orally. It is certain that injections are more demanding in terms of quality control.
Production of multi-component Bitespiramycin by the corresponding bacteria is stemmed from multi-component characteristics of spiramycin. Being a homogeny of Platenomycin, it is a macrolide antibiotic, its main nucleus being a 16-membered lactone ring. It contains three sugar molecules: forosamine, mycaminose and mycarose, whereas the main component of Bitespiramycin is an isovalerylation derivative of the hydroxyl group in 4″-position of the mycarose moiety in spiramycin molecule. Because the existence of acyltransferase gene in the bacteria producing spiramycin, 3-position of the lactone ring in spiramycin molecule can be acetylated to form spiramycin component II; propionylated to form spiramycin component III; and when the 3-position of the lactone ring is de-acylated, spiramycin component I is formed. Therefore Bitespiramycin is also a mixture of at least three components: isovaleryl spiramycins I, II, III. The structures of three main components of Bitespiramycin are as follows:
wherein:                Isovaleryl spiramycin III R1═COCH2CH3 R2═COCH2CH(CH3)2         Isovaleryl spiramycin II R1═COCH3 R2═COCH2CH(CH3)2         Isovaleryl spiramycin I R1═H R2═COCH2CH(CH3)2
Researches showed that single components of isovaleryl spiramycin I, II and III all have antibiotic activities, there are no significant differences in their activities [patent application number: 201010119745.1]. According to present quality standard set for Bitespiramycin, the contents of isovaleryl spiramycins (I+II+III) should be no less than 60%. Therefore, a single component (content higher than 60%) can be used to substitute the multi-component mixture. To reduce the production of multi-components, this laboratory constructed bacterium stain WSJ-2 by blocking the 3-O-acyl transferase gene using gene recombination technology in Bitespiramycin generating bacterium WSJ-1. WSJ-2 produced only the isovaleryl spiramycin I [Chunyan Ma et al. Current Microbiology, 2011, 62:16-20]. However, this strain showed very low fermentation unit, it is thus not conducive to large-scale production. It is the intention of this invention to regulate gene acyB2 to modify WSJ-2 strain, to increase the yield of the single component isovaleryl spiramycin I and its content in the mixture. This will lay the foundation for the development of a new drug: single component of the Bitespiramycin homolog, isovaleryl spiramycin I for clinic use.
It is known that the isovaleryltransferase gene ist from heat-resistant streptomyces is linked with regulatory gene acyB2, the presence of the regulatory gene can activate the expression of ist gene. The model streptomyces strain: Variable Lead Green Streptomyces containing complete ist—as well as acyB2-regulatory genes was able to convert 67-79% of the externally added tylosin to 4″-isovaleryl tylosin, whereas the same strain of Streptomyces containing only ist gene, or ist gene with incomplete acyB2 gene, converted only 0-2.4% of the added tylosin [Arisawa A et al: Biosci Biotechnol Biochem 1993, 57(12): 2020-2025]. By transferring recombinant plasmid of autonomous replication form (vectors pIJ702 or pIJ943) containing ist- and acyB2 genes into tylosin producing bacterium (Streptomyces fradiae), under the condition of external addition of a drug (thiopeptin), the transformant mainly produced tylosin in fermentation, besides a minor amount of 4″-isovaleryltylosin (ca. 56 g/mL)[Arisawa A. et al: J Antibiotics 1996,49(4):349-354] could be detected. However, no reports on the increase of 4″-isovaleryltylosin yield or higher content of single component in the mixture by transferring ist- and acyB genes into tylosin producing bacterium have been published up to now.
acyB2 regulatory gene and the transcriptional regulatory protein Srm28c in the spiramycin producing bacterium (Streptomyces ambofaciens) are homologous [Fatma Karray et al Microbiology 2007,153,4111-4122], their degree of identity is 69%, the degree of identity of acyB2 and regulatory protein tylR in tylosin producing bacterium (Streptomyces fradiae) is 41%, tylR is the positive regulatory protein of the biosynthesis in tylosin producing bacterium, it regulates the expression of a polyketide synthase module (tylGI) in tylosin producing bacterium, and plays a regulatory role on the tylosin glycosyl synthesis as well as the polyketone ring oxidation. High expression of tylR gene in the tylosin producing bacterium can increase the yield of tylosin [George S. et al., Mol. Microbiology 2004,54(5):1326-1334]. However, the method of integration of ist gene into the spiramycin producing bacterium, which is homologous as the acyB2, by means of chromosome-recombinant plasmid homologous DNA recombination technology, only resulted in the production of mixture of isovaleryl spiramycin, with a yield of as high as 800 mg/mL [Shang Guangdong et al. Chinese Journal of Biotechnology, 1999,15(2):171]. This demonstrated that only by transferring ist gene into a strain containing regulatory gene similar with acyB2 would not be able to increase significantly the yield and component content of the target product.
This laboratory demonstrated that by concatenating ist gene using genetic engineering technique, to increase the copy number of ist gene in spiramycin producing bacterium to increase ist gene dosage, the capability of the bacteria to isovalerylate was also increased; it was also demonstrated that by substituting the original ist gene promoter sequence with a promoter with strong activity, such as erythromycin resistance gene ermE promoter sequence, the expression of ist gene could be increased. This increases the production of isovaleryl spiramycin by 62% with the gene engineered bacterium [Patent application No. 200910148767.8].
The aim of this invention is to obtain bacterial strains yielding high content of Bitespiramycin single component—isovaleryl spiramycin I, as well as high productivity by means of expression of ist gene linked with regulatory gene acyB2 in a strain, which has already been obtained, capable of producing only the component of isovaleryl spiramycin I, using a highly efficient and stable expression system. To attain this aim, it is necessary to overcome the obstacles of the restriction of the antibiotic producing bacteria of practical value on the gene modification by exogenous gene, thereby improving the conversion rate of the exogenous DNA. Meanwhile, it is necessary to select vector systems for stable express, such that the genetically engineered bacteria can be suitable for large-scale industrial production. This invention proposes to adopt an integrated vector for non-autonomous replication in Streptomyces, such a vector contains the Streptomyces phage integrase enzyme as well as the attachment sites, and contains only the E. coli replicon, to facilitate the preparation in E. coli; meanwhile the vector lacks Streptomyces replicon. When it enters Streptomyces cells, the integration relies on the attachment sites (attP) on the carrier and specific attachment sites of the host bacteria. Therefore, the exogenous gene may be stably expressed in large scale production. The researches on the co-expression of said isovaleryl acylase gene ist and the regulatory gene acyB2 in isovaleryl spiramycin I producing bacterium to increase the yield and content of isovaleryl spiramycin I, as well as the studies on pilot-scale experimental production, have not been found reported to date at home and abroad.

Genetically engineered strain WSJ-IA for producing isovaleryl spiramycin I


A device for treating human keratinous material, in particular with the aid of an electric current. The device includes a reservoir containing a composition, in particular cosmetic or dermatological, to be applied to the keratinous material, and an end fitting for the application of the composition contained in the reservoir, the end fitting comprising a plurality of application members and a distributor. The distributor includes at least one storage cavity for the composition and supply orifices to conduct the composition from the storage cavity or cavities to the application members, and the distributor being configured so that the flow rate of the composition arriving at the application members is identical to within 20% for at least two application members, better for each application member.

The present invention relates to devices intended to carry out a treatment, in particular cosmetic or dermatological, of keratinous material, in particular of the skin, of the scalp, or of the hair. By "cosmetic or dermatological composition" is meant any composition such as defined in Directive 93/35/CEE of the Council of Jun. 14 1993.
The invention relates in particular to devices for the treatment, in particular cosmetic or dermatological, of keratinous material with the aid of an electric current.
It is known that the application of an electric current to the skin may facilitate the penetration of an active agent. It is thus known to treat human keratinous material with the aid of iontophoresis devices. Iontophoresis allows the diffusion of active agents through the skin by virtue of an electrical stimulation in a non-invasive manner. The current administered may be adjustable in terms of intensity and polarity (anodic or cathodic current). The transcutaneous diffusion of the molecules via iontophoresis is based on two principles, namely electro repulsion and electro-osmosis.
Electro repulsion is the migration of an ionized molecule by repulsion of charge of the same sign. Thus, a positively charged substance will diffuse through the skin at the level of the anode (+).
Electro-osmosis is the migration of a molecule, even non-ionized, by entrainment related to the stream of water from the anode to the cathode during iontophoresis. Under the effect of a current, the dissolved substances are entrained by the water or a solvent during migration.
Patent U.S. Pat. No. 5,090,402 pertains to an electric current applicator also exhibiting a massaging function, comprising a plurality of balls, all the balls being immersed in the composition reservoir which extends under a support of the balls.
The subject of patent U.S. Pat. No. 5,131,384 is a massaging applicator comprising a plurality of balls, including a central ball supplied directly with product. This massaging applicator is devoid of a system for applying an electric current.
In application US 2005/0107832, the applicator comprises a matrix of electrodes and is devoid of conducting pieces intended for distributing the composition.

Device for treating human keratinous material, in particular with the aid of an electric current


A coating apparatus coats a liquid material on a substrate in a coating chamber. A first liquid supply system that supplies the liquid material is provided in the coating chamber. A second liquid supply system is provided in the first liquid supply system that supplies a liquid that cleans or that deactivates the liquid material remaining in the coating chamber and/or in the first liquid supply system. A coating apparatus, a thin film forming method, a thin film forming apparatus, a semiconductor device manufacturing method, an electro-optic device, and an electronic instrument are provided that enable a high performance thin film with few defects and with a high degree of reproducibility to be obtained, that allow maintenance of the apparatus to be performed efficiently and safely, and that enable a thin film to be formed at low cost.

1. Field of the Invention
Priority is claimed on Japanese Patent Application No. 2003-126317, filed May 1, 2003, the content of which is incorporated herein by reference.
The present invention relates to a technology for forming a thin film using a liquid material, and, in particular, to a coating apparatus, a thin film forming method, a thin film forming apparatus, a semiconductor device manufacturing method, an electro-optic device, and to an electronic instrument.
2. Description of Related Art
Conventionally, semiconductor devices employed in various types of electronic instrument are typically formed by thin films such as a semiconductor film, an insulating film, and a conducting film. In the formation of these films, a chemical vapor deposition (CVD) method and a sputtering method are mainly used. CVD methods include normal pressure CVD, low pressure CVD, plasma CVD, and optical CVD. Sputtering methods include an AC type and a DC type. An AC type is used for forming an insulating film, while a DC type is used for forming a conducting film.
In conventional CVD methods and sputtering methods, a vacuum apparatus, a power supply unit for generating plasma and the like, a gas supply apparatus for thin film formation, and control of a substrate temperature and the like are necessary. Moreover, the gas used in thin film formation is often toxic, flammable, and prone to spontaneous ignition. Consequently, a variety of ancillary equipment is necessary to ensure safety such as gas leak detectors, noxious substance removal apparatuses for rendering exhaust gas harmless, and exhaust systems in gas containers and gas pipe sections. Accordingly, conventional thin film formation apparatuses have the drawback of being high in cost and large in size. There are also an extremely large number of apparatus conditions contributing to the control of film thickness and film quality, so that conventional thin film formation apparatuses have the drawback that it is difficult to ensure uniformity and reproducibility. Furthermore, in these methods, because a solid phase thin film is formed from a gas phase, conventional thin film formation apparatuses have the drawback of poor productivity. In recent years, methods of manufacturing semiconductor devices and the like in which thin films are formed using methods that are different from the above conventional film formation methods have been proposed as methods for solving the above described problems.
For example, one method involves forming a desired thin film by forming a coating film by coating a liquid material on a substrate, and then heat processing the coating film. The basic thin film formation steps include a coating step in which a coating film is formed by coating a liquid material on a substrate, and a heat processing step for obtaining a desired thin film by performing heat processing on the coating film. According to these steps, a thin film can be formed at low cost and with a high degree of productivity using a small size, low cost apparatus. As a result, a low cost thin film device can be manufactured.
Coating methods such as a spin coating method or liquid discharge method (i.e., an inkjet method) are typically used for the coating step. In the spin coating method, for example, a spinner in which the task of attaching and detaching a cover that is required with any change in the processing solutions is simple (see, for example, Japanese Patent Application Unexamined Publication No. 5-154430), and a coating apparatus capable of supplying a coating solution to a substrate being processed with a lid of a rotating container in a closed state (see, for example, Japanese Patent Application Unexamined Publication No. 8-83762) have been proposed. In the inkjet method, an apparatus has recently been proposed (see, for example, Japanese Patent Application Unexamined Publication No. 9-10657) that forms a coating film having excellent uniformity on a substrate being coated by discharging a liquid from micro nozzles of an inkjet head onto the substrate being coated, while causing the substrate being coated and the inkjet head to move relatively between the area on the rotation shaft side and the area furthest therefrom as the substrate being coated and the inkjet head are rotated relatively.
Moreover, for the heat processing step, a method has been proposed in which an insulating film is baked in a kiln whose oxygen concentration has been adjusted to a fixed value or less (see, for example, Japanese Patent Application No. 9-213693). Furthermore, in a series of steps that includes a coating step and a heat processing step, a coating film formation method has been proposed (see, for example, Japanese Patent Application Unexamined Publication No. 11-262720) in which, for example, a coating solution is dripped onto a surface of an object being processed so that the coating solution is spread uniformly over the surface of the object being processed. A portion of this coating solution that is used to form a film seeps onto the bottom surface of the outer edge of the object being processed, and in that state, the object being processed is transported to a decompression drying apparatus and is dried to a certain extent. It then undergoes heat drying.
However, as was shown in the conventional technology, although a thin film forming apparatus that continuously performs a coating step and a heat processing step, and a variety of coating apparatuses and heat processing apparatuses that are used in the various steps have been proposed, further improvements are required in order, particularly, to improve the performance of the coating apparatus and heat processing apparatus, as well as achieve a reduction in both the size and cost thereof, which in turn will bring about an improvement in the performance of the overall thin film forming apparatus as well as achieve a reduction in both the size and cost thereof.
Moreover, some liquid materials used to form a coating film have problems with regard to safety. For example, because the liquid material normally contains an organic solvent, it is flammable. Consequently, as far as possible, metal materials are used for the members constituting the thin film forming apparatus, and no flammable materials such as plastic materials are used at least in the chamber where the coating step is performed. In addition, other measures need to be implemented such as providing a structure for expelling vapor from the organic solvent. It cannot be said, however, that conventional coating apparatuses and thin film forming apparatuses are always formed in this manner.
If the liquid material is one that requires particular care as regards safety, such as liquid materials that generate noxious gas, or that are prone to spontaneous combustion in an oxygen atmosphere, then it has not been possible, essentially, to use such a liquid material in a conventional coating apparatus and thin film forming apparatus.
Furthermore, when forming a semiconductor film or metal film from a liquid material, it is necessary to strictly control the processing atmosphere in the coating and heat processing steps. However, there has not been satisfactory control of the processing atmosphere in conventional thin film forming apparatuses. For example, when forming a Si film, if the coating step and heat processing step are performed in an atmosphere in which even a small amount of oxygen is present, a silicon oxide film ends up being formed in the Si film, resulting in a deterioration in the performance thereof as a semiconductor film. It is necessary in the formation of this type of thin film to control the oxygen concentration to, for example, 10 ppm or less, however, the specific structure required for this has not been proposed conventionally.
Moreover, if the liquid material is left unused for a long period of time, a rise in viscosity and precipitation of solid components is brought about by the volatility of the solvent and chemical reactions and the like. As a result, problems arise such as blockages occurring in the liquid material supply and control systems, and a thin film that contains a large number of defects being formed. In conventional coating apparatuses and thin film forming apparatuses, however, sufficient countermeasures against such problems have not been provided.
The present invention was conceived in view of the above circumstances, and it is an object thereof to provide a coating apparatus, a thin film forming method, a thin film forming apparatus, a semiconductor device manufacturing method, an electro-optic device, and an electronic instrument that enable a high performance thin film with few defects to be obtained, that allow maintenance of the apparatus to be performed efficiently, and that enable a thin film to be formed with a high level of safety.

Coating apparatus, thin film forming method, thin film forming apparatus, and semiconductor device manufacturing method, electro-optic device and electronic instrument


An organic light emitting device and a method for manufacturing that same are discussed, which can reduce thickness and weight of the device as well as the manufacturing cost. The organic light emitting device includes according to an embodiment an organic light emitting diode (OLED) formed on a glass substrate; an adhesive layer formed to cover the OLED; and a metal foil formed on the adhesive layer to seal the OLED and bonded to the glass substrate, wherein the metal foil is formed of an alloy having the same or substantially the same thermal expansion coefficient as that of the glass substrate.

1. Field of the Invention
Embodiments of the present invention relate to an organic light emitting device and a method for manufacturing the same, which can reduce the manufacturing cost as well as thickness and weight of the device.
2. Discussion of the Related Art
A liquid crystal display device has been widely used as a flat panel display device. However, the liquid crystal display device requires a back light as a separate light source and has also technical limitations in brightness, contrast ratio, and viewing angle.
Recently, an organic light emitting device, which does not require a separate light source due to its self light-emission and has relatively excellent brightness, contrast ratio and viewing angle, has received much attention.
This organic light emitting device may be divided into a passive matrix type organic light emitting device and an active matrix type light emitting device in accordance with a driving mode.
In the passive matrix type organic light emitting device, a thin film transistor (TFT) is not separately provided and pixels are arranged in a matrix arrangement. Also, since each pixel is driven by sequential driving of scanning lines, higher voltage and higher current should instantaneously be applied to the passive matrix type organic light emitting device as the scanning lines are increased. Accordingly, power consumption is increased and there is limitation in resolution.
On the other hand, in the active matrix type light emitting device, a TFT is formed at each of pixels arranged in a matrix arrangement. Also, each pixel is driven by switching driving of the TFT and voltage charging of a storage capacitor Cst.
The active matrix type light emitting device is advantageous in that it has lower power consumption and higher resolution than the passive matrix type light emitting device. Accordingly, the active matrix type light emitting device is suitable for a display device that requires high resolution and a large display area.
Hereinafter, an active matrix type organic light emitting device according to a related art will be described with reference to the accompanying drawings. In this specification, the active matrix type organic light-emitting device will briefly be referred to as an organic light emitting device.
FIG. 1 is a cross-sectional view illustrating a frit sealing type organic light emitting device according to the related art.
A light emitting region of an entire region of the organic light emitting device is only shown in FIG. 1. In FIG. 1, a TFT array region where a switching TFT and a driving TFT for driving an organic light emitting diode (OLED) 20 are formed is not shown.
Referring to FIG. 1, the organic light emitting device according to the related art includes a glass substrate 10, which is a base substrate, an OLED 20 emitting light depending on a current input by driving of the switching TFT and the driving TFT, a frit 30 protecting the OLED 20, and a sealing glass (or encap glass) 40 for sealing pixels.
In this case, the frit 30 includes a glass powder for protecting the OLED 20 from an external factor such as moisture.
The glass substrate 10 may be made of a transparent glass having a plate shape, and may be formed using a material such as potassium lime, soda lime or quartz.
Although not shown, the organic light emitting device according to the related art may further include a polarizing layer for polarizing light from the OLED 20, a cover glass arranged on a display panel, and an adhesive layer for attaching the cover glass to the display panel.
FIG. 2 is a brief diagram illustrating a light emitting structure of the OLED according to the related art.
Referring to FIG. 2, the OLED 20 is a transparent electrode on the glass substrate 10, and is provided with an anode electrode 21 used as a positive electrode.
A hole injection layer 22, a light emitting layer 23 and an electron injection layer 24 are sequentially deposited on the anode electrode 21. A cathode electrode 25 used as a negative electrode is formed on the electron injection layer 24.
If electrons generated by the cathode electrode 25 and holes generated by the anode electrode 21 are injected into the light emitting layer 23, the electrons and holes are combined with one another to generate excitons. When the generated excitons are shifted from an exited state to a ground state, light is emitted, whereby picture images are displayed.
FIG. 3 is a cross-sectional view illustrating a front sealing type organic light emitting device according to the related art.
Referring to FIG. 3, the front sealing type organic light emitting device according to the related art includes a glass substrate 10, which is a base substrate, an OLED 20 emitting light depending on a current input by driving of a switching TFT and a driving TFT, a passivation layer 50 formed to cover the OLED 20, an adhesive layer 60 formed to cover the passivation layer 50, and a sealing glass (or encap glass) 40 formed on the adhesive layer 60 to seal the OLED 20.
The passivation layer 50 is to protect the OLED 20 from an external factor such as moisture, and is formed to cover the OLED 20. The adhesive layer 60 is formed on the passivation layer 50, and the sealing glass 40 is formed on the adhesive layer 60.
The sealing type organic light emitting device according to the related art planarizes the glass substrate 10 through the adhesive layer 60. The sealing glass 40 is attached onto the adhesive layer 60 to seal the OLED 20 from the external factor such as moisture.
The organic light emitting device according to the related art, which has the aforementioned structures of FIG. 1 and FIG. 3, is manufactured by sequentially performing the steps of forming a TFT in an array region, manufacturing the OLED by depositing an organic material, and sealing the light emitting region.
However, the OLED 20 of the related art, which should be sealed from the outside due to its vulnerability to moisture, has problems as follows.
Since the frit sealing type organic light emitting device according to the related art shown in FIG. 1 seals the OLED 20 from the external factor such as moisture by using the glass powder, the frit 30 and the sealing glass 40 are used.
Also, the front sealing type organic light emitting device according to the related art shown in FIG. 3 seals the OLED 20 from the external factor such as moisture by forming the passivation layer 50 and the adhesive layer 60 on the OLED 20 and forming the sealing glass 40.
In this case, as the sealing glass 40 is formed on the OLED 20, a problem occurs in that the thickness is increased. A problem also occurs in that the manufacturing cost is increased as the sealing glass 40 is used.

Organic light emitting device and method for manufacturing the same


A self-regulating oscillator circuit and method are disclosed. Specifically, a method is described whereby an oscillator having an active device is operated. The oscillator is operated by providing a current through the active device, as well as through a reference device connected in series with the active device of the oscillator. A reference voltage across the reference device is sampled, and a regulated voltage is generated by adding a predetermined voltage to the sampled reference voltage. Finally, the regulated voltage is applied to the active device of the oscillator. In one circuit embodiment, the oscillator as described includes a gallium arsenide FET structure which cooperates with a resonant structure to produce a reflection-type oscillator. In addition, a regulator circuit is described including an isolating op amp which samples the reference voltage from the active device of the oscillator and provides its output to a voltage source device. The voltage source device adds an additional fixed voltage to the sampled voltage and the additional voltage is connected through a pn junction to provide a regulated output voltage. The regulated output voltage is connected to the active device of the oscillator, thereby maintaining the voltage drop across the active device to improve oscillator performance.

Oscillator circuits are commonly used in many contemporary circuit applications. Further, as the telecommunications industry advances, higher oscillator frequencies are quite common. For example, under current technology, microwave frequencies on the order of 1 to 300 gigahertz are often used in circuit applications. Typical microwave circuit applications include the use of oscillators for either downward or upward frequency conversion in microwave radio systems. In these microwave applications, as well as for others, it is often very important that the oscillator oscillate only when desired, and that a specific oscillating frequency be maintained during operation. Thus, scientists have invested many years of research and development into building oscillators to meet these goals.
Many different considerations have been examined in order to accomplish the goals set forth above. One key consideration which has been addressed is the bias potential drop across the active device of the oscillating circuit during operation. Specifically, it is beneficial to maintain a constant voltage drop across the active device. This voltage maintenance is important for two reasons. First, a manufacturer of the active device typically provides test data for the device given a specified set of DC criteria. For example, the scattering parameters for the active device are guaranteed by the manufacturer for a stated given DC voltage drop across the active device. Thus, a circuit designer implementing the device typically attempts to match the voltage drop/current flow specified by the manufacturer in order to guarantee these scattering parameters once the active device is operated as part of an oscillator. A second consideration for maintaining a constant voltage drop across an active oscillator device arises from variations in current flow that occur from device-to-device. For example, in a field effect transistor (FET), a known saturation drain-to-source current (I.sub.dss) is expected to flow through the device. Nonetheless, the specific I.sub.dss of an FET is likely to vary from device-to-device. This variation is likely to change the voltage drop across the respective active device. As a result, for oscillators using these devices, oscillation frequency from oscillator-to-oscillator may differ. This result may degrade performance of the overall circuit utilizing the oscillator.
In the prior art, various attempts have been derived in order to individually adjust the voltage drop across the active device of an oscillator. These attempts seek to correct for fluctuations from device-to-device. For example, one technique used in the prior art is to provide an adjustable resistance in series with the active oscillator device and its power supply. The adjustable resistance has been accomplished by way of a potentiometer, or by providing several groups of different values of resistors, any of which may be individually selected and connected between the active device and the power supply. In each instance, the value of the resistance is adjusted or selected to correspondingly adjust the voltage dropped across the resistance. Assuming the supply voltage is constant, this change causes a corresponding change in voltage drop across the active oscillator device in series with the resistance. Accordingly, the voltage drop across the active oscillator device is manually adjustable, thereby allowing bias adjustment and correcting for device-to-device parameter fluctuations.
The manual tuning or selection prior art approaches provide numerous disadvantages. For example, increased time and labor are required for adjusting each oscillator to operate at the necessary or desired voltage bias. Further, these processes quite often require a fairly high degree of technical expertise on the part of the technician. Thus, even with a given level of competence, the manual process is subject to human error. Additionally, device parameter variations may occur after tuning the device. For example, many active devices are known to conduct a different amount of current and, hence, drop a different amount of voltage, when the device is exposed to varying ranges of temperature. As a result, even after a specific oscillator has been hand-tuned, a change of temperature may consequently change the current/voltage biasing the device and, therefore, may alter the oscillation frequency of the device.
In view of the above, it therefore should be appreciated that a need has arisen for an improved circuit and methodology for maintaining the voltage drop across the active device of an oscillator circuit to a given value, thereby minimizing the effects commonly caused by a changing voltage drop.

Self-regulating oscillator circuit and method


A separation process for recovering organic components from liquid streams. The process is a combination of pervaporation and decantation. In cases where the liquid stream contains the organic to be separated in dissolved form, the pervaporation step is used to concentrate the organic to a point above the solubility limit, so that a two-phase permeate is formed and then decanted. In cases where the liquid stream is a two-phase mixture, the decantation step is performed first, to remove the organic product phase, and the residue from the decanter is then treated by pervaporation. The condensed permeate from the pervaporation unit is sufficiently concentrated in the organic component to be fed back to the decanter. The process can be tailored to produce only two streams: an essentially pure organic product stream suitable for reuse, and a residue stream for discharge or reuse.

1. Separation of liquid mixtures
Separation of liquid dispersions or mixtures may be achieved by a number of techniques, including simple gravity separation (decantation), centrifugal separation, impaction methods such as coalescing or flotation, and electrotreating. Of these, by far the cheapest and simplest under most circumstances is decantation. For decantation to be effective, however, the concentration of the minor phase should be relatively high, and the dispersed phase should be present in the form of relatively large droplets. Also, decanters can typically achieve only a gross separation between phases. Even when an optimum phase separation is achieved, the dispersed phase may be slightly soluble in the continuous phase, so that a total separation of the two components is not possible. Therefore, it is frequently necessary to subject the residue from the decanter to some form of secondary separation process. Where large volumes of liquid are to be treated, the space required for the decanter vessels may be a problem. Thus, to take advantage of the cheap, simple aspects of decantation as a separation process requires:
1. A relatively concentrated mixture, PA1 2. A relatively small feed volume, if possible, and PA1 3. A second polishing step for optimum separation.
2. Treatment of streams containing dissolved organics
Contamination of industrial effluent waters with dissolved organic solvents, such as methanol, ethanol, methyl ethyl ketone, phenol, benzene, toluene, and trichloroethane, is an important environmental problem. These solvents make water unfit for reuse or direct discharge to municipal sewers, and are difficult to remove, even at low concentrations. Commonly used methods for removing volatile organic compounds include air stripping, biological treatment, carbon adsorption and incineration. Air stripping, in which water is circulated against a current of air in a contacting tower, is the least expensive process. However, air stripping merely exchanges water pollution for air pollution. Air stripping is therefore seldom used if the solvent concentration exceeds 0.1%, and even then only for small streams where the total organic emission is less than 10-100 lb/day. Carbon adsorption, a principal effluent treatment technology, can only be used efficiently for very dilute streams, typically 1,000 ppm or less, and more usually 100 ppm or less. At these very low concentrations, carbon adsorption is a preferred technique, because the size of the plant scales in proportion to the amount of solvent removed. Thus, when the solvent concentration is very low, the amount of wastewater that can be treated by a small carbon adsorption system is high. However, once the feed solution concentration exceeds 1,000 ppm, carbon adsorption systems become very large per gallon of wastewater treated. Also, carbon adsorption systems cannot handle some chlorinated and fluorinated solvents, and generate secondary waste, in the form of spent contaminated carbon that may be sent to landfills. Biological treatment systems work well only for organics that can be fully metabolized by the biomass, and where the process is not compromised by high or fluctuating solvent concentrations. At the high concentration end of the scale, incineration is reliable and effective for very concentrated streams, where the heat value of the solvent reduces the amount of supplemental fuel required. Typically, incineration is impossibly expensive at concentrations below 5%.
Thus, there is a dissolved organic concentration range for which no conventional wastewater treatment method is really suited. Currently this range is avoided by pooling or diluting the waste to the point where it can be treated by carbon adsorption or biological processes, or concentrating it so that incineration can be used. There remains a real and long-felt need for a low-cost method for directly treating contaminated streams, with an organic content of about 0.1% up to about 5 or 10%, to produce an effluent suitable for direct discharge or biological treatment, and a low-volume concentrated stream containing the bulk of the dissolved organics, from which the organic component can be recovered. Likewise, there is a need for efficient methods of separating organic/organic process streams or wastes, particularly where the two organics form an azeotrope or a closely-boiling mixture.
Pervaporation is a relatively new separation technology that is beginning to achieve commercial success. The pervaporation process itself has been known since the 1950s, and is described, for example, in U.S. Pat. Nos. 2,913,507 and 2,953,502 to Binning et al. Organic-selective pervaporation is described in a general way in U.S. Pat. No. 4,218,312 to Perry. Despite the theoretical knowledge embodied in these patents, many years elapsed before commercially viable pervaporation systems could be contemplated, because the technology to make high performance membranes and modules had not been developed. In recent years, a West German company, GFT GmbH, has been selling pervaporation units with water-selective membranes to remove small amounts of dissolved water from solvents. Membrane Technology & Research, Inc., now offers systems with organic-selective membranes for a variety of applications. Work on organic/organic separations by pervaporation is ongoing in several institutions.

Process for recovering organic components from liquid streams


Provided are a heterocyclic carboxylic acid amide ligand and applications thereof in a copper catalyzed coupling reaction. Specifically, provided are uses of a compound represented by formula (I), definitions of radical groups being described in the specifications. The compound represented by formula (I) can be used as the ligand in the copper catalyzed coupling reaction of the aryl halogeno substitute, and is used or catalyzing the coupling reaction for forming the aryl halogeno substitute having C—N, C—O, C—S and other bonds.

Transition metal-catalyzed coupling reaction of aryl halides with suitable nucleophiles, such as organic amines, active methylene compounds, alkynes, phenols, alcohols, thiophenols, sodium sulfinates, sodium sulfide, or phosphates is an effective method to form C—N, C—C, C—O, C—S, and C—P bonds. Generally, aryl iodide and aryl bromide are of higher reactivity, thus can achieve the corresponding coupling reaction when catalyzed by transition metals such as palladium, copper, nickel, etc. Compared with bromine (iodo) aromatic hydrocarbon, chlorination aromatic hydrocarbons are cheaper and of better application prospect, however, C—Cl bond is of high energy (Grushin, V V; Alper, H. Chem. Rev. 1994, 94, 1047.), which makes it difficult for the oxidative addition between C—Cl bond and transition metals. The reaction is not as efficient as the bromide and iodine. The C—N coupling reaction of aryl chlorides catalyzed by palladium and nickel has been reported. The use of large sterically hindered phosphorus ligands to promote the reaction is an effective strategy. In 2005, Hartwig's group has used large steric phosphines with ferrocene structure to successfully complete the coupling reaction of chlorinated aromatic ring or aromatic heterocyclic compound with the primary amine, in which the equivalent of the catalyst and the ligand in the system can be reduced even to one hundred thousandth molar equivalent. For certain aromatic heterocyclic ring substrates, this type of reaction can be achieved at room temperature, which fully demonstrates the high efficiency of the catalyst system. Moreover, the reaction is also compatible with the substituent groups on the benzene ring (Shen, Q.; Shekhar, S Stambuli, J P; Hartwig, J F Angew. Chem. Int. Ed. 2005, 44, 1371.1.

In 2011, Buchwald's team found that chlorinated aromatics can be coupled to primary amines and secondary amines, respectively by employing different phosphine ligands. The system has broad compatibility with substrates. Besides general aliphatic amines, the heterocyclic aromatic amine can also be subjected to the coupling reaction successfully (Maiti, D.; Fors, B P; Henderson, J L; Nakamura, Y.; Buchwald, S L Chem. Sci. 2011, 2, 57.).

Although palladium and nickel are highly efficient in catalyzing the amination reaction of chlorinated aromatic hydrocarbons, there still are some problems in large-scale applications: 1. in the system, the addition of large sterically hindered, complex phosphine ligands or azacarbene ligands is necessary to promote the reaction; 2. the palladium catalyst is expensive, and the reaction operation required for zero-valent nickel is quite demanding, which to some extent has limited the application thereof. Compared with the above, copper catalysts are inexpensive, stable, and readily available, and the ligands used are in simple structure, which obviously avoids those deficiencies. However, the copper-catalyzed coupling reaction substrates reported so far are mostly limited to iodinated and brominated substrates.
In 2007, Pellón's group has achieved the coupling reaction of aliphatic amine with 2-chlorobenzoic acid under the action of ultrasound by and the promoting effects of the ortho-carboxy group of 2-chlorobenzoic acid, and good yield can be obtained for both primary amine and the secondary amine. However, this method is only effective for ortho-carboxy substituted substrates, which cannot be generally applied (Docampo, M L; Pellón, R F; Estevez-Braun, A.; Ravelo, A G Eur. J. Org. Chem. 2007, 4111). This reaction is essentially a nucleophilic substitution reaction rather than a coupling reaction, and the reaction temperature is very high.

Another report on the Ullmann coupling reaction of chlorinated aromatic hydrocarbons was reported by Taillefer's group. They used 2,2,6,6-tetramethyl-3,5-heptanedione as ligand to achieve the C—O coupling of chlorobenzene and phenols. The major disadvantage of this system is that up to 0.8 equivalents of ligand should be added into the reaction, thus reducing the economical efficiency of the reaction (Xia, N.; Taillefer, M. Chem. Eur. J. 2008, 14, 6037.).

In 2012, Ma Dawei's group has used the oxalic acid 2,6-dimethylphenyl monoamide carboxylic acid as a ligand for copper-catalyzed C—N coupling reaction of aryl iodide or bromine with organic amine (Org. Lett 2012, 14, 3056-3059). Recently, they have successfully applied oxalic diamide ligands designed based on that in the coupling reaction of aryl chlorides, and found that various types of nucleophiles can be used in the reaction, including primary amines, cyclic secondary amines, ammonium hydroxide, phenol, etc. This reaction provides coupled products in a good yield (J. Am. Chem. Soc. 2015, 137, 11942-11945; Org. Lett. 2015, 17, 5934-5937.).
In summary, the copper-catalyzed coupling reaction of aryl chlorides has very important application prospects, and suitable ligands are the key to such reactions. There is still a lack of a catalytic system for copper-catalyzed aryl chloride coupling reactions that is simple to be prepared, suitable for industrial applications that enables efficient reaction.

Heterocyclic carboxylic acid amide ligand and applications thereof in copper catalyzed coupling reaction of aryl halogeno substitute