(Ionically and covalently bonded materials are typically electrical and thermal insulators, due to the absence of large numbers of free electrons). Electron delocalization is the origin of good electrical and thermal conductivities in metals. This type of bond can occur in inorganic. Metallic bonding is found in the periodic table for Group IA and IIA elements. Another important observation is that, in the absence of metal ions. This makes them somewhat stronger than a van der Waals interaction, and weaker than fully covalent or ionic bonds. The half cell essentially consists of a metal electrode of a certain metal submerged in an aqueous solution of the same metal ions. In one half cell, the oxidation of a metal electrode occurs, and in the other half cell, the reduction of metal ions in solution occurs. This suggests that the hydrophobicity contrast function may be useful for locating, characterizing, and designing metal binding sites in proteins. Thus interchain hydrogen bonds destabilize metal ion binding by 812 kcal/mol (see below). Ionic bonding occurs between a metal and a non-metal The metal has a nearly empty outer shell and so loses electrons to form a positively charged cation The. An electrochemical cell is comprised of two half cells. In the 23 metal-binding molecules we have examined, the maximum values of the contrast function lie near to observed metal binding sites. This function is large and positive for a sphere of hydrophilic atomic groups (characterized by atomic solvation parameters, delta sigma, having values less than 0) at the center of a larger sphere of hydrophobic atomic groups (characterized by delta sigma greater than 0). This qualitative observation can be described analytically by the hydrophobicity contrast function, C, evaluated from the structure. That is, metals bind at centers of high hydrophobicity contrast. Regardless of the metal and its precise pattern of ligation to the protein, there is a common qualitative feature to the binding site: the metal is ligated by a shell of hydrophilic atomic groups (containing oxygen, nitrogen, or sulfur atoms) and this hydrophilic shell is embedded within a larger shell of hydrophobic atomic groups (containing carbon atoms). The CA active site pocket is hydrophobic: consider how well charge would be stabilized in aqueous solvent compared to in a hydrophobic pocket. Explain how a hydrophobic metal binding site would decrease the pK a of water bound to Zn in CA compared to that of water bound to Zn in “bulk” solution.The environments of metal ions (Li , Na , K , Ag , Cs , Mg2 , Ca2 , Mn2 , Cu2 , Zn2 ) in proteins and other metal-host molecules have been examined. Which step of the mechanism would be nearly impossible in pure water?ġ4. In the active site of carbonic anhydrase, the pK a of water lowered even more, to 7, by the protein environment around the Zn active site.ġ3. Ionic bonding occurs through a process called electron transfer, where one atom gives electrons. For water in 2 in aqueous solution, the pK a is 10. An ionic compound is a compound that is formed by ionic bonding. Bonding always forms a species that is more stable than the atoms from which it is made. A co-ordinate bond (also known as a dative covalent bond) is a covalent bond (a shared pair of electrons) in which both electrons originate from the same atom. Only the valence electrons of an atom are involved in bonding. When hydroxide is needed to carry out hydrolysis reactions, acidic metal ions, like Zn 2 are often used to stabilize the hydroxide nucleophile in order to catalyze the reaction (lower activation energy). The bond between the metal ion and the ligand, where the ligand supplies both electrons, is known as a co-ordinate covalent bond. As you saw earlier, binding water to a metal ion can change its pK a, and make its protons more acidic by stabilizing the hydroxide ion. Thus metals are electropositive elements with relatively low ionization energies. The mechanism for this enzyme is shown around structure of the protein. Metals With the exception of hydrogen, all elements that form positive ions by losing electrons during chemical reactions are called metals. The figure shows the structure of human carbonic anhydrase IV (from PDB 1znc), with a blow up of the Zn active site where Zn is bound to 3 histidine side chains (His). The structure of protein and acitve site were created from PDB 1znc. (CC-BY-SA Kathryn Haas) Some metal ions can bind specifically to the specific base pairs such as CAg -C and T-Hg 2 -T. \): Formation of carbonic acid from carbon dioxide catalyzed by human carbonic anhydraze IV. What is metallic bonding in A-level Chemistry In A-level Chemistry, metallic bonding refers to the chemical bonding that occurs between metal atoms in a.
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The logging policy can be viewed symbolically: a VPN’s commitment to logging as little as possible is representative of their respect for your privacy and how seriously they approach the issue of protecting your data.įor example, for a lot of people, a VPN logging exactly what time they turn the VPN on or off might not be a matter of much concern: but our unwillingness to do even that hopefully signals just how earnestly we protect the data that is generally viewed as more sensitive. 7/24/2023 0 Comments Sotu speech 2019That’ more than 1 million more than the demo second-place holder Fox broadcast and well above CNN and MSNBC’s 946,000 and 478,000 in the demo, respectively. While ahead of the 31.3 million who tuned in for Barack Obama’s final SOTU on January 12, 2016, the big drama of Trump’s talk last night was far behind the 43.5 million who watched Bill Clinton give his JanuSOTU while facing an ultimately unsuccessful impeachment trial in the Senate.Ĭo-anchored by Bret Baier and Martha MacCallum, FNC’s SOTU coverage also snared a night-topping 2.7 million in the coveted news demographic of adults 25-54. In the FNC-dominated 9 – 10:30 PM ET slot, a soundly beaten CNN and MSNBC had audiences of 2.8 million and 2.2 million, respectively. In fact, all nets and cablers were down except FNC, who saw a 2% bop up in viewership. To be specific (and granted we don’t have metrics from PBS, Univision and a few others yet), that’s a 27% plunge overall from last year, which saw a slight bounce from 2018. Topped once again by a surging Fox News Channel and its audience of 11.5 million, the combined results from Fox News, CNN, MSNBC, Fox Business, Fox, ABC, CBS and NBC brought in 34.2 million viewers, a double-digit drop from last year’s final SOTU numbers. Senate Acquits President Donald Trump In Finale To Impeachment Processĭespite one literal and figurative zinger after another, plus a Medal of Freedom given live to Rush Limbaugh, the former Celebrity Apprentice’s latest address to Congress looks to be his least watched ever. 7/24/2023 0 Comments Dell watchdog timer utilityIn some systems the reset signal is directly used to enable the watchdog. When automatically generated, the enabling signal is typically derived from the computer reset signal. In the latter case, the enabling signal may be automatically generated by hardware or it may be generated under software control. Upon power-up, a watchdog may be unconditionally enabled or it may be initially disabled and require an external signal to enable it. Screenshot of wdctl, a program that shows watchdog statusĪ watchdog timer is said to be enabled when operating and disabled when idle. If the computer attempts to kick the watchdog before or after the window, the watchdog will not be restarted, and in some implementations this will be treated as a fault and trigger corrective action. The window begins after a delay following the previous kick, and ends after a further delay. The window timing is usually relative to the previous kick or, if the watchdog has not yet been kicked, to the moment the watchdog was enabled. Some watchdog timers will only allow kicks during a specific time window. The device driver, which serves to abstract the watchdog hardware from user space programs, may also be used to configure the time-out period and start and stop the timer. For example, in the Linux operating system, a user space program will kick the watchdog by interacting with the watchdog device driver, typically by writing a zero character to /dev/watchdog or by calling a KEEPALIVE ioctl. In computers that are running operating systems, watchdog restarts are usually invoked through a device driver. An example of this is the CLRWDT (clear watchdog timer) instruction found in the instruction set of some PIC microcontrollers. Alternatively, some tightly coupled watchdog timers are kicked by executing a special machine language instruction. Kicking is typically done by writing to a watchdog control port or by setting a particular bit in a register. The act of restarting a watchdog timer is commonly referred to as kicking the watchdog. Kicks occurring outside the window have no effect on the timer and may be treated as faults. Some watchdog timers only allow kicks during a time window. In real-time operating systems, a watchdog timer may be used to monitor a time-critical task to ensure it completes within its maximum allotted time and, if it fails to do so, to terminate the task and report the failure.Īrchitecture and operation Restarting For example, a watchdog timer may be used when running untrusted code in a sandbox, to limit the CPU time available to the code and thus prevent some types of denial-of-service attacks. Watchdog timers are also used to monitor and limit software execution time on a normally functioning computer. A watchdog timer is usually employed in cases like these. In robots and other automated machines, a fault in the control computer could cause equipment damage or injuries before a human could react, even if the computer is easily accessed. For example, remote embedded systems such as space probes are not physically accessible to human operators these could become permanently disabled if they were unable to autonomously recover from faults. In such systems, the computer cannot depend on a human to invoke a reboot if it hangs it must be self-reliant. Watchdog timers are commonly found in embedded systems and other computer-controlled equipment where humans cannot easily access the equipment or would be unable to react to faults in a timely manner. Watchdog timers are essential in remote, automated systems such as this Mars Exploration Rover In other computers the watchdog may reside in a nearby chip that connects directly to the CPU, or it may be located on an external expansion card in the computer's chassis. Microcontrollers often include an integrated, on-chip watchdog. The corrective actions typically include placing the computer and associated hardware in a safe state and invoking a computer reboot. The timeout signal is used to initiate corrective actions. If, due to a hardware fault or program error, the computer fails to restart the watchdog, the timer will elapse and generate a timeout signal. Watchdog timers are widely used in computers to facilitate automatic correction of temporary hardware faults, and to prevent errant or malevolent software from disrupting system operation.ĭuring normal operation, the computer regularly restarts the watchdog timer to prevent it from elapsing, or "timing out". One pin receives the timer restart ("kick" ) signal from the computer another pin outputs the timeout signal.Ī watchdog timer (sometimes called a computer operating properly or COP timer, or simply a watchdog) is an electronic or software timer that is used to detect and recover from computer malfunctions. A watchdog timer integrated circuit (Texas Instruments TPS3823). 7/24/2023 0 Comments Chimex companySince December 2014, Chinese people have been willing to wait an average of three hours in front of a Korean-brand chimaek shop to enjoy the food. Uploading pictures of oneself holding a chicken in one hand and a beer in the other on social networks became a trend. Specialty chicken shops have been more numerous in China. Outside Korea Ĭhimaek is also popular in China because of the popular drama My Love From the Star, in which Cheon Song-i, the heroine, said "A snowy day is just perfect for our Chimaek time ." which triggered the phenomenon. In 2013, a chimaek festival in Ningbo, China, drew some 400,000 visitors in its first three days. In Daegu Metropolitan City, a chimaek festival was held in 2013. It is an event to promote Korean food culture abroad by combining chicken and beer. There are many chimaek festivals in Korea, including the Seoul Chimaek Festival which is held in mid-October in downtown Seoul. There is a prospect that various chicken restaurants will be gathered in one place and that world beer and various kinds of chicken will be a specialty of Gimpo city. Ĭhimaek Street is planned to be built in Gimpo, South Korea. The number of chicken restaurants increased from around 10,000 to 25,000 after the World Cup. Public parks would often have large screens to watch the games, and people would dress in red (the colour and nickname of the home team) and gather together to cheer for the World Cup, while eating chicken and drinking beer. The word chicken and beer were not used in conjunction until 2002 with the Korea–Japan World Cup. It was quite strange for Koreans to chop and fry chicken, but its popularity was enormous, especially around the holiday seasons. In 1977, the chicken brand Rims Chicken was founded. In the 1970s, manufacturing workers paid 3,400 South Korean won per chicken, but the price of a boiled chicken was ₩2,500, and 500 cc (18 imp fl oz 17 US fl oz) of beer was ₩450. At this time, chicken and beer were sold together, which eventually led to the creation of chimaek. With the introduction of cooking oil in Korea in 1971, chicken and oil were plentiful, which created an environment where people could eat more chicken. Chicken production increased 13 times as the nation's economy grew. The concept of fried chicken was well-known in Korea since the early Joseon dynasty as Pogye (포계) as it appeared in the Sangayorok (산가요록) cookbook written in 1459. It's so popular that Koreans created the word Chi-neunim, which is a compound word of chicken and God Haneunim in Korean. Today, fried chicken is one of the most popular dishes in Korea. Moreover, the 2002 Korea–Japan World Cup shed more light on the chimaek phenomenon, and the dish has also had a significant impact on Korean drinking culture. While chicken was gaining popularity, a new draft beer which appeared in the 1970s was also becoming very popular, and it became common for the two to be combined as a single menu item. From the roasted chicken that appeared in the early 1960s to the spicy chicken that was adapted to meet Korean tastes, South Korea has imported and developed a growing variety of chicken dishes. Modern chimaek is believed to have been invented in late 20th century, but it is hard to pinpoint the exact time and place. There is a historic record that indicates a similar recipe has existed in Korea since at least 600 years ago, but which was long forgotten until the late 2010s. Chimaek ( 치맥 from Korean chikin 'fried chicken', and maekju 'beer' ) is a pairing of fried chicken (either plain huraideu or spicy yangnyeom) and beer, served as anju (English: food with alcohol) in the evening in many South Korean restaurants, including a number of specialized chains. 7/24/2023 0 Comments Free online quickbooks tutorialYou can view Michelle’s full channel of videos here.
7/24/2023 0 Comments Yacreader wont syncI’m going to enjoy reading comics when I’m in the sauna at the gym, at Starbucks, at the beach, etc. This app is going to make me start reading other comic series because it’s so easy to copy and paste from one folder to another and organization is so important these days for IOS devices. Then I created a few new folders for my other Walking Dead stuff like special editions, Here’s Negan, and so on. The ability to edit and name files once they are in is great as well as leaving notes, bookmarks, etc. I just got this app and loaded my entire, The Walking Dead series on it, issues 1-188 in one folder. This app YACReader is the best $2.99 app that you will ever find, probably for any genre. I love it’s interface and ease to use!ĭon’t going trying to search for a free app because they will be ridden with ads and horrible programming. This is by far the best comic book reader app that you are going to find. Visit the web site at or get support at the web site of YACReader for computers at - YACReader for computer is FREE and is available for all major computer platforms.įind other users and help at: http:- Facebook page -, Twitter - or the YouTube channel. Now, you can also enjoy YACReader in your iOS device. Several thousand users manage and read their comics using YACReader in their computers since 2009. Configure your reading experience with various fit modes, single or double page mode, continuous scroll, automatic margins trimming, and several ways to setup the hot areas in the screen. Do you like Manga? YACReader supports Manga mode reading and webtoon. Enjoy reading comics and do not worry about anything else. YACReader has the easiest method for selecting multiple comics and folders and organize them.Ī single tap is all you need to read your comics from start to finish thanks to the built-in YACReader automatic scroll. Organize your comic library creating folders and copy, cut, paste or delete comics and folders. Import comics from any place in your device thanks to the integration with Document Picker. You can also browse, import ,remote read and sync back the digital comic collections stored in your computer using the desktop version of YACReader (totally free)*. YACReader supports iTunes File Sharing to copy comics between your computer and YACReader. You can use your Dropbox, Google Drive, Box and OneDrive account for synchronizing your comics with YACReader. Importing your comics into your iPad, iPhone or iPod Touch has never been easier. YACReader supports all the common digital comic formats, such as: cbz, cbr, zip, rar, rar5 or pdf. Enjoy your collections of digital comics anywhere. YACReader offers you the best way to read and manage your digital comics. 7/24/2023 0 Comments 18th birthday captionI wish you luck in finding the ideal balance between the two. Having independence and taking some responsibility are two things that come with turning eighteen. A parent’s greatest happiness is seeing their kids prosper. You are now an adult and getting ready for college. A long time from now, life will still have a great deal to offer. You have just stepped through the adulthood doorway. Once you turn 18, you become responsible for your own fate, but keep in mind that freedom also comes with responsibilities. May God grant you health, wisdom, and peace throughout your adult existence. Take off then! Have fun with it! At long last, you have reached the age of 18! Yay! We are just at your side to direct you while you sample the breadth, height, and depth of life. Even so, keep your chin up and your smile wide. You’ve accomplished a significant life landmark, but there is still a ways to go before you get at your final destination. Our family was blessed to have the most beautiful and gentle daughter. Our lives were permanently altered on this day eighteen years ago. Cheers to turning 18!Ĭongratulations on reaching your adulthood! While it’s been a journey, I am certain you are eager to find out where your future will bring you. The best day of your life is right now - this is it. Think exclusively about the things that bring you joy on your bday. You’ve grown so nicely from the little little child to a stunning woman! Happy 18th birthday, honey. Whether you are 18 or 81 years old, you will forever be considered your daddy’s little princess. May each and every one of your dreams take flight and soar higher! Happy 18th birthday, my beauty! You have a lot of potential and deserve the very best in life. Once you become 18, you’ll be able to go on exciting new adventures. However, always keep in mind that I’m here for you anytime you need me. You are now ready to take good care of yourself going ahead. Happy 18th! Don’t let the fact, that you are now an adult, make you act foolishly. I treasure this day just as much as you do. God has provided me with a satisfying life and wonderful friends like you. We should go out to do something nice for you, because you earned it! Happy 18th!Įven though it’s your 18th birthday, today marks your first birthday as an adult. It’s your first day of adulthood, so celebrate with your family or friends and create some genuinely priceless memories! Birthday greetings!Ĭongratulations on starting a new stage of life in which you will be able to enjoy yourself like grownups do. May eternal youth and knowledge be added to your magnificent soul. I wish you only the happiest emotions as you embark on this epic adventure. Set aside your concerns because it’s time to celebrate. You’ve just just began your life’s adventure. I sincerely hope you take full advantage of the freedom and responsibility that adulthood brings. We hope that today will encourage you to move forward, and assist you in making wise choices for greater good. Take pleasure in the delight it has provided you. You’ve been looking forward to today for all these years. Hello, adulthood! Have a happy 18th birthday! You’ll have more obligations, responsibilities, and fun starting today. Congratulations on having reached the age of 18! Congratulations! You will always be my darling little sister, no matter how old you get. The 18th birthday of the princess has arrived! I’m overjoyed for you, my darling. But after that’s through, you’ll start to feel the fire of age and experience. Enjoy your birthday!īest wishes on your 18th birthday! For a couple of days, adulthood can seem sweet. I’m hoping for the best for you in the future. Life is like traveling by boat, and as of today, you are prepared to steer your own vessel. Greetings on reaching the age of 18! I hope your future is wonderful! True maturity is the result of experience. Salutations on turning 18!Ī number is all that age is. It’s time to take some responsibilities so you can show us all that you’re an adult. Happy birthday, !Ĭongratulations on reaching adulthood. Make the most of this unique time in your life. Happy first adult birthday, my love! God’s blessings be with you today and always!Ĭongrats for turning 18! May the future be as happy and prosperous as today. These birthday wishes are the most creative, humorous, and meaningful you can find on the internet. Here is a beautiful collection of congratulatory messages and greetings to send to someone who will be celebrating their birthday soon. After all, adulthood gives people the chance to live freely and make their own decisions. The majority of teens anxiously await this day so they may have a huge party on their 18th birthday. Maybe the most important birthday of all, since it marks the beginning of their adult lives. Happy 18th Birthday Wishes: The eighteenth birthday is a milestone event for any and all teenagers. 7/24/2023 0 Comments Perfect dark maulerTitled Perfect Dark Zero, it takes place three years before the original, with Joanna as a bounty hunter working for both her freelance father and a computer hacker. Perfect Dark later received a full-fledged prequel in Novemfor the Xbox 360. Both games can be used with the Nintendo 64 Transfer Pak add-on as a bonus way to unlock cheats. It also supports two-player multiplayer with use of a link cable. Instead of a traditional first-person shooter, it is played in a third-person overhead perspective with a limited first-person shooting. It is set one year before the events of the main game, as fresh graduate Joanna is sent on her first mission to destroy an illegal cyborg manufacturing facility in the South American jungle. The game also received a handheld adaptation, released for the Game Boy Color on August 2000. Afterwards, the plot twists through espionage, presidential politics, and eventually interstellar warfare. The game begins as Joanna Dark is sent to dataDyne to exfiltrate defecting scientist Dr. The protagonist is Joanna Dark: an agent of the Carrington Institute whose high scores in training earns her the codename "Perfect Dark". The story takes place in the year 2023 involving espionage between two factions: Carrington Institute (a private research & development center) and dataDyne Corporation (a military defense contractor). It is one of the few Nintendo 64 games to require use of the Expansion Pak add-on (restricting the game to a limited version of the game's multiplayer when the add-on is not found) Along with a heavily-enhanced multiplayer mode (dubbed "Combat Simulator"), the game includes numerous gameplay enhancements (including two new ways to experience the campaign: co-operative multiplayer and "counter-operative" multiplayer). The spiritual successor to Rare's earlier first-person shooter GoldenEye 007, Perfect Dark features a new original universe with a futuristic sci-fi storyline. Perfect Dark is a sci-fi espionage first-person shooter developed and published by Rareware for the Nintendo 64 in North America (on May 22, 2000), Europe (on June 30, 2000), and Japan (on October 21, 2000). Overview The protagonist: secret agent Joanna Dark. 7/24/2023 0 Comments 1.8 keystrokes modTo play your first Camera Path, click the Play Button next to the Keyframe Timeline.īy default, the Camera Path starts from the Cursor Position on the Keyframe Timeline.īy clicking while holding the Ctrl key ( Cmd key on Mac), you can however start from the beginning regardless of the Cursor Position.īelow the Render Method Dropdown, you can enter the desired Video Resolution (Width * Height). Do not add a Time Keyframe containing an earlier point in time after another Time Keyframe. Note: Travelling backwards in time is not supported during Camera Paths. Hint: By right-clicking a Time Keyframe on the Keyframe Timeline, you can jump to this Keyframe's Timestamp Value. Two Time Keyframes with the same Timestamp will freeze the Replay time for the duration of their interval. When playing the Camera Path, the Replay's time will interpolate between the set Time Keyframes in the Keyframes' intervals. You can set a Time Keyframe using the "Add Time Keyframe" button.Ī Time Keyframe initially contains the Replay's point in time when creating the Keyframe. Time Keyframes can be used to precisely control time travelling during a Camera Path.Įvery Time Keyframe represents a timestamp in the Replay itself. Troubleshootingĥ.1 No FFmpeg installation found 5.2 Crash while rendering 5.3 Unsupported Launchers 5.4 Compatibility with other Modsĥ.4.1 General information 5.4.2 Shaders Mod 5.4.3 Custom Main Menu 5.4.4 Tickrate Changer 5.4.5 LabyMod 5.4.6 OldAnimationsMod 5.4.7 Orange's 1.7 Animations 5.4.8 Sk1er Club: Patcher 5.4.9 Baritone 5.4.10 RandomPatches 5.4.11 Sodium 5.4.12 Resource Loader 5.4.13 LiteLoader Replayingģ.1.1 Basic Controls 3.1.2 Camera Roll 3.1.3 Spectating Entities 3.2 Controlling Timeģ.2.1 Replay Speed 3.2.2 Jumping in Time 3.3 Camera Pathsģ.3.1 Introduction 3.3.2 Keyframe Timeline 3.3.3 Position Keyframesģ.3.3.1 Path Interpolation 3.3.3.2 Path Preview 3.3.4 Time Keyframesģ.3.4.1 Synchronizing Timelines 3.3.5 Spectator Keyframes 3.3.6 Editing Keyframes 3.3.7 Removing Keyframes 3.3.8 Keyframe Repository 3.4 Renderingģ.4.1.1 Default Rendering 3.4.1.2 Stereoscopic Rendering 3.4.1.3 Cubic Rendering 3.4.1.4 Equirectangular Rendering 3.4.2 Video Settingsģ.4.2.1 Video Resolution 3.4.2.2 Video Framerate 3.4.2.3 Video Encoding and Quality 3.4.3 Advanced Settingsģ.4.3.1 Render Nametags 3.4.3.2 Stabilize Camera 3.4.3.3 Chroma Keying 3.4.3.4 Depth Map 3.4.4 Command Line Settingsģ.4.4.1 Custom Command 3.4.4.2 Command Line Arguments 3.4.5 Rendering Performance 3.5 Ambient Lighting 3.6 Quick Mode 3.7 Player Overview 3.8 Thumbnails 3.9 Event Markers 4. 1.1 Installing the Replay Mod 1.2 Installing FFmpegġ.2.1 Windows 1.2.2 Mac OSX 1.2.3 Linux 1.3 Settings 1.4 Accounts 2. |