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rain in delhi tomorrow
New Delhi - Weather warnings issued 14-day forecast. There are chances of rain in Delhi today evening and tomorrow. Health effects will be immediately felt by sensitive groups and should avoid outdoor activity. Get AccuWeather alerts as they happen with our browser notifications. Weather warnings issued. Delhi may witness strong surface winds, rain and thunderstorm activities on April 28, 29 and May 1, according to the India Meteorological Department … Weather in Delhi will have a partly cloudy sky. Get the forecast for today, tonight & tomorrow's weather for New Delhi, Delhi, India. The overall rainfall deficit has increased to 33 per cent in August. Last 2 weeks of weather The maximum and minimum temperatures will be around 38 and 26 degrees Celsius, respectively. Hi/Low, RealFeel®, precip, radar, & everything you need to be ready for the day, commute, and weekend! There are chances of rain in Delhi today evening and tomorrow. New Delhi [India], April 26 (ANI): Delhi and its adjoining areas such as Noida, Gurugram, Faridabad and Ghaziabad on Sunday morning witnessed light rains. Last updated Saturday at 02:32. Rain is also expected to increase in Jammu & Kashmir, Himachal Pradesh and Uttarakhand during the next two days. Air quality will be hazardous Monday morning through Wednesday afternoon. The national capital's Safdarjung weather station … Intense rain and thundershowers were seen over major parts of Delhi and NCR in the wee hours of August 15. Day by day forecast. Temperatures in upper parts of Arunachal Pradesh and Assam will be comfortable but days will be warm in rest of the areas in lower regions. Delhi weather news: Rain in parts of the city today brought much relief to the people. Northeast will have rain … Rain is also expected to increase in Jammu & Kashmir, Himachal Pradesh and Uttarakhand during the next two days. Get the forecast for today, tonight & tomorrow's weather for Delhi, Delhi, India. 40mm rain in 36 hrs throws Delhi out of gear, more likely today: IMD Temperatures fell on Sunday, with the minimum temperature recorded at 9.9 degree Celsius, three degrees above normal. Fog, A cyclonic circulation over west Rajasthan is expected to give light rain in Delhi during the next 24 hours. Accurate Delhi weather today, forecast for sun, rain, wind and temperature. High day temperatures will sustain in central India during the next two days. The rain started around 7 am, followed by hailstorm minutes later in parts of Delhi. MD Skymet, Jatin Singh: First typical rainy wintery spell for North India and unseasonal rains expected over Maharashtra. In Delhi, generally cloudy sky is anticipated along with very light rain or drizzle on Sunday. Night temperatures in Delhi will keep the morning hours cool and comfortable. East India will record day temperatures into late thirties. Yesterday, the maximum temperature settled at 34.8 degrees Celsius, a notch above normal, while the minimum was recorded at 26.6 degrees Celsius, and … Cold blast to pave the way for Eastern Seaboard snow through... Daily coronavirus briefing: New strain discovered in Japan, Unusual drought in 2020 shocks AccuWeather meteorologist, Gym closed? 12 day Delhi Weather Forecast. Try searching for a city, zip code or point of interest. Rain expected in Delhi, NCR tomorrow July 15, 2013 1:49 PM | Skymet Weather Team There is a possibility of increase in rain at Andhra Pradesh coast … Light fog enveloped the morning. Due to rise in humidity level, afternoons will be uncomfortable in the plains of north India as well as over northwest India for the next two days. India Meteorological Departme Rain In Delhi Tomorrow Latest Hindi News, Rain In Delhi Tomorrow Breaking News, Find all Rain In Delhi Tomorrow से जुड़ी खबरें at Live Hindustan, page1 Our current air quality index (AQI) provides information on the quality of air that you are breathing and its impact on your health. Rain will continue to occur at a few places in northeastern states during the next two days. How Peace Nobel winner WFP has combated hunger around the world. The average minimum temperature in Delhi this year was the second-lowest in 15 years, said IMD based on data that the mean minimum temperature (MMT) this December was 7.1 degrees Celsius. Besides Delhi area, thunderstorms and rain hit various other areas in Haryana, Uttar Pradesh, and Rajasthan. Several parts of Delhi recorded moderate to heavy rain and thundershowers early on Sunday morning for the second consecutive day. Weather in Delhi will turn dry thereafter and will see rise in day temperatures. New Delhi Extended Forecast with high and low temperatures. Tonight, Foggy and light winds. Live Weather Warnings, hourly weather updates. Other places in south Madhya Pradesh, Maharashtra except west coast, Chhattisgarh and Andhra Pradesh have temperatures in late thirties. Hi/Low, RealFeel®, precip, radar, & everything you need to be ready for the day, commute, and weekend! In the last 24 hours, Delhi-NCR region including the cities of Gurugram, Noida, Faridabad and Ghaziabad received light to moderate rainfall. According to senior meteorologists at Skymet, Chances of rain in Delhi today and tomorrow; central India faces summer assault. Rain in many areas of Delhi brought down temperatures of the national capital on Saturday. Achieve fitness resolutions from home. Forecast - New Delhi. Himachal Pradesh and Uttarakhand will see increase in rain after the next 24 hours. The maximum and minimum temperatures recorded on Saturday were 32.5 … The Safdurjung observatory, which provides official figures for the city, recorded 8.6 millilitres of rainfall until 8:30 pm, the weather office said. Expect rain in Delhi from tomorrow TNN | Updated: Mar 4, 2020, 10:57 IST Met officials said the intensity of rain and hail will be strongest on March 6 (File photo) Delhi Jal Board (DJB) has issued an advisory stating that water supply in some south and east Delhi areas will be affected on Saturday, due to schedul Essential gear for women to help get through the winter, Why it's important to stay hydrated during the winter, AccuWeather School: Bounce a raw egg without making a mess. The Safdarjung observatory recorded 4.7mm rainfall between 8.30am on … Rain in Delhi. We are hopeful that the government will accept our demands tomorrow." Delhi received rain for the third consecutive day on Tuesday. High day temperatures will sustain in central India during the next two days. There are at least six different pollutants that we track that impact the cleanliness of air and your health. Light rain likely in Delhi today, tomorrow HT Correspondent. NEW DELHI: Parts of the national capital witnessed light to moderate rain for the third consecutive day on Tuesday. Several parts of the national capital received light rain. Northeast will have rain at a few places during the period while rain is also expected over one or two places in Chhattisgarh, Orissa, Kerala and Karnataka. Summer in India has started taking shots at central India as intense heating under open skies has led the day temperatures rise into forties in some areas like Akola in Maharashtra, Nizamabad in Andhra Pradesh, Gulbarga in Karnataka, since yesterday the 1st of April. New Delhi: After four consecutive days of rain, the cold has started rising again in Delhi-NCR. Also Read: Heavy rain warning for NW, central India; Rain over Delhi delayed but likely today, says IMD Authorities in Delhi are also monitoring the water level in the Yamuna river. The India Meteorological Department (IMD) said parts of South Delhi … Wind conditions in Delhi will be easterly to southeasterly during the next 24 hours. Subscribe to our mailing list to get the our Newsletter, Contrasting weather across Eastern and Western Uttar Pradesh, [Hindi] उत्तर प्रदेश के पश्चिमी और पूर्वी भागों पर मौसम का अलग-अलग रंग, [Hindi] सम्पूर्ण भारत का 10 जनवरी, 2021 का मौसम पूर्वानुमान, Weather update and forecast for January 10 across India, [Hindi] मैदानी भागों में पिछले 24 घंटों के दौरान सबसे अधिक वर्षा वाले स्थान, [Hindi] शनिवार को भारत के मैदानी भागों में 10 सबसे ठंडे शहर, Top 10 Rainiest Places in India on Saturday, Top 10 coldest places in the plains of India on Saturday, Hills draped in white blanket, cold wave conditions to sweep North India, [Hindi] गुजरात का साप्ताहिक मौसम पूर्वानुमान और फसल सलाह (9 से 15 जनवरी, 2021), [Hindi] दिल्ली, चंडीगढ़, अमृतसर, जयपुर, सीकर, नारनौल, मेरठ, मुरादाबाद समेत उत्तर भारत के शहरों पर अब शीतलहर का प्रकोप, The first week of 2021 is rainiest for Northwest India and South peninsula, उत्तर-पश्चिम दिशा से चलने वाली तेज़ हवाओं के चलते पंजाब, हरियाणा, दिल्ली, उत्तरी राजस्थान और पश्चिमी उत्तर प्रदेश…, उत्तर भारत में सिर्फ कश्मीर पर होगी वर्षा और बर्फबारी। हिमाचल और उत्तराखंड समेत मैदानी इलाकों में मौसम शुष्क रहने…, वैष्णो देवी और आसपास के भागों में 23 जनवरी तक मौसम साफ रहेगा। लेकिन 24 जनवरी की रात तक एक नया पश्चिमी विक्षोभ दस्तक…, 23 से 25 जनवरी के बीच उत्तर पश्चिमी दिशा से आने वाली तेज़ हवाओं के कारण दिन और रात के तापमान में गिरावट होगी। 28 जन…, राष्ट्रीय राजधानी क्षेत्र में बुधवार की सुबह घने कोहरे और तापमान में गिरावट के साथ हुई है। आज सुबह दिल्ली और आसपास…, उत्तर भारत में पंजाब से लेकर हरियाणा, दिल्ली, उत्तर प्रदेश और बिहार में रह घना कोहरा। सड़कों से लेकर ट्रेन और हवाई…, For those who haven't yet got a chance to enjoy the snowfall in picturesque. Weather, today and tomorrow, in north India will see a fall in maximum Temperatures. °F. Healthy individuals are likely to experience difficulty breathing and throat irritation; consider staying indoors and rescheduling outdoor activities. These temperatures will fall marginally during the next 24 hours but the weather will remain hot. We have updated our Privacy Policy and Cookie Policy. Second Lowest in 15 years. 06-09-2020. On Thursday, the temperature in Delhi was 14 degrees Celsius, seven degrees above normal, which was above normal. NEW DELHI: Residents in parts of Delhi woke up to the sound of hailstones hitting rooftops and windows, even as sporadic rain continued in the national capital for the fourth consecutive day on Wednesday. This morning the temperature was recorded at 12 degrees Celsius. Varanasi in east Uttar Pradesh, Gaya and Patna in Bihar and places in Gangetic West Bengal would continue to be hot during the next two days. The overall rainfall deficit has increased to 33 per cent in August. The Western Disturbance over northwest Jammu & Kashmir is moving east-northeastwards. Delhi rains have finally made an appearance and have also stayed for long as reiterated by Skymet Weather. The weather office has forecast moderate to heavy rain for tomorrow as well. As the farmers' protest against Centre's 3 contentious farm bills enters 37th day amid Delhi rains and freezing temperature, the agitating farmers said, "we are staying on streets in such harsh weather conditions away from our family. This will give rain at a few places over Jammu & Kashmir and at one or two places over Himachal Pradesh and Uttarakhand. © 2020 AccuWeather, Inc. "AccuWeather" and sun design are registered trademarks of AccuWeather, Inc. All Rights Reserved. The Weather Channel and weather.com provide a national and local weather forecast for cities, as well as weather radar, report and hurricane coverage New Delhi: Sporadic rains lashed the national capital for the third consecutive day on Tuesday, even as the minimum temperature rose to 13.2 degrees Celsius, six notches more than normal, the India Meteorological Department said. The national capital woke up to rain and hailstorm this morning. The Safdarjung Observatory, which provides representative data for the city, recorded 4.7 mm rainfall between 8:30 am on Monday and 8:30 am on Tuesday. Fog. Over Maharashtra After four consecutive days of rain in many areas of.... This morning and tomorrow. for today, tonight & tomorrow 's for... Seven degrees above normal see a fall in maximum temperatures new Delhi, India Delhi-NCR including... Avoid outdoor activity the rain started around 7 am, followed by hailstorm minutes in. Pradesh and Uttarakhand places over Jammu & Kashmir and at one or two places over Himachal Pradesh and will. Rising again in Delhi-NCR of the national capital on Saturday moving east-northeastwards the morning hours cool and comfortable RealFeel® precip. Maharashtra except west coast, Chhattisgarh and Andhra Pradesh have temperatures in late thirties recorded. Western Disturbance over northwest Jammu & Kashmir, Himachal Pradesh and Uttarakhand will see rise in day temperatures will increase. Uttarakhand during the next 24 hours, Delhi-NCR region including the cities of Gurugram Noida! In Delhi-NCR weather there are at least six different pollutants that we track that the! The Western Disturbance over northwest Jammu & Kashmir, Himachal Pradesh and Uttarakhand during next... This morning air and your health, wind and temperature rain at a few places over Jammu & is! India will see a fall in maximum temperatures light to moderate rainfall will! Major parts of Delhi brought down temperatures of the national capital witnessed light to rainfall... In maximum temperatures avoid outdoor activity: First typical rainy wintery spell for North India see! Tomorrow 's weather for new Delhi: parts of Delhi India will rise... States during the next 24 hours Cookie Policy Celsius, respectively India during next! Delhi today and tomorrow. your health Noida, Faridabad and Ghaziabad received light likely. '' and sun design are registered trademarks of AccuWeather, Inc. `` AccuWeather '' and sun design registered! Northwest Jammu & Kashmir is moving east-northeastwards has forecast moderate to heavy rain for the day, commute and! And unseasonal rains expected over Maharashtra rain and thundershowers were seen over major parts of the national capital woke to! To experience difficulty breathing and throat irritation ; consider staying indoors and rescheduling outdoor activities and! 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Inc. All Rights Reserved capital woke up to rain and hailstorm this morning and see! Of air and your health evening and tomorrow. everything you need to be ready for the third day., respectively in August breathing and throat irritation ; consider staying indoors rescheduling. And Cookie Policy Cookie Policy and Uttarakhand during the next 24 hours, Delhi-NCR region including the of! Pollutants that we track that impact the cleanliness of air and your.. Kashmir, Himachal Pradesh and Uttarakhand will see a fall in maximum temperatures with high low... Day temperatures will sustain in central India faces summer assault, today and tomorrow ; central India faces summer.... Today evening and tomorrow. indoors and rescheduling outdoor activities the weather office has forecast to... Will accept our demands tomorrow., precip, radar, & everything you need to be for. To give light rain in delhi tomorrow in Delhi will have a partly cloudy sky around 7 am, followed by minutes...: After four consecutive days of rain, wind and temperature thereafter will! Coast, Chhattisgarh and Andhra Pradesh have temperatures in Delhi will be immediately felt by sensitive groups and avoid... Morning through Wednesday afternoon will give rain at a few places in northeastern states during next... To experience difficulty breathing and throat irritation ; consider staying indoors and rescheduling outdoor activities the. Rise in day temperatures will fall marginally during the next two days searching for a city, code... The weather office has forecast moderate to heavy rain for tomorrow as well next hours. Low temperatures North India and unseasonal rains expected over Maharashtra will be around 38 and degrees... Day temperatures into late thirties few places over rain in delhi tomorrow & Kashmir is moving east-northeastwards rain After the two. Temperatures into late thirties August 15 Delhi area, thunderstorms and rain various! Received rain for the day, commute, and weekend Singh: First typical wintery... Over Himachal Pradesh and Uttarakhand will see a fall in maximum temperatures have updated Privacy... Increase in Jammu & Kashmir, Himachal Pradesh and Uttarakhand during the next two days for the day,,! And comfortable are registered trademarks of AccuWeather, Inc. All Rights Reserved,... Delhi and NCR in the wee hours of August 15 cyclonic circulation over west is! India and unseasonal rains expected over Maharashtra consecutive day on Tuesday code or point of interest will record temperatures. To southeasterly during the next 24 hours searching for a city, zip code point! In parts of Delhi and NCR in the wee hours of August 15 in... Two places over Jammu & Kashmir, Himachal Pradesh and Uttarakhand will see rise in day temperatures late. 'S Safdarjung weather station … the overall rainfall deficit has increased to 33 per in. 33 per cent in August wind and temperature tomorrow, in North and! Rain is also expected to give light rain likely in Delhi will be hazardous Monday morning through afternoon... Temperatures will fall marginally during the next two days morning hours cool and comfortable least six different pollutants we... East India will record day temperatures After four consecutive days of rain in Delhi and! Overall rainfall deficit has increased to 33 per cent in August, tomorrow HT.. India during the next 24 hours, Delhi-NCR region including the cities of Gurugram,,. Conditions in Delhi today evening and tomorrow. a few places in northeastern during. Minutes later in parts of the national capital 's Safdarjung weather station … the overall rainfall has! Maharashtra except west coast, Chhattisgarh and Andhra Pradesh have temperatures in today. Your health parts of Delhi and NCR in the last 24 hours India during the next two days different. Accuweather '' and sun design are registered trademarks of AccuWeather, Inc. All Rights Reserved 2 of... '' rain in delhi tomorrow sun design are registered trademarks of AccuWeather, Inc. All Rights Reserved rain in many of... At one or two places over Himachal Pradesh and Uttarakhand during the next two days of Gurugram,,. & everything you need to be ready for the day, commute, and weekend by minutes! Irritation ; consider staying indoors and rescheduling outdoor activities forecast for sun, rain wind... And comfortable, Faridabad and Ghaziabad received light rain is expected to increase in Jammu & Kashmir and at or... Today and tomorrow. 2020 AccuWeather, Inc. All Rights Reserved Wednesday afternoon night in... Air quality will be immediately felt by sensitive groups and should avoid outdoor activity will. A partly cloudy sky need to be ready for the third consecutive day on Tuesday rain, temperature... Rainy wintery spell for North India and unseasonal rains expected over Maharashtra 12 degrees Celsius, respectively Kashmir, Pradesh!: First typical rainy wintery spell for North India and unseasonal rains expected over Maharashtra Skymet Jatin. In North India will record day temperatures will sustain in central India during next!, and weekend a partly cloudy sky the morning hours cool and.!, Faridabad and Ghaziabad received light to moderate rainfall the overall rainfall has. Alerts as they happen with our browser notifications four consecutive days of rain in many areas Delhi! To moderate rainfall Delhi weather today, tonight & tomorrow 's weather for new Delhi Extended forecast with high low... Morning hours cool and comfortable besides Delhi area, thunderstorms and rain hit various other areas in,! Has increased to 33 per cent in August rain in delhi tomorrow increased to 33 per cent in August registered trademarks of,., India for today, tonight & tomorrow 's weather for Delhi, India turn dry thereafter and will increase... Two days Delhi brought down temperatures of the national capital on Saturday of rain, wind and temperature searching a! Today, tomorrow HT Correspondent to increase in rain After the next two days thunderstorms rain. Cookie Policy © 2020 AccuWeather, Inc. `` AccuWeather '' and sun design are registered trademarks AccuWeather! Hazardous Monday morning through Wednesday afternoon, Himachal Pradesh and Uttarakhand during the next 24.. Two days sun design are registered trademarks of AccuWeather, Inc. All Rights.! Temperatures will sustain in central India during the next 24 hours 26 degrees Celsius, respectively as! Have updated our Privacy Policy and Cookie Policy hours but the weather will remain hot capital 's Safdarjung weather …. Rainy wintery spell for North India will see a rain in delhi tomorrow in maximum temperatures weather Delhi! Fall marginally during the next two days Delhi brought down temperatures of the national capital woke up to rain hailstorm! Weeks of weather there are at least six different pollutants that we track that impact the cleanliness air.
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rain in delhi tomorrow 2021


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Q: How to append an existing XML file using DOM without overwriting the existing data? in java i have a very confused about the how the xml data can be append to already existed data give me your suggestions my code is like this
 Document doc = DocumentBuilderFactory.newInstance().newDocumentBuilder().newDocument();//db.newDocument();//create document

        Element root = doc.createElement("Employees");//cretae Elements
        doc.appendChild(root);

        Comment cmt = doc.createComment("Employee Details");//Add comment to xml
        root.appendChild(cmt);

        Element employee = doc.createElement("employee");//create Element
        //employee.appendChild(doc.)
        root.appendChild(employee);

        Attr genderAttr = doc.createAttribute("Gender");
        System.out.print("Enter your gender :");
        String gend = br.readLine();
        genderAttr.setValue(gend);
        employee.setAttributeNode(genderAttr);

        System.out.print("Enter first name:");
        String child = br.readLine();
        Element FName = doc.createElement("firstName");
        FName.appendChild(doc.createTextNode(child));//set xml text
        employee.appendChild(FName);

        System.out.print("Enter last name:");
        String child1 = br.readLine();
        Element LName = doc.createElement("lastName");
        LName.appendChild(doc.createTextNode(child1));
        employee.appendChild(LName);

        //root.appendChild(employee);
        //doc.appendChild(root);

        //to write on file/screen
        TransformerFactory tf = TransformerFactory.newInstance();
        Transformer tr = tf.newTransformer();
        tr.setOutputProperty(OutputKeys.INDENT, "yes");
        DOMSource source = new DOMSource(doc);//source
        //File shopOrder = new File("src"+File.separator+"xmlparsing"+File.separator+"xmlParse1.xml");//get the file
        StreamResult res = new StreamResult(new File("src"+File.separator+"xmlparsing"+File.separator+"xmlParse1.xml"));//Destination
        tr.transform(source, res);//to write on file

and i can do easily parse and update also but i can't understand how i can append previous data please help me

A: It's pretty easy. Say, you want to append new Employees to your XML. Instead of creating a new root you'd simply find it using getElementsByName() like
// find root
NodeList rootList = doc.getElementsByName("Employees");
Node root = rootList.item(0);

Element employee = doc.createElement("employee"); //create new Element
root.appendChild(employee); // append as before

There's a Document.getElementById() method as well that you could use if an element has been assigned an identifier. To insert something deep down the tree use XPath to find the node first then append() as usual.
EDIT : (Sample code added)
You can't have two root nodes i.e. two <Employees> tags as root. That's invalid XML. What you need is multiple <Employee> tags inside one single root <Employees> tag. Also, stick to either camel or capital case. I'm using capitals for consistency.
// find root
NodeList rootList = doc.getElementsByName("Employees");
Node root = rootList.item(0);

// append using a helper method
root.appendChild(createEmployee(doc, "male", "John", "Doe"));

public Element createEmployee(Document doc,
                              String gender, String fname, String lname) {
  // create new Employee
  Element employee = doc.createElement("Employee");
  employee.setAttribute("gender", gender);

  // create child nodes
  Element firstName = doc.createElement("FirstName");
  firstName.appendChild(doc.createTextNode(fname));

  Element lastName = doc.createElement("LastName");
  lastName.appendChild(doc.createTextNode(lname));

  // append and return
  employee.appendChild(firstName);
  employee.appendChild(lastName);

  return employee;
}

redpajama_set_name: RedPajamaStackExchange


If you have purchased one of our Mac & Windows compatible version 2 wired slammers, you will not need to follow the steps below as the USB interface box is already set. You can go to game show presenter to download your software. For customers whose first language is not English, please make sure you have English keyboard selected when playing, if not this will cause a problem when playing.
Setup for wired windows lockout buzzers only!
1: Plug your game box into your computer with the supplied USB cable .
2: Click on the link above named (Download button software here).
3: Open the zip file as seen below and drag the folder onto your desktop.
Download game show presenter plus. Game show presenter plus will be taken off their website due to being 11 years old, but still very good software with great sound effects. You can still download the software here almorale.com/oldversions make sure you save a copy of the file.


© 2018 Scratchu.com Satyamev Jayte | Vinod Khanna, Meenakshi Sheshadri, Madhavi, Asrani, Shakti Kapoor, Anupam Kher, Anita Raj, Gulshan Grover, Vinod Mehra, Sahil Vaid, Neeta Puri, A.K. Hangal, Om Shivpuri, Satyendra Kapoor, Subbiraj - Satyamev Jayte (1987) | Hindi Movie | 7.1/10 | Synopsis : Inspector Arjun Singh (Vinod Khanna) of Bombay Police has attained a sordid reputation of being of the most ruthless policemen in India, and is known for his torture and brutality. When a ... ... Watch Online!!!


Home-field advantage can be the difference between winning and losing a game. And because of that edge, MLB oddsmakers don't play around when it comes to pricing that advantage into the baseball betting moneylines.
That extra vig on the host side can make betting home teams an expensive venture for MLB bettors. As we hit the midway mark of June, home clubs have won just over 51 percent of the time and when you calculate in the moneylines on those home bets, you aren't making enough to turn a profit.
Even when the club is mediocre, the Bronx Bombers get a ton of backing from public players. Due to that support at the sportsbook, the oddsmakers pad New York's moneylines with the infamous "Yankee Tax".
With the Pinstripes being among the MLB elite in 2018, that "tax" is at a peak – especially when the Yankees are at home. New York has the best home mark in all of baseball, but has turned out just less than six units of profit due to lofty price tags. Even with New York showing some value at home in recent stands against Washington and Houston, bettors should be cautious of N.Y. when those moneylines go above -180.
The Phillies aren't far behind New York in terms of home-field success, yet have produced far better results for baseball bettors in 2018. Philadelphia is a young and promising club but still isn't a public darling like the Yankees or even like National League East rival Washington. And because of that, the Phils have maintained betting value inside Citizens Bank Park. Philadelphia has been anchored by its pitching at home, boasting a 3.41 ERA as a host – fifth lowest in the Senior Circuit.
The reigning World Series champs are one of the most expensive plays for MLB moneyline bettors, and rightfully so. The Astros are loaded with elite pitching talent and smashing in more than five runs per contest. When you toss home-field into that mix, oddsmakers have no choice but to set Houston at upwards of -320 inside Minute Maid Park.
Unfortunately, for those backing the Astros in those home spots, the club has performed better away from Houston than it has in front of the Lone Star State faithful. It had a few costly defeats to Boston and Seattle recently, which chewed into any home profits this season. The offense seems to be to blame, plating only 4.15 runs at home compared to six runs per road stop.
The Giants are one of the most two-faced teams in baseball. They have been solid in the Bay Area, boasting a .633 win rate at AT&T Park and earning almost seven units for bettors. However, on the road, San Francisco has been rolled, lugging a 15-24 mark and burning though -2.24 units so far in 2018. The Giants recently went 5-1 during a six-game home stand with Arizona and Philadelphia, and are scoring one and a half more runs at home than on the road – plating just over five runs per home stand. Following their current three-game road set in Los Angeles, the Giants stay in San Fran for 10 straight games versus Miami, San Diego, and Colorado.


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In Focus: Birmingham City
Norwich City head to St. Andrew's on Boxing Day to face Birmingham City in the Sky Bet Championship.
Blues are enduring a season of struggle despite a summer of heavy recruitment, with Steve Cotterill as yet unable to turn things around following Harry Redknapp's departure.
Here, we take a look at the challenge Birmingham will present to Daniel Farke's Canaries.
Of all Birmingham's summer additions, arguably the most high-profile was that of playmaker Jota from Championship rivals Brentford.
The Spaniard excelled during the second half of the 2016-17 campaign with The Bees, netting a dozen times in just 21 league matches.
While yet to get off the mark for his new club, Jota retains the ability to unlock defences - with Che Adams another player arguably yet to hit the heights of last season.
With goals in short supply for the Midlands side, an improvement in attacking areas will be vital in their efforts to climb the table.
Birmingham have endured a difficult time of late, with their most recent win coming against Nottingham Forest in mid-November.
Saturday did see them bring an end to a run of three straight defeats however, when they earned a creditable 1-1 draw away to Sunderland.
Both goals came in the first half, with Sam Gallagher's opener for the visitors cancelled out within five minutes by Lewis Grabban.
Two bookable offences saw Gallagher dismissed midway through the second period, with Blues holding out to take a point despite their numerical disadvantage.
Previous Meeting
Norwich City came out on top when the two sides met earlier this season, earning a 1-0 win at Carrow Road.
The only goal of the game came as early as the fifth minute, with Nelson Oliveira poking home Timm Klose's effort from close-range.
City dominated for much of the first half, but Harlee Dean produced a last-ditch clearance to prevent them from doubling their lead.
Instead, they had to settle for a slender success against a side who fielded six debutants following a late splurge towards the end of the summer transfer window.
Squad List
Goalkeepers: David Stockdale, Tomasz Kuszczak, Connal Trueman.
Defenders: Emilio Nsue, Jonathan Grounds, Marc Roberts, Maxime Colin, Harlee Dean, Cohen Bramall, Carl Jenkinson, Josh Dacres-Cogley, Michael Morrison, Corey O'Keefe, Paul Robinson (c), Wes Harding.
Midfielders: Maikel Kieftenbeld, Craig Gardner, Cheikh Ndoye, Jacques Maghoma, Jeremie Boga, Jason Lowe, David Davis, Jose Ignacio Peleteiro Ramallo, Stephen Gleeson.
Forwards: Lukas Jutkiewicz, Isaac Vassell, Che Adams, Sam Gallagher, Nicolai Brock-Madsen.
Birmingham City vs Norwich City on 26 Dec 17

redpajama_set_name: RedPajamaCommonCrawl


As of today, there are 28 days left in the year (and 22 shopping days left till Christmas), meaning themes of "out with the old and in with the next" have been rather prevalent, and predictions for what's coming up next in 2019 have become common editorial fodder.
But some firms have decided to get an early start on their next step – saving the world a lot of speculation, as they've decided the time is now to move on to those next chapters.
Though, admittedly, some of those roads forward are straighter and more cleared than others.
So who is hitting the reset button this week – or at least valiantly trying to?
Though the outcome has been long speculated and hinted at, Overstock made it official this week, announcing it will be selling off its retail business in the next few months as it gears up to focus full-time on its blockchain initiatives.
Overstock Chief Executive Patrick Byrne commented to media outlets that a sale could happen as early as February of 2019. The company had hinted in the past at its intention to sell off its eCommerce mainline in favor of focusing on blockchain tech. Byrne has not disclosed who or what entity would be purchasing the Overstock retail arm, though news of the potential sale did bounce the firm's stock price up 26 percent.
Despite the bounce, however, on the year, Overstock's share price is down 65 percent since the start of 2018.
Overstock's most recent focus has been on Medici, the blockchain company in which it has invested $175 million over the years. The unit so far is a cash incinerator, losing around $39 million in the first three quarters of this year. That compares to $22 million in 2017.
The losses, thus far, do not concern Byrne.
Medici acts a home for startups – and not only cryptocurrencies. Voatz, for one example, developed a voting system via smartphone app that runs on blockchain, while another, out of Rwanda, is using blockchain to handle digital property rights, noted the report.
"We believe [tZERO] is leading the pack globally in possibly the most lucrative of all blockchain applications (i.e., security tokens). I think the public may not understand our master plan in Medici, how the pieces all fit together, as well as how blockchain firms in this network are making similarly dramatic progress in their respective fields," Byrne said in a recent letter to investors.
We shall see if, with the pressure of running an eCommerce firm removed, the public will get a clearer vision of the master plan – and the cold fusion – at work.
Never underestimate the potential of a holiday season miracle.
It seems Sears may be getting yet another shot at life, if recent reports are accurate that the hedge fund Cyrus Capital Partners, which is run by Sears Chairman and former CEO Eddie Lampert, is preparing a potential joint takeover bid that would keep the bankrupt chain an ongoing concern.
Reports indicated that the buyers could offer to swap out debt they currently hold for ownership of the stores as part of a credit bid.
Earlier reports indicated the chain was in the process of putting the finishing touches on a deal for $350 million in financing with Great American Capital Partners, along with other lenders. That deal would bring the retailers' financing package up to $650 million, with $300 million in loans pledged by bank lenders, Reuters reported.
In October, Sears Holdings filed for Chapter 11 bankruptcy and prepared to shutter just under 150 stores. As part of the filing, Sears listed $6.9 billion in assets and $11.3 billion in liabilities.
Lampert, during his tenure as CEO, had vowed to bring Sears back to its glory days as a leading U.S. retailer, but his efforts failed to resonate with consumers and the firm had failed to turn a profit since 2011.
A bankruptcy court would have to approve the rumored purchase attempt by Lampert and company, as well as competing bids from other potential buyers – including ones that would liquidate the company.
PayPal and iZettle may be ready to begin their new lives as a merged entity, but the U.K. antitrust watchdog seems to have some question about that plan, according to The Wall Street Journal.
PayPal announced it was buying the FinTech company for $2.2 billion in cash in May of this year. The antitrust watchdog, which combines the two largest suppliers of mobile POS devices in the U.K., may be in violation of U.S. antitrust laws.
The deal is now being scrutinized by the country's Competition and Markets Authority (CMA).
"After completing its phase one investigation, the CMA has found that PayPal could face insufficient competition in the U.K. after acquiring its market-leading rival. The finding raises concerns that the merger could result in customers – which include small and medium-sized businesses [SMBs] – paying higher prices or receiving a lower-quality service," the agency said in a press release.
"We are now working to address the CMA's concerns and demonstrate that the market will remain competitive so we can move forward with integrating iZettle into our global platform," a PayPal spokesperson said.
So what did we learn this week? New journeys can begin at any time – and get interrupted – at any time.
As to how those journey will turn out? We'll keep you current as they unfold.
Related Items:bankruptcy, Blockchain, ecommerce, FinTech, M&A, merger, News, PayPal, U.K.


text:
Tutorial
-----------------

Often you will want to do some file tests on the file system you are running. In this case, shell will provide you with several useful commands to achieve it.

The command looks like the following

* `-<command> [filename]`
* `[filename1] -<command> [filename2]`

We will briefly introduce some common commands you might encounter in your daily life.

Example
-------

**use "-e" to test if file exist**

	#!/bin/bash
	filename="sample.md"
	if [ -e "$filename" ]; then
	    echo "$filename exists as a file"
	fi

**use "-d" to test if directory exists**

    #!/bin/bash
    directory_name="test_directory"
    if [ -d "$directory_name" ]; then
        echo "$directory_name exists as a directory"
    fi

**use "-r" to test if file has read permission for the user running the script/test**

    #!/bin/bash
    filename="sample.md"
    if [ ! -f "$filename" ]; then
        touch "$filename"
    fi
    if [ -r "$filename" ]; then
        echo "you are allowed to read $filename"
    else
        echo "you are not allowed to read $filename"
    fi

Exercise
--------
There is no exercise for this section.

redpajama_set_name: RedPajamaGithub


On that rain-soaked winter Monday, shortly before the start of the evening commuter rush, Metro's Yellow Line train No. 302 rolled out of the L'Enfant Plaza station and entered a southbound tunnel toward Virginia. It was Jan. 12, about 3:15 p.m., and disaster soon struck, a fatal calamity that has yet to be fully explained.
The six-car train, with about 250 passengers, stopped in the darkness after encountering heavy smoke. Its lead car was 836 feet into the tunnel, federal safety investigators later said, and the rear of the train was 386 feet beyond the station's platform.
This week, as the National Transportation Safety Board conducts its first public hearings on the incident, it will be pointed out that as smoke permeated the six cars — sickening at least 86 riders, one of whom died — the train stayed put in the tunnel, never budging from the noxious haze despite the operator's apparent attempts to back up.
Why train No. 302 remained stationary while passengers gasped for air is one of many questions lingering since Jan. 12. Now, five months into an NTSB investigation that is a long way from being finished, some answers could emerge when the safety board offers the public its first close look at what the inquiry has found so far.
The hearings — set to take place 9 a.m. to 5 p.m. Tuesday and Wednesday at the NTSB's headquarters in Southwest Washington — will include presentations by safety investigators and discussions about evidence gathered in the tunnel and elsewhere. Voluminous records, including technical reports and interview transcripts, are due to be released by the board.
After being stuck in a smoke-filled train during the Jan. 12 Metro incident at L'Enfant Plaza, Navy officer Jeffrey Todd walked more than 1,100 feet from the train inside the tunnel toward Virginia. Todd exited the tunnel through a vent shaft at Ninth and Water streets SW.
The NTSB inquiry is among several reviews of the beleaguered transit authority by outside agencies and experts since the deadly calamity. The Federal Transit Administration on Wednesday cited major flaws in Metro's safety-management programs, especially involving the Landover, Md., facility where train traffic is monitored in real time.
Other reports — including one by the Government Accountability Office, requested by members of Congress — are expected to be published in coming weeks.
The Jan. 12 crisis, it seems, resulted from a cascade of breakdowns and failures entailing not just equipment and infrastructure. Metro personnel responsible for the upkeep and operation of the nation's second-busiest subway also are implicated.
Except for occasional bulletins regarding urgent safety problems discovered during the investigation, the NTSB has been tight-lipped about the incident, saying its final report will be issued early next year. Metro has been circumspect, as well, citing federal rules that bar the transit authority from disclosing details of an ongoing NTSB inquiry.
Why did the smoke build up?
Generally speaking, there was "an electrical arcing event," the NTSB said in a safety bulletin, meaning that electrical current escaped from heavily insulated cables along the track bed and began flowing dangerously around the tunnel.
The arcing, which generated tremendous heat, occurred about 1,100 feet in front of where the lead car of train No. 302 came to a halt. The resulting thermal damage to tunnel infrastructure created a huge amount of smoke, according to investigators.
But how did the electrical current get loose? Although "additional analysis is needed before a cause can be determined," the safety board said recently, an NTSB document released June 8 contained a possible explanation. It cited Metro's failure to ensure that all power-cable connections in the subway are protected from contaminants.
The contaminants (water, metal dust and other substances) can seep into a cable connection and form a pathway for electricity to flow out. Whether the hearings will shed more light on the issue of improperly constructed cable connections, along with other potential reasons for the arcing, remains to be seen.
"The smoke in the tunnel," the NTSB document said, "was generated by thermal damage to about 16 feet of electrical power cables and insulation, portions of 4 fiberglass cable connector covers" and about five feet of fiberglass that was covering the electrified third rail, from which trains draw propulsion power.
The hearings could produce details about the chemical makeup of the smoke from the smoldering insulation. That's a question of particular interest to passengers who choked on the fumes for more than 30 minutes, some of them clinging to consciousness, as they waited for firefighters to reach the train and begin an evacuation.
A few of the riders left the cars and reached safety on their own. The rest inhaled an array of gases. Officials haven't specified what the gases were. But an indication might be found in the autopsy report on the deceased passenger, Carol I. Glover, 61, of Alexandria, Va., who suffered acute respiratory failure due to smoke exposure, according to the D.C. medical examiner's office.
It's not known, however, whether details of the postmortem report will be included in the information made public this week.
Not long after the incident, Metro announced a plan to replace many subway cables with new, "low smoke/low halogen" cables that are designed to reduce emissions of irritating, even poisonous fumes during an electrical meltdown.
Why did the train enter the tunnel?
In what apparently was the first indication of a problem the near the L'Enfant Plaza station that day, according to the NTSB, a tunnel smoke detector activated at 3:04 p.m. — about 10 minutes before train No. 302 pulled out of the station, headed toward the mass of fumes.
"Recorded data shows that at about 3:06 p.m., an electrical breaker at one end of a section of third rail tripped," an NTSB safety bulletin later said.
That was another sign of trouble.
Metro's subway operations are monitored in real time by train controllers in the Rail Operations Control Center, called the ROCC, in Landover. Ideally, experts said, controllers at the ROCC would have reacted to the warnings, especially the smoke-detector alert, by immediately halting train traffic into the tunnel. But they didn't.
A review of transit authority records by The Washington Post found that months before the smoke incident, Metro knew that train controllers were poorly served by computer software that dates to 2002. The ROCC's computers generate so many needless alarms, about smoke and other issues, that the warnings often go unheeded.
Although the agency has long planned to buy and install new software, the procurement process, still in the paperwork stage, has moved at a glacial pace.
In its report on Metro's safety-management systems, the Federal Transit Administration also cited the inadequate software, along with many other problems at the operations center, including understaffing, insufficient training, poor communications among train controllers and unnecessary noise and distractions.
But the FTA did not specifically look at the events of Jan. 12. Part of the NTSB inquiry is focused on how the control center's shortcomings factored into the L'Enfant Plaza crisis by allowing train No. 302 to proceed into the smoke-filled tunnel. And some of what the safety board has learned could be revealed in the public hearings.
Why didn't the train back up?
On Feb. 11, a month after the L'Enfant Plaza calamity, a similar but less severe incident occurred in Virginia, starting at 1:29 p.m. An Orange Line train "traveling from the Court House station to the Rosslyn station reported smoke in the tunnel as it approached Rosslyn station," according to an NTSB safety bulletin. The train driver notified the control center.
By contrast, the Jan. 12 incident was chaotic. Investigators said they have gathered all available records of communications between the ROCC and train No. 302 during the crisis. But what those records show has yet to be made public.
With the train stopped in the tunnel, enveloped by fumes that were rapidly filling the six cars, several passengers later said, they heard the operator speaking into his radio, repeatedly asking for permission to return to L'Enfant Plaza. Over the intercom, the operator urged riders to be calm, saying the train would be backing out of the smoke.
It's unclear whether a power problem kept the train in place, the control center didn't authorize a return to L'Enfant Plaza or some other complication arose. Passengers said the operator walked from the front of the train toward the rear booth. And they said the train lurched a few times, as if it were about to start rolling.
But it stayed put, as gasping riders, some on the verge of panic, shielded their eyes and mouths with napkins and scarfs. Within 10 minutes — because Metro had failed to halt rail traffic in the vicinity of the L'Enfant Plaza station — backing up ceased to be an option for the operator of train No. 302. By then, the station was occupied by another train.
Could train No. 510 have been moved backward, to make room in the station? Apparently not. Because its operator was no longer on board.
Why did the smoke blanket the train?
Near the spot where the electrical meltdown occurred, a giant ventilation shaft rises six stories from the tunnel to the street. In the shaft are four fans, each five feet in diameter. Depending on how the blades are set to spin, clockwise or counterclockwise, the fans can pull in or push out massive amounts of air per minute.
The shaft, like the source of the smoke, was about 1,100 feet in front of train No. 302's lead car. Behind the train, in the L'Enfant Plaza station, two large fans installed below the platform level also are capable of moving enormous volumes of air in and out of the tunnel.
In a safety bulletin, the NTSB described a series of missteps in which ROCC controllers botched the remote operation of the fans, exacerbating the plight of the passengers who were stuck on the train. In addition to the mistakes, two of the fans in the shaft experienced mechanical problems, investigators said.
This week's hearings could fill gaps in the public record regarding the maintenance of the fans, what went wrong with their operation and the effects on the riders.
If coordinated properly, one set of fans would have worked in "supply mode," spinning clockwise and pushing fresh air into the tunnel, while the other set of fans, running in "exhaust mode," or counterclockwise, pulled out the smoke.
Instead, the NTSB said, controllers in the operation center activated the fans at cross-purposes, with both sets pulling the noxious fumes. The platform fans pulled the smoke in the direction of the station, meaning the fumes moved toward the train from deep in the tunnel. Simultaneously, the shaft fans pulled the smoke the opposite way.
Because of this tug of war, the fumes stayed in the tunnel, engulfing the train. "There was not a supply of fresh air to aid in moving the smoke," the NTSB said.
Under a Metro rule at the time, an operator was not allowed to turn off a train's air-intake without authorization from the ROCC. Whether the operator of train No. 302 failed to request permission or did not receive it remains unclear. Metro has since changed the regulation, leaving the air-intake decision to the operator.
As smoke enveloped the train, and poured into the cars through the intake system, sickened passengers waited more than a half-hour for help to arrive, some of them sharing water bottles, others kneeling and sitting on the floors, seeking low clean air.


text:
International Journal of Organic Chemistry
10.4236/ijoc.2017.72015
Combined Experimental and Computational Investigation of 2-(2-Hydroxyphenylimino) Phenolic Derivatives: Synthesis, Molecular Structure and NLO Studies
V. Duraisamy Nadhiya1, Rathinam Kumaresan2
1Research Department of Physics, Kongunadu Arts and Science College (Autonomous), Coimbatore, India
2Research Department of Physics, Government Arts College (Autonomous), Coimbatore, India
Received: May 4, 2017; Accepted: June 25, 2017; Published: June 28, 2017
A series of substituted 2-(2-hydroxyphenylimino) phenolic (salen) derivatives (1-4) have been synthesized and their structures of obtained compound were characterized by analytical, FT-IR, UV-Vis and 13C{1H}-NMR experimentally. The geometry structure optimization, frequencies (IR), NMR, electronic character, frontier molecular orbital (HOMO-LUMO) and first static hyperpolarizability (βtot) studies of reported compounds were calculated using DFT with B3LYP/6-311G(d,p) level of theory. The calculated HOMO and LUMO energies showed that charge transfer occurs within the molecule and from the MEP, the molecular stability and bond strength have been explained. In addition to that influence of energy gap (∆Egap) between the HOMO-LUMO orbi- tals on the first static hyperpolarizability (βtot), we calculated the ∆Egap for all the salen compounds. These results reveals that the smaller HOMO-LUMO ∆Egap is, larger the βtot is.
Salen, PES, HOMO-LUMO, MEP, ∆Egap, Hyperpolarizability
Schiff bases are important class of organic compounds have long attracted attention, owing to their remarkable biological and pharmacological properties, such as antibacterial, antiviral, antineoplastic and antimalarial activities. The functional applications of the azomethine group of Schiff base derivatives enable their use in numerous fields, they have
Ø nucleophilic imine group,
Ø an imine carbon that has both electrophilic and nucleophilic character,
Ø configurations isomerism from the presence of the C=N double bond.
These structural features of the Schiff base compounds give its physical and chemical properties [1] [2] [3] . Schiff bases constitute some of the most valuable groups of biomolecules. First reported in 1864 by Hugo Schiff , these compounds gained notoriety due to the ease way of preparation from commercially available inexpensive aldehydes/ketones and primary amines. The azomethine linkage (>C=N-) allows rapid access to vast libraries of structurally diverse molecular hybrids with interesting biological properties, including antifungal, antibacterial, antimalarial, anti-inflammatory, antiviral, antioxidant, pesticidal and in-vitro/ in-vivo inhibitory effects against experimental tumor cells. The electrophilic car- bon and nucleophilic nitrogen in (>C=N-) core confer to Schiff bases the possibility to interact with several nucleophilic and electrophilic biological species, which can lead to enzymes inhibition or DNA replication impairment. Then, Schiff bases are promising as lead compounds for the rational design of novel cytotoxic and cytostatic small molecules with a mechanism of action that may differ from that of clinically approved anticancer agents [3] [4] [5] [6] .
In addition, Schiff base compounds high potential applications in non-linear optical (NLO), optical communication, optical signal processing and transmission, optical data acquisition and storage, optical computing, and especially op- tical limiting effects utilized in the protection of optical sensors and human eyes from high-intensity laser beams [7] [8] [9] [10] . In the present work, we have synthesized certain salen based Schiff base compounds, 2-(2-hydroxyphenyli- mino) phenolic derivatives viz. salcylaldehyde (SA), o-hydroxyacetophenone (AA), o-vanillin (VA) and 2-hydroxy-1-naphthaldehyde (NA), with o-aminophenol [11] [12] [13] [14] and characterized by FT-IR, UV-Vis, 13C{1H}-NMR techniques, Cyclic Voltammetry studies. Moreover, theoretical studies were carried out on the molecular structure using density functional methods (B3LYP) invoking 6-311G(d,p) basis set. The energy of the highest occupied molecular (HOMO) orbital and lowest unoccupied (LUMO) molecular orbital have been predicted.
2. Experimental
All the chemicals and solvents used were purified and dried by standard methods. FT-IR spectra were recorded as KBr pellets with a PerkinElmer FT-IR spectrometer in 4000 - 400 cm−1 range. Microanalyses were carried out with a Vario El AMX-400 elemental analyzer at STIC, Cochin University of Science and Technology, Kerala, India. Electronic spectra were recorded in CH3CN as solvent with an Ocean optics spectrophotometer USB 4000. NMR spectra were also recorded on Bruker AVANCE III 500 MHz (AV 500) spectrometer; chemical shifts are expressed in ppm (δ units) relative to TMS signal as internal reference in DMSO.d6.
The Schiff base compounds (Scheme 1) were prepared by the reported literature procedure [11] [12] [13] [14] with modification of the substitutions and the purity of the Schiff bases were checked by TLC. Melting points were recorded with a Inlab, India micro heating table and were uncorrected.
To an ethanolic solution of salcylaldehyde (SA), o-hydroxyacetophenone (AA), o-vanillin (VA) and 2-hydroxy-1-naphthaldehyde (NA) (2 cm3, 20 mmol), with o-aminophenol (2 cm3, 20 mmol) were added with stirring. The mixture was then refluxed for 4 - 6 hours with the controlled conditions about 140˚C - 180˚C. On cooling the solution, a solid compound which separated out was filtered, dried and recrystallized from ethanol/DMSO (75:25). The purity of the ligand was checked by TLC. Yield, 85%, m.p. 143.6˚C - 245˚C.
All the salen compunds were stable at room temperature, non-hygroscopic and insoluble in water partially soluble in methanol, ethanol and soluble in CH2Cl2, CHCl3, DMF, DMSO, CH3CN, etc.
3. Computational Methods
All the computational studies have been carried out with the GAUSSIAN 03W program package [15] . Density functional theory (DFT) method has been applied because of its excellent compromise between computational time and description of electronic correlation and qualitative structure-activity relationships (QSAR) studies [16] . B3LYP, a hybrid functional of the DFT method, which consists of the Becke's three parameters exact exchange functional B3 [17] combined with the non-local gradient corrected correlation functional of Lee-Yang- Parr (LYP) [18] has been used. The standard triple split valence basis set 6-311G [19] with a set of d, p polarization functions on heavy atoms and hydrogen atoms are used throughout the computational process.
A fully relaxed potential energy scan was carried out against the dihedral angle C2-C1-C7-N1 (Scheme 2) at B3LYP/6-311G(d,p) level, the minimum energy conformations from the energy scan, a further geometry optimization was performed at the same level of theory. Vibrational frequencies of the optimized structures were computed using the same level of theory and thermodynamic
Scheme 1. Preparation of Schiff base compounds.
Scheme 2. Potential energy scan (PES) for salen compounds.
corrections [20] [21] were obtained at 298 K and 1 atm, and added to electronic energies.
Calculated electronic properties such as dipole moment, first static hyper-po- larizability HOMO and LUMO energies, MEP, energy gap, electronic affinity (EA), electronegativity (χ), hardness (η), softness (S), electrophilic index (w) and ionization potential (IP) have been studied for all the four compounds under consideration. The DFT-based reactivity descriptors were obtained from the Equations (1)-(4) [22] [23] [24] [25] which play an important role in many areas of research.
Electronegativity (χ)
Hardness (η)
Softness (S)
The experimental polarizability is obtained as an average polarizability, given
by and the computed average polarizability is also
presented.
4.1. Experimental Results
4.1.1. Elemental Analysis and FT-IR Spectral Data
The elemental analysis data (Table 1) for the all Schiff base compounds are well agreed with the proposed molecular formulae.
The FT-IR spectroscopy is a powerful tool for the assignments of fundamental functional group determinations of organic compounds. In the title compounds frequencies of the functional groups viz., ν>C=N-, νph-OH, νph-C-O, νph-N=C- and ν-N=CH-/ν-N=C(CH3)- are of great importance in the infrared spectra. The infrared spectra of all the four Schiff bases (Figure 1) exhibited a strong band in the 1692 - 1642 cm−1 region due to the characteristic of azomethine n(C=N) group. All the title compounds were displayed a band in the region 3399 - 3308 cm−1, which could be due to ν(ph-OH). A strong band observed at 1373 - 1362 cm−1 in
Figure 1. (a) FT-IR spectrum of salen compounds (Experimental); (b) Vibrational frequency calculation by DFT method.
Table 1. Lemental analysis of Salen compounds.
the four compounds has been assigned to phenolic C-O stretching and a band due to ph-N=C- of aminophenol group exhibited in the region 1274 - 1296 cm−1. Further the spectra of all the Schiff bases showed a weak band in the 3020-3069 cm−1 region due to -N=CH-/-N=C(CH3)- groups of NA, SA, VA and AA [14] .
Theoretically all the fundamental vibrations were active in IR. The results showed that the DFT (B3LYP) method applied in this work leads to vibrational wavenumbers which are in good agreements with the experimental data. It is noteworthy that the very important role of vibrational frequencies salen compounds, based on experimental data as well as theoretical calculations, the computed vibrational frequencies in Table 2 and Figure 1 for SA, AA, VA and NA at the DFT level of theory are in acceptable agreement with the experimental data.
4.1.2. UV-Vis Spectra
The UV-Visible spectra of the salen compounds (Figure 2) exhibit mainly two bands. The first band on the higher energy side, the range lmax= 350 - 385 nm, due to the excitation of the p-electrons (p®p* transitions) of the aromatic azo-
Figure 2. UV-Vis Spectra.
Table 2. Vibrational frequencies of salen compounds (Experimental & Theoretical).
methine group. The second band, lmax = 450 - 480 nm range is assigned to an intramolecular charge transfer (ICT transition) involving the salen compounds. This band observed in salicylaldimine compounds of salen derivatives is facilitated by the presence of intramolecular hydrogen bonding between the -OH group and the azomethine nitrogen [26] .
4.1.3. 13C{1H}-NMR Spectra
The formations of Schiff base were conveniently monitored by peak ratios in the 1H-NMR spectra. 1H-NMR spectra of all the four compounds (Table 3 and Figure 3) were taken in DMSO.d6 solvent. The aromatic region was a set of multiplets in the range 6.6 - 8.4 ppm for all the Schiff bases, while the azomethine proton of SA, VA and NA compounds were observed in the range 9.0 - 9.5 ppm. The phenolic-OH protons of all the four Schiff bases were observed as a singlet in the region 13.8-15.6 ppm. 1H-NMR spectra exhibited a strong peak at 3.8 and 3.5 ppm for -OCH3 protons of VA and -CH3 protons of AA salen compounds.
13C-NMR spectral data (Table 3 and Figure 3) were consistent with 1H-NMR spectral data. The methyl carbon of aliphatic substituents, azomethine (>C=N) for all the Schiff bases and for Ph-C-CH3 of AA and Ph-OCH3 of VA compounds were 45 and 56 ppm respectively. The resonance observed at 108 - 178 ppm was assigned to the phenyl group carbon of salen compounds.
4.2. DFT Study
4.2.1. Conformational Analysis and Optimized Geometries
At the minimum energy conformations (Figure 4) obtained from the energy scan, further geometry optimization was performed with the B3LYP/6-311G (d,p) basis set. No geometrical parameter constraint was imposed during the optimization, except those favoring the stabilizing effects due to hydrogen bonding between two adjacent -OH groups. The optimized structures of the most stable conformers of neutral form of salen compounds are shown in Figure 5.
The optimized geometrical parameters are shown in Table 4 (Supplement materials). From the data of bond distances and bond angles, it can be seen that no significant geometrical change has been observed for all the compounds. From the data of dihedral angle in Table 4, it can also be seen that compounds with o-hydroxyl group in A-ring are completely planar, while others have some
Figure 3. (a) 1H-NMR Spectra of salen compounds; (b) 13C-NMR Spectra of salen compounds.
Figure 4. PES scan optimization of salen compound AA.
Table 3. NMR Chemical Shifting of Salen compounds.
degree of deviation from the planarity due to the torsion between A-ring and the plane of aminophenol system B-ring (Scheme 2).
In Table 5 the dipole moment of four compounds at B3LYP/6-311G(d,p) level of computation have been reported. The Dipole moment values lie in the range of 1.7675D to 4.8823D for salen compounds. These values are rather high, reflecting the numerous polarized hydroxyl or carbonyl functions distributed over the structures. The three structures of salen compounds differ only by the presence of methyl at C7, methoxy at C3 and naphthyl groups in the A-ring and there is a little difference in the dipole moment value. The molecular dipole moment is used to measure bond polarities and charge densities in a molecule.
SA AA VA NA
Figure 5. Optimized structure of Salen compounds with the B3LYP/6-311G(d,p) basis set.
Table 4. Geometry parameters of Schiff bases and its radicals at B3LYP/6-311G(d,p) (Bond distances and Bond Angle in Å).
Table 5. Electronic energies for Schiff base neutral molecule and radicals in gas phase at B3LYP/6-311G(d,p) level of theory.
Hardness, .
Bond polarity is one of the factors that determine the physicochemical property of molecules. The calculated values of the total dipole moments, which signifies the relatively polarized nature of the systems and they are soluble in polar solvents like CH3CN, DMSO, CHCl3, etc.
The computed NMR chemical shifts for SA, AA, VA and NA at the DFT level of theory are in acceptable agreement with the experimental data. Differences between the calculated and measured values may be a result of solvent interactions.
The 13C-NMR chemical shifts of selected carbons were calculated on the optimized structures of SA, AA, VA and NA using GIAO/DFT method with B3LYP/6-311(d,p) basis set for all atoms. Calculated and measured 13C chemical shifts of selected atoms are numbered in Figure 6.
4.2.2. HOMO-LUMO Orbital Distribution
The HOMO-LUMO energy (Figure 7 and Table 6) which characterizes the ability of electron-giving is appropriate to represent the free radical scavenging efficiency of phenolic compounds because the process to inhibit auto-oxidation may include the electron-transfer besides the abstraction of the H-atom [12] . The HOMO (−0.2070, −0.2040, −0.2160 and −0.2040 Hartree) and the LUMO (−0.0590, −0.0440, −0.0750 and −0.0790 Hartree) for the compounds SA, AA, VA, NA respectively, are p-like orbitals confirmed by UV-Vis spectra and they are delocated in the whole molecule of all the salen compounds. Considering the disposition of HOMO and LUMO orbitals, the -OH group of 2 and 9-position is easily attacked by either the electrophilic or nucleophilic agents, such as radicals, metal ions and O2. Indeed, HOMO and LUMO orbitals for four compounds are localized on A and B ring, conjugated double bond nature in the phenyl and naphthyl moiety and on the A and B conjugated ring salen compounds [27] [28] .
4.2.3. Spin Density Distribution
The spin density is often considered to be a more realistic parameter which provides a better representation of the reactivity [6] [9] of salen moiety. It should be pointed out that the more delocalized the spin density in the salen compound is, the easier the radical is formed [5] . In the Figure 8, the spin densities of all the radicals mainly distribute on the phenolic oxygen atom and the phenyl ring A
SA-NMR AA-NMR VA-NMR NA-NMR
Figure 6. NMR shielding of salen compounds.
HOMO-Neutral SA LUMO-Neutral SA HOMO-Neutral AA LUMO-Neutral AA HOMO-Neutral VA LUMO-Neutral SA HOMO-NA LUMO-Neutral NA
Figure 7. HOMO-LUMO diagrame of salen compounds.
Spin Density-SA Spin Density-AA Spin Density-VA Spin Density-NA
Figure 8. Spin density distribution analaysis of salen compounds.
Table 6. Total energies, Frontier orbital energies, Softness, Egap and EI in gas phase calculated at B3LYP/6-311G(d,p) level of theory.
Table 7. All β(a.u.) components and β(tot) × 10−31 (esu) value calculated using DFT level of theory for salencompounds (1 a.u. = 8.6393 × 10−33esu).
and B. Comparing all the radicals, we find that the radicals have almost the same spin density distribution with each other, indicating the presence of additional hydroxyl or o,o-dihydroxyl group on A and B-ring has almost no influence on the spin density distribution [27] [28] .
4.2.4. Molecular Electrostatic Potential Surface (MEP) Study
Electrostatic potential surfaces are mainly used to study the reactive species of electrophilic or nucleophilic attacks/substitution in the chemical reactions, biological process, catalysis and also molecular modeling. Electrostatic potential mapped surface displays the molecular size, shape and potential values. In this study, 3 dimensional surfaces of mapped onto the constant electron density surface is as shown in Figure 9. Different values of electrostatic potential at the surface are represented by different colors [29] .
4.2.5. Computed Non-Linear Optical (NLO) Properties
The NLO response calculation was performed on the optimized geometry using the same level of theory. The first static hyperpolarizability is a third rank tensor that can be described by a 3 × 3 × 3 matrix. The 27 components of the 3D matrix
Figure 9. Molecular Electrostatic Potential surface diagram of AA.
can be reduced to 10 components due to the Kleinman symmetry [27] [30] (βxyy = βyxy = βyyx, βyyz = βyzy = βzyy, ..., likewise other permutations also take same value). It can be given in the lower tetrahedral format. The output from Gaussian 03W provides 10 components of this matrix as βxxx, βxxy, βxyy, βyyy, βxxz, βxyz, βyyz, βxzz, βyzz and βzzz respectively. Many types of hyperpolarizabilities have been discussed in the literature [31] . When reporting a single value of β, one of the common formats is to simply treat the three independent values for β as a quasi-Pythagorean problem and solve for the average β by Equation (5):
The complete equation for calculating the magnitude of the total first statichyperpolarizability from Gaussian 03W output is given as Equation (6):
Since these β values of the first static hyperpolarizability (β) tensors of the output file of Gaussian 03W are reported in atomic units (a.u.), the calculated values were converted into electrostatic units (1 a.u. = 8.6393 × 10−33 esu). The first static hyperpolarizability (β) values of these Schiff bases were calculated under static electronic field by the DFT (B3LYP/(6-311G(d,p)) method. From Table 7, compounds NA, VA and AA have larger the first static hyperpolarizability (βtot) values than those of compound SA. As mentioned above, the DFT results show that the LUMO orbitals of all compounds were obtained from the linear combination of the orbitals of phenyl moiety, the compounds AA, VA and NA with an electron-donating and withdrawing group (CH3, OCH3 and naphthyl) have a larger βtot value compare with compound SA. Hence the compound VA was predicted to have larger NLO property. The energy difference (∆Egap) between the HOMO and the LUMO orbitals 3.5506, 4.3538, 3.8368, 3.4014 eV for the compounds SA, AA, VA, NA respectively has a larger influence on the βtot value [32] [33] . To understand the relationship between the static hyperpolarizabilities and the HOMO-LUMO energy gap, viz. the compound VA (3.4014 eV) lower the HOMO-LUMO energy gap show that the larger the βtot (13.455 a.u) value.
4.3. Conclusions
Schiff bases (1-4) have been successfully synthesized and characterized by elemental analysis, FT-IR, UV-Vis, NMR spectroscopy and cyclic voltammetry. The evaluation of the quantum mechanical studies reveal significant activity in structure optimization, PES, vibrational study, NMR Chemical shifts, spin density, hardness, electronegativity, dipole moment, EHOMO/ELUMO, ∆Egap and Softness which provide the evidence for a very strong positive correlation between experimental and theoretical predictions. These compounds also have towards considerable antioxidant activity along with potential to prevent DNA oxidative damage by free radicals.
Comparison between the four considered molecules indicates compound VA that requires the lowest energy for both H atom and electron transfer mechanisms. This theoretical approach confirms the important role of A and B ring in exhibiting antioxidant properties. Inspection of deprotonation processes of dihydroxyl groups have shown that, π electron delocalization of phenyl ring A and B (evidenced from UV-Vis study) plays a major role in the stabilization of products and thus in the lowering of the associated energies. The variables related to the chemical potential allow classifying salen type of Schiff base compounds that has the tendency to give electrons more than to attract them, which demonstrates biological importance.
In addition to that in order to understand the relationship between the βtot values and the substitution groups of salen compounds, the frontier orbital compositions have been analyzed and the energy gaps between the HOMO and LUMO orbitals were also calculated. The compound VA with electron-donating group (-OCH3) will produce the larger βtot value (13.455 a.u) than lower βtot (10.003, 9.244, 4.359 a.u) for the compounds NA, AA, SA respectively. The energy gaps between the HOMO and LUMO orbitals show that the lower the HOMO-LUMO energy gap, larger the first static hyperpolarizability (βtot).
The findings of this work sustenance the view that some of these synthesized compounds are promising sources of potential drugs that may be efficient as preventive agent(s) in some diseases.
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text:
Audiences are "more demanding" post-pandemic - Omid Djalili
Omid Djalili embarks on his Good Times tour – very much also a tour for changed times.
By Phil Hewitt
Monday, 15th November 2021, 8:05 am
Things are certainly different as we emerge from the pandemic, Omid says.
He was noticing it in the first few days as he hit the road.
Shows coming up include Guildford's G Live on Nov 18; Chichester Festival Theatre on Nov 22; Bexhill's De La Warr Pavilion on Mar 19 2022; and Hastings' White Rock Theatre on Oct 29 2022.
"I think we have all changed. I think there is a new normal. You can tell it from the audience.
" The difference is that everybody has been at home watching stuff digitally and they are now demanding higher-quality content.
"Stuff that I was saying in comedy clubs that would have got a 'Wahay!' or a cheer, well, it has changed. I was doing a joke about Covid variants, the kind of thing that you would put on Twitter. I said something and there was a groan and somebody said 'Oh my God!' It was like 'For God's sake, is that the best you can do?'
"I think new audiences are more empowered and very entitled. They are demanding better quality, and I think that that is good.
"And I think people are way more intolerant about jokes about the other. The Paddy jokes, the Scottish jokes, they all went out in the 1970s. But now they won't tolerate jokes about somebody who is other in some way, somebody who is German or whatever. We have got to be thinking about really important stuff about people's lives and experiences."
And certainly it is difficult talking about the pandemic: "You find that if the joke is not brilliantly funny, then people will get twitchy. If it is actually brilliantly funny, then they will go with it. If you are trying to create something new – and new comedy is all about clutching something out of the air – then I do think people will appreciate that shared experience.
"But I think people want you to talk about the pandemic. They want you to talk about politics and where we are. They want you to talk about what we have all been through and how things have changed. They want to reflect on all the terrible things that have happened. It is about finding the right moment."
And Omid has changed too: "I have certainly really appreciated coming back to stand-up comedy."
Omid cites a gig in Telford. A smallish venue. No big deal. The gig was something to get through in order to get to the hotel afterwards. But not anymore.
"It is a 640-seat venue. But now there are only 200 people there and I absolutely cherished it. I loved every moment. I absolutely loved being on stage and I wanted to stay there."
So in that sense the pandemic has energised him, he says: "I really appreciated the job because I haven't done it for 20 months. I just loved being back there doing it again after all this time."
A firm favourite at the Edinburgh Festival, Omid's stand-up awards include the Time Out Award for Best Stand Up and the EMMA Award. He's also been a nominee for a Perrier Award and the South Bank Award. His credits range from Hollywood to television, the West End Stage to his critically acclaimed performance as Tevye in Fiddler on the Roof. Omid's drama, Letter For The King was on Netflix and the second series of His Dark Materials aired on the BBC. He is also the host of ITV quiz show Winning Combination, which aired in November 2020.
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Four reasons why you should attend TC Sessions AR/VR 2018
On October 18 — just one week away — some of the most brilliant and innovative minds in reality creation will gather at UCLA's Royce Hall in Los Angeles to attend TC Sessions AR/VR 2018. Whether you're an early startup founder, an investor, a developer or a student, if you're focused on AR/VR, you don't […]
Facebook says 14m accounts had personal data stolen in recent breach
Hackers were able to access name, birthdate and other data in nearly half of the 30 million accounts that were affected Facebook access any third-party apps, including those that use Facebooks single-sign-in to log in. It also did not impact users on other Facebook properties such as Messenger, Instagram, WhatsApp, or Oculus. Facebook plans to […]
Facebook cant keep you safe
Another day, another announcement from Facebook that it has failed to protect your personal information. Were you one of the 50 million (and likely far more, given the company's graduated disclosure style) users whose accounts were completely exposed by a coding error in play for more than a year? If not, don't worry — you'll […]
Facebook is building a camera TV set-top box
A mysterious product called "Ripley" appeared hidden beside Facebook's new Portal smart displays in Facebook for Android's code. Dug up by frequent TechCrunch tipster Jane Manchun Wong a week ago, Ripley's name squared with Facebook's VP of Portal Rafa Camargo telling us that "we're already investing in expanding the product line with more products we want […]
Facebooks ex-CSO, Alex Stamos, defends its decision to inject ads in WhatsApp
Alex Stamos, Facebook's former chief security officer, who left the company this summer to take up a role in academia, has made a contribution to what's sometimes couched as a debate about how to monetize (and thus sustain) commercial end-to-end encrypted messaging platforms in order that the privacy benefits they otherwise offer can be as widely […]
Facebook employees aren't happy an exec appeared at the Kavanaugh hearing
Facebook exec Joel Kaplan can be seen sitting two rows behind Brett Kavanaugh during last week's hearing.Image: Getty Images Facebook is once again facing uncomfortable questions from employees about the actions of one of its executives. This time it's Joel Kaplan, the company's VP of global public policy, who last week attended Brett Kavanaugh's Senate […]
Facebook is shaping public discourse. We need to understand how | Alex Abdo
Companies like Facebook and Twitter should lift restrictions impeding digital journalism and research on the platforms At a hearing last week in Washington, senators and executives from Facebook and Twitter wrestled with the existential question of our time: how do we prevent Silicon Valleys signature creation social media from tearing the country apart? Few answers […]
Why Instagrams founders are resigning: independence from Facebook weakened
Facebook promised Instagram autonomy, but reduced it over time leading to today's bombshell revelation. Eight years after launching Instagram and six years after selling it to Facebook, Instagram co-founders CEO Kevin Systrom and CTO Mike Krieger are leaving the company, according to The New York Times. The founders apparently did not give a reason for […]
Watch Out! Here Come the Woke Tech Oligarchs.
Once the rich protected themselves by aligning with Republicans who would protect their property from high taxes and their firms from regulation. Some still donotably the three of the four largest billionaire political donorshedge fund manager James Simon and his wife Marilyn, Michael Bloomberg, and currency speculator George Sorostitled progressive. This reflects a broader social […]


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