units, while still providing defense against tradeoff attacks.
and memory organization of the recent Intel and AMD processors.
work applications with no threats from side-channel timing attacks.
protection and brute-force cost savings due to time-memory tradeoffs.
applications.  May have any length from 0 to 2**32 - 1 bytes.
for password hashing.  Salt must be unique for each password.
take any integer value from 1 to 2**24-1.
o  Tag length T may be any integer number of bytes from 4 to 2**32-1.
o  Associated data X may have any length from 0 to 2**32-1 bytes.
The Argon2 output is a T-length string.
are described in later section.
1.  Establish H_0 as the 64-bit value as shown in the figure below.
little-endian encoding of the integer.
Here integers are padded to 4 bytes and encoded in little endian.
differently for Argon2d, Argon2i, and Argon2id.
8.  The output tag is computed as H'(C).
tag length in bytes, encoded in little-endian as 32-bit integer.
very last index from R is excluded.
The value of z gives the reference block index in R.
The modular additions in G are combined with 64-bit multiplications.
CPU using 4 cores -- Argon2id with 8 lanes and 4 GB of RAM.
a 2 GHz CPU using 2 cores - Argon2id with 4 lanes and 6 GB of RAM.
CPU using 2 cores - Argon2id with 4 lanes and 1 GB of RAM.
wiping option in the library call.
t of passes must exceed binary logarithm of memory minus 26.


Dragon's Dogma GoreChimera Boss for 4th Edition Dungeons & Dragons (Epic Tier Level 21 Composite Solo Monster).
The final form of Asmodeus is a Level 34 Super-solo Brute!
This is a simple trick for maximising encounter difficulty without increasing the level of the encounter. Its especially useful for solo monster encounters.
Details Asmodeus for 4th Edition as a Level 33 SUPER-Solo Monster!


Home World Affairs Philippines: Indonesian hostage held by terrorists swam his way to freedom.
Philippines: Indonesian hostage held by terrorists swam his way to freedom.
In the Philippines, an Indonesian hostage held by terrorists swam his way to freedom while his companion drowned. Another Malaysian captive was shot in the back while escaping, the officials said.
The Phillipine marines gunned down three terrorists who were trying to chase the two Indonesians at sea. The three hostages were kidnapped from Malaysia's Sabah state on Borneo island in December last year and taken by speedboat to Sulu province in Phillipines.
Military spokesman Lt. Col. Gerry Besana said that the hostages escaped while the Marines were attempting to rescue them from Simus Island in Sulu. At least three more hostages are still in the custody of the Abu Sayyaf terrorist group.
In a separate incident, army troops yesterday clashed with about 80 terrorists of Abu Sayyaf group in Sulu's mountainous Patikul town. The gun battle left three soldiers and four terrorists dead and several wounded on both sides, the military said.
Previous articleMaldives: Polling going on smoothly for election to 19th parliament.


text:
Q: In django user model what does @propery represents Below is the code from sample custom user model with staff field. I am new to Django framework. Can anyone explain what is the difference between @propery and without specifying it?
It's not making sense with or without it in terms of accessing it.
Does @propery provides any additional functionality like setting the fields values.
Correct me if I am wrong
@property
def is_staff(self):
    "Is the user a member of staff?"
    return self.staff

def is_staff(self):
    "Is the user a member of staff?"
    return self.staff

A: In Python, not only in Django, property is a decorator that could be used to decorate a method in order to compute some value.
As stated in the docs about property:

A typical use is to define a managed attribute

is_staff with the property decorator is a value you can access in your instance as follows
instance.is_staff

The @property decorator turns the is_staff() method into a "getter" for a read-only attribute with the same name.
is_staff without the property decorator is a method you can call in your instance as follows:
instance.is_staff()

A: @property is a built-in for python. It is a great way to add properties to a class that require some sort of evaluation and it isn't just a Django concept. In this example it doesn't seem like @property is being used as I would expect. In this example it is only returning the staff property. The @property decorator allows you to access is_staff as property of the instance. Here is an example.
class Num:
    def __init__(self, x):
        self.x = x

    @property
    def is_even(self):
        return self.x % 2 == 0

a = Num(2)
a.is_even #returns True

redpajama_set_name: RedPajamaStackExchange


Newtonian Physics and Scientology – OTVIIIisGrrr8!
Newton's First Law of Motion states that a body at rest will remain at rest unless an outside force acts on it. According to Newtonian physics, then, Scientology's Ideal Orgs will remain at rest for all of eternity unless acted upon by the FBI, earthquakes, or some other outside force.
That there is no activity or motion occurring inside the Ideal Orgs has led some physicists to speculate that these buildings exist at, or near, the temperature of absolute zero (-273.15 Celsius) where all atomic motion ceases.
And the Ideal Orgs will certainly remain completely free of bothersome new members.
As a recent study showed, the last "new person" to officially join the Church of Scientology was New York City resident Franconi Allesandro in 2004. Allesandro, who died in 2005 from injuries sustained during a bizarre and mysterious sec checking accident related to his $75,000 repayment request, is remembered unfavorably as a thetan who pulled in his own death in an attempt to make the Church of Scientology wrong.
Allesandro was posthumously declared an SP for his evil purposes. His monies on account were not returned to his estate as no law in America requires the Church of Scientology to return any donations.
I don't recall Wayne saying anything about bodies resting or in motion. All I know is that he probably agreed with Elvis that Scientology was just after his money.
My experiments with a chromatograph and cloud-chamber hooked up to the Mk. XXVIII Strabismus Psychotimeter have detected definite traces of gaseous Newtonian motion within some Ideal Orgs. My assistant Miss Tsai-Chin Proutley conjectures this is due to the Sea Org diet of rice'n'beans.
Einsteinian physics says E=MC2, therefore Entire ideal org numbers = Man (8 billion) times Church members, all squared.
See, DM is right. Ideal orgs will likely fall under their own weight.
Miscavige is likely to die of of alcohol poisoning before any of these empty shells see any movement, and then it will be to the auction block.
> Scientology's Ideal Orgs will remain at rest for all of eternity unless acted upon by the FBI, earthquakes, or some other outside force.
But this is where SUPER-EVIL, SUPER-VILLAIN DAVID MISCAVIGE comes to the rescue! His theta mind rays can fill an org in an instant! His super-evil OT powers let him do this!


text:
// Type: Highsoft.Web.Mvc.Stocks.AreaSeriesDataLabelsVerticalAlign

namespace Highsoft.Web.Mvc.Stocks
{
    public enum AreaSeriesDataLabelsVerticalAlign
    {
        Null,
        Top,
        Middle,
        Bottom,
    }
}

redpajama_set_name: RedPajamaGithub


NSK HR30307J bearings Israel r min.
NSK HR30307J bearings Israel r1 min.
NSK HR30307J bearings Israel da min.
NSK HR30307J bearings Israel Da max.
NSK HR30307J bearings Israel db max.
NSK HR30307J bearings Israel Db min.
NSK HR30307J bearings Israel ra max.
NSK HR30307J bearings Israel rb max.


text:
Home News, Analysis & Opinion Will Colombia catch the coronavirus? What you need to know.
News, Analysis & Opinion
Will Colombia catch the coronavirus? What you need to know.
Steve Hide
A new flu-type virus could be the next pandemic. Here's a Q&A to keep you up to date…
Coronavirus Colombia: Health post in Amazonas state: services in remote areas are often run down bringing challenges for outbreak response. Photos: Steve Hide
Should we be worried about the coronavirus?
According to the World Health Organisation (WHO), yes. The UN body has just declared the '2019n-CoV' bug a global health emergency. The virus, which jumped the species barrier from animals to humans in China late last year, can cause severe pneumonia-type illness with fatalities. According to the latest World Health Organisation stats (January 30), 10,000 people have been diagnosed worldwide with 220 deaths. Most cases have been recorded in China, but the bug has also spread to Europe, the US and Canada.
How bad can it get?
Hard to say. Viruses are fickle foes. They can mutate to become more deadly…or fizzle out. Public health influencers walk a fine line between prevention and panic. Past declared global health emergencies – SARS, MERS, Ebola – have not spread worldwide as feared. One game-changer with 2019n-CoV is we now know it can pass between humans, not just from animals. This means people with no direct contact with the source in China can also catch it. The WHO now says the transmission risk is "high at the global level."
Will the coronavirus come to Colombia?
Probably. Although eight suspected cases have tested negative in the country in the last week, the bug's high rate of contagion – facilitated by international global travel – suggests that it will get here eventually.
What can Colombia do to prevent its spread?
Not much, partly because the bug is capable of 'asymptomatic transmission' meaning people can catch and spread the virus without themselves getting sick. This means screening at borders – for example testing airline passengers for fevers as they arrive at airports – is ineffective. And quarantining sufferers will have limited effect because the bug takes days or weeks to show up: A patient has already passed it on before being isolated. On data collected from China so far, each patient tested positive has already infected at least three other people.
Is everyone at risk?
No. Analysis of cases in China shows deaths occurred mostly in middle-aged male patients with other chronic diseases such as diabetes or heart conditions. Younger, female and generally healthy people have more chances of fighting off the virus. Some children who tested positive for the virus never even got sick. On the evidence so far, experts say that 2019n-CoV is not as deadly as other types of coronavirus such as SARS, which also originated in China and killed nearly 800 people worldwide in 2002-03. However, experts also say less 'deadly' viruses are likely to be more contagious and spread further, eventually affecting more people.
Can't I take a pill?
No. New viruses require vaccines, which need time to develop, maybe months or years. Infected people rely on their own immune system to fight it off, and if necessary, hospital care to treat the symptoms.
Many areas of Colombia are only reachable by river. Isolation can reduce the risk of coronavirus transmission, but also delay patients reaching proper medical care in case of infection.
How do you know you have the bug?
Symptoms are similar to flu with fever, cough, shortage of breath, and in severe cases kidney failure and death. But some infected people never get sick at all. One problem is lack of testing; at present patient sputum samples are molecule tested to prove the presence of 2019n-CoV. The WHO is scrambling to establish a worldwide network of labs that can process these samples, and biomedical companies are working around the clock to produce a cheaper test for rapid diagnosis. Colombia health authorities can send samples to the U.S. for gene testing, which is costly and time-consuming: it can take several days for a test result.
How ready is Colombia for this coronavirus?
As a tropical country, Colombia is used to dealing with virus epidemics – i.e. chikungunya, zika – and fared well in the H1N1 swine flu pandemic of 2009. It also revamped its quarantine capabilities during the Ebola scare of 2014-16, and has systems in place to protect health staff. Colombia's public health body the Insituto Nacional de Salud has a robust disease surveillance system and is busy producing guidelines and updates to health professionals.
Read our latest coverage on the coronavirus in Colombia
In a worst-case scenario, can Colombia cope with the coronavirus?
With difficulty. Despite high levels of technical expertise in-country, the semi-privatised health system is weak and concentrates quality care in urban centres. Cities like Bogotá have overcrowded transport systems such as the TransMilenio which could spark rapid transmission of the virus. And in remote rural areas – where services are often chronically under-resourced – people already face a struggle to reach adequate health care, often hours away by boat or mule. And we know from previous flu outbreaks that speed of attention is a critical factor in patient survival. With high case numbers, frightened health staff could abandon their posts, especially if they lack protective clothing. There is potential for system collapse.
What about Venezuela?
Colombia shares a 2,000-kilometre open border with neighbouring Venezuela, which has economically collapsed causing a health emergency with drug shortages and many health staff fleeing the country. This country-wide crisis makes the population there uniquely vulnerable to the 2019n-CoV virus, though, so far, no cases have been reported. But if cases do arise, Colombian health officials will be watching border areas with concern.
Wash hands, here comes Coronavirus! WHO recommends it as the best way to avoid infection. Alcohol gels – available in pharmacies – come in handy when you're out on the street.
What can I do for now?
Protect yourself. For this, WHO recommends frequent hand washing with soap and water or alcohol-based hand rubs, particularly in public places where other people are touching common surfaces (i.e. handrails on escalators). We actually spread flu and cold viruses more by hand-mouth contact and inadvertently touch our mouth hundreds of times a day. Face masks can help in crowded public places. And stay informed. We'll keep you posted.
Virus Colombia
Will the coronavirus come to Colombia
Omicron in Colombia: What you need to know
Colombia vaccination certificate: New rules if you're entering from abroad
Colombia to require vaccination certificates from November 16
peterman March 27, 2020 at 10:17 am
Walter Talley March 8, 2020 at 9:23 am
It is stupid for any country to allow a person from a country that has the corona virus active and dangerous arrive by airplane. I have a ticket to arrive in Bucaramanga next week and I will cancel it for my protection and the protection of the Colombian people. I DO NOT HAVE THE CORONA VIRUS. And I don't want it.

redpajama_set_name: RedPajamaCommonCrawl


While I encourage all women to find their own definition of beauty, it would be silly of me not to say that the conventional beauty that we see everywhere doesn't have an influence on us or myself. I'm definitely influenced by what I see, in particular the ideals set for by Asian beauty spreads where the girls seem to be on a whole other level of otherworldly perfection. As someone into makeup, it's hard to stand firm to body image independence and also gush over the next pretty release. Case in point, the new Clinique Beyond Perfecting Foundation + Concealer. As someone who wears only light coverage foundation, this would be my first venture into full coverage foundation and I was definitely worried that the look of flawless perfection that it claims to provide would be too seductive to resist! So was it? Read on to find out!
The Clinique Beyond Perfecting Foundation + Concealer is a two-in-one foundation and concealer that provides full coverage for 12 hours, regardless of sweat or humidity. Its oil-free formula helps conceal imperfections while still allowing skin to breath and is designed for dry to combination skin.
The Clinique Beyond Perfecting Foundation + Concealer comes in 20 shades ranging from a pinky-ivory, to a warm molasses brown. If you've even glanced at any of the reviews online, selecting the correct shade is very tricky, even more so than normal. Clinique states that due to its highly pigmented formula, the shades will typically appear darker when first applied and then will change to blend into skin as it dries down. I'd definitely recommend swatching these in-store first before purchasing as at first I thought I would be somewhere in the mid-range with Golden Neutral, but I settled upon the second lightest shade, Creamwhip!
Trimethylsiloxysilicate - performs similar functions as the previous ingredients.
Other ingredients of note are Sodium Hyaluronate (moisturizing) and Hydrolyzed soy protein (antioxidant).
A 30 ml bottle retails for $34 and is available at Sephora and wherever Clinique is sold. The Beyond Perfecting's heavy glass bottle feels weighty and luxurious in the palm and is slim enough to be easily packed away for travel. What's really unique about this foundation though is the brush. Lately, brands have been really innovating with their foundation brushes and the Clinique Beyond Perfecting Foundation + Concealer is no exception. The brush is long with a bristly doe-foot applicator. At the tip of the brush, is a little well that contains a tiny reservoir of product. To use, simply dab and swipe the foundation directly onto your face using the wand, then blend away. Typically, since I really wanted that full coverage feeling, I may dip my wand twice to fully cover my face.
I'm simply in love with the silky, velvety feeling that this foundation gives my face. It literally erases away any scars or unevenness, giving me a perfectly even base upon which to apply the rest of my makeup. I was expecting this foundation to feel heavy and cakey, but it actually felt utterly weightless and once set, it didn't seem to budge all day. After a few hours, I do get a little bit of shine as per normal, but it was manageable. The foundation didn't oxidize at all and there was no caking either.
In terms of concealing, it does a great job at covering up dark circles, redness and hyper-pigmentation, but only provided around 90% coverage of the acne scars around my mouth. I found I had to apply a second layer of foundation to really cover that area.
The biggest mistake I made with this foundation was not using the right brush. Initially, I used my normal go-to, which is the Bobbi Brown Foundation Brush, but I found that the stiff bristles weren't a good fit for the creamy thickness of the Clinique. Sadly, my Bobbi Brown only swirled this foundation around and caused it to sit in a thick layer on my skin. Using my fingers didn't improve things much either. Within a week, this foundation caused me to break out like mad. Luckily, I'd already ordered a replacement brush - the Urban Decay Good Karma Optical Blurring Brush. This brush is AMAZING with this foundation. Its thick, dense head gently and thoroughly buffs this foundation into my skin and it spreads it wonderfully so that I don't need a lot to get maximum results. Best $26 ever.
Even though I'd now figured out (painfully) how to properly wear this foundation and I'm absolutely in love with the finish, I think it's safe to say that this won't be my regular foundation moving forward. Something in me objects to putting such heavy makeup on my face everyday. As lightweight as this one is, it still contains a lot of silicones, which I believe block your skin from breathing and could trap in dirt. I also believe that the more makeup you wear, the more your skin becomes dependent on it. Your makeup becomes a crutch to hide behind, instead of a way to bring out your natural beauty more. Sadly, I've decided to be strong and keep this on my shelf as my go-to for dates, parties, and events, and keep my light foundation and BB's in my regular rotation.
Buy - a painful learning process to shade match and to find the right application tools, but once you find these things, then say hello to the most flawless skin you'll ever have!


text:
A battle begins against poverty through education
The Little Sisters of Mary Immaculate of Gulu have inaugurated a significant battle against poverty through education in a remote village called Indriani. The village, formally invested by the Lord's Resistance Army of Joseph Kony for more than 10 years, is located on the Eastern part of the River Nile in Adjumani district and within the territory of the Diocese of Arua in Uganda.
Sr. Susan Clare Ndeezo describes the situation of the children of Indriani as very appalling. She observes, "the girls in the area try to go to the only primary school around, but drop out extensively from level 4 and 5. By the time they could reach level 7, they girls are already preparing for marriage. As a result there are lots of child mothers in Indriani, forming almost 75% of the women population in the area. Most children are at home with no chance of exposure to an elevated life like in other parts of Uganda".
In March 2015, the Little Sisters started to address the situation of the children by opening a temporary shelter named Bishop Angelo Negri Kindergarten. Currently, there are 50 kids attending the kindergarten. The Sisters have also started a horticulture in the area to provide paid labour for mothers to get something to take home for food. The next target is to establish animal husbandry where the Sisters will rear animals to improve the chance for these mothers to change diet in their families.
Acording to the Mother General, Sr. Susan Clare Ndeezo, the vision of the LSMIG is "to develop an Education Centre named Mary Immaculate Education Centre. This will a Complex Centre consisting of several educational levels: Kindergarten named Bishop Angelo Negri, Holy Cross Girls Primary School Indriani, Cardinal Filoni Girls Secondary School Indriani, Mary Immaculate Apprentice Vocational College Indriani and Cardinal Filoni Convent Indriani (residence of the Directors)".


text:
Officials arrested, auto firm may not be listed in 2019
VEAM trucks being manufactured. Recent arrests of former VEAM leaders have shocked the company's investors and threatened its HoSE-listing plan in the near future. - Photo vietnamnet.vn
HÀ NỘI – The recent arrest of former directors at the Vietnam Engine and Agricultural Machinery Corporation (VEAM) has derailed the company's future business plan.
VEAM is trading more than 1.3 billion shares on the Unlisted Public Company Market (UPCoM) with code VEA.
The company planned to switch its listing to the Hồ Chí Minh Stock Exchange in 2019. The plan was approved at the firm's annual shareholder meeting on June 30.
Since its UPCoM debut on July 2, 2018, VEAM shares gained 152 per cent to a peak of VNĐ64,500 (US$2.77) per share on July 26.
Since then, the firm's shares have been declining. The shares ended August 19 at VNĐ49,300 per share, down 23.5 per cent from the previous peak.
The fall of VEAM shares has shown no signs of stopping and the major reason is the arrest of the company's former leader in early August.
On August 3, the police arrested and prosecuted VEAM former general and vice general directors and two other officials for misuse and mismanagement of State assets, causing severe losses.
Inappropriate actions in the past had left VEAM with capital losses when former leaders decided to invest in a number of projects.
For example, the group lost VNĐ331.8 billion when investing in a manufacturing facility in the northern province of Bắc Kạn between 2010 and June 2018. Those former leaders also exceeded the required capital invested in some associate and member units.
The biggest problem for investors now is the inventory of trucks, which was valued at VNĐ1.2 trillion. Analysts have said it would not be easy to sell those trucks to recover some of the capital losses because the trucks were old and damaged; they also do not meet current environmental standards.
Though the corporation later announced the arrests would not harm its business and measures were being taken to stabilise the business operation in the future, investors have shown sign of worries with the current situation. Since July 26, VEAM shares were hit hard three times, falling between 4.8 per cent and 7.2 per cent on July 30, August 12 and August 13.
Investors were also concerned about the firm's financial condition, which had been dragged down by the misuse of State capital in poor investments.
Financial problems are now also preventing the company from moving its shares from UPCoM to HoSE. In 2017 and 2018, the company failed to provide accurate financial statements to the market regulator. – VNS


text:
package ee.pdfarve.common.posorder;

public interface GridConstants {

	int
	/**
	 * PDFBox library has this number for A4 page size width in pixels
	 */
	A4_WIDTH_PX = 596,

	/**
	 * PDFBox library has this number for A4 page size height in pixels
	 */
	A4_HEIGHT_PX = 838,

	/**
	 * No grid cell is split into smaller cells if it contains less than or
	 * equal to this number of data points
	 */
	MIN_NUMBER_OF_DATA_POINTS_IN_CELL = 2,

	/**
	 * Minimum side length for a cell, so that cells do not become too small
	 */
	MIN_CELL_LENGTH_PX = (A4_WIDTH_PX - 4) / 4;

}


text:
The Johnstonian News
SearchHelpSubscriptions
'It's where I need to be'
A retired pastor returns to pottery
Top newsLocal newsArts
Debbie Herrera | Johnstonian News
Frank Grubbs' pottery wheel and kiln have followed him all over Eastern North Carolina.
Grubbs signs all of his pieces.
Some of Grubbs' work is on display in his studio.
Grubbs makes an assortment of mugs, plates, bowls, urns and vases.
By Debbie Herrera
dherrera@johnstoniannews.com | 919-284-2295
SMITHFIELD — Frank Grubbs' path to becoming a self-taught potter began in his youth.
As a boy in Duplin County, he would dig clay from a creek bank near his home and turn it into toys and other figures, which he dried in the sun.
"I enjoy the feel of clay," Grubbs said.
In elementary school, he had a teacher who understood how he learned best. "I had a wonderful teacher in the fifth grade who saw each student individually and would bring out of us our unique way of learning," Grubbs said. "She saw me as art and taught me history, math and everything through art."
As a senior at what is now Barton College, Grubbs took a ceramics class. "We had a field trip to Dan Finch's pottery in Bailey, and from that visit, I knew this was something I was going to be doing," he said.
"I took that one course, but I am a self-taught potter," Grubbs said. "The professor we had took a no-hands-on approach and said, 'Here's the equipment, and here's the studio; figure it out.' And that's what we did."
Before he became a potter, Grubbs had other jobs. "I was a minister, a wildlife technician; I have done a little bit of everything," he said.
But mostly, Grubbs was a minister — for 45 years in all, including more than two decades as pastor of Selma Original Free Will Baptist Church.
Still, pottery remained an important part of his life, Grubbs said. "The first money I saved when I got out of college was to purchase a wheel, then save some more to purchase a kiln," he recalled. "I have that kiln, and it still works. I got it in the late '70s, and it was my first one."
Grubbs had his first studio in Pink Hill in his native Duplin County, where the pottery he made served a practical purpose. "Since I was a minister, this was a way of supplementing my income from time to time, and the pottery equipment just followed me all over Eastern North Carolina," he said.
These days, Grubbs teaches pottery at Mount Olive University, a job that grew out of an art show he did with John Williams, a fellow pastor who turns wood.
"We had a very successful show, and from there, folks from the university started asking questions," Grubbs said,
"They did not have a ceramics department, but they needed one because they wanted to offer a degree in art education," he explained. "Without ceramics, you can't get that degree."
The university turned to him for advice.
"They invited me to come and said, 'Here's a space. What would you do with it?' " Grubbs recalled. "I got a little bit of architectural work in my background, so I drew a scale model of the studio, and they built it."
Grubbs remembers visiting the university one day to check on the studio's progress. "As they were building it, they invited me back to the space to see and said, 'We would like you to teach,' " he said. "To that, I said, 'I don't have a degree to teach.' And they said, 'We all have a degree, but we don't know how to teach it, but you know how.' "
Today, Grubbs teaches two classes — an introduction to ceramics and advanced techniques. "They want me to develop a sculpture class in ceramics," he said of university leaders. "It will be introduced to the committee this spring, and I hope it will be offered in the fall."
When he's not teaching, Grubbs makes what he calls functional pottery — mugs, plates, vases and urns. "I enjoy making things that people can use," he said.
Grubbs gives each piece his full attention. "I am not going to rush through making a piece," he said. "One thing I tell my students is if you pay attention to detail, you have a better chance of selling. Whereas if you don't, people will just pick it up and set it back down."
Though he has been fashioning things from clay for almost as long as he can remember, Grubbs was always reluctant to call himself a potter. "It has only been in the last 10 to 12 years that I felt comfortable saying I am a potter," he said. "It was always a hobby or something I liked to dabble in. It was occasional, it was sporadic, and I could never put much time into it as I wanted to because it demanded all my time."
Now, Grubbs relishes the process of making pottery. "It's where I need to be," he said. "If you are where you need to be and enjoy what you are doing, I think all is well."
More Top news
Johnston has free N95, KN95 masks
SMITHFIELD — The Johnston County Public Health Department is making free N95 and KN95 masks availabl...
Kenly's Super Seniors off to small but fun start
KENLY — Kenly seniors gathered Thursday at Kenly Park for bingo, line dancing and trivia. It was the...
To increase revenue, Selma Civic Center might ease some rules
By Scott Bolejack
SELMA — The Selma Civic Center is losing money, and the rules governing its use aren't helping, Town...
Johnston schools closed Friday
SMITHFIELD — With snow in the forecast, Johnston County's public schools will be closed Friday for s...
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Avions militaires
Index des appareils du reste du monde nico2, le Feb. 14, 2013, 8:07 a.m. nico2
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Hongdu L-15
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le Jan. 11, 2018, 9:29 p.m. 16 6,901 nico2
clansman, le Oct. 19, 2011, 9:12 p.m. nico2
Chengdu J-10
clansman, le Jan. 12, 2011, 8:48 p.m. jericho
le Jan. 9, 2018, 4:13 p.m. 18 8,107 jericho
le Jan. 9, 2018, 4:13 p.m.
AVIC AG600 ciders, le July 23, 2016, 10:40 a.m. ansierra117
le Dec. 29, 2017, 3:32 a.m. 12 2,538 ansierra117
le Dec. 29, 2017, 3:32 a.m.
HAL HF-24 Marut clansman, le May 16, 2010, 10:08 a.m. jericho
le Aug. 16, 2017, 10:03 p.m. 8 3,186 jericho
le Aug. 16, 2017, 10:03 p.m.
Shenyang J-15
jericho, le Nov. 24, 2012, 10:54 p.m. ciders
le July 2, 2017, 10:03 a.m. 21 7,734 ciders
le July 2, 2017, 10:03 a.m.
Avro CF-105 Arrow ironman, le May 20, 2010, 12:52 p.m. clansman
le June 12, 2017, 8:07 a.m. 10 5,200 clansman
le June 12, 2017, 8:07 a.m.
Qaher 313
sefianiy, le Feb. 4, 2013, 4:27 p.m. nico2
le April 24, 2017, 9:59 p.m. 17 4,281 nico2
le April 24, 2017, 9:59 p.m.
KAI KT-1 Woong-Bee clansman, le June 14, 2011, 12:41 p.m. ouakamois
le April 20, 2017, 1:27 p.m. 12 4,884 ouakamois
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Le futur chasseur chinois : fake ou pas ? (J-20)
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Philippine Ambassador to Abu Dhabi Hjayceelyn Quintana informed the DFA that UAE authorities are coordinating with the Philippine Embassy for Jennifer Dalquez's flight home scheduled Nov. 1.
A native of General Santos City, Jennifer was sentenced to death in 2015 after she was found guilty of murdering her employer. She was later acquitted after the Philippine Embassy appealed her case.
Meanwhile, DFA yesterday expressed its gratitude to Saudi Arabia after Riyadh agreed to Manila's request to take temporary custody of 19 Filipinas who were arrested during a raid at a Halloween party there five days ago.
"We thank our Saudi friends for agreeing to release our people to the custody of the Philippine Embassy in Riyadh," Foreign Affairs Secretary Teodoro L. Locsin, Jr. said shortly after he was informed that the 19 women have been turned over to Ambassador to Saudi Arabia Adnan V. Alonto.
"This gesture is very much appreciated," Locsin said.
The 19 women who were initially detained at the Al Nizah Jail in Malaz, Riyadh, were turned over to Alonto at 1:20 p.m. Riyadh time (6:20 p.m. in Manila).
The Ambassador said Saudi authorities will decide what charges to file against the 19 women once they conclude their investigation of the case.
Yesterday, the DFA alson sent a consular team to Saipan to assist overseas Filipino workers in the Northern Marianas who were displaced after Typhoon Rosita swept across the islands this week.
A two-man team from the Philippine Consulate General in Agana travelled to Saipan to extend relief assistance to affected OFWs.
De Borja said some Filipinos were reported to have lost their houses in the typhoon and have limited access to food and water.


text:
The Eagles' loss and their lost season are nothing new. Under Jeffrey Lurie, they've been here before. | Mike Sielski
Posted: November 30, 2020 - 11:54 PM
Mike Sielski | @MikeSielski | msielski@inquirer.com
Eagles head coach Doug Pederson reacts after the Seattle Seahawks intercepted a pass during the fourth quarter of Monday night's 23-17 loss.
DAVID MAIALETTI / Staff Photographer
The longer Jeffrey Lurie's tenure as the Eagles' owner goes – and that tenure logs in at more than a quarter century now – the better a coach Andy Reid becomes. You can look at the Eagles' 23-17 loss Monday to the Seahawks as just the latest bad night in a bad season, bad for Carson Wentz, bad for Doug Pederson, bad for a team that, as hard as it is to remember these days, won a Super Bowl less than three years ago. Or you can look at it in the context of the entire Lurie era. And once you do, something becomes clear: You've seen this before. The Eagles have been here before.
Lurie has hired four head coaches since taking over the franchise in 1994, and among them, a pattern has developed that only Reid has managed to break. From 5-11 to two 11-5 seasons to two 12-4 seasons to 13-3 and a Super Bowl appearance, Reid may have frustrated people with his mumbly press conferences and fondness for throwing the football. But through his first six seasons here, the Eagles improved until they reached a lofty plateau among the NFL's top teams, then stayed there. Neither his predecessor nor his successors can say that, and it's time to acknowledge the common thread here: If you're not one of the greatest coaches in NFL history, which Reid is, there's a way that things are going to go for you when you coach the Eagles under Lurie.
Eagles' 'fearless' fourth-down gambles fell flat, as has been the case all season
The Eagles offense is an organizational disaster. There is no fix. Happy Thanksgiving. | David Murphy
Ray Rhodes was the NFL's coach of the year in 1995, when the Eagles went 10-6 and won a playoff game. The team went 10-6 in his second season, too. Then the Eagles went 9-22-1 over his final two seasons, including a 3-13 embarrassment in 1998, before Lurie fired him.
Chip Kelly was 10-6 in 2013, and the Eagles won the NFC East. They were 10-6 in 2014 but missed the playoffs. After Lurie gave in to Kelly's power play, the Eagles went 6-9 under Kelly in 2015 before Lurie, fed up, fired him.
Now, there's Pederson, and though he reached the one incandescent goal that his mentor never could here – winning a championship – he has proved to be no better than Rhodes or Kelly in avoiding the inevitable regression, complete with the instability at quarterback. For Rhodes, it was Rodney Peete, Ty Detmer, and Bobby Hoying. For Kelly, it was Nick Foles, Mark Sanchez, and Sam Bradford. For Pederson, it's 2017 Wentz, 2018-19 Wentz, and 2020 Wentz – with Jalen Hurts waiting for his turn.
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Understand: What's happening with the Eagles now is predictable – not Wentz's descent into confusion and the baffling nature of his poor play, but the logical presumption that his descent will cost Pederson his job. It's true that, for a couple of weeks now, Pederson has been answering questions and calling plays and making decisions like a man who either wants to be fired or has a pretty good feeling he's about to be. There's a reason for that. He had to know that, ultimately, that victory in Super Bowl LII would buy him only so much time, because Lurie was grading him on an additional scale, one that, in the eyes of an NFL owner, is often more important than victory in the only NFL game played each February.
Pederson's primary assignment was to develop and protect Lurie's most prized asset: Wentz. When an NFL owner pours $128 million into a player who is supposed to be the face of his franchise, who is supposed to be a star for a long time, that owner wants his money's worth. Pederson's job was to make sure that Wentz justified Lurie's investment, just as Reid had years ago with Donovan McNabb, and it looks more and more like Pederson hasn't done what was required of him.
» READ MORE: Carson Wentz played well enough to keep his job as the Eagles' starting QB | Marcus Hayes
You can blame him. You can blame Wentz's recklessness and plain bad luck for the injuries that have hampered him. You can blame Howie Roseman for his failure to draft well enough to surround Wentz with enough talent to succeed – and every one of DK Metcalf's 10 catches and 177 yards Monday was a painful reminder of Roseman's failure in that regard. At some point, though, you have to ask why the pattern remains a pattern. It is Lurie who insists that the Eagles, at all times, pursue a throw-throw-throw, score-score-score strategy, regardless of their offensive personnel. It was Lurie who reportedly undercut Pederson after last season when it came to retaining some assistant coaches. (Has Mike Groh gotten his apology yet?) It is Lurie who wants the Eagles to be seen as a smart, trendy football operation, always ahead of the curve, and who has trusted himself and Roseman most in creating that perception.
"My approach has always been to have weekly dialogue, weekly involvement with all aspects of our operation, and at the same time have enough respect and trust in our head coach, general manager, to let them make the decisions," Lurie said late August, just before this season began. "That's just the way we operate."
Here are the fruits of that approach: a 3-7-1 record, a quarterback lost, a rethinking necessary. Yes, the Eagles have been here before under Jeffrey Lurie. We'll see if he has finally learned enough to prevent them, another three or four years from now, from ending up here again.
Through the years, Eagles owner Jeffrey Lurie has been a very deliberate, cautious coaching shopper
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Dick Vermeil 'surprised, disappointed' that the Eagles fired gifted play-caller Doug Pederson | Marcus Hayes
Marcus Hayes
The Eagles need a shakeup in their thinking. Their new coach has to be that catalyst. | Mike Sielski
Mike Sielski
Doug Pederson says he's inclined to take a year off from coaching | Early Birds
Carson Wentz or Jalen Hurts? The right move is both, and the Eagles should try to pull it off. | David Murphy


text:
The BJOC
Strong hyperconjugative interactions limit solvent and substituent influence on conformational equilibrium: the case of cis-2-halocyclohexylamines
Camila B. Francisco1 ,
Cleverton S. Fernandes1 ,
Ulisses Z. de Melo1 ,
Roberto Rittner2 ,
Gisele F. Gauze1 and
Ernani A. Basso1
Camila B. Francisco
Chemistry Department, State University of Maringá, 5790, Maringá 87020-900, Brazil
All articles from this author
Cleverton S. Fernandes
Ulisses Z. de Melo
Roberto Rittner
Chemistry Institute, University of Campinas, 6154, Campinas 13083-970, Brazil
Gisele F. Gauze
Ernani A. Basso
1Chemistry Department, State University of Maringá, 5790, Maringá 87020-900, Brazil
2Chemistry Institute, University of Campinas, 6154, Campinas 13083-970, Brazil
Associate Editor: P. Schreiner
Beilstein J. Org. Chem. 2019, 15, 818–829. https://doi.org/10.3762/bjoc.15.79
Received 21 Jan 2019, Accepted 20 Mar 2019, Published 01 Apr 2019
The presence of strong stereoelectronic interactions involving the substituents in cis-2-substituted cyclohexanes may lead to results different from those expected. In this work, we studied the conformational behavior of cis-2-fluoro- (F), cis-2-chloro- (Cl), cis-2-bromo- (Br) and cis-2-iodocyclohexylamine (I) by dynamic NMR and theoretical calculations. The experimental data pointed to an equilibrium strongly shifted toward the ea conformer (equatorial amine group and axial halogen), with populations greater than 90% for F, Cl and Br in both dichloromethane-d2 and methanol-d4. Theoretical calculations (M06-2X/6-311++G(2df,2p)) were in agreement with the experimental, with no influence of the solvent or the halogen on the equilibrium. A principal component analysis of natural bond orbital energies pointed to the σ*C–X and σC–H orbitals and the halogen lone pairs (LPX) as the most significant for the hyperconjugative interactions that influenced the equilibrium. The σC–H → σ*C–X hyperconjugation and the interactions involving the LPX counterbalance each other, explaining the non-influence of the halogen on the conformational equilibrium. These interactions are responsible for the strong preference for the ea conformer in cis-2-halocyclohexylamines, being strong enough to restrain the shift in the equilibrium due to other factors such as steric repulsion or solvent effects.
Keywords: conformational equilibrium; cyclohexane derivatives; dynamic NMR; hyperconjugation; principal component analysis
cis-2-Substituted cyclohexanes are interesting from the conformational point of view, since one of the substituents should be axial. Generally, bulky substituents prefer the equatorial position to avoid steric repulsions [1]. Nevertheless, two distinct groups may provoke a competition of interactions, with regard to their volumes and steric repulsions, and the particular effects of the solvation medium on them, besides the intrinsic stereoelectronic effects. The sum of these factors in a system may lead to results different from those expected by considering just simple generalizations [2-9].
In the case of cis-2-halocyclohexylamines, the balance of interactions occurs between an amine group, which is known to be sensitive to the solvent [2,10,11], and the halogen, where the size increases considerably from F to I.
Batchelor reported the solvent effects on cis-2-methylcyclohexylamine [11], where the variation from aprotic to protic solvent causes a significant shift in the equilibrium, changing the axial preference of the amine group, which becomes equatorial with the protonation of the nitrogen.
The variation in the halogen size is also expected to cause some effect on the conformational equilibrium. Freitas and co-workers have demonstred this effect on trans-1,2-dihalocyclohexanes [12], where the diequatorial repulsion between the bulky halogens make the diaxial conformer more stable. Similarly, in trans-2-halocyclohexanols the OH–X interaction that stabilizes the diequatorial conformer loses strength for steric repulsions in going from F to I [13]. However, in the behavior observed by Basso and co-workers for cis-2-halocyclohexanols [14], the axial preference of the halogen (about 60–70%) is not greatly affected by the increase in the halogen size. Instead, the equilibrium is influenced by solute–solvent hydrogen bonding with the hydroxy group.
Besides the classical effects, interactions such as hyperconjugation has been pointed out as relevant in several studies involving cyclohexane derivatives [4,12,15-20]. Since the positions of both bonding and antibonding orbitals of the substituents change with the ring inversion, a conformation where a given substituent favors these interactions by performing them more effectively, may, in fact, govern the equilibrium. The C–X bonds have already been reported as excellent electron-density acceptors, and their presence in a system suggests the possibility of these interactions [17,21].
Although there have been several works on the conformational preference of 1,2-disubstituted cyclohexanes [4,11-14,20,22-29], cis-2-halocyclohexylamines have not yet been consistently studied. This is quite surprising, due to the possibilities of effects that add up or compete with each other in the presence of these two groups. This gap in the literature may be attributed to experimental difficulties in obtaining these derivatives.
Therefore, in this work, we developed the study of cis-2-fluorocyclohexylamine (F), cis-2-chlorocyclohexylamine (Cl), cis-2-bromocyclohexylamine (Br) and cis-2-iodocyclohexylamine (I), the latter being only theoretical (due to experimental difficulties). We evaluated the conformational equilibrium between ae (axial amine group and equatorial halogen) and ea (equatorial amine group and axial halogen) conformers (Figure 1) by dynamic NMR (DNMR) and theoretical calculations.
Figure 1: Conformations of cis-2-halocyclohexylamines, where X = F, Cl, Br and I.
Jump to Figure 1
Experimental conformational population
Low-temperature NMR experiments allow the identification of the individual conformers and their population at equilibrium, determined through the integration of 1H and 13C NMR spectra at −80 °C. Figure 2 illustrates the changes in the 1H NMR spectra of cis-2-chlorocyclohexylamine in dichloromethane-d2 by varying the temperature from 25 to −80 °C.
Figure 2: Variable-temperature 1H NMR spectra (500.13 MHz) for cis-2-chlorocyclohexylamine in dichloromethane-d2.
Figure 2: Variable-temperature 1H NMR spectra (500.13 MHz) for cis-2-chlorocyclohexylamine in dichloromethane-...
At 25 ºC, the signal at 2.89 ppm corresponds to H1, vicinal to nitrogen, and the signal at 4.32 ppm to H2, vicinal to chlorine (Figure 2). These 1H resonances, at room temperature, correspond to the average of the conformers at equilibrium. Table 1 shows the spectral data for F, Cl and Br at 25 and −80 °C, where 3JH–H refers to the individual coupling constants with the vicinal hydrogens, and W is the sum of all couplings, the latter being useful when there is loss of definition or signal broadening, common in low-temperature experiments [29].
Table 1: Chemical shifts (δ, ppm), coupling constants (3JH–H, Hz) and half-height line width (W, Hz) for cis-2-halocyclohexylamines in different solvents at 25 °C and −80 °C.
Hydrogen δa 3JH-Hb W δa 3JH-Hb W δa 3JH-Hb W
Fluorine Chlorine Bromine
dichloromethane-d2 25 °C H1 2.73 10.21c 19.21 2.89 8.96 19.42 2.97 9.81 17.83
H2 4.60 4.74c 11.36 4.32 5.72 12.99 4.68 5.65 11.10
−80 °C H1ax 2.62 11.86c 22.76 2.81 11.48 20.61 3.03 d d
H1eq 3.37 d 16.89 3.25 3.33 10.54 3.52 d d
H2ax 4.55 d 23.18 4.17 10.69 22.46 4.80 d d
H2eq 4.72 d 10.16 4.46 d 10.15 4.88 d d
methanol-d4 25 °C H1 2.70 10.83c 19.32 2.86 9.48 19.45 2.90 d 18.53
H2eq 4.65 2.56c 8.10 4.41 d 8.10 4.67 d d
aIn relation to TMS as reference. bLargest H–H coupling constant at three bonds. cMeasured considering only the 3JH–H coupling, disregarding 2JH–F. dJ and W were not measured due to loss of resolution or signals broadening at −80 °C.
According to the coupling constants (3JH–H) and half-height line widths (W) measured at 25 °C, the dominant conformation is ea. The higher values of J and W for H1 indicate the diaxial coupling of this hydrogen with the axial hydrogen of C6 (Figure 1). This behavior was observed for all compounds, in both solvents, as shown in Table 1.
At −80 °C, two signals for H1 and H2 are observed, which correspond to ae (H1ax and H2eq) and ea (H1eq and H2ax) conformers individually (Table 1). The values of 3JH–H, δ and W at −80 °C allow the assignment of the signals to the respective conformers, and by the integrals, determination the percentage of each in the equilibrium.
In the case of the bromine derivative, due to the broadening of both 1H and 13C signals and the loss of signal resolution at low temperature, the assignments at −80 °C were made by considering the attributions at 25 °C. So, we assume the ea conformer to be the major, attributing the most intense signals set at −80 °C to this conformer.
The populations determined by the integration of both 1H and 13C NMR spectra at −80 °C and the relative conformational energies are shown in Table 2. The equilibrium is shifted strongly toward the ea conformer, with 90% population for F and Cl and 91% for Br in dichloromethane-d2, while in methanol-d4 the populations were 95, 94 and 91% for F, Cl and Br, respectively. These results clearly show that the equilibrium is non-sensitive to halogen size and solvent effects.
Table 2: Conformational populations and relative conformational energies of cis-2-halocyclohexylamines at −80 °C in different solvents.
1H 13C Average
% ea ΔGºa % ea ΔGºa % ea ΔGºa
dichloromethane-d2 90 −0.84 90 −0.84 90 −0.84
methanol-d4 95 −1.13 96 −1.22 95 −1.13
dichloromethane-d2 91 −0.89 b – – –
methanol-d4 91 −0.89 b – – –
aΔG = − RT ln K, where K = nea/nae being nea the population of ea conformer and nae the population of ae conformer. A negative value means that ea is more stable. b 13C integration was not possible due to signal broadening.
A similar axial preference of cyclohexane halo derivatives was observed by Basso and co-workers in cis-2-halocyclohexanols [14], and by de Oliveira and Rittner in trans-3-halocyclohexanols [30]. However, in both studies this preference was not so pronounced as that observed in this work, with a small difference between the populations of the two conformers at equilibrium.
The equatorial preference for the amine group was somehow expected, due to classical steric effects (syn-1,3-diaxial repulsion). On the other hand, the amine group is usually very sensitive to the solvent effect. In addition, the increase in the halogen size could lead to a shift toward the ae conformer (equatorial halogen). In the studied system, no change was observed, and this behavior suggests that other effects can be acting. So, theoretical calculations were performed in order to understand which mechanisms control the conformational preference of these compounds.
Theoretical study
Conformer energy
The potential energy surface (PES) for the dihedral C2–C1–N–H (M06-2X/aug-cc-pVDZ) shows that each conformer has three lower-energy rotamers, identified according to the orientation of the nitrogen lone pair as anti (a) and gauche (gX and gH) to H1 (Figure 3).
Figure 3: Potential energy surfaces (PESs) for cis-2-halocyclohexylamines for the C2–C1–N–H dihedral angle rotation at M06-2X/aug-cc-pVDZ in ae (top) and ea (bottom) conformers.
Figure 3: Potential energy surfaces (PESs) for cis-2-halocyclohexylamines for the C2–C1–N–H dihedral angle ro...
Optimization and frequency calculations were performed for these rotamers at different theory levels. A table showing the energies of each rotamer is available in Supporting Information File 1 (Table B1).
We compiled in Table 3 the energy differences between ea and ae conformers (ΔEea), at four different theory levels, together with the theoretical ea populations. The ΔEea values were calculated by the weighted averages of both conformers, considering the rotational populations in each. The negative values, both in gas phase and in solution, indicate that ea is the more stable conformation.
Table 3: Variation of conformational energy (ΔEea, kcal mol−1) and populations of ea conformer determined theoretically in cis-2-halocyclohexylamines.
Gas phase Dichloromethane Methanol
ΔEea % ea ΔEea % ea ΔEea % ea
M06-2X/aug-cc-pVDZ F −0.32 74 −0.69 88 −0.66 86
Cl −0.46 79 −0.66 86 −0.70 88
Br −0.49 81 −0.89 92 −0.88 92
I −0.48 81 −1.02 94 −1.06 94
RMSDa 0.131 0.270
M06-2X/6-311++G(2df,2p) F −0.36 76 −0.67 86 −0.69 87
MP2/aug-cc-pVDZ F −0.22 71 −0.61 78 −0.73 88
MP2/6-311++G(2df,2p) F −0.16 68 −0.68 86 −0.68 87
aRoot mean square deviation of experimental and theoretical ΔGº, being the last available in Supporting Information File 1 (Table B2).
A trend in energy values was observed at all the theory levels employed in this study, there being a small decrease of ΔEea from gas phase to solution. However, when we compare the ΔEea values for dichloromethane and methanol, the energy variation is too small (Table 3). Likewise, the nature of the halogen also showed a minimal variation in ΔEea values over the series, both in gas phase and in solution. These energetical reports are in agreement with the experimental.
The calculations performed in M06-2X/6-311++G(2df,2p) showed results closer to the experimental, with the lower root mean square deviation (RMSD) error values of 0.004 in dichloromethane and 0.230 in methanol. This shows the efficiency of this theory level to describe the studied systems. The agreement of the energy values in gas phase with those in solution confers reliability to calculations such as natural bond orbitals (NBOs), which are made in the gas phase.
With regard to rotamers, gX in ae conformer and a in ea are the least stable, with smaller populations (calculated in M06-2X/6-311++G(2df,2p)), as shown in Figure 4. This was observed for the calculations performed in the gas phase, and in dichloromethane and methanol.
Figure 4: Populations of rotamers a, gX e gH in ae (top) and ea (bottom) conformers of cis-2-halocyclohexylamines in the gas phase, dichloromethane and methanol.
Figure 4: Populations of rotamers a, gX e gH in ae (top) and ea (bottom) conformers of cis-2-halocyclohexylam...
Even though previous works involving cyclohexane halo derivatives reported the axial preference of halogens, as mentioned before, the pronounced ea preference observed in our case led us to investigate the specific effects that may be responsible for this behavior.
Delocalization, electrostatic and steric interactions
In order to determine which effects are responsible for the stabilization of each conformer, we carried out studies of hyperconjugative, steric and electrostatic effects.
The deletion of all non-Lewis natural bond orbitals (M06-2X/6-311++G,2df,2p) disregard all hyperconjugative effects, allowing us to evaluate the conformational preference in the absence of these interactions. Therefore, the total energy of each conformer (Etotal) can be expressed as the sum of Eloc, the localized energy after the deletion of the hyperconjugation, and Edeloc, the delocalization energy [31].
These calculations also provide the total steric exchange energy (Esteric), which describes the electron cloud repulsion [32]. Another parameter evaluated was the total electrostatic energy, Eelect, according molecular mechanics calculations employing the Amber force field GAFF [33].
So, after the deletion of hyperconjugative interactions, we should analyze the delocalization energy, where higher values indicate stronger effects. In Table 4 only the most stable rotamers for each conformation were analyzed. The values of ΔEdeloc show an inversion of the conformational preference for all compounds in the absence of hyperconjugative interactions, and ae becoming the most stable conformer. It is worth noting the increase in the difference of the delocalization energy along the series, suggesting the influence of the halogen in this effect.
Table 4: Variation in total (ΔEtotal), localized (ΔEloc) and delocalization (ΔEdeloc) energies; and absolute total steric exchange (Esteric) and total electrostatic (Eelect) energies, in kcal mol−1, for cis-2-halocyclohexylamines.
ΔEtotala
ΔEloca
ΔEdeloca
Esterica
Eelectb
ae 0.25 0.00 3.46 507.05 −0.50
ea 0.00 3.21 0.00 509.24 −0.22
ea 0.00 5.52 0.00 532.02 0.18
aM06-2X/6-311++G(2df,2p) in the gas phase. bCalculated using the Amber force field GAFF. Positive values indicate more repulsive interactions.
Taking into account the localized energy (ΔEloc), the ea conformer presented the highest values, and it is consistent with the values of Esteric and Eelect. It shows that, although ea is the most stable conformation, it has the greater steric and electrostatic repulsions.
Analyzing all these effects together, we could observe that hyperconjugation is an important factor to describe the conformational preference. Despite the evident influence of the halogen on hyperconjugation, the balance of these energies reflects in the unchanged equilibrium along the series.
With respect to the rotamers, neither hyperconjugation nor total steric exchange energies can explain the rotational behavior, which is attributed to electrostatic effects only. In the most unstable rotamers of each conformer (gX for ae and a for ea) the nitrogen electron lone pair is oriented toward the halogen, as illustrated in Figure 5, resulting in greater electrostatic repulsions. The values of localized, delocalized, steric and electrostatic energies for all rotamers are available in Supporting Information File 1 (Table B3).
Figure 5: Nitrogen lone pair in rotamers gX (ae) and a (ea) oriented towards the halogen, making these rotamers less stable in their respective conformation.
Figure 5: Nitrogen lone pair in rotamers gX (ae) and a (ea) oriented towards the halogen, making these rotame...
Although there is a sum of effects that can govern a conformational equilibrium, for cis-2-halocyclohexylamines the rotational preference is due to electrostatic effects, while the strong and non-sensitive conformational preference for ea can be explained by hyperconjugation. This arouses the interest for a deeper analysis of hyperconjugative interactions.
Principal component analysis (PCA) of natural bond orbitals (NBOs)
In order to interpretate the large number of interactions present in the compound structures, we applied PCA to NBO energies.
For each individual bond, the sum was made of all hyperconjugative stabilization energies (Eij) involving both bonding and antibonding orbitals, as well as the energies of nitrogen and halogen lone-pair interactions (LPN and LPX, respectively), resulting in 22 variables corresponding to all the bonds of the structure of the most stable rotamer in each conformation (see Supporting Information File 2 for full numerical data).
In the PCA (Figure 6), two principal components described 94% of the results. The PC1 is able to differentiate the variables according to the halogens, while the PC2 distinguish the two conformations.
Figure 6: PCA for 22 variables corresponding to the hyperconjugative interactions for all rotamers in ae and ea conformers of cis-2-halocyclohexylamines. Note that the correlation vectors with the strongest black color has the greater contribution for the PC's.
Figure 6: PCA for 22 variables corresponding to the hyperconjugative interactions for all rotamers in ae and ...
The fact of the PC1, which has the higher variance in relation to the others, distinguish the halogens following a chemical trend is quite important, since the change in the halogen and consequently in the size of the orbitals directly affects the electronic delocalization.
According to the correlation vectors, the LPX differentiate the variables between the halogens, with the greater weight for the fluoro derivatives. If we analyse the vectors perpendicular to the groups of conformers, it is clear that the variables corresponding to C1–H, C2–X and C3–Hax bonds distinguish the ea conformer from ae.
Then, considering all the interactions existent in both conformations, the ones involving the LPX are important for both conformers. However, what differs them are the interactions with the highest weight for ea.
It is worth mentioning that the variables corresponding to the N–H bonds and LPN has no contribution for the PC's, confirming that the rotational preference has no influence on the hyperconjugation.
Analyzing the bonds pointed by the PCA as electron density donors (bonding orbitals) or acceptors (antibonding orbitals) in Figure 7, it is clear that the most significant interactions are those involving the C2–X bond acting as electronic density acceptor (σ*C2–X orbital), and the C1–H (σC1–H orbital) and LPX acting as donor.
Figure 7: Sum of bonding (donor) and antibonding (acceptor) orbitals interactions of C1–H, C2–X and C3–Hax bonds and LPX in cis-2-halocyclohexylamines.
Figure 7: Sum of bonding (donor) and antibonding (acceptor) orbitals interactions of C1–H, C2–X and C3–Hax bo...
This shows that hyperconjugative interactions are dependent on the halogen: as the size of the halogen increases, the donor or acceptor ability of the respective orbitals (C–X bonds and antibonds) increases in the same way; however, the LPX follows the reverse order, with a decrease in the donor ability as LPF > LPCl > LPBr > LPI.
These observations allow us to analyze which specific orbitals are responsible for the great stabilization of the ea conformer. Table 5 presents the stabilization energy values (Eij), the difference in energy between the orbitals (Ei − Ej) and the Fock matrix elements (F(i:j)) for the main hyperconjugative interactions.
Table 5: Stabilization energy, Eij (kcal mol−1), orbitals energy difference Ei − Ej (a. u.) and Fock matrix elements F(i;j) (a. u.) of main hyperconjugative interactions in ea conformer of cis-2-halocyclohexylamines.
Eij
Ei - Ej
F(i;j)
σC1–H → σ*C2–X
F 5.83 0.86 0.063
Cl 7.88 0.72 0.067
Br 9.13 0.66 0.069
I 9.44 0.64 0.069
σC3–Hax → σ*C2–X
LPX → σ*C–Ca
LPX → σ*C2–H8
aσ*C2–C3 for F, and σ*C1–C2 for Cl, Br and I.
The Eij values for σC1–H → σ*C2–X and σC3–Hax → σ*C2–X clearly show a trend from F to I, where these interactions become considerably more intense (higher Eij values) with the increase in the halogen size. It is also possible to observe that the difference in energy between these orbitals (Ei − Ej) decreases from F to I, which means that the acceptance of electron density by the C–X bond is more effective when we have the larger halogens. The Ei − Ej values decrease from 0.86 for F to 0.64 atomic units for I in σC1–H → σ*C2–X; and from 0.87 for F to 0.65 atomic units for I in σC3–Hax → σ*C2–X. The same trend is observed for the Fock matrix element (F(i:j)), which concerns to the orbital overlap and also increases from F to I .
On the other hand, the interactions involving the LPX follow the reverse order (Table 5). The Eij values decrease steadily from F to I, going from 6.09 and 6.26 to 2.52 and 2.15 kcal mol−1 for LPX → σ*C–C and LPX → σ*C2–H8, respectively. In the same way, the Fock matrix element decreases considerably comparing the LPF and LPI interactions, going from 0.068 and 0.069 for LPF to 0.038 and 0.037 atomic units for LPI, in LPX → σ*C–C and LPX → σ*C2–H8, respectively.
This tendency in the halogen series observed in both hyperconjugative interactions describes the observed in PCA; the LPX interactions counterbalance the σC–H → σ*C2–X, in the sense that the LPX is more important for the fluoro derivatives, while the σC–H → σ*C2–X has the greater weight for the larger halogens.
The acceptor ability of σ*C–X orbitals has already been described in the literature [17], and has an inverse correlation with electronegativity: the electronegativity decreases from F to I and the acceptor ability of σ*C–X orbitals increases in the order σ*C–F < σ*C–Cl < σ*C–Br < σ*C–I, as observed in this work.
As σC1–H, σ*C2–X and σC3–Hax are antiperiplanar, they favor orbital overlap, as illustrated in Figure 8. The orbital σ*C–X acting as electron density acceptor of σC1–H and σC3–Hax can explain the great axial preference of the halogens. While in the ea conformer the donors σC1–H and σC3–Hax are antiperiplanar to the acceptor σ*C–X, in the ae conformer the corresponding donor orbitals are from C–C bonds (due to equatorial halogen orientation). Previous publications have already reported the C–H bond as slightly better donor than C–C bond [34,35].
Figure 8: Orbitals overlap of σC1–H → σ*C2–X (left) and σC3–Hax → σ*C2–X (right) hyperconjugations in ea conformer.
Figure 8: Orbitals overlap of σC1–H → σ*C2–X (left) and σC3–Hax → σ*C2–X (right) hyperconjugations in ea conf...
Therefore, in the sum of interactions existent in the studied systems the hyperconjugation stands out, explaining the axial halogen and equatorial NH2 (ea) preference in all compounds.
The conformational behavior of the cis isomers of 2-fluoro-, 2-chloro- and 2-bromocyclohexylamine was determined experimentally through DNMR at −80 °C, with populations of the ea conformer (equatorial amine group and axial halogen) higher than 90% in dichloromethane-d2 and methanol-d4. The conformational preference was affected neither by the solvent polarity nor the halogen size, suggesting the presence of strong stereoelectronic effects being responsible for the conformational behavior in these systems.
Theoretical calculations are in agreement with experimental data, the ea conformer being the most stable for all series, both in the gas phase and in solution. For the C–N rotation, the most unstable rotamers are gX for the ae conformer and a for ea, due to the orientation of the nitrogen lone pair electrons toward the halogen, which provides greater electrostatic repulsions.
The non-sensitivity to halogen size along the series can be attributed to a balance of steric, electrostatic and hyperconjugative interactions, being the strong conformational preference for ea explained by hyperconjugations involving mainly the C–X bond. The greater acceptor ability of the σ*C–X orbital, axial in the ea conformer, enables strong interactions with the neighboring σC–H orbitals, and this acceptor ability increases along the halogen series (F < Cl < Br < I). However, interactions involving the halogen lone pair electrons follows the reverse order, counterbalancing the σC–H → σ*C–X interactions along the series.
The strongly shifted and non-sensitive conformational equilibrium governed by a strong hyperconjugative interaction in cis-2-halocyclohexylamines shows that the conformational analysis of small molecules can still provide surprising results.
trans-2-Fluorocyclohexanol was prepared according the literature [36] to provide cis-2-fluorocyclohexylamine.
cis-2-Fluorocyclohexylamine (F) was obtained by a Mitsunobu–Gabriel reaction, as described by Thvedt and co-workers [37]. Under nitrogen atmosphere, trans-2-fluorocyclohexanol (6.00 mmol), triphenylphosphine (6.60 mmol) and phthalimide (6.60 mmol) were dissolved in THF (40 mL). To this mixture was slowly added a solution of diisopropyl azodicarboxylate (DIAD, 40% in THF) and the mixture was stirred at room temperature for 18 h. The solvent was removed under reduced pressure and the reaction mixture was re-dissolved in CH2Cl2 (20 mL) and 10 mL of a 10% K2CO3 solution and stirred for 1 h. The resulting mixture was washed with distilled water (3 × 10 mL), the organic layer dried with Na2SO4 and concentrated under reduced pressure, and the crude product purified by silica-gel column chromatography (ethyl acetate/hexane 20%), resulting in 1.18 g (80%) of the cis-Gabriel amine. The free amine was obtained by the hydrazinolysis of the cis-Gabriel amine (0.40 mmol), in methanol (0.50 mL) with hydrazine hydrate (25%, 0.20 mL), stirred at room temperature for 24 h. To the mixture was added HCl until pH ≈ 2, forming a precipitate, which was filtered, and to the aqueous phase was added NaOH until pH ≈ 14 and the product extracted exhaustively (6 × 10 mL) with CH2Cl2. The organic layer was dried with Na2SO4 and the pure cis-2-fluorocyclohexylamine (0.19 g, 35%), a yellowish liquid concentrated under reduced pressure.
2-Chloro- and 2-bromocyclohexanone were synthetized as previously described [38,39], to provide cis-2-chloro (Cl) and cis-2-bromocyclohexylamine (Br), respectively, by a reductive amination [40].
To a sealed tube were added the corresponding ketone (10 mmol), ammonium acetate (100 mmol) and sodium cyanoborohydride (10 mmol) in methanol (30 mL) and the mixture stirred for 48 h at room temperature. To the mixture was added concentrated HCl until pH ≈ 2, forming a white precipitate (protonated amine), which was filtered and dissolved in distilled water, which was washed with CH2Cl2 (3 × 20 mL). To the aqueous layer was added NaOH until pH ≈ 14 and the product extracted exhaustively with CH2Cl2 (6 × 20 mL). The crude mixture was purified by silica-gel column chromatography (acetone/chloroform 10% for Cl and 25% for Br), and the cis isomer was isolated corresponding to a yellowish liquid for Cl (0.04 g, 15%) and a white amorphous solid for Br (0.03 g, 10%).
cis-2-Fluorocyclohexylamine: 1H NMR (500.13 MHz, methanol-d4) δ 4.64 (dddd, 1H, H2), 2.70 (dddd, 1H, H1), 2.01 (m, 1H, 1H3), 1.74–1.64 (m, 2H, 1H5, 1H6), 1.61–1.42 (m, 4H, 1H3, 2H4, 1H6), 1.34 (m, 1H, H5); 13C NMR (125.77 MHz, methanol-d4) δ 93.58 (C2), 52.80 (C1), 30.84 (C3, C6), 20.85 (C4), 24.88 (C5); HRMS (ESI/QTOF) m/z: [M + H]+ calcd for C6H12FN, 118.0953; found, 118.0991.
cis-2-Chlorocyclohexylamine: 1H NMR (500.13 MHz, dichloromethane-d2) δ 4.30 (ddd, 1H, H2), 2.80 (ddd, 1H, H1), 2.04 (m, 1H, 1H3), 1.78 (m, 1H, 1H3), 1.70–1.60 (m, 2H, 1H5, 1H4), 1,54 (m, 2H, 2H6), 1.40 (m, 1H, 1H4), 1.30 (m, 1H, 1H5); 13C NMR (125.77 MHz, dichlorotmethane-d2) δ 68.47 (C2), 53.22 (C1), 33.16 (C3), 31.30 (C6), 23.76 (C5), 21.10 (C4); HRMS (ESI/QTOF) m/z: [M + H]+ calcd for C6H12ClN, 134.0658; found, 134.0692.
cis-2-Bromocyclohexylamine: 1H NMR (500.13 MHz, dichloromethane-d2) δ 4.68 (ddd, 1H, H2), 2.97 (ddd, 1H, H1), 2.18 (m, 1H, H3), 1.93 (m, 1H, H3), 1.77–1.63 (m, 4H, 1H4, 1H5, 2H6), 1.50 (m, 1H, H4), 1.37 (m, 1H, H5); 13C NMR (125.77 MHz, dichlorotmethane-d2) δ 62.19 (C1), 53.42 (C2), 33.67 (C3), 30.08 (C5), 23.87 (C6), 21.28 (C4); HRMS (ESI/QTOF) m/z: [M + H]+ calcd for C6H12BrN, 178.0153; found, 178.0189.
NMR experiments
¹H and ¹³C NMR spectra were acquired on a Bruker Avance III HD spectrometer, operating at 500.13 MHz for 1H nuclei and 125.77 MHz for 13C nuclei in solutions with approximate concentration of 0.01 mol L–1 in dichloromethane-d2 and methanol-d4, using tetramethylsilane as internal reference. The probe was coupled to a liquid nitrogen evaporator system to decrease the temperature from 25 to −80 °C. Typical 1H NMR spectra were run with a spectral window of approximately 10000 Hz (20 ppm) for 1H spectra, and 30000 Hz (238 ppm) for 13C spectra, with number of points 32k, resulting in a digital resolution of 0.12 Hz/point. The spectral data are available in Supporting Information File 1.
Theoretical calculations
Theoretical calculations were performed with the software package Gaussian 09 [41]. To determine the lowest energy structures for each conformer, we built a PES (in M06-2X/aug-cc-pVDZ), varying the C2–C1–N–H dihedral angle in steps of 15° manually, to avoid nitrogen inversion.
Optimization and frequency calculations were performed for the three lower-energy rotamers for each conformer, both in the gas phase and in solution (Cartesian coordinates are available in Supporting Information File 1). The calculations were performed using the M06-2X density functional method, and the second-order Möller–Plesset perturbation method (MP2), associated with the Pople 6-311++G(2df,2p), and Dunning aug-cc-pVDZ basis set. The mixed basis set function LanL2DZ-ECP was employed for the iodine atom. Solvation calculations were performed in dichloromethane and methanol, with the the implicit model IEF-PCM and the description of the molecular cavity through Bondi's atomic radii.
Molecular Mechanics calculations were performed using the software Avogadro 1.2.0 [42], employing the Amber force field GAFF [33].
NBO calculations were performed in the optimized structures in the gas phase (M06-2X/6-311++G(2df,2p)), through the module NBO 5.9 [43] from Gaussian 09. For the PCA, it was used the software R, version 3.5.0 [44], with the graphical interface RStudio, version 1.0.153 [45].
Supporting Information File 1: 1H and 13C NMR spectra at 25 and −80 °C, supplementary theoretical values, RScript for PCA and the Cartesian coordinates of the structures.
Format: PDF Size: 1.2 MB Download
Supporting Information File 2: NBO data for PCA.
Format: XLSX Size: 13.4 KB Download
The authors would like to thank the Brazilian Council for Scientific and Technological Development (CNPq) for the fellowships to E.A.B. and R.R., and for the scholarship to C.S.F.; and the Coordination for the Improvement of Higher Education Personnel (CAPES) for the scholarships to C.B.F. and U.Z.M. Thanks also go to the São Paulo Research Foundation (FAPESP) (Grant 2016/24109-0) for the financial assistance and to the National Center for High Performance Computing (CENAPAD-UFC) for the computational cluster disponibility.
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de Oliveira, P. R.; Viesser, R. V.; Guerrero, P. G., Jr.; Rittner, R. Spectrochim. Acta, Part A 2011, 78, 1599–1605. doi:10.1016/j.saa.2011.02.010
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de Oliveira, P. R.; Rittner, R. Spectrochim. Acta, Part A 2008, 70, 1079–1086. doi:10.1016/j.saa.2007.10.016
Duarte, C. J.; Freitas, M. P. J. Mol. Struct. 2009, 930, 135–139. doi:10.1016/j.molstruc.2009.05.004
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36. Wittig, G.; Mayer, U. Chem. Ber. 1963, 96, 329–341. doi:10.1002/cber.19630960141
34. Alabugin, I. V. J. Org. Chem. 2000, 65, 3910–3919. doi:10.1021/jo991622+
35. Alabugin, I. V.; Manoharan, M. J. Org. Chem. 2004, 69, 9011–9024. doi:10.1021/jo048287w
43. NBO 5.0; Theoretical Chemistry Institute, University of Wisconsin: Madison, 2001.
44. R: A Language and Environment for Statistical Computing, Version 3.5.0; R Foundation for Statistical Computing: Vienna, Austria, 2018.
42. Hanwell, M. D.; Curtis, D. E.; Lonie, D. C.; Vandermeersch, T.; Zurek, E.; Hutchison, G. R. J. Cheminf. 2012, 4, 17. doi:10.1186/1758-2946-4-17
40. Borch, R. F.; Bernstein, M. D.; Durst, H. D. J. Am. Chem. Soc. 1971, 93, 2897–2904. doi:10.1021/ja00741a013
41. Gaussian 09, Revision B.01; Gaussian, Inc.: Wallingford, CT, 2010.
37. Thvedt, T. H. K.; Fuglseth, E.; Sundby, E.; Hoff, B. H. Tetrahedron 2010, 66, 6733–6743. doi:10.1016/j.tet.2010.06.081
38. Lautens, M.; Bouchain, G. Org. Synth. 2002, 79, 251. doi:10.15227/orgsyn.079.0251
39. Allinger, J.; Allinger, N. L. Tetrahedron 1958, 2, 64–74. doi:10.1016/0040-4020(58)88024-2
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Online Beilstein Talk with Hermann A. Wegner March 16 – Register for free!
Beilstein Glyco-Bioinformatics Symposium 2023 - June 20 to 22, 2023, Limburg, Germany
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© 2019 Francisco et al.; licensee Beilstein-Institut.
This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0). Please note that the reuse, redistribution and reproduction in particular requires that the authors and source are credited.
The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc)
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Francisco, C. B.; Fernandes, C. S.; de Melo, U. Z.; Rittner, R.; Gauze, G. F.; Basso, E. A. Beilstein J. Org. Chem. 2019, 15, 818–829. doi:10.3762/bjoc.15.79


text:
package com.opensymphony.xwork2.util.finder;

import java.net.URL;
import java.util.Collection;
import java.util.Set;

/**
 * Allows create different ClassFinders which should help support different Java versions
 */
public interface ClassFinderFactory {

    ClassFinder buildClassFinder(ClassLoaderInterface classLoaderInterface, Collection<URL> urls, boolean extractBaseInterfaces, Set<String> protocols, Test<String> classNameFilter);

}


For this week's CURE Talks Cancer podcast, we're continuing on the theme of Family Caregivers Month. We spoke with Peg Myrick, a colon cancer survivor and former cancer caregiver, as well as Martha Raymond, the founder and CEO of the Raymond Foundation.
The two women talk about the ins and outs of caregiving, including some of the aspects that they weren't expecting when first taking on the role. They also give practical advice for caregivers, and discuss some resources that care providers can turn to.


text:
Kampen om Næsbygård is a 1964 Danish family film directed by Ib Mossin and Alice O'Fredericks.

Cast
 Asbjørn Andersen as Godsejer Martin
 Karen Berg as Helene
 Ole Wisborg as Torben
 Poul Reichhardt as Præsten Prip
 Inger Stender as Præstekonen Anna
 Agnes Rehni as Tante Thyra
 Ib Mossin as Anker
 Jane Thomsen as Præstedatteren Rosa
 Ole Neumann as Martin Jr.
 Helga Frier as Kokkepigen Marie
 Marie-Louise Coninck as Stuepigen Erna
 Einar Juhl as Sagføreren
 Knud Schrøder as Bookmaker
 Holger Vistisen as Bookmaker
 Yvonne Ekmann as Torben's kæreste
 Palle Huld as Lægen
 Peter Malberg as Gartneren Ole
 Christian Arhoff as Gartneren Nick
 Gunnar Hansen as TV reporter

References

External links

1964 films
Danish children's films
1960s Danish-language films
Films directed by Alice O'Fredericks
Films scored by Sven Gyldmark
ASA Filmudlejning films

redpajama_set_name: RedPajamaWikipedia


text:
package com.orctom.laputa.service.domain;

import java.util.Date;
import java.util.Objects;

public class Category {

  private Long id;
  private String name;
  private Date date;

  public Category() {
  }

  public Category(Long id, String name) {
    this.id = id;
    this.name = name;
  }

  public Category(Long id, String name, Date date) {
    this.id = id;
    this.name = name;
    this.date = date;
  }

  public Long getId() {
    return id;
  }

  public void setId(Long id) {
    this.id = id;
  }

  public String getName() {
    return name;
  }

  public void setName(String name) {
    this.name = name;
  }

  public Date getDate() {
    return date;
  }

  public void setDate(Date date) {
    this.date = date;
  }

  @Override
  public boolean equals(Object o) {
    if (this == o) return true;
    if (!(o instanceof Category)) return false;
    Category category = (Category) o;
    return Objects.equals(id, category.id) &&
        Objects.equals(name, category.name);
  }

  @Override
  public int hashCode() {
    return Objects.hash(id, name);
  }

  @Override
  public String toString() {
    return "Category{" +
        "id=" + id +
        ", name='" + name + '\'' +
        ", date=" + date +
        '}';
  }
}


health and productivity by detecting emergencies and hidden risk factors in real-time.
Our system is built with proprietary algorithms and cutting-edge cognitive technologies.
We apply a decade's worth of practical knowledge on translating signal and time series data into meaningful information.
Our algorithms are able to identify events or states over time that go beyond of what would have been statistically expected.
By modeling IoT and contextual data, we are enabling the discovery of trends and provide actionable insights.
We find similarities and trends in unstructured data to detect changes at an early stage.
By analyzing motion data from wearables we are able to identify specific human movements and interpret actions.


For how long have you been playing ?: five years!
GL, you know my vote. I'll post some screens for you when I get back home.
These are the only games I have with you atm, well played.
thx for the screens! and I didnt know Oracle was ShadowFlameZ ... :o I dont think we ever played each other?
thats the spirit yopa takk!
I have only been on rC TS twice so far but you never never there :P on woop tho! btw: could someone activate me on rC TS so I can actually use it?


Gizmodo compiled this impressive chart of battery times for the iPhone 3G as reported by various reviewers.
Most reviewers found the iPhone 3G did have around 5 hours of talk time which was amongst the best for 3G handsets that were testing. The "mixed" use included web browsing and had far more variable results. In those tests, the iPhone 3G ranged from 2 hours and 52 minutes of use as high as 5 hours and 49 minutes.
Hardware site Anandtech actually performed dedicated web browsing tests for the iPhone 3G compared to the original iPhone on EDGE. They found that iPhone 3G (in 3G mode) could browse for 3 hours and 17 minutes, while the original iPhone browsing on 2G could browse for 5 hours and 42 minutes.


This week we have a great treat for you! Our very own Mommy Extraordinaire Monica has come up with some wonderful tips for kids and cars. Monica knows firsthand how having 2 small children and a dog can make any car drive an eventful exercise in driving safety, negotiations, and compromise. Here are her 5 tips for any car ride!
My kids love to snack so I always make sure to pack goldfish for them. I also never forget something to drink because we will be driving for literally 2 minutes and they will be asking for water. So, always bring a sippy cup.
I also tell them they can bring 1 toy in the car with them, my son Dominic usually sneaks in 3 hot wheels (I let it slide) and my daughter Arianny brings her Anna & Elsa doll from FROZEN. I also always have a few extra toys and books in the middle seat between them so they can grab what they want during the drive.
I always set ground rules for them before we get in car. For example: If you drop anything on floor, you will need to wait until we park the car to grab it. Mommy is driving and cannot pick it up for you.
I also have a "Mommy Emergency Kit" in my car at all times. This kit includes: tissues, wipes, band aids, an extra pair of clothes, diapers and Tylenol. This is so I don't have to stress about going to the store real quick (because any mother knows that statement is never true). These are items I would need on any given day and they are easily accessible in my back seat. Less stress= Happy Mama!
I also think it's super important to set a good example for them from an early age. I am extra mindful of staying calm when another driver cuts me off. I know by modeling safer driving skills, not only am I protecting my kids now, but I am also protecting them down the road by teaching them smart driving habits they will need when it is their turn to climb behind the wheel.
Thanks Monica! Those are some really wonderful tips! Do YOU have any tips for driving safely in the car with children? Comment below, we would love to hear about them!


text:
2023 1 oz Gold American Eagle Coins PCGS MS70 FDOI
PRESALE ITEM: Shipping on or around - February 3rd, 2023
Volume Pricing Current Spot Price: $1,936.59
Customers Note: This is a presale item and is not expected to ship until around February 3rd, 2023. EVERY order containing this item will be held from shipping until that date. Please note that this date is a rough estimate and solely depends on the mint meeting their production schedule.
The Gold Eagle from the United States Mint debuted in 1986 and became the first American gold coin struck in more than 50 years. The coins in this series come with four weights, with the 1 oz gold the most popular choice for many investors. Today, certified-perfect 2023 1 oz Gold American Eagles are available to you online at Silver.com.
Available to ship to you inside protective plastic slabs from the PCGS!
38th coin in the Gold American Eagle Series!
Availability of certified perfect coins is limited!
Consists of One Troy ounce of actual gold content.
The face value of $50 (USD) is fully backed by the US government.
Graded Mint State 70 by the Professional Coin Grading Service.
First Day of Issue.
On the obverse is Liberty.
The reverse features an American bald eagle.
The last American gold coins issued by the US Mint were the US Eagles, circulation coins that were last struck in 1933. Following the end of the gold standard during the Great Depression, no further gold coins were struck by the US Mint. In 1986, the US Mint's launch of gold bullion coins in the Gold Eagle Series marked the restart of American gold coining.
All of these 2023 1 oz Gold American Eagles are available to purchase in perfect condition. Coins with this grade have full, original mint luster and bear no detractions of any kind. First Day of Issue specimens are those the PCGS receives for certification within 24 hours of release from the mint.
On the obverse of 2023 Gold American Eagles is a portrait of Liberty. This front-facing bust of Liberty shows her full-length figure walking toward you with a torch in her right hand, an olive branch in her left, sun rays on the horizon, and a ring of stars around the field. The U.S. Capitol Building is also visible on the field.
The reverse side of the 2023 1 oz Gold Eagle features a new depiction of the American bald eagle. Designed by Jennie Norris in 2020, this vision of the bald eagle replaced Miley Busiek's original design created for the coins in 1986. This elegant design captures the majesty of the eagle with its head in left-profile relief.
Please contact Silver.com if you have any questions. Our team can assist you at 888-989-7223, chat with you live online, or respond to your written inquiries via email.
Grade: MS70 FDOI
Grade Service: PCGS
Face Value: $50
Obverse Designer: Augustus Saint-Gaudens
Reverse Designer: Jennie Norris
Edge Design: Reeded with Anti-Counterfeit Variation
Packaging Type: PCGS Plastic Slab