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Showing posts with label chemical. Show all posts
Showing posts with label chemical. Show all posts

Tuesday, 1 August 2017

On this day in science history: oxygen was identified

In 1774, Joseph Priestley, British Presbyterian minister and chemist, identified a gas which he called "dephlogisticated air" - later known as oxygen. Priestley found that mercury heated in air became coated with "red rust of mercury," which, when heated separately, was converted back to mercury with "air" given off. Studying this "air" given off, he observed that candles burned very brightly in it. Also, a mouse in a sealed vessel with it could breathe it much longer than ordinary air. A strong believer in the phlogiston theory, Priestley considered it to be "air from which the phlogiston had been removed." Further experiments convinced him that ordinary air is one fifth dephlogisticated air, the rest considered by him to be phlogiston.

Joseph Priestley, by Charles Turner [Public domain], via Wikimedia Commons
However, oxygen was in fact first discovered earlier, by Swedish pharmacist Carl Wilhelm Scheele. He had produced oxygen gas by heating mercuric oxide and various nitrates in 1771–2. Scheele called the gas "fire air" because it was the only known supporter of combustion, and wrote an account of this discovery in a manuscript he titled Treatise on Air and Fire, which he sent to his publisher in 1775. That document was published in 1777. 

Because Priestly published his findings first, he is usually given priority in the discovery.

The French chemist Antoine Laurent Lavoisier later claimed to have discovered the new substance independently. Priestley visited Lavoisier in October 1774 and told him about his experiment and how he liberated the new gas. Scheele also posted a letter to Lavoisier on September 30, 1774 that described his discovery of the previously unknown substance, but Lavoisier never acknowledged receiving it (a copy of the letter was found in Scheele's belongings after his death). Long before this, one of the first known experiments on the relationship between combustion and air was conducted by the 2nd century BCE Greek writer on mechanics, Philo of Byzantium. In his work Pneumatica, Philo observed that inverting a vessel over a burning candle and surrounding the vessel's neck with water resulted in some water rising into the neck. Philo incorrectly surmised that parts of the air in the vessel were converted into the classical element fire and thus were able to escape through pores in the glass. Many centuries later Leonardo da Vinci built on Philo's work by observing that a portion of air is consumed during combustion and respiration.

In the late 17th century, Robert Boyle proved that air is necessary for combustion. English chemist John Mayow (1641–1679) refined this work by showing that fire requires only a part of air that he called spiritus nitroaereus. In one experiment, he found that placing either a mouse or a lit candle in a closed container over water caused the water to rise and replace one-fourteenth of the air's volume before extinguishing the subjects. From this he surmised that nitroaereus is consumed in both respiration and combustion.

Mayow observed that antimony increased in weight when heated, and inferred that the nitroaereus must have combined with it. He also thought that the lungs separate nitroaereus from air and pass it into the blood and that animal heat and muscle movement result from the reaction of nitroaereus with certain substances in the body. Accounts of these and other experiments and ideas were published in 1668 in his work Tractatus duo in the tract "De respiratione".

Robert Hooke, Ole Borch, Mikhail Lomonosov, and Pierre Bayen all produced oxygen in experiments in the 17th and the 18th century but none of them recognized it as a chemical element. This may have been in part due to the prevalence of the philosophy of combustion and corrosion called the phlogiston theory, which was then the favored explanation of those processes.

Established in 1667 by the German alchemist J. J. Becher, and modified by the chemist Georg Ernst Stahl by 1731, phlogiston theory stated that all combustible materials were made of two parts. One part, called phlogiston, was given off when the substance containing it was burned, while the dephlogisticated part was thought to be its true form, or calx.

Highly combustible materials that leave little residue, such as wood or coal, were thought to be made mostly of phlogiston; non-combustible substances that corrode, such as iron, contained very little. Air did not play a role in phlogiston theory, nor were any initial quantitative experiments conducted to test the idea; instead, it was based on observations of what happens when something burns, that most common objects appear to become lighter and seem to lose something in the process. The fact that a substance like wood gains overall weight in burning was hidden by the buoyancy of the gaseous combustion products.

This theory, while it was on the right track, was unfortunately set up backwards. Rather than combustion or corrosion occurring as a result of the decomposition of phlogiston compounds into their base elements with the phlogiston being lost to the air, it is in fact the result of oxygen from the air combining with the base elements to produce oxides. Indeed, one of the first clues that the phlogiston theory was incorrect was that metals gain weight in rusting (when they were supposedly losing phlogiston).

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Tuesday, 30 May 2017

On this day in science – the rubber fire hose was patented

In 1821, a fire hose of cotton web lined with rubber was patented by James Boyd of Boston, Mass. He invented it to replace riveted leather hose. Leather hose had many drawbacks, including drying out, cracking and bursting from excessive pressure. The introduction of rivets (1807), to replace stitching, had allowed higher pressures and greater delivery of water on the fireground. The improved hose now was 40 to 50 feet in length and weighed more than 85 pounds with the couplings. Hose oilers were developed to keep the leather supple and pliable. Various types of oils and other substances were used to keep the hose in shape. By 1871, the Cincinnati Fire Department was using the B.F. Goodrich Company's new rubber hose reinforced with cotton ply.

Indoor fire hose with a fire extinguisher, by Raysonho @ Open Grid Scheduler / Grid Engine (Own work) [CC0], via Wikimedia Commons
Modern fire hoses use a variety of natural and synthetic fabrics and elastomers in their construction. These materials allow the hoses to be stored wet without rotting and to resist the damaging effects of exposure to sunlight and chemicals. Modern hoses are also lighter weight than older designs, and this has helped reduce the physical strain on firefighters. Various devices are becoming more prevalent that remove the air from the interior of fire hose, commonly referred to as fire hose vacuums. This process makes hoses smaller and somewhat rigid, thus allowing more fire hose to be packed or loaded into the same compartment on a fire fighting apparatus.

There are several types of hose designed specifically for the fire service. Those designed to operate under positive pressure are called discharge hoses. They include attack hose, supply hose, relay hose, forestry hose, and booster hose. Those designed to operate under negative pressure are called suction hoses.

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Tuesday, 16 May 2017

Diesels pollute more than lab tests detect

Because of testing inefficiencies, maintenance inadequacies and other factors, cars, trucks and buses worldwide emit 4.6 million tons more harmful nitrogen oxide (NOx) than standards allow, according to a new study co-authored by University of Colorado Boulder researchers.

The study, published in Nature, shows these excess emissions alone lead to 38,000 premature deaths annually worldwide, including 1,100 deaths in the United States.

The findings reveal major inconsistencies between what vehicles emit during testing and what they emit in the real world - a problem that's far more severe, said the researchers, than the incident in 2015, when federal regulators discovered Volkswagen had been fitting millions of new diesel cars with "defeat devices."

Red Diesel Tank, by Meena Kadri [CC BY 2.0 (http://creativecommons.org/licenses/by/2.0)], via Wikimedia Commons
The devices sense when a vehicle is undergoing testing and reduce emissions to comply with government standards. Excess emissions from defeat devices have been linked to about 50 to 100 U.S. deaths per year, studies show.

"A lot of attention has been paid to defeat devices, but our work emphasizes the existence of a much larger problem," said Daven Henze, an associate professor of mechanical engineering at CU Boulder who, along with postdoctoral researcher Forrest Lacey, contributed to the study. "It shows that in addition to tightening emissions standards, we need to be attaining the standards that already exist in real-world driving conditions."

The research was conducted in partnership with the International Council on Clean Transportation, a Washington, D.C.-based nonprofit organization, and Environmental Health Analytics LLC.

For the paper, the researchers assessed 30 studies of vehicle emissions under real-world driving conditions in 11 major vehicle markets representing 80 percent of new diesel vehicle sales in 2015. Those markets include Australia, Brazil, Canada, China, the European Union, India, Japan, Mexico, Russia, South Korea and the United States.

They found that in 2015, diesel vehicles emitted 13.1 million tons of NOx, a chemical precursor to particulate matter and ozone. Exposure in humans can lead to heart disease, stroke, lung cancer and other health problems. Had the emissions met standards, the vehicles would have emitted closer to 8.6 million tons of NOx.

Heavy-duty vehicles, such as commercial trucks and buses, were by far the largest contributor worldwide, accounting for 76 percent of the total excess NOx emissions.

Henze used computer modeling and NASA satellite data to simulate how particulate matter and ozone levels are, and will be, impacted by excess NOx levels in specific locations. The team then computed the impacts on health, crops and climate.

"The consequences of excess diesel NOx emissions for public health are striking," said Susan Anenberg, co-lead author of the study and co-founder of Environmental Health Analytics LLC.

China suffers the greatest health impact with 31,400 deaths annually attributed to diesel NOx pollution, with 10,700 of those deaths linked to excess NOx emissions beyond certification limits. In Europe, where diesel-passenger cars are common, 28,500 deaths annually are attributed to diesel NOx pollution, with 11,500 of those deaths linked to excess emissions.

The study projects that by 2040, 183,600 people will die prematurely each year due to diesel vehicle NOx emissions unless governments act.

The authors say emission certification tests, both prior to sale and by vehicle owners, could be more accurate if they were to simulate a broader variety of speeds, driving styles and ambient temperatures. Some European countries now use portable testing devices that track emissions of a car in motion.

"Tighter vehicle emission standards coupled with measures to improve real-world compliance could prevent hundreds of thousands of early deaths from air pollution-related diseases each year," said Anenberg.

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Tuesday, 17 January 2017

Simple fats, amino acids to explain how life began

Life is a process that originated 3.5 billion years ago. It emerged when the basic components of the cells that we know today, in other words, inanimate chemical molecules, gradually joined, merged, assembled themselves and interacted. At a given moment they became alive, or what amounts to the same thing, they turned into autonomous systems. As the years passed they gradually evolved until achieving their current complexity and diversity. A piece of research by the UPV/EHU is working on the start of this trajectory by studying how the chemical molecules assembled themselves so that life could begin.

A section of DNA. Zephyris at the English language Wikipedia [GFDL (http://www.gnu.org/copyleft/fdl.html) or CC-BY-SA-3.0 (http://creativecommons.org/licenses/by-sa/3.0/)], via Wikimedia Commons
DNA, RNA, proteins, membranes, sugars, …cells are made up of all kinds of components. In biology, and in the studies dealing with the origin of life specifically, it is very common to focus on one of these molecules and put forward hypotheses on how life originated by analysing the specific mechanisms related to it. "Basically, these studies are looking for the 'molecule of life', in other words, they set out to establish which was the most important molecule in making this milestone happen," said Kepa Ruiz-Mirazo, researcher in the Biophysics Unit and of the UPV/EHU's Department of Logic and Philosophy of Science. However, bearing in mind that "life involves activity among a huge variety of molecules and components, a change of approach has been taking place in recent years and research that takes into account various molecules at the same time is gaining strength," he added.

Besides emerging in favour of this fresh approach, Ruiz-Mirazo's group, in collaboration with the University of Montpellier, through an internship of the UPV/EHU PhD student Sara Murillo-Sánchez, has been able to show that interaction exists between some molecules and others. "Our group has expertise in research into membranes that are created in prebiotic environments, in other words, in the study of the dynamics that fatty acids, the precursors of current lipids, may have had. 

The Montpellier group for its part specialises in the synthesis of the first peptides. So when the knowledge of each group is put together, and when we experimentally blended the fatty acids and the amino acids, we could see that there was a strong synergy between them."

As they were able to see, the catalysis of the reaction took place when the fatty acids formed compartments. As they are in an aqueous medium, and due to the hydrophobic nature of lipids, they tend to join with each other and form closed compartments; in other words, they take on the function of a membrane; "at that time the membranes obviously weren't biological but chemical ones," explained Ruiz-Mirazo. In their experiments they were able to see that the conditions offered by these membranes are favourable for amino acids. "The Montpellier group had the prebiotic reactions of the formation of dipeptides very well characterised, so they were able to see that this reaction took place more efficiently in the presence of fatty acids," he added.

Besides demonstrating the synergy between fatty acids and amino acids, Ruiz-Mirazo believes it is very important to have conducted the study using basic chemical components, in other words, molecular precursors. "Life emerged out of these basic molecules; therefore, to study its origin we cannot start from the complex phospholipids that are found in today's membranes. We have demonstrated the formation of the first coming together and formation of chains on the basis of molecular precursors. Or to put it another way, we have demonstrated that it is possible to achieve diversity and complexity in biology by starting from chemistry."

In his studies, in addition to the experimental work, Ruiz-Mirazo is working in another two spheres so in the end he is studying the origin of life from three pillars or perspectives: "firstly, we have the experimental field; another is based on theoretical models and computational simulations, which we use to analyse the results obtained in the experiments, and the third is a little broader, because we are studying from the philosophical viewpoint what life is, the influence that the conception held about life exerts on the experimental field, since each conception leads you to carry out a specific type of experiment," he explained. "These three methodologies mutually feed each other: an idea that may emerge in the philosophical analysis leads you to carry out a new simulation, and the results of the simulations mark out the path for designing the experiments. Or the other way round. Most likely we will never manage to find the answer to how life began, but we are working on it: all of us living beings on Earth have the same origin and we want to know how it happened."

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Tuesday, 15 November 2016

What molecules you leave on your phone reveal about your lifestyle

We leave behind trace chemicals, molecules and microbes on every object we touch. By sampling the molecules on cell phones, researchers at University of California San Diego School of Medicine and Skaggs School of Pharmacy and Pharmaceutical Sciences were able to construct lifestyle sketches for each phone's owner, including diet, preferred hygiene products, health status and locations visited. This proof-of-concept study, published November 14 by Proceedings of the National Academy of Sciences, could have a number of applications, including criminal profiling, airport screening, medication adherence monitoring, clinical trial participant stratification and environmental exposure studies.

"You can imagine a scenario where a crime scene investigator comes across a personal object - like a phone, pen or key - without fingerprints or DNA, or with prints or DNA not found in the database. They would have nothing to go on to determine who that belongs to," said senior author Pieter Dorrestein, PhD, professor in UC San Diego School of Medicine and Skaggs School of Pharmacy and Pharmaceutical Sciences. "So we thought - what if we take advantage of left-behind skin chemistry to tell us what kind of lifestyle this person has?"

Mobile phone evolution. By Anders (Own work) , via Wikimedia Commons

In a 2015 study, Dorrestein's team constructed 3D models to illustrate the molecules and microbes found at hundreds of locations on the bodies of two healthy adult volunteers. Despite a three-day moratorium on personal hygiene products before the samples were collected, the researchers were surprised to find that the most abundant molecular features in the skin swabs still came from hygiene and beauty products, such as sunscreen.

"All of these chemical traces on our bodies can transfer to objects," Dorrestein said. "So we realized we could probably come up with a profile of a person's lifestyle based on chemistries we can detect on objects they frequently use."

Thirty-nine healthy adult volunteers participated in Dorrestein's latest study. The team swabbed four spots on each person's cell phone - an object we tend to spend a lot of time touching - and eight spots on each person's right hand, for a total of nearly 500 samples. Then they used a technique called mass spectrometry to detect molecules from the samples. They identified as many molecules as possible by comparing them to reference structures in the GNPS database, a crowdsourced mass spectrometry knowledge repository and annotation website developed by Dorrestein and co-author Nuno Bandeira, PhD, associate professor at the Jacobs School of Engineering and Skaggs School of Pharmacy and Pharmaceutical Sciences at UC San Diego.

With this information, the researchers developed a personalized lifestyle "read-out" from each phone. Some of the medications they detected on phones included anti-inflammatory and anti-fungal skin creams, hair loss treatments, anti-depressants and eye drops. Food molecules included citrus, caffeine, herbs and spices. Sunscreen ingredients and DEET mosquito repellant were detected on phones even months after they had last been used by the phone owners, suggesting these objects can provide long-term composite lifestyle sketches.

"By analyzing the molecules they've left behind on their phones, we could tell if a person is likely female, uses high-end cosmetics, dyes her hair, drinks coffee, prefers beer over wine, likes spicy food, is being treated for depression, wears sunscreen and bug spray - and therefore likely spends a lot of time outdoors - all kinds of things," said first author Amina Bouslimani, PhD, an assistant project scientist in Dorrestein's lab. "This is the kind of information that could help an investigator narrow down the search for an object's owner."

There are limitations, Dorrestein said. First of all, these molecular read-outs provide a general profile of person's lifestyle, but they are not meant to be a one-to-one match, like a fingerprint. To develop more precise profiles and for this method to be more useful, he said more molecules are needed in the reference database, particularly for the most common foods people eat, clothing materials, carpets, wall paints and anything else people come into contact with. He'd like to see a trace molecule database on the scale of the fingerprint database, but it's a large-scale effort that no single lab will be able to do alone.

Moving forward, Dorrestein and Bouslimani have already begun extending their study with an additional 80 people and samples from other personal objects, such as wallets and keys. They also hope to soon begin gathering another layer of information from each sample - identities of the many bacteria and other microbes that cover our skin and objects. In a 2010 study, their collaborator and co-author, Rob Knight, PhD, professor in the UC San Diego School of Medicine and Jacobs School of Engineering and director of the Center for Microbiome Innovation at UC San Diego, contributed to a study in which his team found they could usually match a computer keyboard to its owner just based on the unique populations of microbes the person left on it. At that time, they could make the match with a fair amount of accuracy, though not yet precisely enough for use in an investigation.

Beyond forensics, Dorrestein and Bouslimani imagine trace molecular read-outs could also be used in medical and environmental studies. For example, perhaps one day physicians could assess how well a patient is sticking with a medication regimen by monitoring metabolites on his or her skin. Similarly, patients participating in a clinical trial could be divided into subgroups based on how they metabolize the medication under investigation, as revealed by skin metabolites - then the medication could be given only to those patients who can metabolize it appropriately. Skin molecule read-outs might also provide useful information about a person's exposure to environmental pollutants and chemical hazards, such as in a high-risk workplace or a community living near a potential pollution source.

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Tuesday, 4 October 2016

The chemistry behind the aroma of coffee

The Aroma of Coffee (Compound Interest
What is it about that delicious smell of coffee? Or, more specifically, what lies behind it? The graphic above takes a look at a selection of the chemical compounds behind this aroma. 

So that's the chemistry, but what about the biology of coffee?

Several species of shrub of the genus Coffea produce the berries from which coffee is extracted. The two main species commercially cultivated are Coffea canephora (predominantly a form known as 'robusta') and C. arabica. C. arabica, the most highly regarded species, is native to the southwestern highlands of Ethiopia and the Boma Plateau in southeastern Sudan and possibly Mount Marsabit in northern Kenya. C. canephora is native to western and central Subsaharan Africa, from Guinea to Uganda and southern Sudan. Less popular species are C. liberica, C. stenophylla, C. mauritiana, and C. racemosa.

All coffee plants are classified in the large family Rubiaceae. They are evergreen shrubs or trees that may grow 5 m (15 ft) tall when unpruned. The leaves are dark green and glossy, usually 10–15 cm (4–6 in) long and 6 cm (2.4 in) wide, simple, entire, and opposite. Petioles of opposite leaves fuse at base to form interpetiolar stipules, characteristic of Rubiaceae. The flowers are axillary, and clusters of fragrant white flowers bloom simultaneously. Gynoecium consists of inferior ovary, also characteristic of Rubiaceae. The flowers are followed by oval berries of about 1.5 cm (0.6 in). When immature they are green, and they ripen to yellow, then crimson, before turning black on drying. Each berry usually contains two seeds, but 5–10% of the berries have only one; these are called peaberries. 

Arabica berries ripen in six to eight months, while robusta take nine to eleven months.

Coffea arabica is predominantly self-pollinating, and as a result the seedlings are generally uniform and vary little from their parents. In contrast, Coffea canephora, and C. liberica are self-incompatible and require outcrossing. This means that useful forms and hybrids must be propagated vegetatively. Cuttings, grafting, and budding are the usual methods of vegetative propagation. On the other hand, there is great scope for experimentation in search of potential new strains.

In 2016, Oregon State University entomologist George Poinar, Jr. announced the discovery of a new plant species that's a 45-million-year-old relative of coffee found in amber. Named Strychnos electri, after the Greek word for amber (electron), the flowers represent the first-ever fossils of an asterid, which is a family of flowering plants that not only later gave us coffee, but also sunflowers, peppers, potatoes, mint — and deadly poisons.

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Tuesday, 16 August 2016

What are Olympic medals made of?

So, the Olympic medals are made of gold, silver and bronze right? Wrong! Pure gold medals would cost an awful lot, so what are the medals really made from? 

The graphic below looks at the different metals used.

Graphic: Compound Interest

So, what of real gold? Let’s find out more:

Gold is a chemical element with the symbol Au (from Latin: aurum) and the atomic number 79. In its purest form, it is a bright, slightly reddish yellow, dense, soft, malleable and ductile metal. Chemically, gold is a transition metal and a group 11 element. It is one of the least reactive chemical elements, and is solid under standard conditions. The metal therefore occurs often in free elemental (native) form, as nuggets or grains, in rocks, in veins and in alluvial deposits. It occurs in a solid solution series with the native element silver (as electrum) and also naturally alloyed with copper and palladium. Less commonly, it occurs in minerals as gold compounds, often with tellurium (gold tellurides).

Gold's atomic number of 79 makes it one of the higher atomic number elements that occur naturally in the universe. It is thought to have been produced in supernova nucleosynthesis and from the collision of neutron stars and to have been present in the dust from which the Solar System formed. Because the Earth was molten when it was just formed, almost all of the gold present in the early Earth probably sank into the planetary core. Therefore, most of the gold that is present today in the Earth's crust and mantle is thought to have been delivered to Earth later, by asteroid impacts during the Late Heavy Bombardment, about 4 billion years ago.

Gold resists attack by individual acids, but aqua regia (literally "royal water", a mixture of nitric acid and hydrochloric acid) can dissolve it. The acid mixture causes the formation of a soluble tetrachloroaurate anion. It is insoluble in nitric acid, which dissolves silver and base metals, a property that has long been used to refine gold and to confirm the presence of gold in metallic objects, giving rise to the term acid test. Gold also dissolves in alkaline solutions of cyanide, which are used in mining and electroplating. Gold dissolves in mercury, forming amalgam alloys, but this is not a chemical reaction.

Gold is a precious metal used for coinage, jewellery, and other arts throughout recorded history. In the past, a gold standard was often implemented as a monetary policy within and between nations, but gold coins ceased to be minted as a circulating currency in the 1930s, and the world gold standard was abandoned for a fiat currency system after 1976. The historical value of gold was rooted in its relative rarity, easy handling and minting, easy smelting and fabrication, resistance to corrosion and other chemical reactions (nobility), and distinctive colour.

The world consumption of new gold produced is about 50% in jewellery, 40% in investments, and 10% in industry. Gold's high malleability, ductility, resistance to corrosion and most other chemical reactions, and conductivity of electricity have led to its continued use in corrosion resistant electrical connectors in all types of computerized devices (its chief industrial use). Gold is also used in infrared shielding, coloured glass production, gold leafing, and tooth restoration. Certain gold salts are still used as anti-inflammatories in medicine.

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