Thursday, September 26, 2019
Sources of Tort law Essay Example | Topics and Well Written Essays - 2000 words
Sources of Tort law - Essay Example Judicial acknowledgment of spontaneous standards brings about a declaratory (more willingly than constitutive) function that cares for custom as a legal reality. The legal system finds the law by being acquainted with social standards, but does not "create" the law (Fisheries, 1951, International Court of Justice, Kontou, 1994). The most distinguished demonstration is the organization of tort law, where, devoid of a central legislative power, custom positions adjacent to treaties as a principal source of law. (Statute of the International Court of Justice, Article 38 section 1). At any time they are provided with legitimate position in a legal system, customary rules are frequently provided with the similar impact as other key sources of law. Even though frequently secondary to formal legislation, customary rules obtain their power from the agreement of a standardized practice and an individual conviction that obedience to them is mandatory (opinio iuris), devoid of essentially being officially integrated into any written body of law (Malanczuk, 1997, NorthSea Continental Shelf, Roht-Arriaza, 1995, Sands, 2003, Scott, 2000). Consequently, they are more often than not characterized as irrelevant sources of law (Brownlie, 1990, The Corfu Channel, 1949, Trendtex Trading Corporation, 1977, Vierdag, 1982, Weber, 1978, Baxter, 1970, Brownnlie, 1987, De Vattel, 1960, Goldsmith and Posner, 1999). This conception entails that the custom continues to be the definite source of law notwithstanding following its judicial recognition. In this context, the judicial assess ments that are on familiar terms with a custom present merely persuasive evidence of its subsistence and do not themselves turn out to be foundations of law. Sequentially, this puts off the doctrine of stare decisis from shaping up customary law. Contemporary legal systems commonly distinguish customary rules that have materialized either within the boundaries of positive legislation (consuetudo secundum legem) or in fields that are not regimented by positive law (consuetudo praeter legem). Where custom is in open disagreement with legislation (custom contra legem) the latter more often than not wins through. In some cases in point, nonetheless, a custom supplants previous legislation (abrogative custom), and a number of arguments have been completed in favor of the up-and-coming practices that run counter to outdated stipulations of public tort law (desuetudo) (Kontou, 1994, International Law Commission, 1962. Internatinal Law Commission, 1966, Mendelson, 1998, Tunkin, 1974). The perception of opinio iuris initiates a difference involving mere behavioural regularities and internalized responsibilities. This difference may possibly be associated to the parties' responsiveness of the anticipated collective payoffs from the game, a difference that is significantly vital in the normative context (Weber, 1978). A couple of groupings of social rules are commonly recognized. These include those that reveal simple behavioural arrangements that are not indispensable to the legal order. Another is those that reveal an internalized conviction that the implementation is essential or publicly sought-after. A simple behavioural regularity, missing the qualitative component of opinio iuris, does not produce a customary rule. In legal terminology, such behaviour is a sheer usage; in economic contexts it merely stands for an
Wednesday, September 25, 2019
Reading journal APOC Assignment Example | Topics and Well Written Essays - 500 words
Reading journal APOC - Assignment Example At the hospital, they stayed with me and consoled me even as I writhed in pain. My parents arrived later on and thanked my colleagues for standing with me. Indeed the hospital route turned out to be the best remedy to the writerââ¬â¢s problem. She finally withdrew and got the necessary counseling thereafter. It surprises, however, why the writerââ¬â¢s caretakers had not thought of this alternative ever since the problem manifested itself. The delay has made the writer lose much in terms of personal development. The writer was worried how she would put to a halt the whole issue of drinking and using. She seemed quite concerned about the past, recalling how frequent she drank and used. Venita urges her to focus on one day at a time as that is an easier way to adjust. That means the writer should close her eyes to the past and future and instead focus on today. The quote portrays Venita as informative, encouraging, and determined. She wants to see the writer at her best. Challenges and mysteries are part of life. I once realized that no one is born perfect. People fail, but the failures serve as steps towards improvement. I once recorded poor academic performances during my middle classes in primary school. This was caused by my affiliation to jokers. When my parents and teachers counseled me, I turned a blind eye to all that had happened and my results became impressive then onwards. Venita was quite instrumental to the changes that occurred in the writerââ¬â¢s life. From withdrawal from drinking and using to graduating from the university with a special award, the writer has recorded a massive change in life that no one would ever imagine from the start of the novel. It all sounds miraculous, but wherever God is involved, miracles are bound to
Tuesday, September 24, 2019
Development of Scratch Radio to the Station Manager Essay
Development of Scratch Radio to the Station Manager - Essay Example The main objective of the study is to recognize and determine current involvement in Radio Listening amongst BCU undergraduate scholars in the City North campus. It is mainly because there are various competitors for the Scratch Radio as well as it is also very much necessary to identify the thoughts of BCU undergraduate students towards Scratch Radio and its selected competitors. The study includes the questionersââ¬â¢ analysis which will help to identify the current involvement and future development of Scratch Radio. Thirst for knowledge is the fundamental human condition. Research methodology is the systematic process of exploring knowledge. The research can be conducted in many ways. The methodology of the research is decided in relation to the nature of the study and the type of sample and the data collection. In this study the researcher tries to explore the information about the current involvement in Radio Listening between BCU undergraduate students and also to evaluate the attitudes of BCU undergraduate students towards Scratch Radio. ââ¬Å"Methodology is the pathway or an approach to get the needed information by locating the data from different sources which are primary & secondaryâ⬠. In this research paper, the data gathering was done using various research instruments. The research instruments have helped to carry out the interview process and data gathering more easily. The study will be a pilot survey, to test the questionnaire and the survey methods and to generate some exploratory data which may be useful to decision makers of marketing division. Sample size taken to conduct the survey is 20. All the students that took part in the survey are students of BCU undergraduate course in the City North campus. And also this sample survey includes male and female students of each study year. Personal interviews are carried out to collect most significant information from the target audience. The sample size selected was quite enough and usef ul for this research. The survey was conducted in the same method, but the people interviewed were different. The tools used in this research are really working and useful to carry out a detail study. Questionnaires are one of the ways used to collect information from the target customers to acquire the relevant information. The questionnaires are well planned. Both open ended and closed ended questionnaires are used to collect information. Open ended questionnaires are carried out to acquire the information in the deliberate style. Closed ended questionnaires are used to acquire the information in the single words such as the questionnaires comprises of the YES or NO type questions. ââ¬Å"A Questionnaire can be quite inexpensive to administer. Time is also an important resource that questionnaires can maximizeâ⬠(Stasko & Oââ¬â¢Brien n.d.). 4) Summary of the Key Findings: This pilot survey we have conducted has helped to find out the opinions and recommendations of the stu dent listeners of Scratch radio of BCU. The sample size of
Monday, September 23, 2019
Comparison between KFC (uk) and Nando's chickenland Ltd huddersfield Essay
Comparison between KFC (uk) and Nando's chickenland Ltd huddersfield - Essay Example is the highest in the hierarchy and it is very important for a company to be consistent with its strategies so that it can have competitive advantage in the market. Competitive advantage in a company grows when the company is able to provide its clients with quality products and services at the appropriate time and place. Nandos chicken land has used information technology for them to grow at the intended time and send new products and services. The supply system in Nandos chicken land has used information technology in maintaining competitive advantage. A product has competitive value when it provides more value to the users than a competitive product or services. This value can be in symbolic terms of attributor or both. In the past century, Nandos chicken land has been using information technology for operational and management of the company. It is until recently that the company is using information technology to get significant competitive advantage (Khosrowpour, 2002, p. 15). For instance, it was the first to establish online order entry in restaurants and now they dominate the hotel delivering business. Nandos chicken land has set up ways to make reservations through a computer application, which has made it impossible for other companies to overcome them. The importance of products and services offered through the computer by Nandoââ¬â¢s chicken land system does not lie on how the information technology is sophisticated or the reports it delivers. But, they are established by examining how they play in the companyââ¬â¢s need for competitive advantage (Khosrowpour, 2002, p. 35). These are known as strategic information systems that help in shaping and supporting the competitive advantage of the restaurant. They are plans that help in gaining and maintaining the competitive advantage. KFC (UK) uses commercial advertisement in advertising their products. The commercial advertisement features a live band where the singer swallows fire. The company has a logo
Sunday, September 22, 2019
International Business Term Paper Example | Topics and Well Written Essays - 2000 words
International Business - Term Paper Example 54). Factor conditions discuss countryââ¬â¢s consideration about production factors (e.g. skilled HR required in a certain industrial area) (Johnson, 2003, p. 54). Demand conditions evaluate countryââ¬â¢s national market demand for the good/service to be produced. Related and supporting industries discuss the existence of internationally competitive industries in the home market. Firm strategy, structure and competition are issues defining principles of organizationsââ¬â¢ creation, development and management in the home market. 3. Three common characteristics of Multi National Enterprise Multinational Enterprise has three general features: a large corporation with central office and many other branches worldwide. MNE make direct investments in local firms and considers peculiarities of product adaptation to the needs to every particular market (Johnson, 2003, p. 14). 4. Five basic steps in the strategic management process Strategic management is based on five basic steps. Fi rst of all, strategy, vision and mission must be developed (Kline, 2005, p. 67). This initial stage is crucial for any company because it sets the main principles of further companyââ¬â¢s development. The next step is analysis of internal and external factors. In other words, on this stage company analyzes structural peculiarities of their company and discusses external factors influencing their business. The third step concerns ââ¬Ëdistillationââ¬â¢ of the best choices and possible steps. The fourth step is strategic plan development, which step-by-step describes strategic measures taken by a company. The fifth step is implementation and evaluation of steps considered above. 5. Foreign Direct Investment reasons Foreign direct investment implies companyââ¬â¢s physical investment from one country into building a factory/creating some kind of a project etc in another country. Currently, there are several reasons for FDI (Johnson, 2003, p. 71). A desire to be global and to be a successful competitive participant in the international arena, reach potential clients overseas and access a new market are wide spread features of potential FDI. It is also important to note that once export of goods or services produced becomes critically increased then it is more efficient and cost effective to make FDI. 6. As political system change, economic system follows. Statement explanation. A change of political system is a natural process happening in every country. A constantly changing nature of mankind is explained by mankind development and thus countriesââ¬â¢ development. When certain political processes take place, then internal income of the country, wealth and occupation of people is gradually changing. Economic development exerts influence on income equality. At this point linearity theory may be applied. In accordance with this theory economic development is a direct way to urbanization leading to communication and higher level of education and finally, to Democracy. Thus we can see a perfect interdependence between political and economic systems. 7. Privatization benefits Privatization is a kind of structural reform occurring in both developed and developing countries. The main goal of privatization is to reach more profound microeconomic efficiency and foster economic growth (Kline, 2005, p. 77). Abundance of inefficient
Saturday, September 21, 2019
Race in America since the 1960s Essay Example for Free
Race in America since the 1960s Essay America has come a long way since the dark days when slavery marred the continent. The journey to equality was not always a smooth one, and only in the last half-century have African-Americans been granted their complete rights and freedoms. Now that they have these equal rights, they are taking their place to take advantage of their equal opportunities, but there still seems to be a glass ceiling preventing their further progress. White Americans still cite racial progress in many areas, while the reality remains that much of this progress is illusion. With the election of Barack Obama as the President of the United States, it seems safe to say that racial relations in the country have certainly improved in the past fifty years. In the 1950s, many African-Americans could not even vote in many parts of the country, with racist leaders and citizens doing everything in their power to deny this most basic of rights. Once desegregation took effect and was enforced by the federal government, it seemed that African-Americans had finally achieved equality. However, this was largely a myth based on the horrible conditions they once faced, and the current conditions still often view them as a marginalized race. Couple this with the massive influx of Latin Americans into the U. S. , and race relations are just as explosive as they were in the 1960s. One program designed to aid racial equality is affirmative action, which has been both a blessing and a curse for minorities. Originally conceived as a means to redress discrimination, affirmative action has created racial preferences that have instead promoted discrimination. And rather than fostering harmony and integration, these preferences have divided many businesses and college campuses across the country. In no other area of public life is there a greater disparity between the rhetoric of preferences and the reality than with affirmative action. Many have cited lesser qualified applicants hired or accepted to colleges based on race, not qualifications or need. If preferences were truly meant to remedy disadvantage, they would be given on the basis of disadvantage, not on the basis of race, so that a poor, qualified white student would stand a better chance of being admitted than the under-qualified son of a black doctor. This illustrates a problem with the idealism of affirmative action and how remedying some racial issues have merely created unfairness in other areas. Instead of a remedy for disadvantage, many supporters now claim that preferences promote diversity. This same push for diversity also has led colleges like Stanford University to create racially segregated dormitories, racially segregated freshman orientation programs, racially segregated graduation ceremonies and curricular requirements in race theory and gender studies (Sacks Thiel, 1996). But if diversity was really the goal, then preferences would be given on the basis of unusual characteristics, not on the basis of race. The underlying assumptionââ¬âthat only minorities can add certain ideas or perspectivesââ¬âis offensive not merely because it is untrue but also because it implies that all minorities think a certain way. While affirmative action is a noble effort, it is perhaps antiquated. Today, while African-Americans enjoy greater freedom and equality, Latinos have come to represent the current racial crisis. Many conservative Americans demand that they learn English, adopt American culture, and assimilate or leave. Additionally, Middle Eastern Americans are finding life equally difficult and face often violent retributions for crimes that they did not commit. This xenophobic behavior may be largely from the scares encouraged by global terrorism, but may also be representative of the fact that not much has really changed except the language used to discuss race. The only way to truly understand the state of race in America and make a balanced assessment is to measure the equality of each race. The sad state is that many of the minorities in America are still marginalized, make less money, and have far less influence politically than the dominant white culture. Progressive and liberal legislation may continue to chip away at long held racial prejudices, but Americans cannot achieve complete equality unless it is an endeavor equally valued by all. Unfortunately, as history has shown, those in power will be reticent to relinquish that power, and those in power in America are still largely male, largely white, and largely though subtly fearful of difference. With a president with parent that are black and white, much of the racial future of America rests with a man that represents better than anyone the progress made in the past fifty years, as well as the distance left to travel until true racial harmony is achieved.
Friday, September 20, 2019
Using Thin Layer Chromatography To Monitor Reactions Environmental Sciences Essay
Using Thin Layer Chromatography To Monitor Reactions Environmental Sciences Essay Thin layer chromatography (TLC) is a very useful technique for monitoring reactions. It can also be used to determine the proper solvent system for performing separations using column chromatography. TLC stationary phases are usually alumina or silica. They are polar for standard experiments or non-polar for reverse phase chromatography. The mobile phase is a solvent whose polarity is chosen by the person conducting the experiment. In most laboratory work standard phase silica plates are used. Different compounds will travel different distances up the plate depending on the polarity of the components of the mixture. The more polar compounds will be more attracted to the polar silica gel and travel shorter distances on the plate. Mon-polar substances will spend more time in the mobile phase and as a result will travel larger distances on the plate. The measure of the distance a compound travels is called the retention factor (Rf ) value. The retention factor, or Rf, is defined as the distance traveled by the compound divided by the distance traveled by the solvent. For example, if a compound travels 2.1 cm and the solvent front travels 2.8 cm, the Rf is 0.75: The Rf for a compound is a constant from one experiment to the next only if the chromatography conditions below are also constant: solvent system adsorbent thickness of the adsorbent amount of material spotted temperature Since these factors are difficult to keep constant from experiment to experiment, relative Rf values are generally considered. Relative Rf means that the values are reported relative to a standard, or it means that you compare the Rf values of compounds run on the same plate at the same time. 1.1 Thin Layer Chromatography There have been a numbered of important milestones in the evolution of chromatography in the last 100 years. Each of these milestones has signalled the start of an important branch of chromatography. Some examples of these are; partition chromatography (1941), gas chromatography (1951-1952), high performance liquid chromatography (mid- 1960s), capillary electrophoresis (1980) and capillary electrochromatography (past decade). In all the chromatographic techniques mentioned, separation is carried out in a column. However, it is also possible to carry out separations on a planar surface. Two examples of this are paper chromatography (1944) and thin-layer chromatography (1937-1938). Thin-layer chromatography (TLC) replaced paper chromatography as the most popular, routine chromatographic technique. TLC was first used in 1937 to 1938 by Nikolai A. Izmailov and Maria S. Shraiber at the Institute of Experimental Pharmacy of the State University of Kharkov. At the time Izmailov was the head of the institute and Shraiber was his graduate student. They were searching for a method for the rapid analysis of galenic pharmaceutical preparations (plant extracts). As classical column chromatography would have taken too much time they felt that if the absorbent would be prepared in the form of a thin-layer on a glass plate. They believed that it would behave like a column but the characterization time would be much shorter. They coated microscope slides with a suspension of various adsorbents (calcium, magnesium and aluminium oxides). They deposited one drop of the sample solution on this layer and added one drop of the same solvent used in a column to develop separation. The test was a success as the separated sample components appeared as concentric rings that fluoresced in various colour s under a UV lamp. They showed that the sequence of the concentric multicoloured rings on the plate would have been identical to the sequence of coloured rings obtained on a normal chromatographic column. They called this technique spot chromatography and the result on the microscope slides ultrachromatograms. The paper on this experiment was published in a Russian pharmaceutical journal that was practically unknown outside the then Soviet Union. Its abstract was included in a Russian review journal and through it in chemical Abstracts. It was then read by M. OL. Crowe of the New York State Department of Health. He then adapted the technique for his own use. Crowe prepared the adsorbent layer in a Petri dish, added a drop of the sample solution in the centre and then added the developing solvent dropwise until sufficient separation was obtained. In 1947 T.I. Williams described a further improvement of the method of Izmailov and Shraiber in his textbook on chromatography. He prepared the adsorbent-coated glass plates in the form of a sandwich. The adsorbent layer was covered by 2 glass plates and had a small hole which the sample drops could be applied through. Meinhard and Hall made the next major step in the development of TLC at the University of Wisconsin. They used corn starch, which acted as a binder, to hold the coating on the glass plate and added a small amount of Celite powder to the adsorbent particles to improve the consistency of the layer. They called this surface chromatography. They used it to separate inorganic ions. Modern TLC started 50 years ago with the work Department of Agriculture Fruit and Vegetable laboratory in Southern California. He investigated the flavour components of the juices of citrus fruits. However, he stated that very large volumes had to be processed because the amount of flavour material was extremely small. Another problem was in finding an analytical method for the investigation of the juice concentrate composition. He followed the method of Meinhard and Hall that he read in Chemical Abstracts. However, instead of adding just a drop of the developing solvent he developed the plates as in paper chromatography. The plates were developed in a closed chamber and one side was dipped into the solvent. The solvent then ascended through the plate by capillary action. It carried with it the sample components and they were separated as a result. The experiments carried out were published and are considered the start of modern TLC. Egon Stahl was responsible for TLC becoming a universally accepted technique. He was also the first to use the term thin-layer chromatography to characterize the technique. This choice of name was almost immediately accepted. Stahl investigated various essential oils and obtained good results using adsorbent-coated glass plates. However, neither the method nor the adsorbent to be used had been optimized. Also, the adsorbents had to be modified and treated before they could be used for the coating of plates. Stahl started investigating the operational parameters and the adsorbent preparations. In the spring of 1958 his efforts were fulfilled as the necessary basic instrumentation, made by Desaga and silica gel G according to Stahl for TLC, made by E. Merck were both introduced at the international Achema exhibition of chemical equipment in Frankfurt. Stahl also published an article outlining the use of the system and a wide range of applications. Because of this standardized method TLC became a widely used laboratory technique. He also went on to publish a TLC handbook in 1962. Although TLC had a wide application it was still thought to be a qualitative technique for the analysis of simple mixtures. As a result advances were directed toward improving the technique. Instrumentation which permitted more precise spotting of the sample onto the plates and the quantitative evaluation of the separated spots was developed. Faster analysis and higher separation power was also achieved. As a result of the higher performance ability the name was change to high-performance TLC (HPTLC) by R.E. Kaiser, who was instrumental in its development. The particle size and range of the adsorbent was the main difference between TLC and HPTLC. The silica gel for TLC had broad particle sizes of 10-60à µm with an average of 20à µm whereas HPTLC has an average of only 5à µm. the HPTLC plates were also smaller in comparison with TLC plates, 10 x 10cm and 20 x 20cm respectively. The improved method and design allowed reduction in the diameter of the starting spots. These improvements lowered the analysis time and increased the efficiency. Problems arose with flow rate which Kaiser overcame by applying pressure to the TLC plate. This in turn led to forced-flow TLC. Due to the constant condensation-evaporation process associated with developing TLC plates in developing chambers problems can be encountered because of the changing velocity of the mobile phase. To overcome this forced-flow TLC (FFTLC) was developed by Tyihà ¡k, Mincsovics and Kalà ¡sz. In this method the spotted plates (dry) are placed into a pressurized development chamber. The stationary-phase layer is tightly covered and sealed on its side by an elastic membrane and pressurized by an inert gas or water filling up the cushion above the layer. The mobile phase is delivered via a pump at a constant velocity through a slit in the membrane to the stationary phase. There are various configurations which can be handled using this method. TLC is a very simple technique. As a result very little instrumentation is needed. Application of samples to the stationary-phase is carried out using a micropipette or syringe. The developing chambers are simple glass structures. Detection is carried out by visual inspection or made visible by spraying the plate with reagent. Also, a wide variety of precoated plates are available so coating equipment isnt needed. In more advanced systems the samples may be spotted by automated loading devices (dosimeters). This allows the application of small and uniform sample spots. More sophisticated developing chambers are also available (FFTLC). The plates can be scanned by densitometers and quantitatively analysed using absorbance or fluorescence measurements. Chromatograms with peaks of the individual separated spots recorded against the length of the plate are produced with such analyses. Their area is also a proportion to the amount present. More complex systems can also be created by combining TLC systems with other systems such as mass spectrometry and Fourier transform infrared. 1.2 Ink Analysis Ink analysis is a very important forensic procedure. It can reveal useful information about questioned document. Modern inks contain many substances which are aimed at improving the ink. The most important component of the ink is the colouring material. It comes in the form of a dye, pigment or a combination of both. Dyes are soluble in the liquid body of the ink, also known as the vehicle. Pigments are finely ground multi-molecular granules that are insoluble in the vehicle. The vehicles composition affects the flowing and drying characteristics of the ink and can consist of oils, solvents and resins. 1.3 Chromatography Studies Djozan et al developed a new and fast method for the differentiation of inks on a questioned document. They designed specific image analysis software for evaluating thin layer chromatograms. They sampled forty-one blue ballpoint pens which were purchased from their local markets in Iran (Table 1). They first wrote a circle of diameter 5 mm uniformly by pen on a paper. One fourth of this was then punched out for extraction. They carried out extraction in 1 ml glass tubes and added 0.1 ml of methanol. This was then vigorously shaken for 1 min. the ink component was then fully dissolved in methanol. The supernatant methanoic solutions were then used to spot the TLC plates. A blank sample of paper with equal dimensions was also treated in the same way. Table 1. List of blue ballpoint pens studied List of blue ballpoint pens studied 1 Cello pyramid 0.7 mm fine TC ball 2 OBA 3 AIHAO 4 Bic 01 5 Cenator 6 PARKER 7 A.T.CROSS FINE 8 Pelikan STICK 918 9 Marvy SB-10 1.0 mm 10 Bic 02 11 PIANO crystal 12 My pen 2001 PENS High Quality Bluce CE 13 AIBA 14 STAEDTLER Stick 430M A IRAN 15 Reynolds Medium 048 France 16 EIFEL Elegance 17 CASPIAN STICK 2001 M 18 STABILO liner 308 19 FABER-CASTELL 1.0 mm Medium (transparent) 20 BIC 08 21 Bocheng A-100 22 SCHNEIDER TOPS 505 M Germany 23 FIBER-CASTELL 1.0 mm Medium 24 MILAN PI 1 mm 25 Reform 26 PAPER = MATE FLEXGRIP ultra MED 27 PARKER UK 28 CANDID-DINI 2853 29 STABILO-galaxy 818 M 30 No name 31 No name 32 Zebra Rubber 101 33 SANFORD SAGA 34 Bensia 35 Girls 36 EUROPEN 37 PARS swiss Refill 606 38 STAEDTLER stick 430 M TBRITAIN 39 Lus HF 500 40 No name 41 STABILO bill 508 TLC analysis was carried out on Merck (Darmstadt, Germany) 20 cm x 20 cm silica gel 60 TLC plates without fluorescent indicator. The plates were activated at 60 à °C for 20 min and immediately spotted after cooling in a desiccator. The plates were developed in a developing chamber. The mobile phase used was: ethyl acetate/ absolute ethanol/ distilled water (70:35:30, v/v/v). Chromatographic development of the plates was carried out at room temperature for 40 min. All mobile phases were prepared daily with analytical grade chemicals. Enough was prepared to supply the tank for each run. The plates were air-dried after development. The separated compounds were visible on the plate by their natural colour and the plates were scanned into a computer using an office scanner. An IBM compatible PC (Pentium IV) with a 2.6 GHz microprocessor, 256 MB random access memory (RAM) and a hard disk with 40 GB capacity for external storage was used for processing the colour images. The computer was equipped with an on-board graphic card (NviDiA Geforce 7300LE) and a scanner (CanoScan 4200F) was connected to the computer for scanning (300 dpi) TLC plates as digital images. The images were saved as bmp files. Matlab (Version 6.5, The Math Works, Inc.) was used to write a new program to process the previously saved images. Previous studies indicated that Pyridine is the solvent used with ballpoint pen inks. Djozan et al preformed extraction with different solvents using various extraction modes. These modes were immersion of paper into solvent and simple agitation for 1 min, ultra-sound assisted extraction and micro-wave assistance extraction. The results showed that the immersion of paper into methanol or pyridine and simple agitation resulted in complete extraction of the inks from paper (Table 2). Table 2. List of solvents used for extraction of ink components from paper Solvent Solubility of ink colours Ethyl acetate Ethanol Acetic acid Acetone Butanol 1,2-Dichloroethane Butyl acetate Tetrachloroethane Acetyl acetate Cyclohexane Methanol Pyridine Slightly Slightly Slightly Slightly Slightly Slightly Slightly Slightly Slightly Slightly Soluble Soluble No improvement was found using ultra-sound or micro-wave assisted extraction. Methanol was chosen as the extraction solvent due to the safety of the solvent. The selection of the plate was down to the fact that silica gel plates provided the best resolution of dye spots. They selected five mobile phases (Table 3) and found that ethyl acetate/ absolute ethanol/ distilled water (70:35:30, v/v/v) was effective in separating nearly all the dye mixtures. The spot capacity obtained was more than 15. Table 3. Different solvent systems used to develop plate Solvent System Ratio Spot capacity Butanol:ethanol:H2O Ethyl acetate:cyclohexane:methanol:NH3 Ethyl acetate:Butanol:NH3 Ethyl acetate:ethanol:H2O Toluene:acetone:ethanol:NH3 50:15:10 70:15:10:5 60:35:5 70:35:30 30:60:7:2 9 5 10 15 5 Fig. 1. Typical TLC results of 10 different ink samples (Djozan et al, 2008) Fig. 1. shows a typical chromatogram that they achieved in their experiment. To confirm complete separation of all components in the studied sample, two-dimensional (2D) TLC was carried out using various solvent systems. The results proved that the one-dimensional (1D) TLC is able to provide sufficient separation. The first stage carried out was colour image normalization. A function of the input images was computed that is invariant to confounding scene properties but was discriminative with respect to desired scene information. The calculation is as follows: Stage 2 is to compute a colour image profile. The intensity profile of an image is the set intensity values taken from regularly spaced points along a line segment in an image the intensity values are interpolated for points that dont fall on the centre pixel they computed an intensity profile for r, g and b images along the line passing through the centre of the image on the chromatographic development straight of each ink spot. Fig. 2. RGB characteristic of an ink after TLC (Djozan et al, 2008) In stage 3 the colour image profiles were correlated. The intensity profiles were considered as sequences and the normalized cross-correlation of sequences were computed. Cross-correlation is a measure of similarity of two signals. It is used to find features in an unknown signal and compared to a known signal. It is calculated as follows for discrete functions: Eq. (1) For image-processing applications in which the brightness of the images can be due to lighting and exposure conditions, the images can be first normalized. It is calculated as follows: Eq. (2) Stage 4 involved computing image similarity. The weighted mean of and were computed as follows: Eq. (3) The ability of the method to differentiate between various blue ballpoint pens was evaluated by comparing the similarity of different inks according to Eq. (3). Fig. 3. Screen shot of Matlab software running (Djozan et al, 2008) Fig. 4. All possible combination of comparing inks with TLC-IA (Djozan et al, 2008) In 2006 Liu et al published a paper on the classification of black gel pen inks by ion-pairing high-performance liquid chromatography. They stated that black gel inks usually contain several dye components. These components all have different colours and are mixed together proportionally to give the black colour. They used reverse-phase ion-pairing high performance chromatography (RP-IP-HPLC). It was done in such a manner as the dyes couldnt be reversed on the C18 column due to their high polarities. The maximum UV absorption bands of the black gel pen inks obtained were between 500 and 700 nm. The wavelength of the detector was set to 580 nm as most of the dyes had a maximum UV adsorption near 580 nm. They investigated the influence of both volatile and non-volatile ion-pairing reagents on the HPLC analysis of black gel pen ink dyes. All the reagents had different alkyl chain, ammonium acetate, triethylamine (TEA), tributylamine (TBA), dihexylamine (DHA) and tetrabutylammonium bromide (TBABr). The results revealed that the dyes were nearly not retained using ammonium acetate or TEA as the ion-pairing reagent. Using TBABr, TBA and DHA as the ion-pairing reagent, individually, the dyes were separated. TBABr was selected as the ion-pairing reagent as the retention times were shorter than the others and sharper peaks were obtained. They also investigated the buffer solution concentrations and the effect of pH on the separation. The optimum result was: 40 mmol/L TBABr buffer solution (pH 7) with acetonitrile as the organic modifier for IP-HPLC analysis and an identical proportion of the buffer and acetonitrile (v/v = 40:60) at a flow rate of 1.0 mL/min. these optimum conditions were used to separate 50 dye-based black gel pen inks by IP-HPLC. Liu et al carried out another study on ion-pairing HPLC in 2006. This time, however, they studied the degradation of blue gel pen dyes and also used electrospray tandem mass spectrometry. They used ion-pairing reversed phase liquid chromatography as the inorganic compounds they were analysing have weak retention on the ordinary reversed stationary phases when separating on HPLC. This is due to their high polarities. The UV detector was set at 580 nm for the analysis as most dyes have a normal maximum absorption near 580 nm. The UV absorptions of the fluorescence whitening reagents in paper are usually below 500 nm and they had no interference for the detection of the gel pen dyes at 580 nm. Fig. 5. Chromatograms of blue gel pen inks using different ion pairing reagents (Liu et al, 2006) The tested various mobile phases: eluent A: eluent B (acetonitrile) = 50:50 (v/v); eluent A was the buffer of ion pairing reagent with concentration of 40 mmol Là ¢Ãâ ââ¬â¢1 (pH 7.0), and the ion pairing reagent was (a) ammonium acetate, (b) TEA acetate, (d) TBA acetate, (e) DHA acetate and (f) TBABr, respectively. (c) Ammonium carbonate as eluent A (40 mmol Là ¢Ãâ ââ¬â¢1, pH 9.5) and eluent A:eluent B (acetonitrile) = 50:50 (v/v). they found that 10 mmol-1 TBA acetate (pH 7.0) was suitable ion-pairing agent for the purpose and ink samples stored in different conditions were analyzed by IP-HPLC. Significant changes of ink composition were observed. The noticed that the natural aged inks had the similar but weaker degradation trend than the light aged inks. They used HPLC-MS/MS with ammonium carbonate as ion-pairing reagent to obtain the information of the light aged inks and their photodegradation mechanism. In 1994, Varshney et al analysed ink from typed script of electronic typewriters by HPTLC. They used script from seven electronic typewriters. They used the resultant Rf values and in-situ visible spectra of each resolved band of all the chromatograms indicated that the same chemical composition is being used in six typewriter ribbon inks. However, the seventh one is completely different. Fig. 6. Wavelength maxima values of in-situ visible spectrum bands of electronic typewriter scripts (Varshney et al, 1994) Fig. 6. shows the densitograms obtained after scanning and integration of the chromatograms of tracks of individual typewriters and blank paper. The seven electronic typewriter inks could be categorised into two groups after analysis. The first group resolved the sample to four bands including the base. The second group did not resolve the samples at all with the solvent systems used. Several varieties of blue ballpoint pen inks were analysed by HPLC and IR spectroscopy by Kher et al in 2006. The chromatographic data extracted at four wavelengths (254, 279, 370 and 400 nm) was analyzed individually and at a combination of these wavelengths by the soft independent modeling of class analogies (SIMCA) technique. They used principal components analysis (PCA) to estimate the separation between the pen samples. Linear discriminant analysis (LDA) measured the probability with which an observation could be assigned to a pen class. The best resolution was obtained by HPLC using data from all four wavelengths together, differentiating 96.4% pen pairs successfully using PCA and 97.9% pen samples by LDA. PCA separated 60.7% of the pen pairs and LDA provided a correct classification of 62.5% of the pens analyzed by IR. They stated that HPLC coupled with chemometrics provided a better discrimination of ballpoint pen inks compared to IR. Kher et al effectively combined LDA and PCA to classify the HPLC and IR data. PCA gives a general idea of how different a given pair of pens is, whereas LDA can quantify the predictive ability of a generated classification model. The two techniques of PCA and LDA were shown to be complimentary to each other. The PCA and LDA results indicated that although IR cannot differentiate between all classes of pen inks, it can still provide a reasonable discrimination, which can be enhanced further by improving the quality of the spectra. The analysis of such an enhanced IR data with chemometric analyses would provide a valuable non-destructive tool for forensic analyses. Raman Spectroscopy Studies Mazzella and Buzini used Raman spectroscopy to analyse blue gel pen inks in 2004. They sampled 55 blue gel pens. They first separated them into two groups using a preliminary solubility test in methanol. They discovered that 36 were pigmented inks, which arent soluble in methanol, and 19 were dye-based inks, which are soluble in methanol. They applied Raman spectroscopy to the 36 pigmented blue gel inks. Raman spectroscopy is a non-destructive technique. Spectra were first obtained using the 514.5 nm argon ion laser which proved the observation of 4 different groups. They then used the 830 nm NIR diode laser and divided the inks into three groups. They then combined the two lasers and a separation into 5 groups was obtained. They then attempted to identify the pigments contained in the gel by comparison to standard pigments. Two main pigments were detected in the analysed samples: PB15 and PV23. PB 15 is pigment blue 15 and belongs to the class of phthalocyanines. PV23 is the pigment violet 23 and belongs to the class oxazines. The argon laser allowed the detection of a mixture of PB 15 and PV 23. This was a better result than using the NIR diode laser. The results showed that the same gel pen ink (same model and brand) from different geographical locations showed the same Raman spectra. However, it was stated that the Raman technique obtained low discriminating values. 2. Materials and Method 2.1 Materials: Blue ballpoint pens Merck silica gel 60 TLC plates (20 cm x 20 cm) Methanol Ethyl acetate Ethanol (absolute) Paper Dessicator Developing chamber Puncher Glass tubes (0.1 ml) Capillary tubes 2.2 Experimental 13 blue ball-point pens (Table 1) were bought from a number of different shops in the town. A circle with a diameter of 5mm was written by the pen on paper. One fourth of it was punched out for extraction. The samples are placed in 1 ml glass tubes. 0.1ml of methanol was added and vigorously shaken for 1 min. The ink component was fully dissolved in methanol. The supernatant methanoic solutions were used for spot application on TLC plate. A blank of paper only is also treated as was a control which was a permanent marker. TLC analyses were preformed using Alugram 20 cm x 10 cm silica gel/UV plates (Macherey-Nagel). The plates were activated at 60à °C for 20 min and immediately after, cooled in a desiccator, and spotted. The plates were developed in a horizontal developing chamber. The solvent system included: ethyl acetate/absolute ethanol/ distilled water (70:35:30, v/v/v). Development was preformed at room temperature for 40 min. All mobile phases were prepared daily. After develo pment the plates were air-dried. All 13 different pens were tested in triplicate. Retention factors were calculated using the results from the plates and photographs taken using a digital camera were loaded onto the computer and analysed using image analysis software. Table 1: List of pens analysed Number Description 1 No Brand (blue) 2 Pilot G-207 3 BIC ReAction 4 BIC Medium (Bought in Tesco) 5 BIC Medium (Bought in Dunnes) 6 No Brand (Purple) 7 Staedtler Stick 430M 8 Roller Pen 9 Papermate 1.2M 10 Scripto Stick Pen 11 Papermate Write Bros. 12 Comfort Touch 13 No Brand (Tesco Click Pen) 3. Results and Discussion Before carrying out the experiment it needed to be researched. This research pointed out the importance of the correct solvent to remove the ink from the document. Djozan et al used methanol as their choice of solvent after considering other solvents (Table 2). They stated that Pyridine was the reported solvent used with ball-point pen inks. However, they carried out extractions with different solvents using various extraction modes. They realised that immersion of the paper into methanol with agitation resulted in complete extraction of the inks from the paper. Methanol was also chosen because of its safety. Table 2: List of solvents used for the extraction of ink components from paper Solvent Solubility of ink colours Ethyl acetate Slightly Ethanol Slightly Acetic Acid Slightly Acetone Slightly Butanol Slightly 1,2-Dichloroethane Slightly Butyl acetate Slightly Tetrachloroethane Slightly Acethyl acetate Slightly Cyclohexan Slightly Methanol Soluble Oyridine Soluble Different concentrations of the solvent system (Table 3) were analysed to see which gave the greater separation. It was found that the concentration given by Djozan et al, (ethyl acetate, ethanol, and water (70:35:30, v/v/v)) gave the best results. The Alugram silica Gell/UV plates were also found to work better than the suggested, Merck silica gel 60, plates without fluorescent indicator. Table 3: Concentrations of solvent system investigated Number Solvent system 1 ethyl acetate, ethanol, water (70:35:30, v/v/v) 2 ethyl acetate, ethanol, water (70:30:35, v/v/v) 3 ethyl acetate, ethanol, water (70:25:40, v/v/v) 4 ethyl acetate, ethanol, water (70:40:25, v/v/v) Table 4: Retention factors for all separated components pen spot 1 spot 2 spot 3 spot 4 spot 5 Solvent RF1 RF2 RF3 RF4 RF5 1.1 70 73 0.958904 1.2 70 73 0.958904 1.2 70 73 0.958904 2.1 62 69 73 0.849315 81.24194 2.2 62 69 73 0.849315 81.24194 2.3 62 69 73 0.849315 81.24194 3.1 57 60 62 70 0.814286
Subscribe to:
Posts (Atom)