Characterisation of cellulose- and lignin-based materials using x-ray scattering methods

Wood is an important material for the construction and pulping industries. Using x-ray diffraction the microfibril angle of Sitka spruce wood was studied in the first part of this thesis. Sitka spruce (Picea sitchensis [Bong.] Carr.) is native to the west coast of North America, but due to its fast growth rate, it has also been imported to Europe. So far, its nanometre scale properties have not been systematically characterised. In this thesis the microfibril angle of Sitka spruce was shown to depend significantly on the origin of the tree in the first annual rings near the pith. Wood can be further processed to separate lignin from cellulose and hemicelluloses. Solid cellulose can act as a reducer for metal ions and it is also a porous support for nanoparticles. By chemically reducing nickel or copper in the solid cellulose support it is possible to get small nanoparticles on the surfaces of the cellulose fibres. Cellulose supported metal nanoparticles can potentially be used as environmentally friendly catalysts in organic chemistry reactions. In this thesis the size of the nickel and copper containing nanoparticles were studied using anomalous small-angle x-ray scattering and wide-angle x-ray scattering. The anomalous small-angle x-ray scattering experiments showed that the crystallite size of the copper oxide nanoparticles was the same as the size of the nanoparticles, so the nanoparticles were single crystals. The nickel containing nanoparticles were amorphous, but crystallised upon heating. The size of the nanoparticles was observed to be smaller when the reduction of nickel was done in aqueous ammonium hydrate medium compared to reduction made in aqueous solution. Lignin is typically seen as the side-product of wood industries. Lignin is the second most abundant natural polymer on Earth, and it possesses potential to be a useful material for many purposes in addition to being an energy source for the pulp mills. In this thesis, the morphology of several lignins, which were produced by different separation methods from wood, was studied using small-angle and ultra small-angle x-ray scattering. It was shown that the fractal model previously proposed for the lignin structure does not apply to most of the extracted lignin types. The only lignin to which the fractal model could be applied was kraft lignin. In aqueous solutions the average shape of the low molar mass kraft lignin particles was observed to be elongated and flat. The average shape does not necessarily correspond to the shape of the individual particles because of the polydispersity of the fraction and due to selfassociation of the particles. Lignins, and especially lignosulfonate, have many uses as dispersants, binders and emulsion stabilisers. In this thesis work the selfassociation of low molar mass lignosulfonate macromolecules was observed using small-angle x-ray scattering. By taking into account the polydispersity of the studied lignosulfonate fraction, the shape of the lignosulfonate particles was determined to be flat by fitting an oblate ellipsoidal model to the scattering intensity.

Measurement of the Single Top Quark Production Cross Section at CDF

We report a measurement of the single top quark production cross section in 2.2 ~fb-1 of p-pbar collision data collected by the Collider Detector at Fermilab at sqrt{s}=1.96 TeV. Candidate events are classified as signal-like by three parallel analyses which use likelihood, matrix element, and neural network discriminants. These results are combined in order to improve the sensitivity. We observe a signal consistent with the standard model prediction, but inconsistent with the background-only model by 3.7 standard deviations with a median expected sensitivity of 4.9 standard deviations. We measure a cross section of 2.2 +0.7 -0.6(stat+sys) pb, extract the CKM matrix element value |V_{tb}|=0.88 +0.13 -0.12 (stat+sys) +- 0.07(theory), and set the limit |V_{tb}|>0.66 at the 95% C.L.

Search for single top quark production in pp̅ collisions at √s=1.96 TeV in the missing transverse energy plus jets topology

We report a search for single top quark production with the CDF II detector using 2.1 fb-1 of integrated luminosity of pbar p collisions at sqrt{s}=1.96 TeV. The data selected consist of events characterized by large energy imbalance in the transverse plane and hadronic jets, and no identified electrons and muons, so the sample is enriched in W -> tau nu decays. In order to suppress backgrounds, additional kinematic and topological requirements are imposed through a neural network, and at least one of the jets must be identified as a b-quark jet. We measure an excess of signal-like events in agreement with the standard model prediction, but inconsistent with a model without single top quark production by 2.1 standard deviations (sigma), with a median expected sensitivity of 1.4 sigma. Assuming a top quark mass of 175 GeV/c2 and ascribing the excess to single top quark production, the cross section is measured to be 4.9+2.5-2.2(stat+syst)pb, consistent with measurements performed in independent datasets and with the standard model prediction.

Observation of single top quark production and measurement of |Vtb| with CDF

We report the observation of electroweak single top quark production in 3.2  fb-1 of pp̅ collision data collected by the Collider Detector at Fermilab at √s=1.96  TeV. Candidate events in the W+jets topology with a leptonically decaying W boson are classified as signal-like by four parallel analyses based on likelihood functions, matrix elements, neural networks, and boosted decision trees. These results are combined using a super discriminant analysis based on genetically evolved neural networks in order to improve the sensitivity. This combined result is further combined with that of a search for a single top quark signal in an orthogonal sample of events with missing transverse energy plus jets and no charged lepton. We observe a signal consistent with the standard model prediction but inconsistent with the background-only model by 5.0 standard deviations, with a median expected sensitivity in excess of 5.9 standard deviations. We measure a production cross section of 2.3-0.5+0.6(stat+sys)  pb, extract the value of the Cabibbo-Kobayashi-Maskawa matrix element |Vtb|=0.91-0.11+0.11(stat+sys)±0.07  (theory), and set a lower limit |Vtb|>0.71 at the 95% C.L., assuming mt=175  GeV/c2.

Observation of single top quark production and measurement of |Vtb| with CDF

We report the observation of electroweak single top quark production in 3.2 fb-1 of ppbar collision data collected by the Collider Detector at Fermilab at sqrt{s}=1.96 TeV. Candidate events in the W+jets topology with a leptonically decaying W boson are classified as signal-like by four parallel analyses based on likelihood functions, matrix elements, neural networks, and boosted decision trees. These results are combined using a super discriminant analysis based on genetically evolved neural networks in order to improve the sensitivity. This combined result is further combined with that of a search for a single top quark signal in an orthogonal sample of events with missing transverse energy plus jets and no charged lepton. We observe a signal consistent with the standard model prediction but inconsistent with the background-only model by 5.0 standard deviations, with a median expected sensitivity in excess of 5.9 standard deviations. We measure a production cross section of 2.3+0.6-0.5(stat+sys) pb, extract the CKM matrix element value |Vtb|=0.91+0.11-0.11 (stat+sys)+-0.07(theory), and set a lower limit |Vtb|>0.71 at the 95% confidence level, assuming m_t=175 GeVc^2.

Measurement of the Single-Top-Quark Production Cross Section at CDF

We report a measurement of the single top quark production cross section in 2.2 ~fb-1 of p-pbar collision data collected by the Collider Detector at Fermilab at sqrt{s}=1.96 TeV. Candidate events are classified as signal-like by three parallel analyses which use likelihood, matrix element, and neural network discriminants. These results are combined in order to improve the sensitivity. We observe a signal consistent with the standard model prediction, but inconsistent with the background-only model by 3.7 standard deviations with a median expected sensitivity of 4.9 standard deviations. We measure a cross section of 2.2 +0.7 -0.6(stat+sys) pb, extract the CKM matrix element value |V_{tb}|=0.88 +0.13 -0.12 (stat+sys) +- 0.07(theory), and set the limit |V_{tb}|>0.66 at the 95% C.L.

Observation of Electroweak Single Top-Quark Production

We report the first observation of single top quark production using 3.2 fb^-1 of pbar p collision data with sqrt{s}=1.96 TeV collected by the Collider Detector at Fermilab. The significance of the observed data is 5.0 standard deviations, and the expected sensitivity for standard model production and decay is in excess of 5.9 standard deviations. Assuming m_t=175 GeV/c^2, we measure a cross section of 2.3 +0.6 -0.5 (stat+syst) pb, extract the CKM matrix element value |V_{tb}|=0.91 +-0.11 (stat+syst) 0.07(theory), and set the limit |V_{tb}|>0.71 at the 95% C.L.

Optical Tweezers for Single Molecule Biology

Molecular machinery on the micro-scale, believed to be the fundamental building blocks of life, involve forces of 1-100 pN and movements of nanometers to micrometers. Micromechanical single-molecule experiments seek to understand the physics of nucleic acids, molecular motors, and other biological systems through direct measurement of forces and displacements. Optical tweezers are a popular choice among several complementary techniques for sensitive force-spectroscopy in the field of single molecule biology. The main objective of this thesis was to design and construct an optical tweezers instrument capable of investigating the physics of molecular motors and mechanisms of protein/nucleic-acid interactions on the single-molecule level. A double-trap optical tweezers instrument incorporating acousto-optic trap-steering, two independent detection channels, and a real-time digital controller was built. A numerical simulation and a theoretical study was performed to assess the signal-to-noise ratio in a constant-force molecular motor stepping experiment. Real-time feedback control of optical tweezers was explored in three studies. Position-clamping was implemented and compared to theoretical models using both proportional and predictive control. A force-clamp was implemented and tested with a DNA-tether in presence of the enzyme lambda exonuclease. The results of the study indicate that the presented models describing signal-to-noise ratio in constant-force experiments and feedback control experiments in optical tweezers agree well with experimental data. The effective trap stiffness can be increased by an order of magnitude using the presented position-clamping method. The force-clamp can be used for constant-force experiments, and the results from a proof-of-principle experiment, in which the enzyme lambda exonuclease converts double-stranded DNA to single-stranded DNA, agree with previous research. The main objective of the thesis was thus achieved. The developed instrument and presented results on feedback control serve as a stepping stone for future contributions to the growing field of single molecule biology.

Polymeereillä stabiloitu amorfinen formulaatio

Nowadays growing number of new active pharmaceutical ingredients (API) have large molecular weight and are hydrophobic. The energy of their crystal lattice is bigger and polarity has decreased. This leads to weakened solubility and dissolution rate of the drug. These properties can be enhanced for example by amorphization. Amorphous form has the best dissolution rate in the solid state. In the amorphous form drug molecules are randomly arranged, so the energy required to dissolve molecules is lower compared to the crystalline counterpart. The disadvantage of amorphous form is that it is unstable. Amorphous form tends to crystallize. Stability of amorphous form can be enhanced by adding an adjuvant to drug product. Adjuvant is usually a polymer. Polymers prevent crystallization both by forming bonds with API molecules and by steric hindrance. The key thing in stabilizing amorphous form is good miscibility between API and polymer. They have to be mixed in a molecular level so that the polymer is able to prevent crystallization. The aim of this work was to study miscibility of drug and polymer and stability of their dispersion with different analytical methods. Amorphous dispersions were made by rotary evaporator and freeze dryer. Amorphicity was confirmed with X-ray powder diffraction (XRPD) right after preparation. Itraconazole and theophylline were the chosen molecules to be stabilized. Itraconazole was expected to be easier and theophylline more difficult to stabilize. Itraconazole was stabilized with HPMC and theophylline was stabilized with PVP. Miscibility was studied with XRPD and differential scanning calorimetry (DSC). In addition it was studied with polarized light microscope if miscibility was possible to see visually. Dispersions were kept in stressed conditions and the crystallization was analyzed with XRPD. Stability was also examined with isothermal microcalorimetry (IMC). The dispersion of itraconazole and theophylline 40/60 (w/w) was completely miscible. It was proved by linear combination of XRPD results and single glass transition temperature in DSC. Homogenic well mixed film was observed with light microscope. Phase separation was observed with other compositions. Dispersions of theophylline and PVP mixed only partly. Stability of itraconazole dispersions were better than theophylline dispersions which were mixed poorer. So miscibility was important thing considering stability. The results from isothermal microcalorimetry were similar to results from conventional stability studies. Complementary analytical methods should be used when studying miscibility so that the results are more reliable. Light microscope is one method in addition to mostly used XRPD and DSC. Analyzing light microscope photos is quite subjective but it gives an idea of miscibility. Isothermal microcalorimetry can be one option for conventional stability studies. If right conditions can be made where the crystallization is not too fast, it may be possible to predict stability with isothermal microcalorimetry.