The solid alpha-amino acid isoleucine has been vaporized by laser ablation and expanded in a supersonic jet, where the molecular conformations of the isolated molecule were probed using Fourier transform microwave spectroscopy. Two conformers of neutral isoleucine have been detected in gas phase, the most stable being stabilized by an intramolecular hydrogen bond N-H...O=C and a cis-COOH arrangement. The higher energy form is stabilized by an intramolecular hydrogen bond N...H-O. The sec-butyl side chain of the amino acid adopts the same configuration in the two observed conformers, with a staggered configuration at Cbeta similar to that observed in valine and a trans arrangement of Calpha and Cdelta. Ab initio calculations at MP2/6-311++G(d,p) level reproduce satisfactorily the experimental results.

4-Hydroxypyrimidine (4HP) has two conformational forms (the hydroxyl hydrogen cis or trans with respect to the adjacent nitrogen), which are in tautomeric equilibrium with two ketonic forms, 4-pyrimidinone (4PO) and 6-pyrimidinone (6PO). We have investigated the free jet absorption millimeterwave spectrum of this system, assigning the rotational spectra of 4HPcis and 4PO; the latter species is more stable by 2.0(9) kJ/mol. No lines corresponding to the trans isomer of 4-hydroxypyridine and to 6PO have been observed.

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The effect of drillpipe rotation on hole cleaning during directional well drilling is investigated. An 8" diameter wellbore simulator, 100 ft long, with a 4 1/2" drillpipe was used for the study. The variables considered in this experimental work are: rotary speed, hole inclination, mud rheology, cuttings size, and mud flow rate. Over 600 tests were conducted. The rotary speed was varied from 0 to 175 rpm. High viscosity and low viscosity bentonite muds and polymer muds were used with 1/4" crushed limestone and 1/10" river gravel cuttings. Four hole inclinations were considered: 40, 65, 80, and 90 degrees from vertical. The results show that drillpipe rotation has a significant effect on hole cleaning during directional well drilling, contrary to what has been published by previous researchers who forced the drillpipe to rotate about its own axis. The level of enhancement due to pipe rotation is a function of the simultaneous combination of mud rheology, cuttings size, and mud flow rate. Also it was observed that the dynamic behavior of the drillpipe (steady state vibration, unsteady sate vibration, whirling rotation, true axial rotation parallel to hole axis, etc.) plays a major role on the significance in the improvement of hole cleaning. Generally, smaller cuttings are more difficult to transport. However, at high rotary speed and with high viscosity muds, the smaller cuttings seem to become easier to transport. Generally, in inclined wells low viscosity muds clean better than high viscosity muds, depending on cuttings size, viscosity, and rotary speed level. Introduction Numerous studies on cuttings transport have been conducted for the past two decades. Although several investigators have made observations on the effect of drillpipe rotation, most have focused their studies on mud rheology and annular velocities. This is the first time an extensive experimental study is conducted with the sole purpose of investigating the effect of drillpipe rotation on hole cleaning. In the past, the effect of drillpipe rotation was thought to be minimal. This belief was based on the results of experiments which were conducted in flow loops that used centralizers to constrain the pipe to rotate on its own axis, avoiding any orbital motion. Although the motion of the pipe will change at different positions along the well, it is now believed that in most cases the drillstring will have both rotary and orbital motion, even when in tension. In this case, it is the orbital motion and not the rotation that improves hole cleaning. When the pipe is rotating only along its axis it will cause a shift and a slight increase in the velocity profile in the annular area, causing the velocities on one side of the hole to be higher than on the other. Generally, a no slip condition at the boundaries in the annulus is assumed. These include the boundary between the hole or casing and the fluid, the boundary between the fluid and the drillpipe, and the boundary between the fluid and the cuttings bed. If the pipe is not rotating, the velocity of the fluid particles at these boundaries is zero. When the pipe rotates this boundary condition means that the velocity of the fluid particles adjacent to drillpipe is equal to the rotational speed of the pipe, perpendicular to the hole axis, resulting in a pseudo-helical flow. The minor effects observed in tests conducted under this configuration (using centralizers) indicate that the shift and the increase of the annular velocities are minor and do not affect cuttings transport significantly. On the other hand, the orbital motion of the pipe improves the transport of cuttings significantly in two ways: first, the mechanical agitation of the cuttings in an inclined hole sweeps the cuttings resting on the lower side of the hole into the upper side, where the annular velocity is higher. Second, the orbital motion exposes the cuttings under the drillstring cyclically to the moving fluid particles. P. 459^

2-Azetidinone-water clusters can be considered as appropriate models for investigating the interaction of the peptide functional group with water. The rotational spectra of 2-azetidinone-(H2O)n (n = 1, 2) complexes have been studied in the 6-18 GHz frequency range using a molecular beam Fourier transform microwave spectrometer. Two different isomers have been observed for the 1 : 1 adduct. The most stable (1 : 1a) is stabilized by two hydrogen bonds O-H···O=C and N-H···O with water closing a ring with the peptide group. For the other conformer (1 : 1b), water is placed on the other side of the carbonyl group stabilized by O-H···O=C and C-H···O hydrogen bonds. In 2-azetidinone-(H2O)2 the water molecules close a ring with the peptide group forming three different hydrogen bonds: O-H···O=C, O-H···O and N-H···O. The spectra of the parent and several isotopologues of each cluster have been investigated in order to determine their structures. The hydrogen bond geometries show that the dominant interaction is the O-H···O=C hydrogen bond, in good agreement with the observed preference of water to interact with this group in proteins. A comparison between the geometries of the different observed adducts shows clearly how cooperative hydrogen bonding plays an important role in the stabilization of these complexes. No detectable structural changes have been observed for 2-azetidinone upon hydration with one water molecule.

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There are many factors that impact on hole cleaning while drilling directional wells for hydrocarbon recovery. Those that are most prevalent include:annular drilling fluid velocityhole inclination angledrillstring rotationannulus eccentricityrate of penetrationdrilling fluid propertiescharacteristics of drilled cuttings In this paper the authors discuss the above factors and their field limitations. In addition, the key issues that need to be addressed for the development of a universal and reliable model in hole cleaning are identified. Introduction Drilling directional oil/gas wells, including horizontal, has become a routine process in all geographic areas of the world. While the overall directional drilling technology has advanced significantly over the past quarter century, hole cleaning problems are still a deterrent to extended reach drilling (ERD). Inadequate hole cleaning can contribute to several major drilling problems which include: increase in torque and drag that can limit the reach to target, mechanical pipe sticking and difficulties in casing/cementing and logging operations that can increase well cost significantly. Although, there have been many experimental studies and few attempts on mechanistic modeling in cuttings transport, field reports still indicate that hole cleaning is a frequently occurring problem depending on annular drilling fluid velocity, drillstring dynamics, inclination angle of well, drilling mud properties, drilled cuttings size, eccentricity of the annulus and drilling rate. These factors and their limitations in actual field practices are the main points of discussion of this paper. Discussion Annular Fluid Velocity. Regardless of all other factors that impact on hole cleaning, drilling fluid flow rate dominates the cuttings transport process. It is expected that an increase in flow rate will always cause more efficient removal of drilled cuttings out of the annular space. However, an upper limit of the flow rate is dictated by:rig hydraulic power availabilitypermissible equivalent circulating density (ECD)susceptibility of the open hole section to hydraulic erosion Drillstring Rotation. It has been demonstrated in lab studies and reported in field cases, that drillstring rotation with the induced modes of vibrations (torsional, longitudinal, and lateral) has moderate to significant effects on hole cleaning in directional wells. The level of enhancement in drilled cuttings removal due to drillstring rotation is a function of the combination of mud rheology, cuttings size, flow rate, and the dynamic behavior of the string. It is believed that the whirling motion of the string as it rotates is the major contributor to the cleaning process. Mechanical agitation of the cuttings bed and its exposure to higher fluid velocities are the beneficiaries of this motion. Although there is a definite gain in hole cleaning due to drillpipe rotation, it must be recognized also that there are limitations that may have to be imposed as well. For example, pipe rotation cannot be activated during the sliding mode while building hole angle. Also, pipe rotation induces cyclic stresses that can accelerate pipe failure due to fatigue, causes excessive casing wear and in some cases mechanical destruction of the walls of open hole sections.

The pure rotational spectra of 18 and 21 isotopic species of GeSe and GeTe have been measured in the frequency range 5-24 GHz using a Fabry-Pérot-type resonator pulsed-jet Fourier-transform microwave spectrometer. Gaseous samples of both chalcogenides were prepared by a combined dc discharge/laser ablation technique and stabilized in supersonic jets of Ne. Global multi-isotopologue analyses of the derived rotational data, together with literature high-resolution infrared data, produced very precise Dunham parameters, as well as rotational constant Born-Oppenheimer breakdown (BOB) coefficients (δ(01)) for Ge, Se, and Te. A direct fit of the same datasets to an appropriate radial Hamiltonian yielded analytic potential-energy functions and BOB radial functions for the X(1)Σ(+) electronic state of both GeSe and GeTe. Additionally, the electric quadrupole and magnetic hyperfine interactions produced by the nuclei (73)Ge, (77)Se, and (125)Te were observed, yielding much improved quadrupole coupling constants and first determinations of the spin-rotation parameters.