Two discourses, delivered to the Second Presbyterian Society in Newburyport, August 20, 1812, the day recommended by the President of the United States, for national humiliation and prayer

Printed by W.R. and H. G. Allen

Hydration, conformational states and kinetics of yeast hexokinase PII /

The kinetic study of the coupled enzymatic reaction involving monomeric yeast hexokinase PII (HK) and yeast glucose-6-phosphate dehydrogenase (G-6-PDH) yields a Michaelis constant of 0.15 ± 0.01 mM for D-glucose. At pH 8.7 HK is present in monomeric form. The addition of polyethylene glycol (PEG), to the reaction mixture increased the affinity of HK for glucose, independent ofMW of the PEG from 2000 to 10000. The osmotic stress exerted by PEG can be used to measure the change in number of water molecules that accompany enzyme conformational changes (Rand, et al., 1993). Results indicate that the G-6-PDH is not osmotically sensitive and thus, the change in the number of PEG-inaccessible water molecules (ANw) measured in the coupled reaction is only the difference between the glucose-bound and glucosefree conformations of HK. ANw ~ 450 with PEGs of MW > 2000 under conditions for both binding (Reid and Rand, 1997) and kinetic assays. The contribution water may play in the binding of ATP (Km = 0.24 + 0.02 mM) has also been examined. It was found that in this case ANw = (for osmotic pressures < 2.8x10* dynes/cm^), suggesting no additional numbers of waters are displaced when ATP binds to HK. Osmotic pressure experiments were also performed with dimeric HK. It was determined that both the monomeric and dimeric forms of HK give the same ANw under low pressures. If this large ANw is due to conformational flexibility, it would appear that the flexibility is not reduced upon dimerization ofthe enzyme.

An analysis of the photoelectron and Rydberg states of formaldehyde /|nby Carol R. Lessard. -- 260 St. Catharines [Ont.] : Dept. of Chemistry, Brock University,

Although it is generally accepted that Rydberg orbitals are very large and diffuse, and that electron promotion to a Rydberg orbital is not too different from ionization of the molecule, analysis of the two types of transitions proves otherwise. The photoelectron spectrum of the 2B2 (n) ion has very little vibrational structure attached to the origin band; on the other hand, several of the Rydberg transitions which involve the promotion of the n(bZ) electron exhibit a great deal of vibrational activity. In particular, the members of the n=3 Rydberg\ series interact with and perturb each other through pseudo-Jahn-Teller vibronic coupling. The vacuum ultraviolet spectrum contains a number of features which are difficult to explain, and two unusually sharp bands can only be identified as representing some form of electron promotion in formaldehyde.

Elliptical orbital studies of H21 and H2 molecules /|nS. K. Gupta. -- 260 St. Catharines, Ont. : [s. n.],

Calculations are performed on the \S <:Jd ground states of d ' + the H and HC) molecules using a basis set of non-integral ~ ~ I elliptical orbitals. Different variational wavefunctions constructed i- for H~ involved one parameter to three par~~eter variation. In order to l"'educe the ntunber of parameters in most commonly 0- used basis orbitals set, the importance of the term (,+~) Y\ over the term ;u 'Where n is a variational pararneter and the value of cr may be given by boundary condition or cusp condition is outlined in Chapters II and III. It is found that the two parameter -+ bound~ condition, gives lower variational energies than any wavefunction published to date for small and moderate internuclear separations. c;. In order to find out the importance of the term (I +~ ) Y\ over ;U for the two electron problem, the variational energy is computed for the H~ molecule from unrestricted two parameter closed shell wavefunctions including the term U+ft)boundary condition in one case and from the cusp condition in the second case. In order to take into account in-out correlation partially, open shell calculation for the ground state of the hydrogen molecule for R =1.4 (equilibrium internuclear separation) is perfonaed. The results are excellent.

Manpower development and nation-building : Singapore's experience

Manpower is a basic resource. It is the indispensable means of converting other resources to mankind '.s use and benefit. As a process· of increasing the knowledge, skills, and dexterity of the people of a society, manpower development is the most fundamental means of enabling a nation to acquire the capacities to bring about its desired future state of affairs -- a more mighty and wealthier nation. Singapore's brief nation-building history justifies the emphasis accorded to the importance of good quality human resources and manpower development in economic and socio-political developments. As a tiny island-state with a poor natural resource base, Singapore's long-term survival and development depend ultimately upon the quality and the creative energy of her people. In line with the nation-building goals and strategies of the Republic, as conditioned by her objective setting, Singapore's basic manpower development premise has been one of "quality and not quantity". While implementing the "stop-at-two" family planning and population control programs and the relevant immigration measures to guard against the prospect of a "population explosion", the Government has energetically fostered various educational programs, including vocational training schemes, adult education programs, the youth movement, and the national service scheme to improve the quality of Singaporeans. There is no denying that some of the manpower development measures taken by the Government have imposed sacrifice and hardship on the Singapore citizens. Nevertheless, they are the basic conditions for the island-Republic's long-term survival and development. It is essential iii to note that Singapore's continuing existence and phenomenal-success are largely attributable to the will, capacities and efforts of her leaders and people. In the final analysis, the wealth and the strength of a nation are based upon its ability to conserve, develop and utilize effectively the innate capacities of its people. This is true not only of Singapore but necessarily of other developing nations. It can be safely presumed that since most developing states' concerns about the quality of their human resources and the progress of their nation-building work are inextricably bound to those about the quantity of their population, the "quality and not quantity" motto of Singapore's manpower development programs can also be their guiding principle.

Measurement of forces between and within bilayers of neutral phospholipids

Phospholipids in water form lamellar phases made up of alternating layers of water and bimolecular lipid leaflets. Three complementary methods, osmotic, mechanical, and vapour pressures, were used to measure the work of removing water from lamellar phases composed of frozen dipalmitoylphosphatidylcholine ( DPPC ), melted DPPC, egg phosphatidylethanolamine or equimolar mixtures of DPPC and cholesterol ( DPPC/CHOL ), Concurrently the structural changes that resulted from this water removal were measured using X-ray diffraction. The work was divided into that which forces the bilayers together ( F ) and that which compresses the molecules together within the bilayers ( F )# A large repulsive force exists between bilayers composed of each of the lipids studied and this force increases exponentially as bilayer separation is decreased. F is affected by the nature of the head groups, conformation of the acyl chains and heterogeneity of these chains. In general all of the melted phosphatidylcholines ( melted DPPC, egg lecithin and DPPC/CHOL ) have large equilibrium separations in excess water resulting from large repulsive hydration forces between these bilayers. By comparison, egg PE has an increased attractive force, and frozen DPPC has a decreased hydration force; each results in smaller separations in water for these two lipids. The chemical potentials of the water between the bilayers for all these lipids lie on a continuum, indicating that interbilayer water cannot be characterized by two discrete states, usually referred to as "bound" or "non**bound". For all lipids studied a maximum of 25 % of the total work done on the system goes into deforming the bilayers. The method used here viii to separate repulsion from deformation, developed for us by v. A. Parsegian, provides a unique method for the measurement of lateral pressure of a bilayer and its modulus of deformability ( Y ). Lateral pressure is affected by the nature of the head group, conformation and heterogeneity of the acyl chains. For small changes in molecular surface area ( A ) near equilibrium, both melted and frozen DPPC have similar values for the deformability modulus. Thus in this regime it requires about the same force to change the angle of tilt of frozen chains as it does to compress the fluid bilayer. The introduction of cholesterol into bilayers of DPPC reduces dramatically the lateral pressure of the bilayers over a large range of molecular surface areas ( A ). The variation in the magnitude of bilayer repulsion with different phospholipids provides a basis for the mechanism of lipid segregation in mixed lipid systems and suggests that interacting heterogeneous membranes may influence or modulate the composition of the opposing membrane. The measurements of deformabilities of bilayers provides a direct comparison of them with the properties of monolayers.

An analysis of the methyl rotation dynamics in the So (x' A) and T (a A) states of thioacetaldehyde from Pyrolysis jet spectra /

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetaldehyde CH3CHS, CH3CDS, CD3CHS and CD3CDS have been observed over the region 15800 - 17300 cm"^ in a continuous pyrolysis jet. The vibronic band structure of the singlet-triplet n -* n* transition were attributed to the strong coupling of the methyl torsion and aldehydic hydrogen wagging modes . The vibronic peaks have been assigned in terms of two upper electronic state (T^) vibrations; the methyl torsion mode v^g, and the aldehydic hydrogen wagging mode v^^. The electronic origin O^a^ is unequivocally assigned as follows: CH3CHS (16294.9 cm"'' ), CH3CDS (16360.9 cm"'' ), CD3CHS (16299.7 cm"^ ), and CD3CDS (16367.2 cm"'' ). To obtain structural and dynamical information about the two electronic states, potential surfaces V(e,a) for the 6 (methyl torsion) and a (hydrogen wagging) motions were generated by ab initio quantum mechanical calculations with a 6-3 IG* basis in which the structural parameters were fully relaxed. The kinetic energy coefficients BQ(a,e) , B^(a,G) , and the cross coupling term B^(a,e) , were accurately represented as functions of the two active coordinates, a and 9. The calculations reveal that the molecule adopts an eclipsed conformation for the lower Sq electronic state (a=0°,e=0"') with a barrier height to internal rotation of 541.5 cm"^ which is to be compared to 549.8 cm"^ obtained from the microwave experiment. The conformation of the upper T^ electronic state was found to be staggered (a=24 . 68° ,e=-45. 66° ) . The saddle point in the path traced out by the aldehyde wagging motion was calculated to be 175 cm"^ above the equilibrium configuration. The corresponding maxima in the path taken by methyl torsion was found to be 322 cm'\ The small amplitude normal vibrational modes were also calculated to aid in the assignment of the spectra. Torsional-wagging energy manifolds for the two states were derived from the Hamiltonian H(a,e) which was solved variationally using an extended two dimensional Fourier expansion as a basis set. A torsionalinversion band spectrum was derived from the calculated energy levels and Franck-Condon factors, and was compared with the experimental supersonic-jet spectra. Most of the anomalies which were associated with the interpretation of the observed spectrum could be accounted for by the band profiles derived from ab initio SCF calculations. A model describing the jet spectra was derived by scaling the ab initio potential functions. The global least squares fitting generates a triplet state potential which has a minimum at (a=22.38° ,e=-41.08°) . The flatter potential in the scaled model yielded excellent agreement between the observed and calculated frequency intervals.

Message from the President of the United States to both Houses of Congress at the commencement of the second session of the twelfth Congress. --

November 4, 1812. Read, and ordered to be printed.

News in the age of empire : two war scandals

This thesis argues that the motivations underpinning the mainstream news media have fundamentally changed in the 21 sl century. As such, the news is no longer best understood as a tool for propaganda or agenda setting; instead it seems that the news is only motivated by the flow of global network capitalism. The author contrasts the work of Noam Chomsky and Edward S. Herman with that of Gilles Deleuze. Chomsky and Herman's 'Propaganda Model' has been influential within the fields of media studies and popular culture. The 'propaganda model' states that the concentration of ownership of the media has allowed the media elite to exert a disproportionate amount of influence over the mass media. Deleuze, on the other hand, regards the mass media as being yet another cog within the global capitalist mechanism, and is therefore separate from ideology or propaganda. The author proposes that 'propaganda' is no longer a sufficient word to describe the function of the news as terms like 'propaganda' imply some form of national sovereignty or governmental influence. To highlight how the news has 'changed from an instrument of propaganda to an instrument of accumulation, the author compares and contrasts the· coverage of the Abu Ghraib Prison Scandal with that of the Haditha Civilian Massacre. Although similar in nature, the author proposes that the Abu Ghraib Prison Scandal received a disproportionate amount of coverage within the mainstream press because of its exciting and sensational nature.

Photograph of Two Girls by R. F. Uren, Photographer, St. Catharines [n.d.]

Two unidentified girls are featured in this black and white cabinet card style photograph by R. F. Uren, of St. Catharines. The photograph is not dated, however, the address of the photographer is printed at the bottom of the cabinet card. This photograph was in the possession of Iris Sloman Bell, of St. Catharines, Ontario. The Sloman - Bell family descendants include former African American slaves who settled in Canada.Richard Frank (R.F.) Uren was a photographer in St. Catharines from 1886-1895. Source: Phillips, Glen C. The Ontario photographers list (1851-1900). Sarnia: Iron Gate Publishing Co., 1990. "Cabinet card photographs were first introduced in 1866. They were initially employed for landscapes rather than portraitures. Cabinet cards replaced Carte de visite photographs as the popular mode of photography. Cabinet cards became the standard for photographic portraits in 1870. Cabinet cards experienced their peak in popularity in the 1880's. Cabinet cards were still being produced in the United States until the early 1900's and continued to be produced in Europe even longer. The best way to describe a cabinet card is that it is a thin photograph that is mounted on a card that measures 4 1/4″ by 6 1/2″. Cabinet cards frequently have artistic logos and information on the bottom or the reverse of the card which advertised the photographer or the photography studio's services." Source: http://cabinetcardgallery.wordpress.com/category/cabinet-card-history/

Two Black Gentlemen Photographed by John Cooper, London/St. Thomas, Ont. [n.d.]

An undated cabinet card of two Black men photographed by John Cooper, who operated as a photographer in London, Ont. and St. Thomas, Ont. from 1857 - 1890. The reverse of the photograph features the photographer's stamp in coloured ink. This photograph was in the possession of Iris Sloman Bell, of St. Catharines. The Sloman - Bell family have relatives who include former Black slaves from the United States. John Cooper is listed as a photographer and daguerrean artist in 1857 - 1890 in London, Ont. and in 1874 in St. Thomas, Ont. Source: Phillips, Glen C. The Ontario photographers list (1851-1900). Sarnia: Iron Gate Publishing Co., 1990. "Cabinet card photographs were first introduced in 1866. They were initially employed for landscapes rather than portraitures. Cabinet cards replaced Carte de visite photographs as the popular mode of photography. Cabinet cards became the standard for photographic portraits in 1870. Cabinet cards experienced their peak in popularity in the 1880's. Cabinet cards were still being produced in the United States until the early 1900's and continued to be produced in Europe even longer. The best way to describe a cabinet card is that it is a thin photograph that is mounted on a card that measures 4 1/4″ by 6 1/2″. Cabinet cards frequently have artistic logos and information on the bottom or the reverse of the card which advertised the photographer or the photography studio's services." Source: http://cabinetcardgallery.wordpress.com/category/cabinet-card-history/

Message from the President of the United States to both Houses of Congress at the commencement of the second session of the twelfth Congress

November 4, 1812. Read, and ordered to be printed. Includes Documents accompanying the Message of the President of the United States to the two Houses of Congress, at the opening of the second session of the twelfth Congress United States. 12th Congress, 2nd session, 1812-1813. House.; United States. 12th Congress, 2nd session, 1812-1813. Senate.; United States. Congress. House.; United States. Congress. Senate. Printed by A. and C. Way

The Synthesis and Coordination Chemistry of Two Families of Polydentate Ligands - Exploring Their Potential for the Preparation of Molecule-Based Magnets

The synthesis and studies of two classes of poly dentate ligands are presented as two projects. In project 1, four new carboxamide ligands have been synthesised via the condensation of 2,2',6,6'-tetrachloroformyl-4,4'-bipyridine or 2,6-dichloroformyl pyridine together with heterocyclic amines containing pyridine or pyrazole substituents. The coordination chemistry of these ligands has been investigated and studies have shown that with a Cu(II) salt, two carboxamide ligands LJ and L2 afford large clusters with stoichiometries [Cu8(L1)4Cl16].CHCl3.5H2O.7CH3OH (I) and [Cu9(L2)6Cl6].CH3OH.5H2O.(C2H5)3N (II) respectively. [molecular diagram availabel in pdf]. X-ray diffraction studies of cluster (I) reveal that it has approximate S4 symmetry and is comprised of four ligands and eight copper (II) centers. Here, coordination takes place via amide 0 atoms, and pyrazole nitrogens. This complex is the first reported example of an octanuclear copper cluster with a saddle-shaped structure. The second cluster comprises nine copper ions that are arranged in a cyclic array. Each ligand coordinates three copper centers and each copper ion shares two ligands to connect six ligands with nine copper ions. The amide nitrogens are completely deprotonated and both amide Nand 0 atoms coordinate the metal centres. The cluster has three-fold symmetry. There are six chloride ions, three of which are bridging two neighbouring Cu(II) centres. Magnetic studies of (I) and (II) reveal that both clusters display weak antiferromagnetic interactions between neighbouring Cu(II) centers at low temperature. In the second project, three complexes with stoichiometries [Fe[N302](SCN)2]2 (III), R,R-[Fe[N3O2](SCN)2 (IV) and R,R-]Fe[N3O2](CN)2] (V) were prepared and characterized, where [N302] is a pentadentate macrocycle. Complex (III) was prepared via the metal templated Schiff-base condensation of 2,2',6,6'-tetraacetyl-4,4'-bipyridine together with 3,6-dioxaoctane-I,8-diamine and comprises of a dimeric macro cycle where the two Fe(II) centres are in a pentagonal-bipyramidal environment with the [N302] ligands occupying the equatorial plane and two axial NCS ligands. Complexes (IV) and (V) were prepared via the condensation of 2,6-diacetylpyridine together with a chiral diamine in the presence of FeCh. The synthetic strategy for the preparation of the chiral diamine (4R,5R)-4,5-diphenyl-3,6-dioxa-I,8-octane-diamine was elucidated. The chirality of both macrocycles (IV) and (V) was probed by circular dichroism spectroscopy. The crystal structure of (IV) at 200 K contains two independent molecules in the unit cell, both of which contain a hepta-coordinated Fe(II) and axial NCS ligands. Variable temperature magnetic susceptibility and structural studies are consistent with a high spin Fe(II) complex and show no evidence of any spin crossover behaviour. In contrast, the bis cyanide derivative (V) crystallizes with two independent molecules in the unit cell, both of which have different coordination geometries consistent with different spin states for the two Fe(II) centres. At 250 K, the molecular structure of (V) shows the presence of both 7- and a 6-coordinate Fe(II) complexes in the crystal lattice. As the temperature is lowered, the molecules undergo a structural change and at 100 K the structural data is consistent with a 6- and 5-coordinate Fe(II) complex in the unit cell. Magnetic studies confirm that this complex undergoes a gradual, thermal, spin crossover transition in the solid state. Photomagnetic measurements indicate this is the first chiral Fe (II) sea complex to exhibit a LIESST.

Letter from Thomas Tudor Tucker, treasurer of the United States: transmitting his accounts for 1816, February 25, 1817

Bound with: Letter from the Secretary of the Treasury transmitting statements of the importations of goods, wares and merchandise... (60 p.).