NMR Chemical Shielding and Spin-Spin Coupling Constants of Liquid NH(3): A Systematic Investigation using the Sequential QM/MM Method

The NMR spin coupling parameters, (1)J(N,H) and (2)J(H,H), and the chemical shielding, sigma((15)N), of liquid ammonia are studied from a combined and sequential QM/MM methodology. Monte Carlo simulations are performed to generate statistically uncorrelated configurations that are submitted to density functional theory calculations. Two different Lennard-Jones potentials are used in the liquid simulations. Electronic polarization is included in these two potentials via an iterative procedure with and without geometry relaxation, and the influence on the calculated properties are analyzed. B3LYP/aug-cc-pVTZ-J calculations were used to compute the V(N,H) constants in the interval of -67.8 to -63.9 Hz, depending on the theoretical model used. These can be compared with the experimental results of -61.6 Hz. For the (2)J(H,H) coupling the theoretical results vary between -10.6 to -13.01 Hz. The indirect experimental result derived from partially deuterated liquid is -11.1 Hz. Inclusion of explicit hydrogen bonded molecules gives a small but important contribution. The vapor-to-liquid shifts are also considered. This shift is calculated to be negligible for (1)J(N,H) in agreement with experiment. This is rationalized as a cancellation of the geometry relaxation and pure solvent effects. For the chemical shielding, U(15 N) Calculations at the B3LYP/aug-pcS-3 show that the vapor-to-liquid chemical shift requires the explicit use of solvent molecules. Considering only one ammonia molecule in an electrostatic embedding gives a wrong sign for the chemical shift that is corrected only with the use of explicit additional molecules. The best result calculated for the vapor to liquid chemical shift Delta sigma((15)N) is -25.2 ppm, in good agreement with the experimental value of -22.6 ppm.

Constraining the dark energy and smoothness parameter with type Ia supernovae and gamma-ray bursts

The existence of inhomogeneities in the observed Universe modifies the distance-redshift relations thereby affecting the results of cosmological tests in comparison to the ones derived assuming spatially uniform models. By modeling the inhomogeneities through a Zeldovich-Kantowski-Dyer-Roeder approach which is phenomenologically characterized by a smoothness parameter alpha, we rediscuss the constraints on the cosmic parameters based on type Ia supernovae (SNe Ia) and gamma-ray bursts (GRBs) data. The present analysis is restricted to a flat Lambda CDM model with the reasonable assumption that Lambda does not clump. A chi(2) analysis using 557 SNe Ia data from the Union2 compilation data (R. Amanullah et al., Astrophys. J. 716, 712 (2010).) constrains the pair of parameters (Omega(m), alpha) to Omega(m) = 0.27(-0.03)(+0.08) (2 sigma) and alpha >= 0.25. A similar analysis based only on 59 Hymnium GRBs (H. Wei, J. Cosmol. Astropart. Phys. 08 (2010) 020.) constrains the matter density parameter to be Omega(m) = 0.35(-0.24)(+0.62) (2 sigma) while all values for the smoothness parameter are allowed. By performing a joint analysis, it is found that Omega(m) = 0.27(-0.06)(+0.06) and alpha >= 0.52. As a general result, although considering that current GRB data alone cannot constrain the smoothness alpha parameter, our analysis provides an interesting cosmological probe for dark energy even in the presence of inhomogeneities.

Advanced CMOS Interfaces for Bio-Nanosensors

The improvement of devices provided by Nanotechnology has put forward new classes of sensors, called bio-nanosensors, which are very promising for the detection of biochemical molecules in a large variety of applications. Their use in lab-on-a-chip could gives rise to new opportunities in many fields, from health-care and bio-warfare to environmental and high-throughput screening for pharmaceutical industry. Bio-nanosensors have great advantages in terms of cost, performance, and parallelization. Indeed, they require very low quantities of reagents and improve the overall signal-to-noise-ratio due to increase of binding signal variations vs. area and reduction of stray capacitances. Additionally, they give rise to new challenges, such as the need to design high-performance low-noise integrated electronic interfaces. This thesis is related to the design of high-performance advanced CMOS interfaces for electrochemical bio-nanosensors. The main focus of the thesis is: 1) critical analysis of noise in sensing interfaces, 2) devising new techniques for noise reduction in discrete-time approaches, 3) developing new architectures for low-noise, low-power sensing interfaces. The manuscript reports a multi-project activity focusing on low-noise design and presents two developed integrated circuits (ICs) as examples of advanced CMOS interfaces for bio-nanosensors. The first project concerns low-noise current-sensing interface for DC and transient measurements of electrophysiological signals. The focus of this research activity is on the noise optimization of the electronic interface. A new noise reduction technique has been developed so as to realize an integrated CMOS interfaces with performance comparable with state-of-the-art instrumentations. The second project intends to realize a stand-alone, high-accuracy electrochemical impedance spectroscopy interface. The system is tailored for conductivity-temperature-depth sensors in environmental applications, as well as for bio-nanosensors. It is based on a band-pass delta-sigma technique and combines low-noise performance with low-power requirements.

Implementation of a VLSI amplifier interfaced with biomedical sensors for ultra wide band data transmission

This thesis presents a CMOS Amplifier with High Common Mode rejection designed in UMC 130nm technology. The goal is to achieve a high amplification factor for a wide range of biological signals (with frequencies in the range of 10Hz-1KHz) and to reject the common-mode noise signal. It is here presented a Data Acquisition System, composed of a Delta-Sigma-like Modulator and an antenna, that is the core of a portable low-complexity radio system; the amplifier is designed in order to interface the data acquisition system with a sensor that acquires the electrical signal. The Modulator asynchronously acquires and samples human muscle activity, by sending a Quasi-Digital pattern that encodes the acquired signal. There is only a minor loss of information translating the muscle activity using this pattern, compared to an encoding technique which uses astandard digital signal via Impulse-Radio Ultra-Wide Band (IR-UWB). The biological signals, needed for Electromyographic analysis, have an amplitude of 10-100μV and need to be highly amplified and separated from the overwhelming 50mV common mode noise signal. Various tests of the firmness of the concept are presented, as well the proof that the design works even with different sensors, such as Radiation measurement for Dosimetry studies.

Sensore e interfacce per la misura di conducibilita con impedenza elettrica

Gli oceani coprono quasi il 75% della superficie della terra ed esercitano una grande influenza sulla vita di tutte le specie viventi e sull’evoluzione del clima a livello planetario. I repentini cambiamenti climatici hanno reso sempre piú importante studiarne i comportamenti. L’analisi della salinitá degli oceani é estremamente importante per gli studi sull’ambiente marino; puó essere usata per tracciare le masse d’acqua, descrivendone i flussi e svelandone la correlazione con i processi climatici, puó essere di aiuto ai biologi per studiare gli organismi marini e costituisce un parametro fondamentale per una vasta gamma di sensori. Un sistema autonomo che misuri conducibilitá e temperatura é il primo strumento per determinare la salinitá dell’acqua, sul mercato sono presenti sí numerosi sensori a elevata accuratezza ma necessitano di ingombranti strumenti di laboratorio per funzionare. Sistemi di ridotte dimensioni non sono invece altrettanto accurati ed affidabili. Questa tesi mira a sviluppare un'interfaccia che permetta di analizzare conducibilitá e temperatura con un elevato livello di accuratezza. Particolare attenzione sará posta all’elaborazione delle misure effettuate e alla caratterizzazione degli errori e dell’accuratezza del sistema. Partendo da queste basi in futuro si potrá creare un sistema autonomo a bassissima potenza, alimentato da batterie, che, basandosi sull’iterazione fra il chip impedenziometrico e il PIC, permetta di fare misure per un ciclo di vita di qualche anno.

Development of a sensorimotor algorithm able to deal with unforeseen pushes and its implementation based on VHDL

Development of a Sensorimotor Algorithm Able to Deal with Unforeseen Pushes and Its Implementation Based on VHDL is the title of my thesis which concludes my Bachelor Degree in the Escuela Técnica Superior de Ingeniería y Sistemas de Telecomunicación of the Universidad Politécnica de Madrid. It encloses the overall work I did in the Neurorobotics Research Laboratory from the Beuth Hochschule für Technik Berlin during my ERASMUS year in 2015. This thesis is focused on the field of robotics, specifically an electronic circuit called Cognitive Sensorimotor Loop (CSL) and its control algorithm based on VHDL hardware description language. The reason that makes the CSL special resides in its ability to operate a motor both as a sensor and an actuator. This way, it is possible to achieve a balanced position in any of the robot joints (e.g. the robot manages to stand) without needing any conventional sensor. In other words, the back electromotive force (EMF) induced by the motor coils is measured and the control algorithm responds depending on its magnitude. The CSL circuit contains mainly an analog-to-digital converter (ADC) and a driver. The ADC consists on a delta-sigma modulation which generates a series of bits with a certain percentage of 1's and 0's, proportional to the back EMF. The control algorithm, running in a FPGA, processes the bit frame and outputs a signal for the driver. This driver, which has an H bridge topology, gives the motor the ability to rotate in both directions while it's supplied with the power needed. The objective of this thesis is to document the experiments and overall work done on push ignoring contractive sensorimotor algorithms, meaning sensorimotor algorithms that ignore large magnitude forces (compared to gravity) applied in a short time interval on a pendulum system. This main objective is divided in two sub-objectives: (1) developing a system based on parameterized thresholds and (2) developing a system based on a push bypassing filter. System (1) contains a module that outputs a signal which blocks the main Sensorimotor algorithm when a push is detected. This module has several different parameters as inputs e.g. the back EMF increment to consider a force as a push or the time interval between samples. System (2) consists on a low-pass Infinite Impulse Response digital filter. It cuts any frequency considered faster than a certain push oscillation. This filter required an intensive study on how to implement some functions and data types (fixed or floating point data) not supported by standard VHDL packages. Once this was achieved, the next challenge was to simplify the solution as much as possible, without using non-official user made packages. Both systems behaved with a series of interesting advantages and disadvantages for the elaboration of the document. Stability, reaction time, simplicity or computational load are one of the many factors to be studied in the designed systems. RESUMEN. Development of a Sensorimotor Algorithm Able to Deal with Unforeseen Pushes and Its Implementation Based on VHDL es un Proyecto de Fin de Grado (PFG) que concluye mis estudios en la Escuela Técnica Superior de Ingeniería y Sistemas de Telecomunicación de la Universidad Politécnica de Madrid. En él se documenta el trabajo de investigación que realicé en el Neurorobotics Research Laboratory de la Beuth Hochschule für Technik Berlin durante el año 2015 mediante el programa de intercambio ERASMUS. Este PFG se centra en el campo de la robótica y en concreto en un circuito electrónico llamado Cognitive Sensorimotor Loop (CSL) y su algoritmo de control basado en lenguaje de modelado hardware VHDL. La particularidad del CSL reside en que se consigue que un motor haga las veces tanto de sensor como de actuador. De esta manera es posible que las articulaciones de un robot alcancen una posición de equilibrio (p.ej. el robot se coloca erguido) sin la necesidad de sensores en el sentido estricto de la palabra. Es decir, se mide la propia fuerza electromotriz (FEM) inducida sobre el motor y el algoritmo responde de acuerdo a su magnitud. El circuito CSL se compone de un convertidor analógico-digital (ADC) y un driver. El ADC consiste en un modulador sigma-delta, que genera una serie de bits con un porcentaje de 1's y 0's determinado, en proporción a la magnitud de la FEM inducida. El algoritmo de control, que se ejecuta en una FPGA, procesa esta cadena de bits y genera una señal para el driver. El driver, que posee una topología en puente H, provee al motor de la potencia necesaria y le otorga la capacidad de rotar en cualquiera de las dos direcciones. El objetivo de este PFG es documentar los experimentos y en general el trabajo realizado en algoritmos Sensorimotor que puedan ignorar fuerzas de gran magnitud (en comparación con la gravedad) y aplicadas en una corta ventana de tiempo. En otras palabras, ignorar empujones conservando el comportamiento original frente a la gravedad. Para ello se han desarrollado dos sistemas: uno basado en umbrales parametrizados (1) y otro basado en un filtro de corte ajustable (2). El sistema (1) contiene un módulo que, en el caso de detectar un empujón, genera una señal que bloquea el algoritmo Sensorimotor. Este módulo recibe diferentes parámetros como el incremento necesario de la FEM para que se considere un empujón o la ventana de tiempo para que se considere la existencia de un empujón. El sistema (2) consiste en un filtro digital paso-bajo de respuesta infinita que corta cualquier variación que considere un empujón. Para crear este filtro se requirió un estudio sobre como implementar ciertas funciones y tipos de datos (coma fija o flotante) no soportados por las librerías básicas de VHDL. Tras esto, el objetivo fue simplificar al máximo la solución del problema, sin utilizar paquetes de librerías añadidos. En ambos sistemas aparecen una serie de ventajas e inconvenientes de interés para el documento. La estabilidad, el tiempo de reacción, la simplicidad o la carga computacional son algunas de las muchos factores a estudiar en los sistemas diseñados. Para concluir, también han sido documentadas algunas incorporaciones a los sistemas: una interfaz visual en VGA, un módulo que compensa el offset del ADC o la implementación de una batería de faders MIDI entre otras.

Assembly of functional Escherichia coli RNA polymerase containing beta subunit fragments.

The Escherichia coli rpoB gene, which codes for the 1342-residue beta subunit of RNA polymerase (RNAP), contains two dispensable regions centered around codons 300 and 1000. To test whether these regions demarcate domains of the RNAP beta subunit, fragments encoded by segments of rpoB flanking the dispensable regions were individually overexpressed and purified. We show that these beta-subunit polypeptide fragments, when added with purified recombinant beta', sigma, and alpha subunits of RNAP, reconstitute a functional enzyme in vitro. These results demonstrate that the beta subunit is composed of at least three distinct domains and open another avenue for in vitro studies of RNAP assembly and structure.

Arguments prepared by Daniel Appleton White for meetings of Phi Beta Kappa, 1796-1797

Three handwritten arguments prepared by Phi Beta Kappa member Daniel Appleton White (1776-1861; Harvard AB 1797) for discussion at meetings of the Alpha chapter at Harvard University in 1796 and 1797. The documents consist of a small paper notebook with a response to the prompt, "Whether the deeper studies, such as metaphysics, mathematics & natural philosophy, are entitled to our chief attention?" dated September 27, 1796, and prepared for debate with classmate Isaac Wellington (died 1797); a one-leaf document with a disputation on, "Whether civilized nations have a right to drive uncivilized nations from the lands they occupy?" dated December 8, 1796; and a small paper notebook containing White’s argument to the prompt, "Would a national university be beneficial for America?" that he debated with John Collins Warren (1778-1856; Harvard AB 1797) during the chapter’s May 16, 1797, meeting.

An oration, 1790

This small paper notebook contains a twenty-one-page handwritten oration on learned societies delivered by Phi Beta Kappa member Thaddeus Mason Harris (1768-1842; Harvard AB 1787) during the anniversary meeting of the Alpha Chapter at Harvard University on September 1, 1790. The oration is followed by five pages of "notes and illustrations" on the text.

An oration delivered at the request of the PBK society, at Cambridge. 1790

This small paper notebook contains a sixteen-page handwritten copy of an oration on "amiable and useful virtues" delivered by Phi Beta Kappa member Thomas W. Hooper (1771-1816; Harvard AB 1789) during the anniversary meeting of the Alpha Chapter at Harvard University on September 1, 1790.

Directory of film evaluations for teachers of business subjects.

Mode of access: Internet.

Hazel Losh in office with student

Professor of astronomy at the University of Michigan, friend of the University's athletes and athletics, and officer of Phi Beta Kappa, Alpha Chapter. Image from a scrapbook page