Danielle Sapse and Nicholas D. K. Petraco
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Danielle Sapse and Nicholas D. K. Petraco John Jay College of Criminal Justice City University of New York. What Quantum Chemistry Can Do for Forensic Science. Amino Acid Alanine Reactivity with the Fingerprint Reagent Ninhydrin. H = E. Outline.

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What quantum chemistry can do for forensic science

Danielle Sapse and Nicholas D. K. Petraco

John Jay College of Criminal Justice

City University of New York

What Quantum Chemistry Can Do for Forensic Science

Amino Acid Alanine Reactivity with the Fingerprint

Reagent Ninhydrin.

H=E


Outline

Outline

  • How a Quantum Chemist can Help Forensic Science

  • History and Trivia on Fingerprints

  • Ninhydrin + Alanine Gives Ruhemann’s Purple

  • Results

  • Future Applications for Forensic Science

    • More fingerprints

    • Explosives detection

    • Probes for illegal drugs


Forensic science quantum chemistry a potential synergy

Forensic Science – Quantum Chemistry A Potential Synergy

  • Opportunity to improve communication between theorists and (bio) analytical chemists and biologists

  • Computer speed always improving and big molecular systems can be treated

  • Theory can't replace the lab but can help!


What can we learn from y

What Can We Learn From Y?

  • Energy and Structures of Molecules

    • Molecular orbitals and relative energetics to help understand reactivity

    • Structures help us understand reactivity and design useful molecules such as materials, drugs and probes

  • Electronic Spectra

  • Vibrational, Rotational Spectra

  • NMR and ESR Spectra

  • Thermodynamic data from Statistical-Mechanics


What quantum chemistry can do for forensic science

A Forensic Science Classic: Fingerprints!

  • Palm prints used for human identification in courts perhaps as early as 1st century Roman Empire

  • 7th century China, was perhaps the first documented use of fingerprints as means of identification.

  • It was probably Faulds (1880) who first proposed exploiting fingerprints for criminalistics in modern times.

  • As a means of identification, fingerprints are still par excellence.1


Fingerprint amplification

Fluorescence, Phosphorescence

I.S.C.

Singlet

Exc. State

Triplet

Exc. State

Fluorescence

Energy

Phosphorescence

Laser

Closed Shell Ground State

Fingerprint Amplification

  • Latent prints, only trace amounts of biomaterial

    • Very hard or impossible to see by themselves.

    • Solution: Use some kind of developing agent.


What quantum chemistry can do for forensic science

Menzel et al.

After

Fingerprint Amplification

  • Fingerprint fluorescence is faint

    • Treat fingerprint with materials to obtain fluorescent or phosphorescent compounds

Menzel et al.

Before


What quantum chemistry can do for forensic science

ninhydrin

Ruhemann’s purple

Ninhydrin-Ruhemann’s Purple System

  • Ninhydrin first suggested to develop latent fingerprints in 1950’s.

  • Ninhydrin reacts with amino acids in fingerprints to produce Ruhemann's purple

    • Brightly colored and easy to identify by eye

    • Fluoresces slightly at the 582 nm and 407 nm when treated with a zinc or cadmium salts

    • Starting material, ninhydrin, is cheap


Motivation

Motivation

  • Synthesize new compounds with properties superior to Ruhemann's purple.

  • No known chemical system which offers significant advantages in color to Ruhemann’s purple.

    • Ultimately we want to help improve chromogenic and fluorogenic properties

  • An unequivocal understanding of the mechanism of formation for Ruhemann’s purple is important!

    • The mechanism for the reaction between amino-acids and ninhydrin was never fully settled.

      • McCaldin Mechanism

      • Lamothe Mechanism

      • Friedman Mechanism

  • We have attempted to understand these mechanisms using ab-inito computations.


Computational methods

Computational Methods

  • Structures of all molecules in McCaldin, Lamothe and Friedman mechanisms optimized at RHF-SCF level using a 6-31G* basis set and analytic derivative methods.

    • Gradients optimized to > 0.0001 a.u.

    • Largest Abelian point groups used

  • Harmonic vibrational frequencies computed for all structures using finite difference of analytic gradients.

    • All computed structures found to be energetic minima

  • Benchmark structures for ninhydrin, alanine and Ruhemann’s Purple were found using DFT B3LYP and a 6-31G**.


What quantum chemistry can do for forensic science

DFT Benchmark Structures

Ruhemann’s Purple

ninhydrin


What quantum chemistry can do for forensic science

CO2

Strecker degradation intermediate

Strecker degradation

ninhydrin + a-amino acid

aldehyde

dehydration

and hydrolysis

hydrindantin and possible side products

several intermediates

Ruhemann’s Purple

General Scheme for the Reaction of Ninhydrin with a-amino acids to form Ruhemann’s Purple


What quantum chemistry can do for forensic science

Our postulated mechanism at 25oC


What quantum chemistry can do for forensic science

New HF-6-31G** Results on Substituted Ninhydrin-Ruhemann’s Purple Systems


Forensic science quantum chemistry

Forensic Science – Quantum Chemistry

  • Future Projects

    • Compute low lying excited electronic and vibrational states to predict fluorescent/ phosphorescent ability

      • Tailor molecules to cheap portable lasers!

        • Ruhemann's Purple-Transition Metal-Halide

        • Explore substituted ninhydrines

        • Derivatives of indanediones

        • Quantum Dots!

          • Clusters of Atoms

          • Exotic quantum properties

          • Phosphoresce well


Forensic science quantum chemistry1

Forensic Science – Quantum Chemistry

  • Explosives Detection

    • Live in an age of terrorism

    • Many articles to examine

    • Ideally testing must be

      • Fast and user friendly

      • Portable

      • Safe and reliable

    • Lanthanide complexes

      • Have been useful for finger prints

      • Phosphoresce well

      • Coordinate well with explosives

      • Quantum Dots


Forensic science quantum chemistry2

Forensic Science – Quantum Chemistry

  • Quantum Chemistry can help with design

    • Metal and Ligand excited states

    • Determine efficiency of metal-ligand energy transfer process

    • Indicate ligand structures to prevent binding of unwanted species

  • Metal-Ligand possibilities

    • Europium, Terbium

    • Derivatives of thenoyiltrifloroacetone and othrophanthrolene

    • Quantum dots

      • CdS, CdSe, GaAs, InAs


Forensic science quantum chemistry3

Forensic Science – Quantum Chemistry

N

N

CF3

S

O

O

thenoyiltrifloroacetone

othrophanthrolene


Forensic science quantum chemistry4

Forensic Science – Quantum Chemistry

  • Molecular Sensors

    • Miniaturization to the molecular level

    • Improve selectivity and detection limits

    • Widen range of detectable analytes

    • Sensor modeling allows optimization of response properties to analyte

      • Important factors

        • Molecular topology

        • Binding site geometry

        • Binding and stabilizing interactions

      • Few probes for illegal drugs, yet many binding sites


Forensic science quantum chemistry5

Forensic Science – Quantum Chemistry

  • Molecular Sensors for canabinols and amphetamines

    • Species are of reasonable size

NH

OH

O

R

O

C5H11

O

Canabinol

3,4-Methylenedioxymethamph.


Forensic science quantum chemistry6

Forensic Science – Quantum Chemistry

R

R

  • Ferrocene based barbiturate sensors

N

O

N

O

HN

HN

R

Fe

N

O

HN

R

Fe

O

N

HN


Acknowledgments

Acknowledgments

  • John Jay College of Criminal Justice

  • Our co-authors:

    • Prof. Anne-Marie Sapse

    • Prof. Gloria Proni

    • Jennifer Jackiw

  • Our collaborators and colleagues:

    • Prof. Thomas Kubic

    • Chris Chen

    • Chris Barden

    • Prof. Jon Riensrta-Kiracofe

    • Detective Nicholas Petraco (NYPD ret.)

    • Officer Patrick McLaughlin (NYPD)


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