Hacking NMRShiftDB

Posted by Rich Apodaca Mon, 04 Sep 2006 17:28:00 GMT

NMRShiftDB is an open web database of peer-reviewed NMR chemical shifts compiled by volunteers. As of this writing, it contains 22,429 measured spectra from 18,986 structures, and reports 927 registered users. The database code itself is open source.

Although NMRShiftDB has a web interface, its architecture is designed to simplify writing programs that use it. A previous article showed how a working PubChem API could be written with just a few lines of Ruby. This time, I'll show how the same thing can be done for NMRShiftDB.

Ingredients

This tutorial uses Arton's excellent Ruby Java Bridge, the installation and use of which has been previously discussed. Also used is Ruby's InChI interface, Rino, for which installation instructions are here.

Create a working directory called nmr. Into this directory, copy cdk-20060714.jar, which can be downloaded here.

Code

Create a file called nmr.rb containing the following Ruby code:

require 'net/http'
require 'smi2inchi'

# A very simple NMRShiftDB Web API.
class NMRFetcher

  # Creates a <tt>Translator</tt> instance.
  def initialize
    @translator = Translator.new
  end

  # Returns an XML record, as a string, for the molecule
  # with SMILES matching <tt>smiles</tt> and spectrum type
  # matching <tt>spectrumtype</tt> (13C, 1H, 15N and 31P).
  def get_record(smiles, spectrumtype)
    body = nil
    inchi = (smi2inchi(smiles)).gsub('InChI=', 'inchi=')
    path = '/NmrshiftdbServlet?nmrshiftdbaction=exportcmlbyinchi&' + inchi + '&spectrumtype=' + spectrumtype

    Net::HTTP.start('nmrshiftdb.ice.mpg.de') do |http|
      response = http.get(path)
      body = response.body
    end

    if !valid_record?(body)
      return nil
    end

    body
  end

private

  def valid_record?(body)
    !body.eql?('No such molecule or spectrum')
  end

  def smi2inchi(smiles)
    @translator.translate(smiles)
  end
end

The magic in the above code is nothing more than a simple HTTP request sent to nmrshiftdb.ice.mpg.de, contained in the get_record method. This request encodes an InChI identifier, which is generated from the SMILES string passed as an argument. We also specify a spectrum type.

Now create a file called smi2inchi.rb, containing the following Ruby code:

ENV['CLASSPATH'] = './cdk-20060714.jar'
require 'rubygems'
require_gem 'rjb'
require_gem 'rino'
require 'rjb'

StringWriter = Rjb::import 'java.io.StringWriter'

SmilesParser = Rjb::import 'org.openscience.cdk.smiles.SmilesParser'
MDLWriter = Rjb::import 'org.openscience.cdk.io.MDLWriter'

# Converts a SMILES string into an InChI identifier using
# the CDK Library (Java) and the Rino Library (Ruby/C).
class Translator

  def initialize
    @smiles_parser = SmilesParser.new
    @mdl_writer = MDLWriter.new
    @mol2inchi = Rino::MolfileReader.new
  end

  # Returns an InChI identifier from the specified SMILES string.
  # Uses the CDK classes SmilesParser and MDLWriter to generate
  # a molfile from a SMILES string. Then this molfile is
  # parsed by Rino::MolfileReader.
  def translate(smiles)
    mol = @smiles_parser.parseSmiles(smiles)

    sw = StringWriter.new

    @mdl_writer.setWriter(sw)
    @mdl_writer.write(mol)

    @mol2inchi.read(sw.toString)
  end
end

The description and use of this code was discussed in a recent article on generating InChI identifiers from SMILES strings.

Before using the code we've just created you'll need to set the LD_LIBRARY_PATH (or equivalent) to point to the native Java libraries. On Linux with Sun's JDK, this is done from the command line with:

$ export LD_LIBRARY_PATH=$JAVA_HOME/jre/lib/i386:$LD_LIBRARY_PATH

Using the NMRFetcher class is just a matter of creating an instance, and invoking get_record with the desired SMILES string and spectrum type (1H, 13C). Doing so returns a CML document containing the structure of the compound and its spectrum. If no record matches, the method returns nil. The code below give an example in which the CML output is pretty-printed using the wonderful Ruby API for XML, REXML:

require "rexml/document"
require 'nmr'

nmr = NMRFetcher.new
smiles = 'c1ccccc1' #benzene, to keep things simple
type = '13C'
record = nmr.get_record(smiles, type)

if record #pretty-print the CML record using REXML
  file = File.new('result.xml', 'w')

  (REXML::Document.new(record)).write(file, 0)

  file.close
else #write an error
  File.open('result.error', 'w') do |file|
    file << 'No record of SMILES: ' + smiles
  end
end
The above code can be put into a file (test.rb) and run: 
$ ruby test.rb

Alternatively, it can be entered interactively and played with using irb:

$ irb
irb(main):001:0>

Output

The program produces the following Chemical Markup Language output in a file called result.xml:

<cml>
  <molecule title='Benzene' id='nmrshiftdb7901' xmlns='http://www.xml-cml.org/schema/cml2/core'>
    <atomArray xmlns='http://www.xml-cml.org/schema'>
      <atom elementType='C' y2='0.7625' x2='-1.4063' id='a1' formalCharge='0' hydrogenCount='0'/>
      <atom elementType='C' y2='0.35' x2='-2.1207' id='a2' formalCharge='0' hydrogenCount='0'/>
      <atom elementType='C' y2='-0.475' x2='-2.1207' id='a3' formalCharge='0' hydrogenCount='0'/>
      <atom elementType='C' y2='-0.8875' x2='-1.4063' id='a4' formalCharge='0' hydrogenCount='0'/>
      <atom elementType='C' y2='-0.475' x2='-0.6918' id='a5' formalCharge='0' hydrogenCount='0'/>
      <atom elementType='C' y2='0.35' x2='-0.6918' id='a6' formalCharge='0' hydrogenCount='0'/>
    </atomArray>
    <bondArray xmlns='http://www.xml-cml.org/schema'>
      <bond atomRefs2='a1 a2' order='S' id='b1'/>
      <bond atomRefs2='a2 a3' order='D' id='b2'/>
      <bond atomRefs2='a3 a4' order='S' id='b3'/>
      <bond atomRefs2='a4 a5' order='D' id='b4'/>
      <bond atomRefs2='a5 a6' order='S' id='b5'/>
      <bond atomRefs2='a1 a6' order='D' id='b6'/>
    </bondArray>
  </molecule>
  <spectrum moleculeRef='nmrshiftdb7901' xmlns:cml='http://www.xml-cml.org/dict/cml' xmlns:cmlDict='http://www.xml-cml.org/dict/cmlDict' xmlns:siUnits='http://www.xml-cml.org/units/siUnits' type='NMR' xmlns:macie='http://www.xml-cml.org/dict/macie' xmlns:units='http://www.xml-cml.org/units/units' id='nmrshiftdb15502' xmlns:subst='http://www.xml-cml.org/dict/substDict' xmlns:nmr='http://www.nmrshiftdb.org/dict' xmlns='http://www.xml-cml.org/schema/cml2/spect'>
    <conditionList xmlns='http://www.xml-cml.org/schema'>
      <scalar dataType='xsd:string' units='siUnits:k' dictRef='cml:temp'>298</scalar>
      <scalar dataType='xsd:string' units='siUnits:hertz' dictRef='cml:field'>Unreported</scalar>
    </conditionList>
    <metadataList xmlns='http://www.xml-cml.org/schema'>
      <metadata name='nmr:OBSERVENUCLEUS' content='13C'/>
    </metadataList>
    <peakList xmlns='http://www.xml-cml.org/schema'>
      <peak xUnits='units:ppm' peakShape='sharp' xValue='128.5' id='p0' atomRefs='a1 a2 a3 a4 a5 a6'/>
    </peakList>
  </spectrum>
</cml>

The kind of output produced by NMRFetcher and NMRShiftDB could be used in a variety of ways. Notice, near the bottom of the document, how peak assignments are made relative the the atom labels in the molecule declaration. It should be possible, for example, to create interactive 2-D structure diagrams from this document in which a user mouses over an atom and gets a C-13 chemical shift.

NMRShiftDB is a valuable and free online resource for NMR spectroscopy. Programatically mixing its capabilities with free software and other online services offers numerous opportunities to build innovative chemical informatics systems.

Hacking PubChem with Ruby

Posted by Rich Apodaca Wed, 30 Aug 2006 06:29:00 GMT

PubChem is an increasingly popular, free-access, online molecular database operated by the National Institutes of Health. Web services are a hot topic, with sites such as Flickr, Google, and eBay offering developers the tools to build rich content through "mashups" of several web APIs. Although there is no formal PubChem API, it's possible to roll your own. As a demonstration, this article will show how structural information can be retrieved from PubChem using some simple Ruby code. The inspiration for this article came from the PubChem module that is part of Chemruby.

The only thing you'll need for this tutorial is Ruby, preferably version 1.8.2 or higher. Create a directory called pubchem and make it your working directory. Then create a file called pubchem.rb containing the following code:

require 'net/http'

# A very simple PubChem Web API.
class PubChem

  # Returns a molfile (as a String) for the molecule with PubChem
  # CID matching compound_id.
  def self.get_molfile(compound_id)
    molfile = nil
    path = '/summary/summary.cgi?cid=' + compound_id + '&disopt=DisplaySDF'

    Net::HTTP.start('pubchem.ncbi.nlm.nih.gov') do |http|
      response = http.get(path)
      molfile = response.body
    end

    molfile
  end

  # Writes a PNG image, for the molecule with PubChem
  # CID matching compound_id, to the file specified by filename.
  def self.write_image(compound_id, filename)
    path = '/image/imgsrv.fcgi?t=l&cid=' + compound_id

    Net::HTTP.start('pubchem.ncbi.nlm.nih.gov') do |http|
      response = http.get(path)
      image = response.body

      File.open(filename, "w") do |file|
        file << image
      end
    end
  end
end
PubChem references each of its compounds by a unique integer identifier, the PubChem CID. This is very handy because retrieving PubChem resources is as simple as encoding a URL containing the CID of interest. The class above illustrates how this system can be used to get a molfile and write a PNG image using just a few lines of Ruby. Using the PubChem class is simplicity itself. To get the molfile for Levonorgestrel (Plan B), which has the CID 13109: 
require 'pubchem'

molfile = PubChem::get_molfile('13109') #=> returns the molfile for Levonorgestrel as a String
To write the 2-D structure diagram of Levonorgestrel as a PNG: 
require 'pubchem'

PubChem::write_png('13109', 'image.png') #=> writes a PNG image of Levonorgestrel
This code saves the image below to your working directory as image.png.
The above two code fragments can either be saved as a file and executed by the Ruby interpreter: 
$ ruby filename.rb

or it they be entered interactively in your console with irb:

$ irb
irb(main):001:0>

As you can see, there's not much to building a PubChem API in Ruby. The same principles discussed here should apply in any programming language. Future articles in this series will show how to build more complex PubChem APIs and integrate them with other software packages and web services.

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