Apparatus for investigating fast chemical reactions by optical detection

• US 4,076,420 A
• Filed: 08/19/1974
• Issued: 02/28/1978
• Est. Priority Date: 02/22/1974
• Status: Expired due to Term

• Current Assignee: Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften e.V. (Max-Planck-Gesellschaft zur Frderung der Wissenschaften e)
• Original Assignee: Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften e.V. (Max-Planck-Gesellschaft zur Frderung der Wissenschaften e)
• Inventors: Rigler, Rudolf, Lehrach, Hans, Riesner, Detlev, Jovin, Thomas M., De Maeyer, Leo C. M., Veil, Lutz Bodo, Rabl, Carl-Roland
• Primary Examiner(s): McGraw, Vincent P.
• Application Number:
  US05/498,816
• Time in Patent Office: 1,289 Days
• Field of Search: 356/72, 356/73, 356/75, 356/85, 356/86, 356/87, 356/96, 356/244, 356/246, 356/103, 356/114, 23/253 R
• US Class Current: 356/73
• CPC Class Codes: G01N 21/253 for batch operation, i.e. multisample apparatus analytical automats G01N35/00
• CPC Class Codes: G01N 21/272 for following a reaction, e.g. for determining photometrically a reaction rate (photometric cinetic analysis)

Abstract

A reaction kinetics measuring system which provides for the application of great variety of reaction initiating methods, as temperature or pressure or electrical field jump methods, mixing methods, flash photolysis method, and combinations of said methods, and for various optical detection methods, as absorption or fluorescence or scattered light or polarized light detection methods. The system features quickly and easily interchangeable optical elements in a number of optical paths, and a multitude of selectively usable measuring cells to adapt the system to the reaction initiating and detection methods used so that reliable and exactly reproducible results are obtained, which are comparable even if obtained under widely differing conditions.

Claims

1. Apparatus for investigating fast chemical reactions by optical detection, said reactions being initiated in a chemical system by an external perturbation, said apparatus comprising means for performing said external perturbation, at least one light path, means for supporting a sample cell in said light path, said sample cell forming a cell chamber for holding a liquid sample of said chemical system, at leat one photodetector, said light path comprising a light source, a monochromator, means for imaging said light source onto the entrance of said monochromator, and means for imaging the exit of said monochromator onto said sample cell chamber, said apparatus comprising also means for directing light from said liquid sample onto said photodetector, the improvement comprising:

(a) a set of at least two different types of sample cells, each of said types having one different means for application of at least one parameter of perturbation, said means comprising;

(a.1) two electrodes facing opposite sides of said chamber for temperature-jump and field-jump perturbation,

(a.2) a pressure autoclave and pressure release means for pressure-jump perturbation,

(a.3) at least one optical window in an auxiliary light path for flash-light perturbation,

(a.4) a mixing chamber and flow-channels for rapid mixing, and

(a.5) two electrodes, a mixing chamber, and flow-channels for combined rapid mixing and temperature-jump perturbation;

each of said sample cells having a specific sample volume at least two optical windows for application of at least one of the following parameters of observation;

optical absorption, fluorescence, scattered light, and parameters of polarization, said sample cells having identical exterior dimensions at least in their middle parts and an identical position of their main optical axis with respect to said exterior dimensions;

(b) at least two different ones of the following perturbation supply means;

(b.1) a high-voltage pulse source,

(b.2) a pressure supply,

(b.3) a flash-light source, and

(b.4) a stopped-flow drive system;

(c) a metallic sample cell holder mating said sample cells and holding one selected sample cell operatively inserted into said apparatus, said holder comprising;

(c.1) a hollow structure having a main axis, enclosing said selected sample cell in close mechanical and thermal contact,

(c.2) threaded fixation means for clamping said sample cell therein,

(c.3) thermostatting channels connected to a liquid thermostatting system,

(c.4) window openings for passing said light path in a direction perpendicular to the main axis of said hollow structure, and

(c.5) means for connecting a high-voltage pulse source at one end of said hollow structure; and

(d) a set of changeable optical elements adapting said light path to the optical dimensions of the chamber of said selected sample cell, said elements comprising at least one lens mounted in an axially adjustable holder and at least one diaphragm modifying the free exit aperture of said monochromator.

2. Apparatus according to claim 1, provided with a first and a second light path, said light source and said monochromator being in said first light path, said second light path serving as a secondary light path for fluorescence and scattered light measurements, both light paths crossing in said cell holder and said cell chamber at right angles in a plane vertical to the main axis of said cylindrical structure, said sample cell having at least three optical windows, said second light path further comprising at least one photodetector, means for light filtering and means for directing light emitted from said liquid sample onto said photodetector.

3. Apparatus according to claim 1, provided with a collimating lens and a collecting lens between said monochromator and said cell holder, said lenses imaging said monochromator exit onto said cell chamber.

4. Apparatus according to claim 3, including an axially movable lens holder for mounting one of said lenses, a supporting device for said lens holder, and scales provided with wavelength and cell corrections.

5. Apparatus according to claim 4, further comprising a set of interchangeable collecting lenses, said lenses being used with said movable lens holder and having different focal lengths.

6. Apparatus according to claim 3, further comprising a polarizing prism between said collimating lens and said collecting lens, said prism being mounted in a rotatable prism holder, said holder giving preferred orientation angles and being removable from said light path.

7. Apparatus according to claim 6, provided with an axially movable combined prism and lens holder interchangeable with a single lens holder and a supporting device for said holders, said holders mounting said collecting lens.

8. Apparatus according to claim 6, wherein said prism holder is shaped as an irregular octogon, further comprising a supporting device mating three adjacent surfaces of said octogon, which give preferred orientation angles of the prism:

0°

, 35.3°

, 45°

, 54.7°

, and 90°

.

9. Apparatus according to claim 6, wherein the light beam between said collimating lens and said collecting lens is slightly convergent towards said collecting lens and said polarizing prism is placed close to the image of the monochromator aperture plane.

10. Apparatus according to claim 6, further comprising a depolarizer in front of said polarizing prism.

11. Apparatus according to claim 10, wherein said depolarizer is mounted on a swivel arm for quick insertation into said light path.

12. Apparatus according to claim 3, further comprising radiant field diaphragms (S₁, S₂) at both sides of said monochromator exit (S), said radiant field diaphragms limiting the lateral dimensions of said light path and being imaged onto the entrance aperture and the exit aperture of said sample cell, respectively.

13. Apparatus according to claim 12, wherein the distance of said lenses is approximately equal to the sum of the focal lengths of both lenses, said radiant field diaphragms being in symmetric positions to the monochromator exit and having equal sizes.

14. Apparatus according to claim 12, further comprising a set of interchangeable radiant field diaphragms and a mounting device holding said diaphragms, said device comprising:

a set of interchangeable plug-in tubes and a holder for said tubes, said holder fixed to the housing of said monochromator, each of said tubes mounting one individual pair of said diaphragms, said tubes and said holder having an oblong hole transvers to said light path and between said diaphragms, said hole passing an interchangeable slit diaphragm used as the monochromator exit slit, said holder further comprising means locking said slit diaphragm.

15. Apparatus according to claim 3, further comprising a beam splitter in said light path prior to said collecting lens, and a further collecting lens and a reference photodetector in the light path separated by said beam splitter.

16. Apparatus according to claim 15, wherein said beam splitter is formed by a thin plate of fused silica glass, said plate being coated by a raster structure of reflecting elements alternating with transmitting elements, said structure having a raster period between 0.1 and 1 millimeters and dividing the incoming light intensity between the light intensity passed to said cell holder and the separated light intensity passed to said reference photodetector by a ratio of 2:

1 to 4;

1.

17. Apparatus according to claim 15, wherein the photocathode of said reference photodetector has an oblong shape, the main axis of said photocathode being perpendicular to the axis of the lamp image at the monochromator exit, said further collecting lens being formed by a sphero-cylindrical lens structure and imaging the monochromator aperture plane in a direction parallel and said monochromator exit in a direction perpendicular to said main axis.

18. Apparatus according to claim 1, provided with a measuring photodetector in said light path following said sample cell and a collecting lens between said sample cell and said photodetector, the position of said collecting lens being adjustable in directions transverse to said light path.

19. Apparatus according to claim 18, wherein the photocathode of said measuring photodetector has an oblong shape, the main axis of said photocathode being perpendicular to the lamp image in said sample chamber, said collecting lens being formed by a sphero-cylindrical lens structure and imaging the monochromator aperture plane in a direction parallel and the monochromator exit in a direction perpendicular to said main axis.

20. Apparatus according to claim 1, further comprising an optical shutter in front of said monochromator.

21. Apparatus according to claim 15, further comprising an optical shutter in the light path between said beam splitter and said sample cell holder.

22. Apparatus according to claim 3, further comprising a filter holder between said collimating lens and said collecting lens.

23. Apparatus according to claim 18, further comprising a filter holder (HF2) between said sample cell and said measuring photodetector (D2).

24. Apparatus according to claim 15, wherein said beam splitter is placed between said collimating lens and said collecting lens, further comprising a changeable aperture diaphragm in front of said beam splitter, also comprising a changeable diaphragm for the exit slit of said monochromator.

25. Apparatus according to claim 1, further comprising changeable condensor optics with said light source which permit a different imaging of said light source onto said monochromator entrance, so that the light gathering powers of said monochromator and said sample cell can be arbitrarily fully exploited and partially exploited.

26. Apparatus according to claim 25, said condensor optics comprising a lens system imaging said light source onto said entrance, a radiant field diaphragm with said lens system, and a field lens with said entrance, said lens system comprising a first half facing said light source and a second half facing said entrance, further comprising at least two interchangeable lenses for said second half, said interchangeable lenses mounted in replaceable tubes and having a shorter and a larger focal length, respectively, wherein at least said lens of shorter focal length has its own radiant field diaphragm, said diaphragm facing said first half and having a smaller aperture than the aperture of said lens of larger focal length.

27. Apparatus according to claim 25, said condensor optics comprising at least two sets of lenses, said sets having different focal lengths and being mounted on a rotary device at different distances from said light source facing said light source, said rotary device comprising a revolving plate mounting said sets, an axis mounting said plate, a bearing holding said axis, and stops for alternatively switching said sets into said light path.

28. Apparatus according to claim 27, wherein said stops locate the sets on the plate in the respective light path.

29. Apparatus according to claim 1, further comprising a reversing prism for rotating the light bundle in said light path by 90°

around its axis.

30. Apparatus according to claim 29, said apparatus further comprising a condensor lens system imaging said light source onto said entrance, said lens system comprising a first half facing said light source and a second half facing said entrance, said light path being collimated between said halves, further comprising an Amici'"'"'s reversion prism between said halves, said prism being rotatable around its main axis and rotating the image of said light source onto said entrance by 90°

.

31. Apparatus according to claim 2, said sample cell having at least one light-collecting window in said second light path, said second light path further comprising with said window at least one light-collecting lens, a filter holder for holding spectral and polarimetric filters, and a photodetector, said light-collecting cell window having an inner surface that equals approximately the dimension of the inner cross section of said sample cell chamber, said light-collecting window and said light-collecting lens forming an optical system of very high light gathering power, said optical system directing the light emitted from said liquid sample through said filters onto said photodetector.

32. Apparatus according to claim 31, said sample cell further comprising two small-angle conical windows in said first light path, said light-collecting window being a wide-angle cone with a spherically ground outside, the conical angles of said windows extending outside.

33. Apparatus according to claim 31, wherein said light-collecting window is a solid light pipe shaped as a small-angle cone, the conical angle extending outside and being at least zero.

34. Apparatus according to claim 31, wherein said sample cell has four optical windows being arranged in one plane at right angles, said plane being perpendicular to the main axis of said cylindrical structure, said second light path extending in a symmetric arrangement at both sides of said cell holder.

35. Apparatus according to claim 31, wherein said sample cell has three optical windows and a spherical second-surface reflector opposite to said light collecting window, said windows and said reflector being arranged in one plane at right angles, said reflector imaging essentially the center of said sample cell onto itself.

36. Apparatus according to claim 31, wherein four sides of said cell chamber and said optical windows are formed by UV-transmitting glass plates, said plates being fused together by black intermediate layers.

37. Apparatus according to claim 36, further comprising convexly shaped lenses at the outside of said glass plates in said secondary light path.

38. Apparatus according to claim 31, wherein said light-collecting lenses are mounted in said cell holder at closest distance to the body of said sample cell, said lenses being mounted in threaded lens holders.

39. Apparatus according to claim 33, wherein said light-collecting lens is a double-lens system (LL3, LL4), said double-lens system being spaced from said light-collecting window (KL3;

KL4) at a distance which is approximately equal to the focal length of said double-lens system, said double-lens system being mounted in a threaded lens holder.

40. Apparatus according to claim 2, further comprising a concave mirror in said first light path behind said sample cell, mounted in a removable holder close to said cell holder.

41. Apparatus according to claim 31, wherein said filter holder is mounted on a revolving device, said revolving device providing a revolving angle of at least 90°

and comprising a stopping device which provides stops at least at angles which correspond to intensity ratios of vertically to horizontally polarized light of 1;

0, 1;

2, and 0;

1.

42. Apparatus according to claim 41, further comprising a sample cell compartment, said revolving device comprising a hollow bearing with a rotor and a stator, said stator having an undercut collar into which a collar of said rotor fits, said collar of said stator having a gap, said gap passing a lever fixed to said rotor, said rotor and stator being mounted onto the outside of the wall of said sample cell compartment and extending inside through a hole in said wall, said rotor mounting said stopping device and said filter holder inside said compartment, thereby providing a light-tight rotary movement of said holder actuated from the outside by said lever.

43. Apparatus according to claim 1, having a first and a second monochromatic light path, both light paths comprising a light source, a monochromator and means for imaging said light source onto said monochromator and further imaging onto said sample cell chamber, said light paths transmitting said sample cell chamber, said apparatus further comprising at least one measuring photodetector with each of said light paths, and means for directing light from said liquid sample onto said photodetectors.

44. Apparatus according to claim 43, further comprising individual beam splitters and reference photodetectors with both light paths.

45. Apparatus according to claim 43, wherein both light paths have a common light source, common condensor optics, and a common monochromator, said monochromator having one input slit and a first and a second exit slit, said first slit being in fixed position and imaged onto said cell chamber, said second exit slit being in adjustable position with respect to said first exit slit, said second exit being provided with a flexible light pipe the exit of which is imaged onto said cell chamber.

46. Apparatus according to claim 45, said flexible light pipe having a rectangular entrance and a round exit.

47. Apparatus according to claim 43, said sample cell having four windows and said second light path crossing said first light path at right angle.

48. Apparatus according to claim 43, said two light paths being superimposed to each other by dichroic mirrors (TF, TF'"'"') and transmitted through said sample cell in parallel directions, said two light paths being again separated by dichroic mirrors (TF, TF'"'"') transmitted through spectral filters (F2, F2'"'"') and directed onto said individual measuring photodetectors measuring absorption (D2, D2'"'"').

49. Apparatus according to claim 48, said two light paths transmitting said sample cell in opposite directions, and said dichroic mirrors serving also as reference beam splitters.

50. Apparatus according to claim 49, said two light paths transmitting said sample cell in equal directions and originating from the same light source via different condensor systems, said second monochromator being formed by a band-pass filter.

51. Apparatus according to claim 43, said two light paths being superimposed to each other by a dichroic mirror and transmitted through said sample cell in parallel directions, said sample cell having at least three windows, one of said light paths being used for measuring absorption, the other one being used for fluorescence excitation, the absorption light being transmitted through a spectral filter and directed onto its photodetector, the fluorescence light emitted at right angle being transmitted through at least one spectral filter and directed onto at least one fluorescence emission photodetector.

52. Apparatus according to claim 51, wherein said two superimposed light paths transmit radiation with respect to said sample cell in opposite directions.

53. Apparatus according to claim 3, modified for fluorescence measurements using the front-on technique, wherein said sample cell has at least one lens-shaped window, said window being placed in said light path and directed towards said monochromator, said collecting lens in front of said cell holder being removed from the said light path and replaced by a light-collecting lens of large aperture, which is inserted into said cell holder close to said sample cell, said light-collecting lens imaging the monochromator aperture plane onto said cell chamber, said light-collecting lens also collecting fluorescence light emitted from said liquid sample and directing it onto a dichroic mirror inserted into said light path, being inclined by 45°

to said light path and reflecting said fluorescence light onto one emission photodetector.

54. Apparatus according to claim 1, wherein said cell holder, said sample cell, and optical elements, which optically follow said monochromator, are contained within a light-tight sample cell compartment, said photodetectors being mounted outside in separate housings and connected to said compartment by light-tight flanges.

55. Apparatus according to claim 54, wherein said standard optical elements have holders and supporting devices, said holders and supporting devices mounted with alignment means and released from said compartment by releasing screws.

56. Apparatus according to claim 55, modified for measurements of optical rotation and circular dichroism, wherein said beam splitter is removed and a polarizing optical modulator is inserted into said light path.

57. Apparatus according to claim 1, provided with movable mirrors for quick interchange of said light source and said photodetector.

58. Apparatus according to claim 1, assembled in the block-building technique, wherein the optical functional units are mounted on optical benches on a shock-insolated mounting plate, said mounting plate being electrically conducting and serving as a reference earth to said apparatus.

59. Apparatus according to claim 58, wherein said mounting plate is formed by a plane plate of light metal, mounted on a steel frame, further comprising a thin layer of shock-insulting and damping plastic material between said plate and said frame, and anti-shock suspension elements mounting said steel frame on a supporting frame.

60. Apparatus according to claim 36, wherein said sample cell is designed for use as a temperature-jump cell, said apparatus further comprising a high-voltage pulse source, said sides of said cell chamber forming a diced glass body, said sample cell further comprising an outer body made of insulating material, two electrodes, and two gaskets, said outer body mounting said glass body by said gaskets and having window openings, said light-collecting window being armoured by a plane-convex lens mounted in said outer body, said electrodes mounted onto the bottom and the cover side of said outer body, said bottom and said cover side made as an insulated and a grounded high-voltage connector, respectively, said cover being detachable for filling said cell chamber.

61. Apparatus according to claim 60, the axial ends of said glass body being ground as hollow half-spheres, said electrodes diving into said half-spheres.

62. Apparatus according to claim 1, wherein said sample cell is designed for use as a rapid-mixing cell, said apparatus further comprising a stopped-flow drive unit, said sample cell further comprising:

a mixing chamber with at least two entrance ports and one exit port, two inlet tubing connectors and one outlet tubing connector, at least two inlet channels connecting said inlet connectors to said entrance ports and one outlet channel connecting said cell chamber to said outlet connector, said exit port being closely connected to said cell chamber, said channels made in chemically inert material, said apparatus further comprising flexible tubings connecting said connectors to said drive unit, said tubings insulating mechanical shocks caused by operation of said drive unit from the optical components of said apparatus.

63. Apparatus according to claim 62, said sample cell further comprising a metal outer body and an inner body of chemically inert material, said inner body comprising said channels and said cell chamber, further comprising an intermediate channel between said exit port and said cell chamber, said cell chamber formed by a capillary bore longitudinally transversed by said light path and by two UV-transmitting cylindrical windows, said windows having a larger diameter as said bore and mounted at both sides of said bore by threaded mounting rings, said bore, said intermediate channel, and said outlet channel forming a Z-type arrangement.

64. Apparatus according to claim 62, comprising a first light path and means for measurements of transmitted light and a second light path and means for measurements of emitted light, said sample cell having at least three windows and at least one light-collecting window in said second light path, said sample cell further comprising:

a cylindrical outer body, a cell chamber formed by a capillary of UV-transmitting material, threaded means mounting said capillary and said mixing chamber, gaskets, and a plane-convex lens with said light-collecting window, the axis of said capillary being centered to the main axis of said body, said mixing chamber contacting one end side of said capillary, said outer body mounting said lens.

65. Apparatus according to claim 64, wherein the outside of said capillary is partly covered by a black light-absorbing glaze, said glaze having openings in reference to said light paths.

66. Apparatus according to claim 64, said body forming diaphragm openings close to said capillary in reference to said light paths.

67. Apparatus according to claim 64, said capillary being formed by four plates of fused silica, said plates being fused together by black intermediate layers, forming a glass body of rectangular cross section.

68. Apparatus according to claim 67, said glass body having in opposite directions thin and thick plates, respectively, further comprising pieces of black filling glass inside, said pieces and said plates forming a Z-shaped flow capillary, the center part of said flow capillary being transversed by said light paths.

69. Apparatus according to claim 67, characterized by a set of glass bodies having identical outer cross sections but various dimensions inside.

70. Apparatus according to claim 64, said mixing chamber facing the lower end side of said capillary, said sample cell having at least two ball valves between said inlet flow channels and said mixing chamber, each of said ball valves comprising:

a ball of chemically inert material, a lower valve plate with a conical bore accepting said ball, and an upper valve plate with noses stopping said ball.

71. Apparatus according to claim 64, said inlet flow channels being formed by thin plastic tubings embedded into said outer body in close thermal contact, said channels acting as heat exchangers, each of said channels having at least a volume which equals the volume of said cell chamber.

72. Apparatus according to claim 64, said sample cell further comprising a plunger movable in said capillary and an adjustable stop with said plunger, said outlet flow channel being formed by a thin metal capillary, said metal capillary moving in said stop, said stop being mounted in said outer body.

73. Apparatus according to claim 62, wherein said sample cell is designed for use as a combined rapid-mixing temperature-jump cell, said apparatus further comprising a high-voltage pulse source, said sample cell further comprising an insulating cell body, a grounded upper electrode connected to a metal cover, and an insulated lower electrode connected to a high-voltage connector, said mixing chamber mounted inside said grounded electrode, said grounded electrode comprising a symmetric arrangement of small capillaries leading into said cell chamber, and gaskets, said insulated electrode comprising a draining gap, said gap connected to said outlet channel, said outlet channel passing a section of said grounded electrode.

74. Apparatus according to claim 73, comprising a first and a second light path, said sample cell having at least three windows and at least one light-collecting window in said second light path, said sample cell further comprising:

a cell chamber formed by capillary body of UV-transmitting material, threaded means mounting said capillary, and a plane-convex lens with said light-collecting window, the axis of said capillary being centered to the axis of said cell body, said cell body mounting said lens.

75. Apparatus according to claim 74, said sample cell comprising a set of replaceable electrodes with and without said mixing chamber and said small capillaries, and with and without said gap, respectively, for alternative use as a combined rapid-mixing temperature-jump cell and as a pure temperature-jump cell.

76. Apparatus according to claim 36, wherein said sample cell is designed for use as a rapid-mixing cell, said cell forming an integral unit with said stopped-flow drive unit, said integral unit comprising:

two drive syringes, a piston actuator actuated via an external tubing by an auxiliary pressurized medium, mechanical coupling means coupling said syringes to said actuator, a mixing chamber facing said cell chamber, said mixing chamber having two entrance ports and one exit port, said exit port connected directly to said cell chamber, a stopping syringe with an adjustable stop provided with a switch, three three-way valves, two inlet and one outlet connector, and internal channels between said valves, said syringes, said mixing chamber, said cell chamber, and said inlet and outlet connectors, said valves alternatively switching said drive syringes to said inlets and said stopping syringe to said outlet, respectively, and to said mixing chamber and to said cell chamber, respectively.

77. Apparatus according to claim 1, the main axis of said cylindrical structure being vertically arranged, wherein said cell holder and sample cells for temperature-jump and field-jump perturbation by a high-voltage DC-pulse have complementary high-voltage connectors at their lower sides, sample cells for supply of hydraulic perturbation energy and for supply of reacting sample solutions have pressure resistant tube connections at their upper sides, and sample cells for supply of optical perturbation energy have at least one auxiliary optical window in the upper half-plane perpendicular to the direction of said light path.

78. Apparatus according to claim 77, said apparatus having a first light path measuring monochromatic absorption and a second light path provided with interchangeable lenses and filters, said apparatus further comprising a flash-light source and means for alternative installation of a photodetector and said flash-light source in said second light path.

79. Apparatus according to claim 77, wherein said cell holder has a system of holes and gaps and a hose connection for supply of purging gas to the windows of said sample cell and to optical elements mounted into the walls of said cell holder, said holes and gaps extending in upward direction and being interconnected by a circular channel.

80. Apparatus according to claim 1, wherein said sample cells have a rotary body and said cell holder has a cylindrical bore, the main axis of said bore being vertical, said cell holder further comprising alternative means for clamping small and large sample cells, the upper part of said bore being threaded for clamping small sample cells by a threaded mounting ring, the upper side of said cell holder having tap holes, said tap holes fitting screws for mounting a flange of large sample cells.

81. Apparatus according to claim 80, wherein said mounting ring comprises a threaded outer ring, an inner ring axially movable in said outer ring, and a spring disk element between said rings, said inner ring pressing on a metal cover of said small sample cells.

82. Apparatus according to claim 80, wherein said cell holder has a flat cone and slot blocks at the circumference of said cylindrical structure, said sample cells have complementary cones and slots at the lower sides of their middle parts, said cones and slot blocks centering and positioning said sample cells.

83. Apparatus according to claim 77, said sample cells having a slim bore in their upper parts, said bore fitting a temperature sensing probe with a very small air gap.

84. Apparatus according to claim 77, wherein said sample cells have rotational lower and middle parts and a box-shaped upper part.

85. Apparatus according to claim 1, further comprising an adapter mating rectangular spectrophotometer cuvettes, said adapter comprising:

a cylindrical metal body having identical outer dimensions as said sample cells at least in its middle part, at least one hole of rectangular cross section in said body, and at least two window openings with said hole, the axis of said hole coinciding with the cylindrical axis of said body, said cross section having two sides parallel to said light path, the axis of said openings having an identical position with respect to said outer dimensions as the main optical axis of said sample cells.

86. Apparatus according to claim 85, comprising a first and a second light path, said light source and said monochromator arranged in said first light path, said light paths and the main axis of said cylindrical structure being perpendicular to each other, said adapter comprising at least three window openings, the axis of adjacent openings being perpendicular to each other and to the axis of said hole.

87. Apparatus according to claim 86, said adapter further comprising a plane-convex lens with at least one window.

88. Apparatus according to claim 85, said adapter further comprising a lift mechanism formed with said hole, said lift having at least two stops and accepting two cuvettes in superimposed positions.

89. Apparatus according to claim 85, said metal body comprising an outer part, a revolving inner part with a handle, and a stopping device, said outer part having a cylindrical bore in excentric position with respect to said outer dimensions, said inner part mating said cylindrical bore and comprising at least two rectangular bores in a symmetric arrangement, said stopping device having one stop position with each of said rectangular bores, said device centering the position of said rectangular bore to the main axis of said body.

90. Apparatus according to claim 1, wherein the hollow structure enclosing the selected sample cell is a cylindrical structure.

91. Apparatus according to claim 1, wherein the hollow structure is formed to have a cylindrical opening;

and an adapter is provided having an outer surface matching the cylindrical opening and an inner cross-sectional area matching the cross section of the sample cell.

92. Apparatus according to claim 91, wherein the inner cross-sectional area is square.

93. Apparatus according to claim 1, for use with rectangular spectrophotometric cuvettes, said apparatus having a first light path measuring monochromatic absorption and a second light path provided with interchangeable lenses and filters, said apparatus further comprising a flash-light source and means for alternative installation of a photo detector and said flash-light source in said second light path.

94. Apparatus according to claim 93, wherein the hollow structure is formed to have a cylindrical opening;

and an adapter is provided having an outer surface matching the cylindrical opening and an inner cross-sectional area matching the cross sectin of the sample cell.

95. Apparatus for investigating fast chemical reactions by optical detection, said reactions being initiated in a chemical system by an external perturbation, said apparatus comprising means for performing said external perturbation, at least one light path, means for supporting a sample cell in said light path, said sample cell forming a cell chamber for holding a liquid sample of said chemical system, at least one photodetector, said light path comprising a light source, a monochromator, means for imaging said light source onto the entrance of said monochromator, and means for imaging the exit of said monochromator onto said sample cell chamber, said apparatus comprising also means for directing light from said liquid sample onto said photodetector, the improvement comprising:

(a) a set of at least two different types of sample cells, each of said types having one different means for application, said means comprising;

(a.1) two electrodes facing opposite sides of said chamber for temperature-jump perturbation, and means for the application of at least one additional parameter of perturbation comprising;

(a.2) a pressure autoclave and pressure release means for pressure-jump perturbation,

(a.3) at least one optical window in an auxiliary light path for flash-light perturbation,

(a.4) a mixing chamber and flow-channels for rapid mixing, and

(a.5) two electrodes, a mixing chamber, and flow-channels for combined rapid mixing and temperature-jump perturbation;

each of said sample cells having a specific sample volume, and at least two optical windows for application of at least one of the following parameters of observation;

optical absorption, fluorescence, scattered light, and parameters of polarization, said sample cells having identical exterior dimensions at least in their middle parts and an identical position of their main optical axis with respect to said exterior dimensions, and at least two further optical windows similar to said two first-mentioned optical windows and capable of passing optical radiation therethrough;

(b) at least two different ones of the following perturbation supply means comprising;

(b.1) a high-voltage pulse source, and at least one of;

(b.2) a pressure supply,

(b.3) a flash-light source, and

(b.4) a stopped-flow drive system;

said flash-light source being located to pass its emitted flash radiation through said two further windows;

(c) a metallic sample cell holder holding said sample cells and holding one selected sample cell operatively inserted into said apparatus, said holder comprising;

(c.1) a hollow structure enclosing said selected sample cell.

(c.2) Threaded fixation means for clamping said sample cell therein,

(c.3) thermostatting channels connected to a liquid thermostatting system,

(c.4) window openings for passing said light path in a direction perpendicular to the cylindrical axis of said hollow structure,

(c.5) means for connecting a high-voltage pulse source at one end of said hollow structure, and

(c.6) said structure including means defining an inner cross section matching the cross section of the selected sample cell and fitting around said cell in close mechanical and thermal contact therewith to place said holder and said sample cell in close mechanical and thermal contact; and

(d) a set of changeable optical elements adapting said light path to the optical dimensions of the chamber of said selected sample cell, said elements comprising at least one lens mounted in an adjustable holder and at least one diaphragm modifying the free exit aperture of said monochromator.

96. Apparatus according to claim 95, wherein the hollow structure enclosing said selected sample cell is a cylindrical structure.

97. Apparatus according to claim 95, wherein said apparatus has a first light path measuring monochromatic absorption and a second light path provided with interchangeable lenses and filters, said apparatus further comprising means for alternative installation of a photodetector and said flash-light source in said second light path.

98. Apparatus according to claim 97, wherein said means defining the inner cross section matching the cross section of the sample cell comprises an adapter mating rectangular spectrophotometer cuvettes, said adapter comprising:

a cylindrical metal body having identical outer dimensions as said sample cells at least in its middle part, at least one hole of rectangular cross section in said body, and at least two window openings with said hole, the axis of said hole coinciding with the cylindrical axis of said body, said cross section having two sides parallel to said light path, the axis of said openings having an identical position with respect to said outer dimensions as the main optical axis of said sample cells.

99. Apparatus according to claim 95, said set of sample cells further comprising a combined flow temperature-jump cell having one flow inlet bore and one flow outlet bore, two electrodes, and at least two optical windows for optical observation, said combined cell being operatively inserted into said cell holder, said flow inlet being connected to a drive syringe containing a liquid sample of said chemical system, said flow outlet being connected to a stopping syringe, said drive syringe being thermostatted by a first thermostat and said cell holder being thermostatted by a second thermostat, said first thermostat being set to a lower temperature than said second thermostat, said apparatus further comprising two temperature sensing probes measuring the temperature difference between said driving syringe and said sample cell, means controlling the high-voltage pulse energy delivered by said pulse source relative to said temperature difference, means actuating said driving syringe, and means triggering said pulse source by said stopping syringe, whereby the high-voltage pulse is released to said electrodes immediately after said stopping syringe has stopped.

100. Apparatus according to claim 99, wherein said controlling means adjust said high-voltage pulse energy automatically to heat a liquid sample contained in the cell chamber of said combined sample cell by a temperature-jump that equals said temperature difference.

101. Apparatus according to claim 99, wherein said inlet flow bore has its axis centered with respect to the cell chamber of said combined sample cell and produces a flow jet when said driving syringe is actuated, said sample cell further comprising an outlet channel symmetrically arranged around said inlet bore and connected to said outlet bore.